CN109134457A - Benzo Féraud oxazoline derivates and its application - Google Patents
Benzo Féraud oxazoline derivates and its application Download PDFInfo
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Abstract
The invention discloses a kind of purposes of benzo Féraud oxazoline derivates and the analog derivative in preparation ORGANIC ELECTROLUMINESCENCE DISPLAYS and lighting technical field, the present invention also provides a kind of organic electroluminescence device, which includes the benzo Féraud oxazoline derivates.Organic electroluminescence device of the invention has better luminescent properties compared to existing organic electroluminescence device, can be driven with lower voltage, power consumption is also lower, longer life expectancy.
Description
Technical field
The invention belongs to field of organic electroluminescence, and in particular, to a kind of benzo Féraud oxazoline derivates further relate to make
With the organic electroluminescence device of the benzo Féraud oxazoline derivates.
Background technique
1998, the Ma Yuguang professor of Jilin University adulterated osmium complex [Os in poly N-vinyl carbazole (PVK)
(CN)2(PPh3)2Bpy] it is prepared for electro phosphorescent device (Synthetic Metals, 1998,94:245-248).The same year,
Thomson cooperates to be entrained in phosphor material octaethylporphyrin platinum (PtOEP) in 8-hydroxyquinoline aluminium (Alq3) with Forrest and make
For the luminescent layer of electroluminescent device, make internal quantum efficiency and external quantum efficiency be respectively increased to 23%, 4% (Nature,
1998,395:151-154；Appl.Phys.Lett.,1999,75:4-6).Since then, organic hair based on phosphorescent metal complex
Optical device just develops rapidly.Different from traditional small organic molecule and conjugate polymer material, transient metal complex can
With simultaneously obtain singlet and triplet excitons, on realization theory maximum internal quantum efficiency be 100% (J.Appl.Phys.,
2001,90:5048-5051；Appl.Phys.Lett.,2002,80:2308-2310).
In classical phosphorescent OLED device, other than luminescent dye, material of main part is similarly indispensable.Phosphorescent coloring
It usually not separately as luminescent layer, but is entrained in suitable material of main part, forms Subjective and Objective luminescence system, to weaken
The high concentration quenching effect of triplet excitons.In order to realize effective energy transmission, usually require that the energy gap of material of main part is greater than
Dyestuff and triplet are higher than the triplet of dye molecule.It in this way could be smoothly T1 state energy from material of main part
It is transferred to phosphorescent coloring or triplet excitons is limited in dye molecule, to realize efficient phosphorescent emissions.In addition, main
The glass transition temperature Tg of body material is related to the film forming and thermal stability of material.The low material thermal stability of Tg temperature is poor
And be easy crystallization or reunite, the service life of device will be substantially reduced, seriously reduces device efficiency.Therefore, find have high-Tg,
High triplet energy level, wide energy gap material of main part just become more difficult, develop novel material of main part with critically important reality
Border application value.
Summary of the invention
Purpose of this disclosure is to provide a kind of benzo Féraud quinoline derivant and its application and organic electroluminescence device, this public affairs
The benzo Féraud quinoline derivant for opening offer is applied in organic electroluminescence device, can reduce driving voltage, improves electric current effect
Rate extends device lifetime.
To achieve the above object, the disclosure provides a kind of benzo Féraud oxazoline derivates, the benzo Féraud oxazoline derivates
With structure shown in following general formula (1-1) or (1-2):
Wherein, R is hydrogen atom or phenyl.
Ar1And Ar2It is identical or different, it is each independently selected from substituted or unsubstituted C6~C30Aryl, it is substituted or unsubstituted
C2~C30Heteroaryl, substituted or unsubstituted C6~C30Arylamino, substituted or unsubstituted C6~C30Heteroaryl amino；
Ar1With Ar2Interconnection or Ar1With Ar2Mutually it is not connected to；
The substituted C6~C30Aryl, substituted C2~C30Heteroaryl, substituted C6~C30Arylamino and substitution
C6~C30Substituent group in heteroaryl amino is selected from halogen group, nitro, C1~C6Alkyl, C1~C6Alkoxy, C6~
C30Aryl.
The disclosure also provides application of the benzo Féraud oxazoline derivates in organic electroluminescence device.
The disclosure also provides a kind of organic electroluminescence device, which includes substrate, anode layer, yin
Pole layer and at least one layer of organic function layer between anode layer and cathode layer；Wherein, in the organic function layer extremely
Few one layer by independent component or include benzo Féraud oxazoline derivates provided by the disclosure in the form of component of mixture.
Compared with prior art, the benzo Féraud oxazoline derivates of the disclosure have the advantages that
1, the benzo phenanthroline group that electronics lacks is connected the acceptor-donor to be formed with the fragrant amino group of electron rich
Type molecule proposes high molecular triplet, can effectively widen exciton recombination region, so that sudden between triplet excitons
It goes out significant decrease, to obtain compared with high triplet, the excellent bipolarity phosphorescent light body material of wider energy gap.
2, the benzo phenanthroline group with biggish conjugated structure is conducive to material molecule evaporation film-forming mistake as parent nucleus
Intermolecular solid-state accumulation in journey, effectively improves charge in intermolecular transfer and transmission capacity, has very high current-carrying
Transport factor, while biggish space structure greatly improves the glass transition temperature Tg of compound, such Organic Electricity
Electroluminescent material heat with higher and chemical stability.
It 3, can be with when bipolar host material of the benzo Féraud oxazoline derivates of the disclosure as doping type luminescent device
The transmission of appropriate balance carrier avoids carrier in the compound of interface, reduces exciton and exist so that exciton be made uniformly to be distributed
Triplet state-triplet state quenching when high concentration.Moreover, the organic function layer based on bipolar materials can be such that device architecture becomes
Simply.
It 4, can also be significantly when the benzo Féraud oxazoline derivates of the disclosure are used as the material of main part of red phosphorescent luminescent layer
The performance for improving organic electroluminescence device, makes it have high brightness, high efficiency, low driving voltage, longer service life.
5, the benzo Féraud oxazoline derivates of aryl or heteroaryl, the benzophenanthrene that the disclosure provides are directly connected to compared to parent nucleus
Sieve oxazoline derivates reduce driving voltage by the transmission of equilbrium carrier, extend device lifetime.
Other feature and advantage of the disclosure will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Fig. 1 is HOMO, LUMO trajectory diagram of parent nucleus benzo phenanthroline.
Specific embodiment
It should be noted that in the present invention, the expression way of Ca~Cb represents the carbon atom number that the group has as a~b,
Unless specifically indicated, it is however generally that the carbon atom number does not include the carbon atom number of substituent group.
In the present invention, the statement for chemical element includes the concept of chemical property identical isotope, such as " hydrogen "
Statement also includes the concept of chemical property identical " deuterium ", " tritium ".
Hetero atom in the present invention is often referred to selected from B, N, O, S, P, P (=O), Si and atom or atomic group in Se.
Benzo Féraud oxazoline derivates of the invention have structure shown in following general formula (1), (2):
Wherein, R is hydrogen atom or phenyl, Ar1And Ar2It is same or different to each other, and is each independently selected from substitution or without taking
The C in generation6~C30Aryl, substituted or unsubstituted C2~C30Heteroaryl, substituted or unsubstituted C6~C30Arylamino or
Person C6~C30Heteroaryl amino；
Ar1With Ar2It is connected with each other or Ar1 and Ar2 is mutually not connected to.
