WO2020253445A1 - 一种有机电致发光材料及包含该材料的有机电致发光器件 - Google Patents

一种有机电致发光材料及包含该材料的有机电致发光器件 Download PDF

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WO2020253445A1
WO2020253445A1 PCT/CN2020/090876 CN2020090876W WO2020253445A1 WO 2020253445 A1 WO2020253445 A1 WO 2020253445A1 CN 2020090876 W CN2020090876 W CN 2020090876W WO 2020253445 A1 WO2020253445 A1 WO 2020253445A1
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carbon atoms
group
substituted
unsubstituted
groups
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PCT/CN2020/090876
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English (en)
French (fr)
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马天天
聂齐齐
冯震
李红燕
沙荀姗
孙占义
王亚龙
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陕西莱特光电材料股份有限公司
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Priority to US17/613,794 priority Critical patent/US11424412B2/en
Priority to JP2021572947A priority patent/JP2022530693A/ja
Priority to KR1020217039789A priority patent/KR20210154989A/ko
Publication of WO2020253445A1 publication Critical patent/WO2020253445A1/zh
Priority to US17/718,174 priority patent/US11778901B2/en

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Definitions

  • the invention relates to the technical field of organic electroluminescence, in particular to an organic electroluminescence material and an organic electroluminescence device containing the material.
  • organic electroluminescent devices OLED, Organic electroluminescent devices
  • OLED Organic electroluminescent devices
  • Common organic electroluminescent devices are composed of an anode, a cathode, and more than one organic layer arranged between the cathode and the anode.
  • the two electrodes When voltage is applied to the cathode and anode, the two electrodes generate an electric field. Under the action of the electric field, the electrons on the cathode side move to the light-emitting layer, and the holes on the anode side also move to the light-emitting layer.
  • the two combine to form excitons and excitons in the light-emitting layer.
  • the process of releasing energy from the excited state to releasing energy from the excited state to releasing energy from the ground state emits light to the outside. Therefore, it is very important to improve the recombination of electrons and holes in OLED devices.
  • multilayer structures are generally used in the devices. These multilayer structures include: hole injection layer, hole transport layer, electron-bloking layer, emitting layer, and electron transport layer )and many more. These organic layers can improve the injection efficiency of carriers (holes and electrons) at the interface of each layer and balance the ability of carriers to transport between the layers, thereby improving the brightness and efficiency of the device.
  • NPD the commonly used hole transport material
  • Tg glass transition temperature
  • Patent document CN107148408A relates to adamantane derivatives and their organic electroluminescent devices, which include a substrate, a cathode and an anode vapor-deposited on the substrate, and an organic layer vapor-deposited between the cathode and the anode, wherein the organic layer contains holes Transport layer, the hole transport layer contains the following structure Adamantane derivatives.
  • these organic electroluminescent materials with excellent properties have been developed one after another, they are all monoamine structures, and the monoamine structure has a low hole transport rate. Therefore, the efficiency and lifetime of the resulting devices still need to be improved. How to design new properties The adjustment of better materials so that all devices can achieve the effects of reducing voltage, improving efficiency and lifespan has always been an urgent problem for those skilled in the art.
  • the purpose of the present invention is to provide an organic electroluminescent material with excellent performance, which can be used as a hole transport layer, an electron blocking layer and the like in an organic electroluminescent device.
  • Another object of the present invention is to provide an organic light emitting device containing the organic electroluminescent material, which has a lower driving voltage, higher luminous efficiency and service life.
