A kind of compound, the organic electroluminescence device comprising it and its application
阅读说明：本技术 一种化合物、包含其的有机电致发光器件及其应用 (A kind of compound, the organic electroluminescence device comprising it and its application ) 是由 黄金华 曾礼昌 于 2019-08-27 设计创作，主要内容包括：本发明提供一种化合物、包含该化合物的有机电致发光器件及其应用,本发明所述化合物具有式I所示结构,其结构中萘1-位同另外一个萘环相连,而2-位则同二芳胺基相连,使得本发明联萘化合物具有大π平面结构,同时能有效改变分子空间结构,有利于改善膜内分子堆积,由于邻位取代限制了N原子上芳环的转动,从而增强了该类材料的稳定性,使得利用该化合物作为有机电致发光器件的空穴传输层材料和/或电子阻挡材料时,可提高发光效率,降低启动电压,延长器件使用寿命。使用本发明的化合物的有机电致发光器件亮度达到3000cd/m<Sup>2</Sup>时,驱动电压低至3.8V以下,电流效率高达10.5cd/A以上；LT95达到152h以上。(The present invention provides a kind of compound, organic electroluminescence device and its application comprising the compound, compound of the present invention has structure shown in Formulas I, naphthalene 1- is connected with another naphthalene nucleus in its structure, and 2- then connect with diaryl-amine base phase, so that dinaphthalene compound of the present invention has big π planar structure, spatial configuration of molecules can effectively be changed simultaneously, be conducive to improve packing of molecules in film, since ortho position substitution limits the rotation of aromatic ring on N atom, to enhance the stability of such material, when so that using the compounds as the hole transport layer material and/or electron-blocking materials of organic electroluminescence device, luminous efficiency can be improved, low start voltage drops, extend device service life.Reach 3000cd/m using the organic electroluminescence device brightness of the compound of the present invention 2 When, driving voltage is down to 3.8V hereinafter, current efficiency is up to 10.5cd/A or more；LT95 reaches 152h or more.)
1. a kind of compound, which is characterized in that the compound has the structure as shown in following formula I:
Wherein, L1And L2It is identical or different, it is each independently singly-bound, C6-C50Substituted or unsubstituted arlydene, C3-C30's Substituted or unsubstituted inferior heteroaryl；
Ar1And Ar2It is identical or different, it is each independently H, C6-C50Substituted or unsubstituted aryl, C6-C50Substitution or do not take For fused-aryl, C3-C30Substituted or unsubstituted heteroaryl, C3-C30Condensed heteroaryl substituted or unsubstituted；
And Ar1When for H, L1It is not singly-bound；Ar2When for H, L2It is not singly-bound；
R1And R2It is identical or different, it is each independently H, halogen, C1-C20Alkyl, C1-C12Alkoxy, C3-C20Cycloalkanes Base, C2-C12Alkenyl, C2-C12Alkynyl, carbonyl, carboxyl, cyano, amido, C6-C50Substituted or unsubstituted aryl, C3- C30Substituted or unsubstituted heteroaryl, C6-C50Fused-aryl, and R1And R2It is connected on naphthalene nucleus in a manner of singly-bound；
M is the integer of 0-6, and n is the integer of 0-7；
When above-mentioned group is there are when substituent group, the substituent group is separately selected from halogen, C1-C10Alkyl, C3-C10Ring Alkyl, C2-C10Alkenyl, C1-C6Alkoxy, C1-C6Thio alkoxy, carbonyl, carboxyl, cyano, amido, C6-C30Monocycle Aromatic hydrocarbons or condensed-nuclei aromatics group, C3-C30Monocycle heteroaryl hydrocarbon or one of condensed ring heteroaryl hydrocarbyl group or a variety of.
2. compound according to claim 1, which is characterized in that the Ar1And Ar2Independently selected from C6-C50Aryl or Fused-aryl, C3-C30Heteroaryl or condensed heteroaryl；L1And L2It independently is singly-bound；R1And R2It independently is hydrogen.
3. compound according to claim 1, which is characterized in that the Ar1And Ar2It is each independently selected from
WhereinRepresent the on-position of group.
4. compound according to claim 1, which is characterized in that the compound has as shown in Formula II or formula III Structure:
Wherein, L1、L2、Ar1、Ar2、R1、R2, m and n it is identical as the definition in the claim 1.
5. compound according to claim 1 or 4, which is characterized in that the Ar1And Ar2It is each independently selected from
6. compound according to claim 1, which is characterized in that the compound of structure shown in the Formulas I is following chemical combination Any one in object P1-P419:
7. a kind of organic electroluminescence device, which is characterized in that the organic electroluminescence device includes first electrode, the second electricity Pole and the organic layer being inserted between the first electrode and second electrode, wherein the organic layer includes such as claim 1-6 Any one of described in compound.
8. organic electroluminescence device according to claim 7, which is characterized in that the organic layer includes hole transport Area, the hole transport area include the described in any item compounds of claim 1-5.
9. organic electroluminescence device according to claim 8, which is characterized in that the hole transport area includes that hole passes Defeated layer and/or electronic barrier layer, wherein including claim at least one layer in the hole transmission layer and electronic barrier layer The described in any item compounds of 1-6.
10. compound according to claim 1-6 is as the hole transmission layer in organic electroluminescence device And/or the application of electronic barrier layer.
Technical field
The present invention relates to a kind of organic luminescent compounds and organic electronic light emitting device fields, more particularly, to a kind of chemical combination Object, the organic electroluminescence device comprising the compound and its application.
Background technique
Organic electroluminescent (OLED:Organic Light Emission Diodes) device is a kind of with class Sanming City The device for controlling structure, including positive and negative electrode film layer and the organic functional material layer being clipped between electrode film layer.To OLED device Electrode applies voltage, and positive charge is injected from anode, and negative electrical charge is injected from cathode, and positive and negative charge is in organic layer under electric field action Migrate the recombination luminescence that meets.Due to OLED device have brightness is high, response is fast, visual angle is wide, simple process, can flexibility etc. it is excellent Point is concerned in novel field of display technology and novel illumination technical field.Currently, the technology be widely used in it is novel The display panel of the products such as illuminator, smart phone and tablet computer further will also show product to large scales such as TVs Application field extension is the novel display technology that a kind of development is fast, technical requirements are high.
As OLED is in the continuous propulsion for illuminating and showing two big fields, people for its core material research also more Concern.This is because the OLED device of an excellent in efficiency, service life length is usually the optimization of device architecture and various organic materials Collocation as a result, this functionalization material for just designing and developing various structures for chemists provides great opportunities and challenges. Common functionalization organic material has: hole-injecting material, hole mobile material, hole barrier materials, electron injection material, electricity Sub- transmission material, electron-blocking materials and light emitting host material and light-emitting guest (dyestuff) etc..
Driving voltage is lower, luminous efficiency is more preferable, the device OLED luminescent device that the service life is longer in order to prepare, and realizes The performance of OLED device is constantly promoted, and not only needs to innovate OLED device structure and manufacture craft, with greater need for OLED Photoelectric functional material in device is constantly studied and is innovated, to prepare the functional material with higher performance.Based on this, OLED Material circle has been devoted to develop new electroluminescent organic material to realize device low start voltage, high-luminous-efficiency and more excellent Service life.