Substituted C6~C30Aryl, substituted C2~C30Heteroaryl, substituted C6~C30Arylamino, substituted C6~C30
Substituent group in heteroaryl amino is each independently halogen group, nitro, C1~C6Alkyl, C1~C6Alkoxy or C6~
C30Aryl.
According to the disclosure, the C6~C30Aryl be it is well-known to those skilled in the art, that is, have 60~30 skeletons
The aryl of carbon atom preferably has 6~20 backbone carbon atoms；Preferably, the aromatic hydrocarbon group includes phenyl, xenyl, three
Xenyl, naphthalene, anthryl, fluoranthene base, phenanthryl, indenyl, benzo fluorenyl, fluorenyl and its derivative, triphenylene, pyrenyl, base,At least one of base and aphthacene base.It is highly preferred that the xenyl includes 2- xenyl, 3- xenyl and 4- biphenyl
Base；The terphenyl includes p- terphenyl -4- base, p- terphenyl -3- base, p- terphenyl -2- base, m- three
Phenyl -4- base, m- terphenyl -3- base and m- terphenyl -2- base；The naphthalene is 1- naphthalene and/or 2- naphthalene；It is described
Anthryl includes at least one of 1- anthryl, 2- anthryl and 9- anthryl；The fluorenyl derivative be selected from by 9,9 '-dimethyl fluorenes,
At least one of 9,9 '-spiral shell, two fluorenes, benzfluorene and indenofluorene；The pyrenyl includes in 1- pyrenyl, 2- pyrenyl and 4- pyrenyl
It is at least one.
According to the disclosure, above-mentioned heteroaryl refers to at least one hetero atom and with certain amount ring skeleton atom
Monocycle or polycyclic aromatic group, the hetero atom include one or more hetero atoms selected from B, N, O, S, P (=O), Si and P；
Preferably, the hetero atom includes one or more hetero atoms for being selected from O, S and N.The C2~C30Heteroaryl has 2-30
Backbone carbon atoms；Preferably, Ar1And Ar2It is each independently selected from substituted or unsubstituted C5~C20(heteroaryl has 5- to heteroaryl
20 backbone carbon atoms)；It is highly preferred that the heteroaryl includes furyl, thienyl, pyrrole radicals, benzofuranyl, benzo thiophene
Two between pheno base, isobenzofuran-base, indyl, dibenzofuran group, dibenzothiophene, carbazyl and its derivative or benzo
Oxole base, wherein the carbazole radical derivative include but is not limited to 9- phenyl carbazole, 9- naphthyl carbazole benzo carbazole,
At least one of dibenzo-carbazole, indolocarbazole.
According to the disclosure, the C6~C30Arylamino is preferably triaryl amino, for example, can for tri- phenylamino of 4- or
Tri- phenylamino of 3-；The C6~C30Heteroaryl amino is preferably three (miscellaneous) arylaminos, which at least contains
One arylamino, such as can be amino 4- [N- phenyl-N- (dibenzofurans -3- base)] phenyl amino or 4- [N- phenyl -
N- (dibenzothiophenes -3- base)] phenyl amino.
According to the disclosure, the substituted C6~C30Aryl, substituted C2~C30Heteroaryl, substituted C6~C30Aryl ammonia
Base and substituted C6~C30Substituent group in heteroaryl amino is preferably C each independently1~C6Alkyl or C1~C6Alcoxyl
Base replaces, the C1~C6Alkyl be more preferably methyl, ethyl, isopropyl or cyclohexyl, the C1~C6Alkoxy
Preferably C1~C3Alkoxy, further preferably methoxyl group, ethyoxyl, propoxyl group, isopropoxy or phenoxy group.
According to the disclosure, Ar1With Ar2It is connected with each other and the nitrogen-atoms being connected between parent nucleus forms cricoid fused-aryl,
Such as Ar1And Ar2Singly-bound ,-O- ,-S- or-C (CH can be passed through3)2It is connected with each other, the fused-aryl also can have substitution
Base.Preferably, Ar1And Ar2It is connected with each other and is formed together the group as shown in formula (2)~(6) with N:
Wherein, * indicates the connection site with parent nucleus, ties shown in general formula (1-1) when benzophenanthrene hello oxazoline derivates have
When structure, the parent nucleus isWhen benzo Féraud oxazoline derivates have shown in general formula (1-2)
Structure when, the parent nucleus is
According to the preferred embodiment of the disclosure, Ar1And Ar2Structure it is identical.Symmetrical structure is convenient for the conjunction of material
At being conducive to the reduction of production cost.
According to the disclosure, the benzo Féraud oxazoline derivates preferably are selected from one of following structural formula, but are not limited to following
Structural formula:
This hair and Féraud oxazoline derivates can be applied to ORGANIC ELECTROLUMINESCENCE DISPLAYS and lighting area.
The present invention also provides a kind of organic electroluminescence devices comprising substrate, anode layer, cathode layer and between sun
At least one layer of organic function layer between pole layer and cathode layer, it is at least one layer of with independent component or mixed in the organic function layer
The form of polymer component includes benzo Féraud oxazoline derivates of the invention.
According to the disclosure, the organic function layer can include but is not limited to hole injection layer, hole transmission layer, electricity
Sub- barrier layer, organic luminous layer, hole blocking layer, electron transfer layer, electron injecting layer etc. preferably include hole injection layer, sky
Cave transport layer, organic luminous layer, electron transfer layer, the hole injection layer are formed on the anode layer, the sky
Cave transport layer is formed on the hole injection layer, and the cathode layer is formed on the electron transfer layer, described
It is organic luminous layer between hole transmission layer and the electron transfer layer；The organic luminous layer includes material of main part and doping
Dyestuff, the material of main part contain the benzo Féraud oxazoline derivates；It is highly preferred that organic electroluminescence device of the invention
Make the material of main part of phosphorescence luminescent layer using compound A1~A60.
Excellent properties of the organic electroluminescence device of the disclosure based on disclosure compound, can reduce device rise it is bright and
Operating voltage improves device efficiency, extends device lifetime.
The substrate in conventional organic luminescence device can be used in the organic electroluminescence device substrate of the disclosure, such as: glass
Glass or plastics are, it is preferable to use glass substrate.Anode material can use transparent high conductivity material, such as indium tin oxygen (ITO),
Indium zinc oxygen (IZO), stannic oxide (SnO2), zinc oxide (ZnO) etc..It is preferable to use ITO to make anode material in device of the present invention.
The hole injection layer of disclosure organic electroluminescence device can be using CuPc, TNATA and PEDT:PSS etc., this hair
Make hole injection layer material using 2-TNATA in bright element manufacturing.Hole transmission layer can use N, N '-two (3- tolyl)-
N, N '-diphenyl-[1,1- xenyl] -4,4 '-diamines (TPD) or N, N '-diphenyl-N, N '-two (1- naphthalene)-(1,1 '-connection
Phenyl) the tri-arylamine groups material such as -4,4 '-diamines (NPB).Wherein NPB is common hole mobile material, in device of the invention
Hole transport layer material in production selects NPB.Thickness of hole transport layer is generally at 5nm-5 μm, it is preferable that more preferably；Common
Electron transport material has Alq3, Bphen, BCP, PBD etc., selects Alq3 to make electron transfer layer material in element manufacturing of the invention
Material.