  • R 2 , R 4 and R 5 are the same or different, and are independently selected from substituted or unsubstituted alkyl groups having 1-20 carbon atoms, substituted or unsubstituted alkenyl groups having 2-20 carbon atoms , Substituted or unsubstituted alkynyl groups with 2-24 carbon atoms, substituted or unsubstituted cycloalkyl groups with 3-20 carbon atoms, substituted or unsubstituted heterocycloalkanes with 2-20 carbon atoms Groups, substituted or unsubstituted aralkyl groups with 7-30 carbon atoms, substituted or unsubstituted heteroaralkyl groups with 2-30 carbon atoms, substituted or unsubstituted carbon atoms with 6-30 Aryl, substituted or unsubstituted heteroaryl with 1-30 carbon atoms;
  • R 1 and R 3 are the same or different, and are each independently selected from a single bond, a substituted or unsubstituted arylene group with 1-30 carbon atoms, and a substituted or unsubstituted heteroarylene group with 1-30 carbon atoms , Substituted or unsubstituted aralkylene groups with 7-30 carbon atoms, substituted or unsubstituted heteroarylene groups with 2-30 carbon atoms;
  • R 1 , R 2 , R 3 , R 4 and R 5 are the same or different, and are each independently selected from deuterium, cyano, nitro, halogen, hydroxyl, and alkyl with 1-40 carbon atoms Group, cycloalkyl group with 3-40 carbon atoms, alkenyl group with 2-40 carbon atoms, alkynyl group with 2-40 carbon atoms, heterocycloalkane with 2-40 carbon atoms Groups, aralkyl groups with 7-40 carbon atoms, heteroaralkyl groups with 2-40 carbon atoms, aryl groups with 6-40 carbon atoms, and 1-40 carbon atoms Heteroaryl groups, alkoxy groups with 1-40 carbon atoms, alkylamino groups with 1-40 carbon atoms, arylamino groups with 6-40 carbon atoms, 1-40 carbon atoms
  • the present application also provides an organic electroluminescent device, comprising a cathode, an anode, and one or more organic layers arranged between the cathode and the anode, at least one of the organic layers includes the electroluminescent material.
  • the organic layer includes a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.
  • the hole transport layer includes the electroluminescent material described in the present application.
  • the electron blocking layer includes the electroluminescent material described in the present application.
  • the application also provides the application of the organic electroluminescent material in organic electroluminescent devices.
  • the present invention has the following beneficial technical effects:
  • the diamine structure contained in the present invention has a higher HOMO energy level and hole mobility, and can exhibit higher efficiency and lifetime than monoamine material devices. Since there are many substitution sites for diamine materials, the substitution of adamantyl groups at different positions can also play a more fine-tuned role in the spatial structure and molecular stacking of the material; especially when the present invention is used as an electron blocking layer, it can play a To better adjust the hole transport rate, thereby further enhancing the efficiency and lifetime of the device by balancing the hole and electron transport efficiency.
  • the diamine structure has a high hole transport efficiency, but due to its small molecular weight and high symmetry, it is easy to crystallize at low temperatures; the diamine structure is combined with an adamantyl group to introduce a large sterically hindered adamantane After base, this phenomenon can be greatly improved, and the glass transition temperature and crystallization temperature can be increased by 30-50°C, thereby effectively inhibiting the crystallization of the material and the resulting problem of low life of the light-emitting device.
  • the organic light emitting device containing the organic electroluminescent material has lower driving voltage, higher luminous efficiency and service life.
  • the number of carbon atoms of a substituted or unsubstituted aryl group refers to the total number of carbon atoms of the aryl group and the substituents on it
  • the number of carbon atoms of a substituted or unsubstituted heteroaryl group refers to the heteroaryl group And the number of all carbon atoms of the substituents.
  • the substituted or unsubstituted aryl group is selected from substituted aryl groups with 30 carbon atoms, all carbon atoms of the aryl group and the substituents thereon are 30; for example, 9,9-dimethyl
  • the fluorenyl group is an aryl group with 15 carbon atoms. If the substituted or unsubstituted heteroaryl group is selected from substituted heteroaryl groups with 12 carbon atoms, all of the carbon atoms of the heteroaryl group and the substituents thereon are 12.
  • substituted or unsubstituted means that the functional group described after the term may or may not have a substituent.
  • hetero means that a functional group includes at least one heteroatom such as B, N, O, S, Se, Si, or P, and the remaining atoms are carbon and hydrogen.
  • the unsubstituted alkyl group may be a "saturated alkyl group" without any double or triple bonds.
  • heterocyclic group optionally substituted by an alkyl group means that an alkyl group may but does not have to be present, and the description includes the scenario where the heterocyclic group is substituted by an alkyl group and the scenario where the heterocyclic group is not substituted by an alkyl group .
  • two substituents connected to the same atom are connected to each other to form a saturated or unsaturated 5- to 18-membered aliphatic ring or 5- to 18-membered aromatic ring with the atoms they are commonly connected to" means connecting Two substituents on the same atom can form a ring but do not have to form a ring, including the situation where the two are connected to form a saturated or unsaturated 5-18-membered aliphatic ring or 5-18-membered aromatic ring. A scenario where the two exist independently of each other.