Up to the present, the development of existing oled light sulfate ferroelectric functional material also lags far behind panel manufacturing enterprise to OLED The requirement of material, therefore the exploitation better organic functional material of performance meets current industry growth requirement and seems especially urgent.
People explore application of the compound of tool binaphthyl structure in OLED, it is desirable to which device can be promoted by finding The material of energy.South Korea patent application KR1020140096227A discloses a kind of dinaphthalene compound containing diaryl-amine, general formula It is as follows:
US20040106003, JP 2003040867A, KR1020160080420A, KR101530266B1, The patents of invention such as US9178001B2, US8829783B2 (application) also disclose several organic electroluminescents containing binaphthyl structure Material.However, these compounds are still unable to satisfy people to the performance requirement of OLED device.In conclusion existing have Electroluminescent material is also improved leeway in terms of luminescent properties, and industry needs to develop new organic electroluminescence material Material.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of compound, include the organic of the compound Electroluminescent device and its application, the OLED device based on the compound of the present invention production have low start voltage, high-incidence light efficiency Rate and more preferably service life can satisfy requirement of the front wall manufacturing enterprise to high performance material.
In order to achieve that object of the invention, the invention adopts the following technical scheme:
On the one hand, the present invention provides a kind of compound, and the compound has the structure as shown in following formula I:
Wherein, L1And L2It is identical or different, it is each independently singly-bound, C6-C50Substituted or unsubstituted arlydene, C3- C30Substituted or unsubstituted inferior heteroaryl；
Ar1And Ar2It is identical or different, it is each independently H, C6-C50Substituted or unsubstituted aryl, C6-C50Substitution or Unsubstituted fused-aryl, C3-C30Substituted or unsubstituted heteroaryl, C3-C30Condensed heteroaryl substituted or unsubstituted；
And Ar1When for H, L1It is not singly-bound；Ar2When for H, L2It is not singly-bound；
R1And R2It is identical or different, it is each independently H, halogen, C1-C20Alkyl, C1-C12 alkoxy, C3-C20's Naphthenic base, C2-C12Alkenyl, C2-C12Alkynyl, carbonyl, carboxyl, cyano, amido, C6-C50Substituted or unsubstituted aryl, C3-C30Substituted or unsubstituted heteroaryl, C6-C50Fused-aryl, and R1And R2In a manner of singly-bound and non-condensed mode connects It connects on naphthalene nucleus；
M is the integer of 0-6, and n is the integer of 0-7；
When above-mentioned group is there are when substituent group, the substituent group is separately selected from halogen, C1-C10Alkyl, C3-C10 Naphthenic base, C2-C10Alkenyl, C1-C6Alkoxy, C1-C6Thio alkoxy, carbonyl, carboxyl, cyano, amido, C6-C30's Mononuclear aromatics or condensed-nuclei aromatics group, C3-C30Monocycle heteroaryl hydrocarbon or one of condensed ring heteroaryl hydrocarbyl group or a variety of.
In the present invention, in the compound naphthalene nucleus 1- be connected with another naphthalene nucleus, the position 2- of naphthalene nucleus and diaryl-amine Base phase connects, hole transport layer material or electronic blocking layer material of such dinaphthalene compound as organic electroluminescence device When, compared with prior art, driving voltage can be further decreased, luminous efficiency is improved and prolongs the service life.
In the compound of the present invention, naphthalene 1- are connected with another naphthalene nucleus, and 2- then connect with diaryl-amine base phase, and And other substituent groups are not amine or arylamine class substituent group, i.e. R on two naphthalene nucleus1And R2It is not amine or arylamine class substituent group.
In the present invention, the C6-C50Substituted or unsubstituted arlydene and C6-C50Substituted or unsubstituted aryl Middle C6-C50Indicate carbon atom number in group, for example, can for 6,8,10,15,18,20,23,25,30,33,35,38,40, 45,50 carbon atoms；Similarly, C3-C30Substituted or unsubstituted inferior heteroaryl and C3-C30In substituted or unsubstituted heteroaryl Carbon atom number can be 3,5,8,10,12,15,18,20,23,25,28 or 30；C1-C20Alkyl in carbon atom number can be 1,3,5,8,10,12,15,18 or 20；C before similarly group limits2-C12Represent carbon atom number can for 2,3,4,5,6,7,8,9, 10,11 or 12；C3-C20Representing carbon atom number can be 3,5,8,12,18,20 etc., the restriction of other same carbon atom number ranges Also illustrate that the carbon atom number of the group can get any one integer in the numberical range.
In the present invention, the m can be 0,1,2,3,4,5 or 6；The n can be 0,1,2,3,4,5,6 or 7.
In the structure shown in Formulas I of the present invention, the connecting key "-" of substituent group streaks the representation of ring structure, indicates Connection site is in the position for arbitrarily capableing of bonding on the ring structure.
In the present invention, " compound of the present invention ", " dinaphthalene compound of the present invention " and " as described aboveization Close object " refer both to the compound in the application with structure shown in Formulas I.
Aryl mentioned in the present invention is also aromatic hydrocarbon group, refers in structure containing plane or close to the cyclic conjugated of plane System, and pi-electron number meets H ü ckel 4n+2 (n=0,1,2 ...) rule, the hydrocarbon with armaticity is known as aromatic hydrocarbon, referred to as virtue The group that hydrocarbon is formed.
Heteroaryl mentioned in the present invention refers to that at least one ring carbon atom in aryl is exchanged for heteroatoms, hetero atom packet Include N, O, S etc..Such as pyrazine, pyrimidine etc..
Monocyclic aromatic hydrocarbon group mentioned in the present invention is also referred to as monocyclic aryl, refers to that with individual ring aromatic structure be basic The hydrocarbon of structural unit, the hydrocarbon being interconnected to form including multiple cyclic aromatic structures with singly-bound.It is common Monocyclic aryl such as phenyl, xenyl, terphenyl, cyclopentadienyl, [18] annulene etc..
Monocycle heteroaryl hydrocarbyl group mentioned in the present invention is also referred to as bicyclic heteroaryl, refers in monocyclic aromatic hydrocarbon group at least One ring carbons is exchanged for heteroatoms, and hetero atom includes N, O, S etc..For example, pyridine, furans, thiophene, pyrroles, bipyridyl, Bithiophene, connection furans, phenylpyridine, tolylthiophene etc..
Condensed-nuclei aromatics group mentioned in the present invention is also referred to as fused ring aryl, refers to two or more monocyclic aromatic rings As by sharing, two ortho position carbon atoms are condensed to be formed phenyl ring.For example, naphthalene, anthracene, phenanthrene, fluorenes, fluoranthene etc..
Condensed ring heteroaryl hydrocarbyl group mentioned in the present invention is also referred to as fused ring heteroaryl, refers in condensed-nuclei aromatics group at least One ring carbon atom is exchanged for heteroatoms, and hetero atom includes N, O, S etc..Such as quinoline, isoquinolin, quinazoline, quinoxaline, Yin Diindyl, benzofuran, benzothiophene, dibenzofurans, dibenzothiophenes, carbazole etc..