The organic luminous layer of disclosure organic electroluminescence device can be also possible to multi-luminescent layer structure for single-shot photosphere；
Luminescent color is unlimited, can be to be such as red, yellow, blue, green, and dopant dye can select Ir (ppy)3、Ir(piq)2acac、Ir(4,
6-dFppy)2(pic) phosphor materials, preferably red phosphorescence material, the more preferable Ir (piq) such as2acac。
Cathode can use metal and its mixture structure, such as Mg:Ag, Ca:Ag, be also possible to electron injecting layer/gold
Belong to layer structure, such as LiF/Al, Li2O/Al common cathode structure.Wherein electron injecting layer can for alkali metal, alkaline-earth metal,
Simple substance, compound or the mixture of transition metal are also possible to the composite cathode structure of multilayer material composition.In device of the invention
Part production in it is preferable to use cathode material be LiF/Al.
It is well known by persons skilled in the art to include in addition to content cited in the above general remark and embodiment
Other technology contents of organic electroluminescence devices, such as production method and general ingredient etc., are also applied in the present invention.The present invention
Compound can also be used with conventionally known luminescent layer host material combination.
Brief description is carried out to the synthetic method of the compounds of this invention below.
Benzo Féraud oxazoline derivates of the invention are reacted by Buchwald, 4, the 9- phenyl-dihalide indicated by formula M
And 1,10- phenanthroline are coupled to obtain with diaryl-amine, representative synthesis path:
X indicates halogen, R, Ar1、Ar2General formula (1-1) and (1-2) description as above, X is preferably Cl.Unless otherwise indicated, originally
Raw materials used in invention, arylamine intermediate is commercial goods；Mass spectrum measures (Britain using ZAB-HS type mass spectrograph in the present invention
The manufacture of Micromass company), elemental analysis measures (Britain Elementar using vario EL type elemental analyser
Analysensysteme GmbH company manufacture).
Synthetic example 1~4 describes the preparation of intermediate M1~M4
The preparation of 1. intermediate M1 of synthetic example, synthetic route are as follows:
2,3- bis- amido naphthalenes (20mmol, 3.16g) and methyl acrylate (60mmol, 5.16g), AlCl3 (60mmol,
7.92g) mixing is dissolved in 50ml dimethylbenzene, is to slowly warm up to return stirring, and TLC monitors reaction end, 5 hours end of reaction.
Add water quenching to go out, extracted with toluene, silicagel column is crossed in extract liquor concentration, and eluent is Shi You Mi ﹕ ethyl acetate=5 ﹕ 1, concentration elution
Agent obtains intermediate M1-A (4.0g, yield 60%).
Intermediate M1-A (12mmol, 4.0g) is dissolved in PPA 40mL, and temperature rising reflux is stirred to react, and TLC monitors reaction end,
2 hours end of reaction.Reaction solution is added to the water and is quenched, is extracted with dichloromethane, anhydrous sodium sulfate dries, filters, decompression rotation
Do to obtain oily intermediate.Oily intermediate obtained as above is dissolved in 50mL dehydrated alcohol, 1g pd/C is added, replaces oxygen 3
Secondary, 50 DEG C of normal pressure are stirred to react 3 hours, and TLC monitors reaction end.Diatomite filtering, decompression are spin-dried for obtaining intermediate M1-B
(1.6g, yield 50%).
Intermediate M1-B (6mmol, 1.6g) is dissolved in phosphorus oxychloride 30mL, is heated to return stirring reaction, TLC monitoring reaction
Terminal, 4 hours end of reaction.Remove phosphorus oxychloride under reduced pressure, remaining liquid is slowly added to be quenched in ice water, be extracted with methylene chloride
It takes, extract liquor concentration, crosses silicagel column, eluent is Shi You Mi ﹕ methylene chloride=10 ﹕ 1, and eluent is concentrated, obtains intermediate M1
(1.25g, yield 70%).
The preparation of 2. intermediate M2 of synthetic example, synthetic route are as follows:
2,3- bis- amido naphthalenes (20mmol, 3.16g) and methyl cinnamate (60mmol, 9.72g), AlCl3 (60mmol,
7.92g) mixing is dissolved in 50ml dimethylbenzene, is to slowly warm up to return stirring, and TLC monitors reaction end, 5 hours end of reaction.
Add water quenching to go out, extracted with toluene, silicagel column is crossed in extract liquor concentration, and eluent is Shi You Mi ﹕ ethyl acetate=5 ﹕ 1, concentration elution
Agent obtains intermediate M2-A (6.0g, yield 63%).
Intermediate M2-A (12mmol, 5.8g) is dissolved in PPA 40mL, and temperature rising reflux is stirred to react, and TLC monitors reaction end,
2 hours end of reaction.Reaction solution is added to the water and is quenched, is extracted with dichloromethane, anhydrous sodium sulfate dries, filters, decompression rotation
Do to obtain oily intermediate.Oily intermediate obtained as above is dissolved in 50mL dehydrated alcohol, 1g pd/C is added, replaces oxygen 3
Secondary, 50 DEG C of normal pressure are stirred to react 3 hours, and TLC monitors reaction end.Diatomite filtering, decompression are spin-dried for obtaining intermediate M2-B
(2.7g, yield 55%).
Intermediate M2-B (6mmol, 2.5g) is dissolved in phosphorus oxychloride 30mL, is heated to return stirring reaction, TLC monitoring reaction
Terminal, 4 hours end of reaction.Remove phosphorus oxychloride under reduced pressure, remaining liquid is slowly added to be quenched in ice water, be extracted with methylene chloride
It takes, extract liquor concentration, crosses silicagel column, eluent is Shi You Mi ﹕ methylene chloride=8 ﹕ 1, and eluent is concentrated, obtains intermediate M2
(1.62g, yield 60%).
The preparation of 3. intermediate M3 of synthetic example, synthetic route are as follows:
Bis- amido naphthalene (20mmol, 3.16g) of 2,3- and triethylamine (60mmol, 6.06g) mixing are dissolved in 50ml methylene chloride
In, it is down to 0 DEG C, acryloyl chloride (50mmol, 4.5g) is added dropwise with constant pressure funnel under stirring, after being added dropwise, is slowly heated up
To being stirred at room temperature, TLC monitors reaction end, 5 hours end of reaction.Add water quenching to go out, is extracted with dichloromethane, extract liquor concentration,
Silicagel column is crossed, eluent is Shi You Mi ﹕ methylene chloride=8 ﹕ 1, and eluent is concentrated, obtains intermediate M3-A (4.3g, yield
88%).
Intermediate M1-A (16mmol, 4.3g) is dissolved in methylene chloride 60mL, and mixed liquor is down to 0 DEG C, uses constant pressure funnel
It is added dropwise Loprazolam (48mmol, 4.6g), after being added dropwise, is warmed to room temperature lower stirring, TLC monitors reaction end, reacts within 2 hours
It finishes.Add water quenching to go out, be extracted with dichloromethane, anhydrous sodium sulfate dries, filters, and decompression is spin-dried for obtaining oily intermediate.Will more than
Gained oily intermediate is dissolved in 50mL dehydrated alcohol, and 1g pd/C is added, and is replaced oxygen 3 times, 50 DEG C of normal pressure to be stirred to react 3 small
When, TLC monitors reaction end.Diatomite filtering, decompression are spin-dried for obtaining intermediate M3-B (2.7g, yield 65%).
Intermediate M3-B (10mmol, 2.6g) is dissolved in phosphorus oxychloride 30mL, is heated to return stirring reaction, and TLC monitoring is anti-
Answer terminal, 4 hours end of reaction.Remove phosphorus oxychloride under reduced pressure, remaining liquid is slowly added to be quenched in ice water, be extracted with methylene chloride
It takes, extract liquor concentration, crosses silicagel column, eluent is Shi You Mi ﹕ methylene chloride=10 ﹕ 1, and eluent is concentrated, obtains intermediate M3
(2.2g, yield 75%).