Preferably, the L1And L2For singly-bound.
Preferably, R1And R2Selected from hydrogen.
Preferably, the Ar1And Ar2Independently selected from C6-C50Substituted or unsubstituted aryl, fused-aryl, C3-C30It takes Generation or unsubstituted heteroaryl.
Preferably, the Ar1And Ar2Independently selected from WhereinRepresent the on-position of group.
Preferably, the compound has the structure as shown in Formula II or formula III:
Wherein, L1、L2、Ar1、Ar2、R1、R2, m and n it is identical as the definition in Formulas I.
Preferably, the Ar1And Ar2It is each independently selected from
Preferably, the compound is any one in following compound P1-P419:
In the present invention, the compound of structure shown in the Formulas I is any one in P1-P419, but be not restricted to that These illustrative compounds.
In the present invention, the synthetic method of the compound is briefly described, the representative synthesis of the compound Path is as follows:
Synthetic route and thinking based on the above compound, it is Ar that those skilled in the art, which can obtain substituent group,1、Ar2、R1With R2Compound.
On the other hand, the application the present invention provides compound as described above in organic electroluminescence device, it is described Compound is used as hole mobile material or electron-blocking materials in organic electroluminescence device.
On the other hand, the present invention provides a kind of organic electroluminescence devices, including first electrode, second electrode and insertion One or more layers organic layer between the first electrode and second electrode, wherein the organic layer includes as described aboveization Close object.
In the present invention, described one or more layers refers at least one layer.
Preferably, the organic layer includes hole transport area, and the hole transport area includes compound as described above.
Preferably, the hole transport area includes hole transmission layer and/or electronic barrier layer, wherein the hole transmission layer With in at least one layer in electronic barrier layer include compound as described above.
In the present invention, the organic layer containing compound of the present invention may be used as but be not exclusively for use in hole transmission layer And electronic barrier layer.
In addition, the compound of the present invention can be applied in organic electronic device, the organic electronic device can enumerate example Such as organic electroluminescence device, illumination component, Organic Thin Film Transistors, organic field effect tube, organic thin film solar electricity Large area sensor, Electronic Paper and the organic EL panels such as pond, information labels, the artificial pieces of skin material of electronics, sheet material type scanner etc..
Next, organic electroluminescence device is described in detail.
Organic electroluminescence device includes being located at first electrode and second electrode, and the organic material between electrode Layer.The organic material can be divided into multiple regions again.For example, the organic material layer may include hole transport area, luminescent layer, electricity Sub- transmission range.
In a particular embodiment, substrate can be used below first electrode or above second electrode.Substrate is tool Have mechanical strength, thermal stability, waterproofness, excellent clarity glass or polymer material.In addition, the base as display Thin film transistor (TFT) (TFT) can also be had on plate.
First electrode can be formed by way of the material for being used as first electrode is sputtered or deposited on substrate.When When first electrode is as anode, indium tin oxygen (ITO), indium zinc oxygen (IZO), stannic oxide (SnO can be used2), zinc oxide (ZnO) Any combination of equal oxidic transparents conductive material and they.It, can be using magnesium (Mg), silver when first electrode is as cathode (Ag), the metal or alloy such as aluminium (Al), aluminium-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) and they Between any combination.
Organic material layer can be formed on electrode by the methods of vacuum thermal evaporation, spin coated, printing.As having The compound of machine material layer can be small organic molecule, organic macromolecule and polymer and their combination.
Hole transport area is between anode and luminescent layer.Hole transport area can be the hole transmission layer of single layer structure (HTL), the single layer hole transmission layer including containing only a kind of single layer hole transmission layer of compound and containing multiple compounds.It is empty Cave transmission range may be including at least one in hole injection layer (HIL), hole transmission layer (HTL), electronic barrier layer (EBL) The multilayered structure of layer.
Hole transport area, when the hole transmission layer in hole transport area is selected from one of dinaphthalene compound of the present invention or appoints When meaning combination, the electronic barrier layer in hole transport area can without or be selected from but be not limited to phthalocyanine derivates such as CuPc, conductive poly- Close the polymer of object or the agent containing conductiving doping for example polyphenylene ethylene, polyaniline/dodecyl benzene sulfonic acid (Pani/DBSA), it is poly- (3, 4- ethylenedioxy thiophene)/poly- (4- styrene sulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyphenyl Amine/poly- (4- styrene sulfonate) (Pani/PSS), for example following HT-1 of aromatic amine derivant to HT-34 compound represented；Or Person's any combination thereof；When the hole transmission layer in hole transport area is selected from but is not limited to phthalocyanine derivates such as CuPc, conducting polymer Or the polymer of the agent containing conductiving doping such as polyphenylene ethylene, polyaniline/dodecyl benzene sulfonic acid (Pani/DBSA), poly- (3,4- second Support dioxy thiophene)/poly- (4- styrene sulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly- (4- styrene sulfonate) (Pani/PSS), for example following HT-1 of aromatic amine derivant to HT-34 compound represented；Or its When meaning combination；The electronic barrier layer in hole transport area is selected from one of dinaphthalene compound of the present invention or any combination.
The material of hole transport area and hole injection region can be selected from but be not limited to compound of the present invention and above-mentionedization Close object；Or any combination thereof.Wherein, hole injection layer can be single compound material, be also possible to multiple compounds Combination.For example, hole injection layer can be using under one or more compounds, or use in the compound in aforementioned present invention State one of HI1-HI3 or multiple compounds；It can also be using one of compound of the present invention or multiple compounds Adulterate one of following HI1-HI3 or multiple compounds.
Luminescent layer includes the luminescent dye (i.e. dopant, dopant) that can emit different wave length spectrum, can also be same When include material of main part (Host).Luminescent layer can be the monochromatic luminescent layer of the solid colors such as transmitting red, green, blue.A variety of differences The monochromatic luminescent layer of color can carry out planar alignment according to pixel graphics, can also be stacked and form colorful light-emitting Layer.When the luminescent layer of different colours is stacked, they can be separated from each other, and can also be connected with each other.Luminescent layer can also To be the single colored hair photosphere that can emit the different colours such as red, green, blue simultaneously.
According to different technologies, emitting layer material can use fluorescence electroluminescent material, electrophosphorescence material, heat Activate the different materials such as delayed fluorescence luminescent material.In an OLED device, single luminescence technology can be used, it can also Using the combination of a variety of different luminescence technologies.These can emit same color by the different luminescent materials of technique classification Light can also emit the light of not same color.
In one aspect of the invention, luminescent layer uses the technology of electrophosphorescence.Its luminescent layer material of main part be selected from but It is not limited to one of GPH-1 to GPH-80 or a variety of combinations.
In one aspect of the invention, luminescent layer uses the technology of electrophosphorescence.Its luminescent layer phosphorescent dopants can be with It is selected from but is not limited to one or more combinations of following enumerated GPD-1 to GPD-47.
Wherein D is deuterium.