The preparation of 4. intermediate M4 of synthetic example, synthetic route are as follows:
Bis- amido naphthalene (20mmol, 3.16g) of 2,3- and triethylamine (60mmol, 6.06g) mixing are dissolved in 50ml methylene chloride
In, it is down to 0 DEG C, cinnamoyl chloride (50mmol, 8.3g) is added dropwise with constant pressure funnel under stirring, after being added dropwise, is slowly heated up
To being stirred at room temperature, TLC monitors reaction end, 5 hours end of reaction.Add water quenching to go out, is extracted with dichloromethane, extract liquor concentration,
Silicagel column is crossed, eluent is Shi You Mi ﹕ methylene chloride=8 ﹕ 1, and eluent is concentrated, obtains intermediate M4-A (7.1g, yield
85%).
Intermediate M4-A (16mmol, 6.7g) is dissolved in methylene chloride 60mL, and mixed liquor is down to 0 DEG C, uses constant pressure funnel
It is added dropwise Loprazolam (48mmol, 4.6g), after being added dropwise, is warmed to room temperature lower stirring, TLC monitors reaction end, reacts within 2 hours
It finishes.Add water quenching to go out, be extracted with dichloromethane, anhydrous sodium sulfate dries, filters, and decompression is spin-dried for obtaining oily intermediate.Will more than
Gained oily intermediate is dissolved in 50mL dehydrated alcohol, and 1g pd/C is added, and is replaced oxygen 3 times, 50 DEG C of normal pressure to be stirred to react 4 small
When, TLC monitors reaction end.Diatomite filtering, decompression are spin-dried for obtaining intermediate M4-B (4.1g, yield 62%).
Intermediate M4-B (10mmol, 4.1g) is dissolved in phosphorus oxychloride 30mL, is heated to return stirring reaction, and TLC monitoring is anti-
Answer terminal, 4 hours end of reaction.Remove phosphorus oxychloride under reduced pressure, remaining liquid is slowly added to be quenched in ice water, be extracted with methylene chloride
It takes, extract liquor concentration, crosses silicagel column, eluent is Shi You Mi ﹕ methylene chloride=10 ﹕ 1, and eluent is concentrated, obtains intermediate M4
(3.1g, yield 70%).
5~synthetic example of synthetic example 64 describes the preparation method of compound A1~A60.
The preparation of 5. compound A1 of synthetic example, synthetic route are as follows:
Under nitrogen protection, diphenylamines 3.38g (molecular weight 169,20mmol) is added in tri- mouthfuls of reaction flasks of 100ml, nothing
Water-toluene 40ml, is cooled to -78 DEG C, and the n-BuLi (2.4M, 21mmol) of 8.8ml is slowly added thereto.Drop finishes, and is stirred to react
30min, temperature rise to -30 DEG C naturally.Intermediate M1 2.83g (molecular weight 298,9.5mmol) is added under nitrogen stream, Pd2
(dba) 3 174mg (molecular weight 916,0.19mmol), 3 55mg of P (tBu) (molecular weight 202,0.27mmol).It finishes, oil bath is slow
Slowly it is heated to back flow reaction, TLC monitors reaction end, 8 hours end of reaction.It is cooling, add water quenching reaction, with 50ml dichloromethane
Alkane extraction, organic phase is dry with anhydrous MgSO4, and organic phase is evaporated, and obtained solid pillar layer separation obtains 4.35g yellow
Solid, molecular weight 564, yield 81%.
Product MS (m/e): 564, elemental analysis (C 40H 28N 4): theoretical value C:85.08%, H:5.00%, N:
9.92%；Measured value C:85.12%, H:5.02%, N:9.86%.
The magnetic resonance spectroscopy data of product: 1H NMR (500MHz, Chloroform) for comp.A1 δ 8.63-8.48 (m,
1H), 7.61 (dd, J=11.1,6.9Hz, 1H), 7.32-7.18 (m, 2H), 7.11-6.92 (m, 3H)
The synthesis of 6. compound A2 of embodiment, synthetic route are as follows:
Step 1: the synthesis of M5
Under nitrogen protection, be added in 100ml reaction flask 2,4- dimethylaniline 2.67g (molecular weight 121,
22mmol), 2,4- dimethyl bromobenzene 3.68g (molecular weight 184,20mmol), sodium tert-butoxide 5.76g (molecular weight 96,
60mmol), 3 121mg of 3 183mg of Pd2 (dba) (molecular weight 916,0.2mmol), P (tBu) (molecular weight 202,0.6mmol).
Dry toluene 50ml.It finishes, oil bath is slowly heated to back flow reaction, and TLC monitors reaction end, 10 hours end of reaction.It is cooling,
Add water quenching reaction, extracted with 50ml methylene chloride, organic phase is dry with anhydrous MgSO4, and organic phase is evaporated, and obtained solid is used
Pillar layer separation obtains 3.8g white solid, molecular weight 225, yield 85%.
Step 2: implementation process with embodiment 5, only changes diphenylamines into intermediate M5, synthesizes product.
Product MS (m/e): 676, elemental analysis (C 48H 44N 4): theoretical value C:85.17%, H:6.55%, N:
8.28%；Measured value C:85.03%, H:6.64%, N:8.33%.
The synthesis of 7. compound A-13 of embodiment, synthetic route are as follows:
Step 1: the synthesis of M6
Method only changes 2,4- dimethylaniline, 2,4- dimethyl bromobenzene into 4- with the synthesis of M5 in embodiment 6 respectively
Hexamethylene aniline, 4- cyclohexyl bromobenzene, pillar layer separation obtain white product 5.5g, yield 83%.
Step 2: implementation process with embodiment 5, only changes diphenylamines into intermediate M6, synthesizes product.
Product MS (m/e): 892, elemental analysis (C62H68N4): theoretical value C:86.05%, H:7.67%, N:6.27%；
Measured value C:86.00%, H:7.63%, N:6.37%.
The synthesis of 8. compound A4 of embodiment, synthetic route are as follows:
Step 1: the synthesis of M7
Method only changes 2,4- dimethylaniline, 2,4- dimethyl bromobenzene into 1- with the synthesis of M5 in embodiment 6 respectively
Amino naphthalenes, bromobenzene, pillar layer separation obtain white product 3.4g, yield 77%.
Step 2: implementation process with embodiment 5, only changes diphenylamines into intermediate M7, synthesizes product.
Product MS (m/e): 664, elemental analysis (C48H32N4): theoretical value C:86.72%, H:4.85%, N:8.43%；
Measured value C:86.51%, H:4.87%, N:8.62%.
The synthesis of 9. compound A-45 of embodiment, synthetic route are as follows:
Step 1: the synthesis of M8
Method only changes 2,4- dimethylaniline, 2,4- dimethyl bromobenzene into 2- with the synthesis of M5 in embodiment 6 respectively
Amino naphthalenes, bromobenzene, pillar layer separation obtain white product 3.1g, yield 70%.
Step 2: implementation process with embodiment 5, only changes diphenylamines into intermediate M8, synthesizes product.
Product MS (m/e): 664, elemental analysis (C48H32N4): theoretical value C:86.72%, H:4.85%, N:8.43%；
Measured value C:86.53%, H:4.90%, N:8.57%.
The synthesis of 10. compound A6 of embodiment, synthetic route are as follows:
Step 1: the synthesis of M9
Method only changes 2,4- dimethylaniline, 2,4- dimethyl bromobenzene into 2- with the synthesis of M5 in embodiment 6 respectively
Amino naphthalenes, 1- bromonaphthalene, pillar layer separation obtain white product 3.8g, yield 71%.
Step 2: implementation process with embodiment 5, only changes diphenylamines into intermediate M9, synthesizes product.
Product MS (m/e): 764, elemental analysis (C56H36N4): theoretical value C:87.93%, H:4.74%, N:7.32%；
Measured value C:87.53%, H:4.92%, N:7.55%.
The synthesis of 11. compound A7 of embodiment, synthetic route are as follows:
Step 1: the synthesis of M10
Method only changes 2,4- dimethylaniline, 2,4- dimethyl bromobenzene into 4- with the synthesis of M5 in embodiment 6 respectively
Phenylaniline, bromobenzene, pillar layer separation obtain white product 4.4g, yield 90%.
Step 2: implementation process with embodiment 5, only changes diphenylamines into intermediate M10, synthesizes product.
Product MS (m/e): 716, elemental analysis (C52H36N4): theoretical value C:87.12%, H:5.06%, N:7.82%；
Measured value C:87.22%, H:5.11%, N:7.67%.
The synthesis of 12. compound A-28 of embodiment, synthetic route are as follows:
Step 1: the synthesis of M11
Method only changes 2,4- dimethylaniline, 2,4- dimethyl bromobenzene into benzene with the synthesis of M5 in embodiment 6 respectively
Amine, 9- bromine are luxuriant and rich with fragrance, and pillar layer separation obtains white product 4.1g, yield 77%.
Step 2: implementation process with embodiment 5, only changes diphenylamines into intermediate M11, synthesizes product.
Product MS (m/e): 764, elemental analysis (C56H36N4): theoretical value C:87.93%, H:4.74%, N:7.32%；
Measured value C:88.05%, H:4.59%, N:7.36%.
The synthesis of 13. compound A9 of embodiment, synthetic route are as follows:
Step 1: the synthesis of M12
Method only changes 2,4- dimethylaniline, 2,4- dimethyl bromobenzene into benzene with the synthesis of M5 in embodiment 6 respectively
Bromo- 9, the 9- dimethyl fluorene of amine, 2-, pillar layer separation obtain white product 5g, yield 88%.
Step 2: implementation process with embodiment 5, only changes diphenylamines into intermediate M12, synthesizes product.
Product MS (m/e): 796, elemental analysis (C58H44N4): theoretical value C:87.41%, H:5.56%, N:7.03%；
Measured value C:87.61%, H:5.59%, N:6.80%.
The synthesis of 14. compound A10 of embodiment, synthetic route are as follows:
Step 1: the synthesis of M14
Method only changes aniline into naphthalidine with the synthesis of M12 in embodiment 13, and pillar layer separation obtains white product
4.76g, yield 71%.
Step 2: implementation process with embodiment 5, only changes diphenylamines into intermediate M13, synthesizes product.
Product MS (m/e): 896, elemental analysis (C66H48N4): theoretical value C:88.36%, H:5.39%, N:6.25%；
Measured value C:88.06%, H:5.59%, N:6.35%.
The synthesis of 15. compound A11 of embodiment, synthetic route are as follows:
Step 1: the synthesis of M14
Method only changes 2,4- dimethylaniline, 2,4- dimethyl bromobenzene into benzene with the synthesis of M5 in embodiment 6 respectively
Amine, 4- methoxybromobenzene, pillar layer separation obtain white product 3.6g, yield 90%.
Step 2: implementation process with embodiment 5, only changes diphenylamines into intermediate M14, synthesizes product.
Product MS (m/e): 624, elemental analysis (C42H32N4O2): theoretical value C:80.75%, H:5.16%, N:
8.97%, O:5.12%；Measured value C:80.35%, H:5.46%, N:8.91%.
The synthesis of 16. compound A12 of embodiment, synthetic route are as follows:
Step 1: the synthesis of M15
Method only changes 2,4- dimethylaniline, 2,4- dimethyl bromobenzene into benzene with the synthesis of M5 in embodiment 6 respectively
Amine, 4- bromine dibenzofurans, pillar layer separation obtain white product 3.3g, yield 65%.
Step 2: implementation process with embodiment 5, only changes diphenylamines into intermediate M15, synthesizes product.
Product MS (m/e): 744, elemental analysis (C52H32N4O2): theoretical value C:83.85%, H:4.33%, N:
7.52%, O:4.30%；Measured value C:83.35%, H:4.46%, N:7.91%.
The synthesis of 17. compound A13 of embodiment, synthetic route are as follows:
Implementation process only changes diphenylamines into carbazole with embodiment 5, synthesizes product.
Product MS (m/e): 560, elemental analysis (C40H24N4): theoretical value C:85.69%, H:4.31%, N:9.99%；
Measured value C:85.70%, H:4.20%, N:10.09%.
The synthesis of 18. compound A14 of embodiment, synthetic route are as follows:
Implementation process only changes diphenylamines into 7H- benzo carbazole, synthesizes product with embodiment 5.
Product MS (m/e): 660, elemental analysis (C48H28N4): theoretical value C:87.25%, H:4.27%, N:8.48%；
Measured value C:87.70%, H:4.20%, N:8.10%.
The synthesis of 19. compound A15 of embodiment, synthetic route are as follows:
Implementation process only changes diphenylamines into 7H- dibenzo-carbazole, synthesizes product with embodiment 5.
Product MS (m/e): 760, elemental analysis (C56H32N4): theoretical value C:88.40%, H:4.24%, N:7.36%；
Measured value C:88.70%, H:4.20%, N:7.10%.
The preparation of 20. compound A16 of synthetic example, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M2, synthesizes product with embodiment 5
Product MS (m/e): 716, elemental analysis (C 52H 36N 4): theoretical value C:87.12%, H:5.06%, N:
7.82%；Measured value C:87.02%, H:5.02%, N:7.96%.
The magnetic resonance spectroscopy data of product: 1H NMR (500MHz, Chloroform) for comp.A16 δ 8.54 (s, 1H),
8.33(s,2H),7.68–7.41(m,4H),7.24(s,4H),7.13–6.90(m,7H).
The synthesis of 21. compound A17 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M2, synthesizes product with embodiment 6
Product MS (m/e): 828, elemental analysis (C60H 52N 4): theoretical value C:86.92%, H:6.32%, N:
6.76%；Measured value C:87.02%, H:6.02%, N:6.96%.
The synthesis of 22. compound A18 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M2, synthesizes product with embodiment 7
Product MS (m/e): 1044, elemental analysis (C76H 76N4): theoretical value C:87.31%, H:7.33%, N:
5.36%；Measured value C:87.02%, H:7.02%, N:5.96%.
The synthesis of 23. compound A19 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M2, synthesizes product with embodiment 8
Product MS (m/e): 816, elemental analysis (C60H40N4): theoretical value C:88.21%, H:4.94%, N:6.86%；
Measured value C:88.02%, H:5.02%, N:6.96%.
The synthesis of 24. compound A20 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M2, synthesizes product with embodiment 9
Product MS (m/e): 816, elemental analysis (C60H40N4): theoretical value C:88.21%, H:4.94%, N:6.86%；
Measured value C:88.03%, H:5.01%, N:6.96%.