In one aspect of the invention, luminescent layer uses the technology of electrophosphorescence.Its luminescent layer phosphorescent dopants can be with It is selected from but is not limited to one or more combinations of following enumerated RPD-1 to RPD-28.
In one aspect of the invention, luminescent layer uses the technology of electrophosphorescence.Its luminescent layer phosphorescent dopants can be with It is selected from but is not limited to one or more combinations of following enumerated YPD-1-YPD-11.
OLED organic material layer can also include the electron-transport area between luminescent layer and cathode.Electron-transport area can be The electron transfer layer (ETL) of single layer structure, including containing only a kind of single layer electronic transport layer of compound and containing there are many chemical combination The single layer electronic transport layer of object.Electron-transport area may be including electron injecting layer (EIL), electron transfer layer (ETL), hole At least one layer of multilayered structure in barrier layer (HBL).
An aspect of of the present present invention, electron transport layer materials can be selected from but be not limited to following enumerated ET-1 to ET-57 One or more combinations.
It can also include the electron injecting layer between electron transfer layer and cathode, electron injecting layer material packet in device It includes but is not limited to the following one or more combinations enumerated: LiQ, LiF, NaCl, CsF, Li2O、Cs2CO3, BaO, Na, Li or Ca。
Compared with the existing technology, the invention has the following advantages:
In the present invention, naphthalene 1- is connected with another naphthalene nucleus in the compound structure, and 2- then same diaryl-amines Base phase connects, so that the compounds of this invention has big π planar structure, while can effectively change spatial configuration of molecules, be conducive to improve Packing of molecules in film, since ortho position substitution limits the rotation of aromatic ring on N atom, so that the stability of such material is enhanced, So that when using the compounds as the hole transport layer material and/or electronic barrier layer of organic electroluminescence device, it can To improve luminous efficiency, low start voltage is dropped, and makes device that there is longer service life.Use the compound of the present invention Organic electroluminescence device brightness reach 3000cd/m2When, driving voltage is down to 3.8V hereinafter, current efficiency is up to 10.5cd/A or more；LT95 reaches 152h or more.
Detailed description of the invention
Fig. 1 is the molecular structure model figure of the compounds of this invention P1；
Fig. 2 is the molecular structure model figure of the compounds of this invention P191；
Fig. 3 is the molecular structure model figure of comparative example compound EMT-3；
Fig. 4 is the molecular structure model figure of comparative example compound EMT-4.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright , the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Solvent for use and reagent in following synthesis example, such as bromo- 9, the 9'- dimethyl fluorene of aniline, naphthalidine, 2- naphthylamines, 2-, 2- bromo dibenzofurans, 2- bromo dibenzothiophenes, 2- aminobphenyl, 2- amino-4-methoxyl -5'- methoxyl group -1,2'- Dinaphthalene, 2- amino -1,2'- dinaphthalene, 2- amino-4-methoxyl -5'- methoxyl group -1,1'- dinaphthalene, 2- amino -1,1'- dinaphthalene, 4- Bromo biphenyl, [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride, tris(dibenzylideneacetone) dipalladium, toluene, petroleum ether, just The chemical reagent such as hexane, methylene chloride, acetone, sodium sulphate, ethyl acetate, ethyl alcohol, triphenylphosphine, tert-butyl potassium alcoholate/sodium, With from domestic chemical products market buy or customize, such as purchase from Chinese medicines group Reagent Company, Sigma-Aldrich company, Lark prestige Reagent Company.In addition, those skilled in the art can also be synthesized by known method.
Synthesis example 1: compound P1 synthesis
In 1000mL single port bottle, 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 15.7g (100mmol) bromine is added Benzene, 0.9g (1mmol) tris(dibenzylideneacetone) dipalladium (i.e. Pd2(dba)3), tri- tertiary butyl phosphine of 0.5mL, 500mL toluene (Toluene), 14.4g (150mmol) sodium tert-butoxide (NaOBu-t), vacuum and exchange nitrogen 3 times, reaction is warming up to 110 DEG C of reactions 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h, filters To pale yellow powder P1, M/Z theoretical value: 421, M/Z measured values: 422.
Synthesis example 2: compound P13 synthesis
In 1000mL single port bottle, 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 8.5g (50mmol) 2- methyl is added Bromobenzene, 0.7g (1mmol) [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride (Pd (dppf) Cl2), 0.5g 2- it is bicyclic oneself Base phosphine -2', 6'- dimethoxy-biphenyl (Sphos), 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 Secondary, reaction is warming up to 90 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, Methanol is added and stirs 1h, suction filtration obtains pale yellow powder M0.
In 1000mL single port bottle, 18g (50mmol) M0,9.5g (50mmol) para-bromoanisole, 0.9g (1mmol) is added Vacuum and exchange nitrogen 3 times, tri- tertiary butyl phosphine of 0.5mL (P (t-Bu) is added in tris(dibenzylideneacetone) dipalladium, 500mL toluene3) Toluene solution is warming up to 110 DEG C of reaction 12h, and solvent is evaporated off in end of reaction, and silica gel column chromatography obtains P13, M/Z theoretical value: 465, M/Z measured values: 466.
Synthesis example 3: compound P34 synthesis
In 1000mL single port bottle, 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 12g (50mmol) 2- bromine connection is added Benzene, 0.7g (1mmol) [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride (Pd (dppf) Cl2), 2- dicyclohexyl phosphine -2', 6'- dimethoxy-biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction is warming up to 90 DEG C reaction 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h, Suction filtration obtains pale yellow powder M0-1.
In 1000mL single port bottle, 21g (50mmol) M0-1,12g (50mmol) is added to bromo biphenyl, 0.9g (1mmol) Vacuum and exchange nitrogen 3 times, tri- tertiary butyl phosphine of 0.5mL (P (t-Bu) is added in tris(dibenzylideneacetone) dipalladium, 500mL toluene3) Toluene solution is warming up to 110 DEG C of reaction 12h, and solvent is evaporated off in end of reaction, and silica gel column chromatography obtains P34, M/Z theoretical value: 573, M/Z measured values: 574.
Synthesis example 4: compound P63 synthesis
In 1000mL single port bottle, it is bromo- that 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 27g (100mmol) 2- is added 9,9'- dimethyl fluorene, 0.9g (1mmol) tris(dibenzylideneacetone) dipalladium (i.e. Pd2(dba)3), tri- tertiary butyl phosphine (P of 0.5mL (t-Bu)3), 500mL toluene (Toluene), 14.4g (150mmol) sodium tert-butoxide (NaOBu-t), vacuum and exchange nitrogen 3 times, Reaction is warming up to 110 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, adds Enter methanol stirring 1h, suction filtration obtains pale yellow powder P63 M/Z theoretical value: 653, M/Z measured values: 654.
Synthesis example 5: compound P93 synthesis
In 1000mL single port bottle, it is bromo- that 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 13.5g (50mmol) 2- is added 9,9'- dimethyl fluorene, 0.7g (1mmol) [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride (Pd (dppf) Cl2)、0.5g 2- dicyclohexyl phosphine -2', 6'- dimethoxy-biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction is warming up to 90 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, is concentrated organic Phase is added methanol and stirs 1h, and suction filtration obtains pale yellow powder M1.
In 1000mL single port bottle, 23g (50mmol) M1,16.1g (50mmol) 4- (the bromo- phenyl of 4-)-dibenzo is added Vacuum and exchange nitrogen 3 times, it is special that 0.5mL tri- is added in furans, 0.9g (1mmol) tris(dibenzylideneacetone) dipalladium, 500mL toluene Butyl phosphine (P (t-Bu)3) toluene solution, 110 DEG C of reaction 12h are warming up to, solvent is evaporated off in end of reaction, and silica gel column chromatography obtains P93, M/Z theoretical value: 703, M/Z measured values: 704.
Synthesis example 6: compound P94 synthesis
In 1000mL single port bottle, it is bromo- that 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 13.5g (50mmol) 2- is added 9,9'- dimethyl fluorene, 0.7g (1mmol) [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride, 0.5g 2- dicyclohexyl phosphine- 2', 6'- dimethoxy-biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction heating To 90 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h is mixed, suction filtration obtains pale yellow powder M1.
In 1000mL single port bottle, 23g (50mmol) M1,16.1g (50mmol) 3- (the bromo- phenyl of 4-)-dibenzo is added Vacuum and exchange nitrogen 3 times, it is special that 0.5mL tri- is added in furans, 0.9g (1mmol) tris(dibenzylideneacetone) dipalladium, 500mL toluene Butyl phosphine toluene solution is warming up to 110 DEG C of reaction 12h, and solvent is evaporated off in end of reaction, and silica gel column chromatography obtains P94, M/Z reason By value: 703, M/Z measured values: 704.
Synthesis example 7: compound P100 synthesis
In 1000mL single port bottle, 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 10.3g (50mmol) 2- bromine is added Naphthalene, 0.7g (1mmol) [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride, 0.5g 2- dicyclohexyl phosphine -2', 6'- diformazan Oxygroup biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction is warming up to 90 DEG C of reactions 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h, filters To pale yellow powder M2.
In 1000mL single port bottle, 23g (50mmol) M1,8.3g (50mmol) bromobenzene, 0.9g (1mmol) three (two is added BENZYLIDENE ACETONE) two palladiums, 500ml toluene, vacuum and exchange nitrogen 3 times, addition tri- tertiary butyl phosphine toluene solution of 0.5mL is warming up to Solvent is evaporated off in 110 DEG C of reaction 12h, end of reaction, and silica gel column chromatography obtains P100, M/Z theoretical value: 471, M/Z measured values: 472。
Synthesis example 8: compound P120 synthesis
In 1000mL single port bottle, be added 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 13g (50mmol) 9- bromine it is luxuriant and rich with fragrance, 0.7g (1mmol) [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride (Pd (dppf) Cl2), 0.5g 2- dicyclohexyl phosphine- 2', 6'- dimethoxy-biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction heating To 90 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h is mixed, suction filtration obtains pale yellow powder M0-2.
In 1000mL single port bottle, 22g (50mmol) M0-2,15g (50mmol) 3,5- diphenyl bromobenzene, 0.9g is added Vacuum and exchange nitrogen 3 times, tri- tertiary butyl phosphine (P of 0.5mL is added in (1mmol) tris(dibenzylideneacetone) dipalladium, 500mL toluene (t-Bu)3) toluene solution, 110 DEG C of reaction 12h are warming up to, solvent is evaporated off in end of reaction, and silica gel column chromatography obtains P120, M/Z Theoretical value: 673, M/Z measured values: 674.
Synthesis example 9: compound P134 synthesis
In 1000mL single port bottle, it is bromo- that 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 13.5g (50mmol) 2- is added 9,9'- dimethyl fluorene, 0.7g (1mmol) [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride, 0.5g 2- dicyclohexyl phosphine- 2', 6'- dimethoxy-biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction heating To 90 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h is mixed, suction filtration obtains pale yellow powder M1.
In 1000mL single port bottle, the bromo- biphenyl of 23g (50mmol) M1,11.5g (50mmol) 3-, 0.9g (1mmol) is added Tris(dibenzylideneacetone) dipalladium, 500mL toluene vacuum and exchange nitrogen 3 times, are added tri- tertiary butyl phosphine toluene solution of 0.5mL, rise Solvent is evaporated off in temperature to 110 DEG C of reaction 12h, end of reaction, and silica gel column chromatography obtains P134, M/Z theoretical value: 613, M/Z actual measurements Value: 614.
Synthesis example 10: compound P147 synthesis
In 1000mL single port bottle, it is bromo- that 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 13.5g (50mmol) 2- is added 9,9'- dimethyl fluorene, 0.7g (1mmol) [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride, 0.5g 2- dicyclohexyl phosphine- 2', 6'- dimethoxy-biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction heating To 90 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h is mixed, suction filtration obtains pale yellow powder M1.
In 1000mL single port bottle, 23g (50mmol) M1,10.4g (50mmol) 2- bromonaphthalene, 0.9g (1mmol) three is added Vacuum and exchange nitrogen 3 times, tri- tertiary butyl phosphine toluene solution of 0.5mL, heating is added in (dibenzalacetone) two palladium, 500mL toluene To 110 DEG C of reaction 12h, solvent is evaporated off in end of reaction, and silica gel column chromatography obtains P147, M/Z theoretical value: 587, M/Z measured values: 588。
Synthesis example 11: compound P170 synthesis
In 1000mL single port bottle, it is bromo- that 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 27g (100mmol) 3- is added 9,9'- dimethyl fluorene, 0.9g (1mmol) tris(dibenzylideneacetone) dipalladium, 0.5g 2- dicyclohexyl phosphine -2', 6'- dimethoxy Base biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction is warming up to 110 DEG C of reactions 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h, filters To pale yellow powder P170, M/Z theoretical value: 653, M/Z measured values: 654.
Synthesis example 12: compound P176 synthesis
In 1000mL single port bottle, it is bromo- that 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 13.5g (50mmol) 2- is added 9,9'- dimethyl fluorene, 0.7g (1mmol) [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride, 0.5g 2- dicyclohexyl phosphine- 2', 6'- dimethoxy-biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction heating To 90 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h is mixed, suction filtration obtains pale yellow powder M1.
In 1000mL single port bottle, 23g (50mmol) M1,13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 0.9g is added Vacuum and exchange nitrogen 3 times, tri- tertiary butyl phosphine toluene of 0.5mL is added in (1mmol) tris(dibenzylideneacetone) dipalladium, 500mL toluene Solution is warming up to 110 DEG C of reaction 12h, and solvent is evaporated off in end of reaction, and silica gel column chromatography obtains P186, M/Z theoretical value: 653, M/Z measured value: 654.