The synthesis of 25. compound A21 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M2, synthesizes product with embodiment 10
Product MS (m/e): 916, elemental analysis (C69H45N3): theoretical value C:89.05%, H:4.84%, N:6.11%；
Measured value C:89.04%, H:4.96%, N:6.00%.
The synthesis of 26. compound A22 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M2, synthesizes product with embodiment 11
Product MS (m/e): 868, elemental analysis (C64H44N4): theoretical value C:88.45%, H:5.10%, N:6.15%；
Measured value C:88.40%, H:5.14%, N:6.16%.
The synthesis of 27. compound A23 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M2, synthesizes product with embodiment 12
Product MS (m/e): 916, elemental analysis (C68H44N4): theoretical value C:89.05%, H:4.84%, N:6.11%；
Measured value C:89.15%, H:4.73%, N:6.12%.
The synthesis of 28. compound A24 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M2, synthesizes product with embodiment 13
Product MS (m/e): 948, elemental analysis (C70H52N4): theoretical value C:88.58%, H:5.52%, N:5.90%；
Measured value C:88.78%, H:5.42%, N:5.80%.
The synthesis of 29. compound A25 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M2, synthesizes product with embodiment 14
Product MS (m/e): 1048, elemental analysis (C78H56N4): theoretical value C:89.28%, H:5.38%, N:
5.34%；Measured value C:89.38%, H:5.43%, N:5.39%.
The synthesis of 30. compound A26 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M2, synthesizes product with embodiment 15
Product MS (m/e): 776, elemental analysis (C54H40N4O2): theoretical value C:83.48%, H:5.19%, N:
7.21%, O:4.12%；Measured value C:83.42%, H:5.17%, N:7.25%.
The synthesis of 31. compound A27 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M2, synthesizes product with embodiment 16
Product MS (m/e): 896, elemental analysis (C64H40N4O2): theoretical value C:85.69%, H:4.49%, N:
6.25%, O:3.57%；Measured value C:85.74%, H:4.52%, N:6.03%.
The synthesis of 32. compound A28 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M2, synthesizes product with embodiment 17
Product MS (m/e): 712, elemental analysis (C52H32N4): theoretical value C:87.62%, H:4.52%, N:7.86%；
Measured value C:87.32%, H:4.72%, N:7.96%.
The synthesis of 33. compound A29 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M2, synthesizes product with embodiment 18
Product MS (m/e): 812, elemental analysis (C60H36N4): theoretical value C:88.64%, H:4.46%, N:6.89%；
Measured value C:88.34%, H:4.66%, N:6.99%.
The synthesis of 34. compound A-13 0 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M2, synthesizes product with embodiment 19
Product MS (m/e): 912, elemental analysis (C68H40N4): theoretical value C:89.45%, H:4.42%, N:6.14%；
Measured value C:89.25%, H:4.47%, N:6.28%.
The preparation of 35. compound A-13 1 of synthetic example, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M3, synthesizes product with embodiment 5
Product MS (m/e): 564, elemental analysis (C40H28N4): theoretical value C:85.08%, H:5.00%, N:9.92%；
Measured value C:85.27%, H:4.85%, N:9.88%.
The magnetic resonance spectroscopy data of product: 1H NMR (500MHz, Chloroform) for comp.A31 δ 8.54 (dd, J=
11.1,6.9Hz, 1H), 7.58 (ddd, J=44.2,20.1,10.9Hz, 3H), 7.32-7.16 (m, 4H), 7.16-6.90 (m,
6H).
The synthesis of 36. compound A-13 2 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M3, synthesizes product with embodiment 6
Product MS (m/e): 676, elemental analysis (C48H44N4): theoretical value C:85.17%, H:6.55%, N:8.28%；
Measured value C:85.27%, H:6.85%, N:7.88%.
The synthesis of 37. compound A-13 3 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M3, synthesizes product with embodiment 7
Product MS (m/e): 892, elemental analysis (C64H68N4): theoretical value C:86.05%, H:7.67%, N:6.27%；
Measured value C:85.27%, H:6.85%, N:7.88%.
The synthesis of 38. compound A-13 4 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M3, synthesizes product with embodiment 8
Product MS (m/e): 664, elemental analysis (C48H32N4): theoretical value C:86.72%, H:4.85%, N:8.43%；
Measured value C:86.57%, H:4.75%, N:8.86%.
The synthesis of 39. compound A-13 5 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M3, synthesizes product with embodiment 9
Product MS (m/e): 664, elemental analysis (C48H32N4): theoretical value C:86.72%, H:4.85%, N:8.43%；
Measured value C:86.59%, H:4.74%, N:8.67%.
The synthesis of 40. compound A-13 6 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M3, synthesizes product with embodiment 10
Product MS (m/e): 764, elemental analysis (C56H36N4): theoretical value C:87.93%, H:4.74%, N:7.32%；
Measured value C:86.69%, H:4.64%, N:8.67%.
The synthesis of 41. compound A-13 7 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M3, synthesizes product with embodiment 11
Product MS (m/e): 716, elemental analysis (C52H36N4): theoretical value C:87.12%, H:5.06%, N:7.82%；
Measured value C:86.69%, H:4.94%, N:8.37%.
The synthesis of 42. compound A-13 8 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M3, synthesizes product with embodiment 12
Product MS (m/e): 764, elemental analysis (C56H36N4): theoretical value C:87.93%, H:4.74%, N:7.32%；
Measured value C:87.69%, H:4.94%, N:7.37%.
The synthesis of 43. compound A-13 9 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M3, synthesizes product with embodiment 13
Product MS (m/e): 796, elemental analysis (C58H44N4): theoretical value C:87.41%, H:5.56%, N:7.03%；
Measured value C:87.69%, H:4.99%, N:7.32%.
The synthesis of 44. compound A40 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M3, synthesizes product with embodiment 14
Product MS (m/e): 896, elemental analysis (C66H48N4): theoretical value C:88.36%, H:5.39%, N:6.25%；
Measured value C:87.69%, H:5.59%, N:6.72%.
The synthesis of 45. compound A41 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M3, synthesizes product with embodiment 15
Product MS (m/e): 624, elemental analysis (C42H32N4O2): theoretical value C:80.75%, H:5.16%, N:
8.97%, O:5.12；Measured value C:80.69%, H:5.39%, N:8.72%.
The synthesis of 46. compound A42 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M3, synthesizes product with embodiment 16
Product MS (m/e): 744, elemental analysis (C52H32N4O2): theoretical value C:83.85%, H:4.33%, N:
7.52%, O:4.30；Measured value C:83.69%, H:4.39%, N:7.62%.
The synthesis of 47. compound A43 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M3, synthesizes product with embodiment 17
Product MS (m/e): 560, elemental analysis (C40H24N4): theoretical value C:85.69%, H:4.31%, N:9.99%；
Measured value C:85.66%, H:4.39%, N:9.95%.
The synthesis of 48. compound A44 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M3, synthesizes product with embodiment 18
Product MS (m/e): 660, elemental analysis (C48H28N4): theoretical value C:87.25%, H:4.27%, N:8.48%；
Measured value C:87.66%, H:4.39%, N:7.95%.
The synthesis of 49. compound A45 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M3, synthesizes product with embodiment 19
Product MS (m/e): 760, elemental analysis (C56H32N4): theoretical value C:88.40%, H:4.24%, N:7.36%；
Measured value C:87.66%, H:4.39%, N:7.95%.