Synthesis example 13: compound P191 synthesis
In 1000mL single port bottle, 13.5g (50mmol) 2- amino -1,2'- dinaphthalene, 15.7g (100mmol) bromine is added Benzene, 0.9g (1mmol) tris(dibenzylideneacetone) dipalladium, tri- tertiary butyl phosphine of 0.5mL, 500mL toluene, 14.4g (150mmol) uncle Sodium butoxide, vacuum and exchange nitrogen 3 times, reaction is warming up to 110 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, it is right Organic phase is concentrated in reaction solution liquid separation, and methanol is added and stirs 1h, suction filtration obtains pale yellow powder P191, M/Z theoretical value: 421, M/Z Measured value: 422.Synthesis example 14: compound P314 synthesis
In 1000mL single port bottle, be added 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 13g (50mmol) 9- bromine anthracene, 0.7g (1mmol) [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride (Pd (dppf) Cl2), 0.5g 2- dicyclohexyl phosphine- 2', 6'- dimethoxy-biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction heating To 90 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h is mixed, suction filtration obtains pale yellow powder M0-3.
In 1000mL single port bottle, 22g (50mmol) M0-3,15g (50mmol) 3,5- diphenyl bromobenzene, 0.9g is added Vacuum and exchange nitrogen 3 times, tri- tertiary butyl phosphine (P of 0.5mL is added in (1mmol) tris(dibenzylideneacetone) dipalladium, 500mL toluene (t-Bu)3) toluene solution, 110 DEG C of reaction 12h are warming up to, solvent is evaporated off in end of reaction, and silica gel column chromatography obtains P314, M/Z Theoretical value: 673, M/Z measured values: 674.
Synthesis example 15: compound P325 synthesis
In 1000mL single port bottle, it is bromo- that 13.5g (50mmol) 2- amino -1,2'- dinaphthalene, 13.5g (50mmol) 2- is added 9,9'- dimethyl fluorene, 0.7g (1mmol) [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride, 0.5g 2- dicyclohexyl phosphine- 2', 6'- dimethoxy-biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction heating To 90 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h is mixed, suction filtration obtains pale yellow powder M2.
In 1000mL single port bottle, the bromo- biphenyl of 23g (50mmol) M1,11.5g (50mmol) 3-, 0.9g (1mmol) is added Tris(dibenzylideneacetone) dipalladium, 500mL toluene vacuum and exchange nitrogen 3 times, are added tri- tertiary butyl phosphine toluene solution of 0.5mL, rise Solvent is evaporated off in temperature to 110 DEG C of reaction 12h, end of reaction, and silica gel column chromatography obtains P325, M/Z theoretical value: 613, M/Z actual measurements Value: 614.
Synthesis example 16: compound P331 synthesis
In 1000mL single port bottle, it is bromo- that 13.5g (50mmol) 2- amino -1,2'- dinaphthalene, 13.5g (50mmol) 2- is added 9,9'- dimethyl fluorene, 0.7g (1mmol) [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride, 0.5g 2- dicyclohexyl phosphine- 2', 6'- dimethoxy-biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction heating To 90 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h is mixed, suction filtration obtains pale yellow powder M2.
In 1000mL single port bottle, the bromo- dibenzofurans of 23g (50mmol) M1,12.3g (50mmol) 2-, 0.9g is added Vacuum and exchange nitrogen 3 times, tri- tertiary butyl phosphine toluene of 0.5mL is added in (1mmol) tris(dibenzylideneacetone) dipalladium, 500mL toluene Solution is warming up to 110 DEG C of reaction 12h, and solvent is evaporated off in end of reaction, and silica gel column chromatography obtains P331, M/Z theoretical value: 627, M/Z measured value: 628.
Synthesis example 17: compound P337 synthesis
In 1000mL single port bottle, it is bromo- that 13.5g (50mmol) 2- amino -1,2'- dinaphthalene, 13.5g (50mmol) 2- is added 9,9'- dimethyl fluorene, 0.7g (1mmol) [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride, 0.5g 2- dicyclohexyl phosphine- 2', 6'- dimethoxy-biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction heating To 90 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h is mixed, suction filtration obtains pale yellow powder M2.
In 1000mL single port bottle, 23g (50mmol) M1,10.4g (50mmol) 2- bromonaphthalene, 0.9g (1mmol) three is added Vacuum and exchange nitrogen 3 times, tri- tertiary butyl phosphine toluene solution of 0.5mL, heating is added in (dibenzalacetone) two palladium, 500mL toluene To 110 DEG C of reaction 12h, solvent is evaporated off in end of reaction, and silica gel column chromatography obtains P337, M/Z theoretical value: 587, M/Z measured values: 588。
Synthesis example 18: compound P371 synthesis
In 1000mL single port bottle, 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 32.2g (100mmol) 9- is added (4- bromophenyl)-carbazole, 0.9g (1mmol) tris(dibenzylideneacetone) dipalladium, tri- tertiary butyl phosphine of 0.5mL, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction is warming up to 110 DEG C of reaction 5h.End of reaction stops anti- It answers.It being cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h, suction filtration obtains pale yellow powder P371, M/Z theoretical value: 751, M/Z measured values: 752.
Synthesis example 19: compound P372 synthesis
In 1000mL single port bottle, 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 32.2g (100mmol) 9- is added (3- bromophenyl)-carbazole, 0.9g (1mmol) tris(dibenzylideneacetone) dipalladium, tri- tertiary butyl phosphine of 0.5mL, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction is warming up to 110 DEG C of reaction 5h.End of reaction stops anti- It answers.It being cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h, suction filtration obtains pale yellow powder P372, M/Z theoretical value: 751, M/Z measured values: 752.
Synthesis example 20: compound P373 synthesis
In 1000mL single port bottle, 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 30.9g (100mmol) 3- bromine is added Terphenyl, 0.9g (1mmol) tris(dibenzylideneacetone) dipalladium, tri- tertiary butyl phosphine of 0.5mL, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction is warming up to 110 DEG C of reaction 5h.End of reaction stops reaction.It is cold But organic phase is concentrated to reaction solution liquid separation to room temperature, methanol is added and stirs 1h, suction filtration obtains pale yellow powder P373, M/Z reason By value: 725, M/Z measured values: 726.
Synthesis example 21: compound P374 synthesis
In 1000mL single port bottle, 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 24.5g (100mmol) 4- bromine is added Dibenzofurans, 0.9g (1mmol) tris(dibenzylideneacetone) dipalladium, tri- tertiary butyl phosphine of 0.5mL, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction is warming up to 110 DEG C of reaction 5h.End of reaction stops reaction.It is cold But organic phase is concentrated to reaction solution liquid separation to room temperature, methanol is added and stirs 1h, suction filtration obtains pale yellow powder P374, M/Z reason By value: 601.31M/Z measured value: 602.
Synthesis example 22: compound P375 synthesis
In 1000mL single port bottle, 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 32.3g (100mmol) 4- is added (4- bromophenyl)-dibenzofurans, 0.9g (1mmol) tris(dibenzylideneacetone) dipalladium, tri- tertiary butyl phosphine of 0.5mL, 500mL first Benzene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction is warming up to 110 DEG C of reaction 5h.End of reaction stops Reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h, suction filtration obtains pale yellow powder P375, M/Z theoretical value: 753, M/Z measured values: 754.
Synthesis example 23: compound P376 synthesis
In 1000mL single port bottle, 13.5g (50mmol) 2- amino 0.5mL-1,1'- dinaphthalene, 10g (100mmol) is added 2- bromonaphthalene, 0.9g (1mmol) tris(dibenzylideneacetone) dipalladium, three tertiary butyl phosphines, 500mL toluene, 14.4g (150mmol) uncle Sodium butoxide, vacuum and exchange nitrogen 3 times, reaction is warming up to 110 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, it is right Organic phase is concentrated in reaction solution liquid separation, and methanol is added and stirs 1h, suction filtration obtains pale yellow powder P376, M/Z theoretical value: 521, M/Z Measured value: 522.
Synthesis example 24: compound P377 synthesis
In 1000mL single port bottle, 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 32.2g (100mmol) (9- is added Phenyl) -3- bromo carbazole, 0.9g (1mmol) tris(dibenzylideneacetone) dipalladium, tri- tertiary butyl phosphine of 0.5mL, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction is warming up to 110 DEG C of reaction 5h.End of reaction stops anti- It answers.It being cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h, suction filtration obtains pale yellow powder P377, M/Z theoretical value: 751, M/Z measured values: 752.
Synthesis example 25: compound P378 synthesis
In 1000mL single port bottle, 6.7g (25mmol) 2- amino -1,1'- dinaphthalene, 20g (100mmol) 4- bromo- 9 is added, Two fluorenes of 9'- spiral shell, 0.9g (1mmol) tris(dibenzylideneacetone) dipalladium, tri- tertiary butyl phosphine of 0.5mL, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction is warming up to 110 DEG C of reaction 5h.End of reaction stops reaction.It is cold But organic phase is concentrated to reaction solution liquid separation to room temperature, methanol is added and stirs 1h, suction filtration obtains pale yellow powder P378, M/Z reason By value: 898, M/Z measured values: 898.
Synthesis example 26: compound P379 synthesis
In 1000mL single port bottle, it is bromo- that 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 13.5g (50mmol) 2- is added 9,9'- dimethyl fluorene, 0.7g (1mmol) [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride, 0.5g 2- dicyclohexyl phosphine- 2', 6'- dimethoxy-biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction heating To 90 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h is mixed, suction filtration obtains pale yellow powder M1.
In 1000mL single port bottle, 23g (50mmol) M1,32.2g (100mmol) 9- (4- bromophenyl)-carbazole is added, Vacuum and exchange nitrogen 3 times, tri- tertiary butyl phosphine of 0.5mL is added in 0.9g (1mmol) tris(dibenzylideneacetone) dipalladium, 500mL toluene Toluene solution is warming up to 110 DEG C of reaction 12h, and solvent is evaporated off in end of reaction, and silica gel column chromatography obtains P379, M/Z theoretical value: 702, M/Z measured values: 703.
Synthesis example 27: compound P380 synthesis
In 1000mL single port bottle, it is bromo- that 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 13.5g (50mmol) 2- is added 9,9'- dimethyl fluorene, 0.7g (1mmol) [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride, 0.5g 2- dicyclohexyl phosphine- 2', 6'- dimethoxy-biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction heating To 90 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h is mixed, suction filtration obtains pale yellow powder M1.
In 1000mL single port bottle, 23g (50mmol) M1,32.2g (100mmol) 9- (3- bromophenyl)-carbazole is added, Vacuum and exchange nitrogen 3 times, tri- tertiary butyl phosphine of 0.5mL is added in 0.9g (1mmol) tris(dibenzylideneacetone) dipalladium, 500mL toluene Toluene solution is warming up to 110 DEG C of reaction 12h, and solvent is evaporated off in end of reaction, and silica gel column chromatography obtains P380, M/Z theoretical value: 702, M/Z measured values: 703.
Synthesis example 28: compound P381 synthesis
In 1000mL single port bottle, it is bromo- that 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 13.5g (50mmol) 2- is added 9,9'- dimethyl fluorene, 0.7g (1mmol) [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride, 0.5g 2- dicyclohexyl phosphine- 2', 6'- dimethoxy-biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction heating To 90 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h is mixed, suction filtration obtains pale yellow powder M1.
In 1000mL single port bottle, 23g (50mmol) M1,16.1g (100mmol) (9- phenyl) -3- bromo carbazole is added, Vacuum and exchange nitrogen 3 times, tri- tertiary butyl phosphine of 0.5mL is added in 0.9g (1mmol) tris(dibenzylideneacetone) dipalladium, 500mL toluene Toluene solution is warming up to 110 DEG C of reaction 12h, and solvent is evaporated off in end of reaction, and silica gel column chromatography obtains P381, M/Z theoretical value: 702, M/Z measured values: 703.
Synthesis example 29: compound P382 synthesis
In 1000mL single port bottle, 13.5g (50mmol) 2- amino-4-methoxyl -5'- methoxyl group -1,1'- connection is added The special fourth of naphthalene, the bromo- 9,9'- dimethyl fluorene of 27g (100mmol) 2-, 0.9g (1mmol) tris(dibenzylideneacetone) dipalladium, 0.5mL tri- Base phosphine, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction is warming up to 110 DEG C of reaction 5h. End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h, suction filtration obtains Pale yellow powder P382, M/Z theoretical value: 713, M/Z measured values: 714.
Synthesis example 30: compound P383 synthesis
In 1000mL single port bottle, 13.5g (50mmol) 2- amino-4-methoxyl -5'- methoxyl group -1,2'- connection is added Naphthalene, the bromo- 9,9'- dimethyl fluorene of 13.5g (50mmol) 2-, 0.7g (1mmol) [1,1 '-bis- (diphenylphosphine) ferrocene] dichloride Palladium, 0.5g2- dicyclohexyl phosphine -2', 6'- dimethoxy-biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide are taken out true Sky changes nitrogen 3 times, and reaction is warming up to 90 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, it is dense to reaction solution liquid separation Contracting organic phase is added methanol and stirs 1h, and suction filtration obtains pale yellow powder M2.
In 1000mL single port bottle, the bromo- dibenzofurans of 23g (50mmol) M1,12.3g (50mmol) 2-, 0.9g is added Vacuum and exchange nitrogen 3 times, tri- tertiary butyl phosphine toluene of 0.5mL is added in (1mmol) tris(dibenzylideneacetone) dipalladium, 500mL toluene Solution is warming up to 110 DEG C of reaction 12h, and solvent is evaporated off in end of reaction, and silica gel column chromatography obtains P383, M/Z theoretical value: 687, M/Z measured value: 688.
Synthesis example 31: compound P387 synthesis
In 1000mL single port bottle, it is bromo- that 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 13.5g (50mmol) 2- is added 9,9'- dimethyl fluorene, 0.7g (1mmol) [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride, 0.5g 2- dicyclohexyl phosphine- 2', 6'- dimethoxy-biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction heating To 90 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h is mixed, suction filtration obtains pale yellow powder M1.