The preparation of 50. compound A46 of synthetic example, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M4, synthesizes product with embodiment 5
Product MS (m/e): 716, elemental analysis (C52H36N4): theoretical value C:87.12%, H:5.06%, N:7.82%；
Measured value C:87.27%, H:4.85%, N:7.88%.
The magnetic resonance spectroscopy data of product: 1H NMR (500MHz, Chloroform) for comp.A46) δ 8.53 (dt, J=
15.0,7.5Hz, 1H), 7.86-7.72 (m, 2H), 7.61 (dd, J=11.1,6.9Hz, 1H), 7.44 (qdd, J=10.1,
7.4,3.6Hz,3H),7.32–7.18(m,5H),7.16–6.91(m,6H)。
The synthesis of 51. compound A47 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M4, synthesizes product with embodiment 6
Product MS (m/e): 828, elemental analysis (C60H52N4): theoretical value C:86.92%, H:6.32%, N:6.76%；
Measured value C:86.67%, H:6.85%, N:6.48%.
The synthesis of 52. compound A48 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M4, synthesizes product with embodiment 7
Product MS (m/e): 1044, elemental analysis (C76H76N4): theoretical value C:87.31%, H:7.33%, N:
5.36%；Measured value C:87.47%, H:7.45%, N:5.08%.
The synthesis of 53. compound A49 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M4, synthesizes product with embodiment 8
Product MS (m/e): 816, elemental analysis (C60H40N4): theoretical value C:88.21%, H:4.94%, N:6.86%；
Measured value C:88.37%, H:4.75%, N:6.88%.
The synthesis of 54. compound A-45 0 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M4, synthesizes product with embodiment 9
Product MS (m/e): 816, elemental analysis (C60H40N4): theoretical value C:88.21%, H:4.94%, N:6.86%；
Measured value C:88.39%, H:4.74%, N:6.97%.
The synthesis of 55. compound A-45 1 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M4, synthesizes product with embodiment 10
Product MS (m/e): 916, elemental analysis (C68H44N4): theoretical value C:89.05%, H:4.84%, N:6.11%；
Measured value C:89.09%, H:4.64%, N:6.27%.
The synthesis of 56. compound A-45 2 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M4, synthesizes product with embodiment 11
Product MS (m/e): 868, elemental analysis (C64H44N4): theoretical value C:88.45%, H:5.10%, N:6.45%；
Measured value C:88.69%, H:4.94%, N:6.37%.
The synthesis of 57. compound A-45 3 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M4, synthesizes product with embodiment 12
Product MS (m/e): 916, elemental analysis (C68H44N4): theoretical value C:89.05%, H:4.84%, N:6.11%；
Measured value C:89.09%, H:4.94%, N:5.97%.
The synthesis of 58. compound A-45 4 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M4, synthesizes product with embodiment 13
Product MS (m/e): 948, elemental analysis (C70H52N4): theoretical value C:88.58%, H:5.52%, N:5.90%；
Measured value C:88.69%, H:5.99%, N:6.32%.
The synthesis of 59. compound A-45 5 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M4, synthesizes product with embodiment 14
Product MS (m/e): 1048, elemental analysis (C78H56N4): theoretical value C:89.28%, H:5.38%, N:
5.34%；Measured value C:88.69%, H:5.59%, N:5.72%.
The synthesis of 60. compound A-45 6 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M4, synthesizes product with embodiment 15
Product MS (m/e): 776, elemental analysis (C54H40N4O2): theoretical value C:83.48%, H:5.19%, N:
7.21%, O:4.12；Measured value C:83.69%, H:5.39%, N:7.32%.
The synthesis of 61. compound A-45 7 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M4, synthesizes product with embodiment 16
Product MS (m/e): 896, elemental analysis (C64H40N4O2): theoretical value C:85.69%, H:4.49%, N:
6.25%, O:3.57；Measured value C:85.61%, H:4.51%, N:6.34%.
The synthesis of 62 compound A-45 8 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M4, synthesizes product with embodiment 17
Product MS (m/e): 712, elemental analysis (C52H32N4): theoretical value C:87.62%, H:4.52%, N:7.86%；
Measured value C:87.66%, H:4.39%, N:7.95%.
The synthesis of 63. compound A-45 9 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M4, synthesizes product with embodiment 18
Product MS (m/e): 812, elemental analysis (C60H36N4): theoretical value C:88.64%, H:4.46%, N:6.89%；
Measured value C:88.66%, H:4.39%, N:6.95%.
The synthesis of 64. compound A60 of embodiment, synthetic route are as follows:
Synthetic method only changes intermediate M1 into intermediate M4, synthesizes product with embodiment 19
Product MS (m/e): 912, elemental analysis (C68H40N4): theoretical value C:89.45%, H:4.42%, N:6.14%；
Measured value C:89.66%, H:4.39%, N:5.95%.
It is described in detail below by way of technical effect of the device embodiments to the compounds of this invention.
Device embodiment
OLED device evaluation and test: ITO (120nm)/HIL (60nm)/HTL (30nm)/EML is carried out using following device architecture
(30nm)/ETL (30nm)/Al (120nm) (above-mentioned abbreviation respectively correspond ito anode/hole injection layer/hole transmission layer/shine
Layer/electron transfer layer/Al cathode, the meaning of above-mentioned abbreviation is identical below), the structural formula of each used material of functional layer in device
It is as follows:
Above-mentioned electroluminescent organic material is all material commonly used in the art, and those skilled in the art are based on known method can be certainly
Row preparation or commercially available.
Device embodiments 1. are using compound A1 as material of main part
The glass plate for being coated with ITO (120nm) 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 completely removes water
Part, with ultraviolet light and ozone clean, and with the low energy cation beam bombarded surface of Satella (ULVAC)；
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 with a thickness of 60nm；It is true on hole injection layer
Sky vapor deposition compound N PB, forms the hole transmission layer with a thickness of 30nm, evaporation rate 0.1nm/s；
Electroluminescence layer, concrete operations are formed on above-mentioned hole transmission layer are as follows: by the compound as luminous layer main body
A1 is placed in the cell of vacuum phase deposition equipment, by (piq) as dopant2Ir (acac) [two-(1- phenyl isoquinolins
Quinoline base) acetylacetone,2,4-pentanedione iridium (III)] it is placed in another room of vacuum phase deposition equipment, two are evaporated simultaneously with different rates
Kind material, (piq)2The mass ratio of Ir (acac) and material of main part compound A1 is 13:87, and vapor deposition total film thickness is 30nm；
This Alq3 of vacuum evaporation forms the electron transfer layer that thick film is 30nm on luminescent layer, and evaporation rate is
0.1nm/s；
On the electron transport layer vacuum evaporation with a thickness of 120nm cathode of the Al layer as device.
Gained red device is 1000cd/cm in brightness2Under driving voltage be 5.6V, current efficiency 16.0cd/A.
Device embodiments 2.
Organic electroluminescence device is prepared using method same as Example 1, difference is, by material of main part
It closes object A1 and replaces with compound A4.
Device embodiments 3.
Organic electroluminescence device is prepared using method same as Example 1, difference is, by material of main part
It closes object A1 and replaces with compound A12.
Device embodiments 4.
Organic electroluminescence device is prepared using method same as Example 1, difference is, by material of main part
It closes object A1 and replaces with compound A13.
Device embodiments 5.
Organic electroluminescence device is prepared using method same as Example 1, difference is, by material of main part
It closes object A1 and replaces with compound A16.
Device embodiments 6.
Organic electroluminescence device is prepared using method same as Example 1, difference is, by material of main part
It closes object A1 and replaces with compound A19.