In 1000mL single port bottle, bromo- 9, the 9'- dimethyl fluorene of 23g (50mmol) M1,13.5g (100mmol) 3- is added, Vacuum and exchange nitrogen 3 times, tri- tertiary butyl phosphine of 0.5mL is added in 0.9g (1mmol) tris(dibenzylideneacetone) dipalladium, 500mL toluene Toluene solution is warming up to 110 DEG C of reaction 12h, and solvent is evaporated off in end of reaction, and silica gel column chromatography obtains P387, M/Z theoretical value: 653, M/Z measured values: 654.
Synthesis example 32: compound P389 synthesis
In 1000mL single port bottle, it is bromo- that 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 13.5g (50mmol) 3- is added 9,9'- dimethyl fluorene, 0.7g (1mmol) [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride, 0.5g 2- dicyclohexyl phosphine- 2', 6'- dimethoxy-biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction heating To 90 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h is mixed, suction filtration obtains pale yellow powder M4.
In 1000mL single port bottle, 23g (50mmol) M4,12g (100mmol) is added to bromo biphenyl, 0.9g (1mmol) three Vacuum and exchange nitrogen 3 times, tri- tertiary butyl phosphine toluene solution of 0.5mL, heating is added in (dibenzalacetone) two palladium, 500mL toluene To 110 DEG C of reaction 12h, solvent is evaporated off in end of reaction, and silica gel column chromatography obtains P389, M/Z theoretical value: 633, M/Z measured values: 634。
Synthesis example 33: compound P396 synthesis
In 1000mL single port bottle, it is bromo- that 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 13.5g (50mmol) 3- is added 9,9'- dimethyl fluorene, 0.7g (1mmol) [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride, 0.5g 2- dicyclohexyl phosphine- 2', 6'- dimethoxy-biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction heating To 90 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h is mixed, suction filtration obtains pale yellow powder M4.
In 1000mL single port bottle, 23g (50mmol) M4,10.5g (100mmol) 2- bromonaphthalene, 0.9g (1mmol) three is added Vacuum and exchange nitrogen 3 times, tri- tertiary butyl phosphine toluene solution of 0.5mL, heating is added in (dibenzalacetone) two palladium, 500mL toluene To 110 DEG C of reaction 12h, solvent is evaporated off in end of reaction, and silica gel column chromatography obtains P396, M/Z theoretical value: 587, M/Z measured values: 588。
Synthesis example 34: compound P405 synthesis
In 1000mL single port bottle, it is bromo- that 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 13.5g (50mmol) 3- is added 9,9'- dimethyl fluorene, 0.7g (1mmol) [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride, 0.5g 2- dicyclohexyl phosphine- 2', 6'- dimethoxy-biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction heating To 90 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h is mixed, suction filtration obtains pale yellow powder M4.
In 1000mL single port bottle, 23g (50mmol) M4,8.7g (100mmol) bromobenzene, 0.9g (1mmol) three (two is added BENZYLIDENE ACETONE) two palladiums, 500mL toluene, vacuum and exchange nitrogen 3 times, addition tri- tertiary butyl phosphine toluene solution of 0.5mL is warming up to Solvent is evaporated off in 110 DEG C of reaction 12h, end of reaction, and silica gel column chromatography obtains P405, M/Z theoretical value: 537, M/Z measured values: 538。
Synthesis example 35: compound P406 synthesis
In 1000mL single port bottle, it is bromo- that 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 13.5g (50mmol) 3- is added 9,9'- dimethyl fluorene, 0.7g (1mmol) [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride, 0.5g 2- dicyclohexyl phosphine- 2', 6'- dimethoxy-biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction heating To 90 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h is mixed, suction filtration obtains pale yellow powder M4.
In 1000mL single port bottle, 23g (50mmol) M4,12g (100mmol) 2- bromo biphenyl, 0.9g (1mmol) three is added Vacuum and exchange nitrogen 3 times, tri- tertiary butyl phosphine toluene solution of 0.5mL, heating is added in (dibenzalacetone) two palladium, 500mL toluene To 110 DEG C of reaction 12h, solvent is evaporated off in end of reaction, and silica gel column chromatography obtains P405, M/Z theoretical value: 613, M/Z measured values: 614。
Synthesis example 36: compound P409 synthesis
In 1000mL single port bottle, it is bromo- that 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 13.5g (50mmol) 3- is added 9,9'- dimethyl fluorene, 0.7g (1mmol) [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride, 0.5g 2- dicyclohexyl phosphine- 2', 6'- dimethoxy-biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction heating To 90 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h is mixed, suction filtration obtains pale yellow powder M4.
In 1000mL single port bottle, 23g (50mmol) M4,17.5g (100mmol) 3- (2- (9,9- dimethyl fluorenes are added Base)) bromobenzene, 0.9g (1mmol) tris(dibenzylideneacetone) dipalladium, 500mL toluene, vacuum and exchange nitrogen 3 times, addition 0.5mL Three tertiary butyl phosphine toluene solutions are warming up to 110 DEG C of reaction 12h, and solvent is evaporated off in end of reaction, and silica gel column chromatography obtains P409, M/Z theoretical value: 729, M/Z measured values: 730.
Synthesis example 37: compound P414 synthesis
In 1000mL single port bottle, it is bromo- that 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 13.5g (50mmol) 3- is added 9,9'- dimethyl fluorene, 0.7g (1mmol) [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride, 0.5g 2- dicyclohexyl phosphine- 2', 6'- dimethoxy-biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction heating To 90 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h is mixed, suction filtration obtains pale yellow powder M4.
In 1000mL single port bottle, 23g (50mmol) M4,15g (100mmol) 3,5- diphenyl bromobenzene, 0.9g is added Vacuum and exchange nitrogen 3 times, tri- tertiary butyl phosphine toluene of 0.5mL is added in (1mmol) tris(dibenzylideneacetone) dipalladium, 500mL toluene Solution is warming up to 110 DEG C of reaction 12h, and solvent is evaporated off in end of reaction, and silica gel column chromatography obtains P414, M/Z theoretical value: 689, M/Z measured value: 690.
Synthesis example 38: compound P418 synthesis
In 1000mL single port bottle, it is bromo- that 13.5g (50mmol) 2- amino -1,1'- dinaphthalene, 13.5g (50mmol) 3- is added 9,9'- dimethyl fluorene, 0.7g (1mmol) [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride, 0.5g 2- dicyclohexyl phosphine- 2', 6'- dimethoxy-biphenyl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum and exchange nitrogen 3 times, reaction heating To 90 DEG C of reaction 5h.End of reaction stops reaction.It is cooled to room temperature, to reaction solution liquid separation, organic phase is concentrated, methanol is added and stirs 1h is mixed, suction filtration obtains pale yellow powder M4.
In 1000mL single port bottle, the bromo- biphenyl of 23g (50mmol) M4,15g (100mmol) 2- phenyl -1-, 0.9g is added Vacuum and exchange nitrogen 3 times, tri- tertiary butyl phosphine toluene of 0.5mL is added in (1mmol) tris(dibenzylideneacetone) dipalladium, 500mL toluene Solution is warming up to 110 DEG C of reaction 12h, and solvent is evaporated off in end of reaction, and silica gel column chromatography obtains P414, M/Z theoretical value: 689, M/Z measured value: 690.
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