Device embodiments 7.
Organic electroluminescence device is prepared using method same as Example 1, difference is, by material of main part
It closes object A1 and replaces with compound A27.
Device embodiments 8.
Organic electroluminescence device is prepared using method same as Example 1, difference is, by material of main part
It closes object A1 and replaces with compound A28.
Device embodiments 9.
Organic electroluminescence device is prepared using method same as Example 1, difference is, by material of main part
It closes object A1 and replaces with compound A-13 1.
Device embodiments 10.
Organic electroluminescence device is prepared using method same as Example 1, difference is, by material of main part
It closes object A1 and replaces with compound A-13 4.
Device embodiments 11.
Organic electroluminescence device is prepared using method same as Example 1, difference is, by material of main part
It closes object A1 and replaces with compound A42.
Device embodiments 12.
Organic electroluminescence device is prepared using method same as Example 1, difference is, by material of main part
It closes object A1 and replaces with compound A43.
Device embodiments 13.
Organic electroluminescence device is prepared using method same as Example 1, difference is, by material of main part
It closes object A1 and replaces with compound A46.
Device embodiments 14.
Organic electroluminescence device is prepared using method same as Example 1, difference is, by material of main part
It closes object A1 and replaces with compound A47.
Device embodiments 15.
Organic electroluminescence device is prepared using method same as Example 1, difference is, by material of main part
It closes object A1 and replaces with compound A48.
Comparative example
Organic electroluminescence device is prepared using method same as Example 1, difference is, by material of main part
It closes object A1 and replaces with compound CBP.
1. the compounds of this invention of table is used as the measurement result of material of main part device
Device embodiments 1~15 are in organic electroluminescence device structure in the identical situation of other materials, system of the present invention
Column compound is instead of CBP in comparative example 1 as feux rouges material of main part.Since benzo Féraud oxazoline derivates of the invention have
There is good double carriers transmission performance, can effectively widen exciton recombination region, so that being quenched between triplet excitons
It significantly reduces, thus can effectively improve luminous efficiency.It can be seen that device embodiments 1 from the device test data in table 1
~15 are compared to comparative example 1, and driving voltage reduces 20% or more, and current efficiency improves about 50%, especially device
Service life improve 40% or more compared with comparative example 1.Other organic functions layer materials are identical in same device architecture
In the case of, using series compound of the present invention as luminescent layer material of main part, device luminescent properties are obviously improved, the service life of device
Significant to extend, this has absolutely proved the excellent effect of benzo Féraud oxazoline derivates of the present invention, has also confirmed benzo of the invention
Féraud oxazoline derivates have excellent carrier transport balance and level-density parameter, are the bipolarity main bodys of function admirable
Material.
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 (12)
1. a kind of benzo Féraud oxazoline derivates, which is characterized in that have structure shown in following general formula (1-1) or (1-2):
Wherein, R is hydrogen atom or phenyl；
Ar1It is identical or different with Ar, it is each independently selected from substituted or unsubstituted C6~C30Aryl, substituted or unsubstituted C2~
C30Heteroaryl, substituted or unsubstituted C6~C30Arylamino, substituted or unsubstituted C6~C30Heteroaryl amino；
Ar1With Ar2Interconnection or Ar1With Ar2Mutually it is not connected to；
Substituted C6~C30Aryl, substituted C2~C30Heteroaryl, substituted C6~C30Arylamino and substituted C6~C30It is miscellaneous
The substituent group of arylamino " is selected from halogen group, nitro, C1~C6Alkyl, C1~C6Alkoxy, C6~C30Aryl.
2. benzo Féraud oxazoline derivates according to claim 1, it is characterised in that: the C6~C30Aryl is selected from benzene
Base, xenyl, terphenyl, naphthalene, anthryl, fluoranthene base, phenanthryl, indenyl, benzo fluorenyl, fluorenyl and its derivative, triphenylene
Base, pyrenyl, base,At least one of base and aphthacene base.
3. benzo Féraud oxazoline derivates according to claim 1, it is characterised in that: the C2~C30Heteroaryl be selected from
Furyl, thienyl, pyrrole radicals, benzofuranyl, benzothienyl, isobenzofuran-base, indyl, dibenzofuran group,
Dioxa between dibenzothiophene, 9- phenyl carbazole, 9- naphthyl carbazole benzo carbazole, dibenzo-carbazole, indolocarbazole, benzo
At least one of cyclopentenyl.
4. benzo Féraud oxazoline derivates according to claim 1, it is characterised in that: the C6~C30Arylamino is 4-
Three phenylaminos, tri- phenylamino of 3-, the C6~C30Heteroaryl amino is 4- [N- phenyl-N- (dibenzofurans -3- base)] phenyl
Amino, 4- [N- phenyl-N- (dibenzothiophenes -3- base)] phenyl amino.
5. benzo Féraud oxazoline derivates according to any one of claims 1 to 4, it is characterised in that: substituted C6~C30Virtue
Base, substituted C2~C30Heteroaryl, substituted C6~C30Arylamino and substituted C6~C30Substituent group in heteroaryl amino
It is each independently methyl, ethyl, isopropyl, cyclohexyl, methoxyl group, ethyoxyl, propoxyl group, isopropoxy, phenoxy group or benzene
Base.
6. benzo Féraud oxazoline derivates according to any one of claims 1 to 4, it is characterised in that: Ar1With Ar2Pass through list
Key ,-O- ,-S- or-C (CH3)2It is connected with each other.
7. benzo Féraud oxazoline derivates according to claim 6, it is characterised in that: Ar1With Ar2Be connected with each other and with N mono-
It rises and forms the group as shown in formula (2)~(6):
Wherein, * indicates the connection site with parent nucleus, when benzophenanthrene hello oxazoline derivates are with structure shown in general formula (1-1),
The parent nucleus isWhen benzo Féraud oxazoline derivates have general formula (1-2)
Shown in structure when, the parent nucleus is
8. benzo Féraud oxazoline derivates according to claim 1, which is characterized in that the benzo Féraud oxazoline derivates
Selected from following structural formula:
。
9. benzo Féraud oxazoline derivates are in ORGANIC ELECTROLUMINESCENCE DISPLAYS and illumination described in any one of claim 1 to 8
Application in technical field.
10. a kind of organic electroluminescence device, including substrate, anode layer, cathode layer and between anode layer and cathode layer
At least one layer of organic function layer, it is characterised in that: in the organic function layer at least one layer with independent component or mixture
The form of component includes benzo Féraud oxazoline derivates described in any one of claim 1 to 8.
11. organic electroluminescence device according to claim 10, the organic function layer includes hole injection layer, hole
Transport layer, organic luminous layer, electron transfer layer, the organic luminous layer include material of main part and dopant dye, it is characterised in that:
The material of main part contains any benzo Féraud oxazoline derivates in claim 1 to 8.
12. organic electroluminescence device according to claim 11, which is characterized in that the dopant dye is red phosphorescent material
Material.
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| CN111943949A (en) * | 2020-08-03 | 2020-11-17 | 清华大学 | Organic compound, application thereof and organic electroluminescent device containing organic compound |
| CN115850274A (en) * | 2022-12-28 | 2023-03-28 | 湖北长江新型显示产业创新中心有限公司 | Benzophenanthroline compound and application thereof |
| WO2024034301A1 (en) * | 2022-08-09 | 2024-02-15 | 株式会社日本触媒 | Phenanthroline compound, and organic thin film and organic semiconductor element using same |
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