  • the non-positioned link in this application refers to the single bond extending from the ring system It means that one end of the link can be connected to any position in the ring system that the bond penetrates, and the other end is connected to the rest of the compound molecule.
  • the naphthyl group represented by the formula (X) is connected to other positions of the molecule through two non-positioned linkages running through the bicyclic ring, and its meaning includes the meaning of the formula (X-1 ) ⁇ Any possible connection shown in formula (X-10).
  • the phenanthryl group represented by the formula (X') is connected to other positions of the molecule through a non-positional bond extending from the middle of the benzene ring on one side. It includes any possible connection modes shown in formula (X'-1) to formula (X'-4).
  • the non-positioned substituent in this application refers to a substituent connected by a single bond extending from the center of the ring system, which means that the substituent can be attached to any possible position in the ring system.
  • the substituent R group represented by the formula (Y) is connected to the quinoline ring through a non-localized linkage, and its meaning includes the following formula (Y-1) to Any possible connection mode shown in formula (Y-7).
  • R 2 , R 4 and R 5 are the same or different, and are independently selected from substituted or unsubstituted alkyl groups having 1-20 carbon atoms, substituted or unsubstituted alkenyl groups having 2-20 carbon atoms , Substituted or unsubstituted alkynyl groups with 2-24 carbon atoms, substituted or unsubstituted cycloalkyl groups with 3-20 carbon atoms, substituted or unsubstituted heterocycloalkanes with 2-20 carbon atoms Groups, substituted or unsubstituted aralkyl groups with 7-30 carbon atoms, substituted or unsubstituted heteroaralkyl groups with 2-30 carbon atoms, substituted or unsubstituted carbon atoms with 6-30 Aryl, substituted or unsubstituted heteroaryl with 1-30 carbon atoms;
  • R 1 and R 3 are the same or different, and are each independently selected from a single bond, a substituted or unsubstituted arylene group with 1-30 carbon atoms, and a substituted or unsubstituted heteroarylene group with 1-30 carbon atoms , Substituted or unsubstituted aralkylene groups with 7-30 carbon atoms, substituted or unsubstituted heteroarylene groups with 2-30 carbon atoms;
  • R 1 , R 2 , R 3 , R 4 and R 5 are the same or different, and are each independently selected from deuterium, cyano, nitro, halogen, hydroxyl, and alkyl with 1-40 carbon atoms Group, cycloalkyl group with 3-40 carbon atoms, alkenyl group with 2-40 carbon atoms, alkynyl group with 2-40 carbon atoms, heterocycloalkane with 2-40 carbon atoms Groups, aralkyl groups with 7-40 carbon atoms, heteroaralkyl groups with 2-40 carbon atoms, aryl groups with 6-40 carbon atoms, and 1-40 carbon atoms Heteroaryl groups, alkoxy groups with 1-40 carbon atoms, alkylamino groups with 1-40 carbon atoms, arylamino groups with 6-40 carbon atoms, 1-40 carbon atoms
  • the unsubstituted alkyl group in the present invention refers to a straight-chain alkyl group having 1-20 carbon atoms, or a branched-chain alkyl group having 1-13 carbon atoms.
  • the alkyl group contains 1 to 4 carbon atoms; in still other embodiments, the alkyl group contains 1 to 3 carbon atoms.
  • the alkyl group may be optionally substituted with one or more substituents described herein. For example, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, isopentyl, hexyl and the like.
  • the substituted alkyl group with 1-20 carbon atoms means that at least one hydrogen atom is replaced by deuterium, F, Cl, I, CN, hydroxyl, nitro, amino, phenyl, biphenyl, terphenyl, naphthyl , Dibenzofuranyl, dibenzothienyl and other substitutions.
  • the unsubstituted alkenyl group in the present invention refers to an alkenyl group with 2-20 carbon atoms, a straight-chain alkenyl group with 2-20 carbon atoms containing a carbon-carbon double bond, or a linear alkenyl group containing 2-20 carbon atoms.
  • 1-13 branched alkenyl For example: vinyl, propenyl, allyl, isopropenyl, 2-butenyl, etc.
  • the substituted alkenyl group having 2-20 carbon atoms means that at least one hydrogen atom is replaced by a deuterium atom, F, Cl, I, CN, hydroxyl, nitro, amino, and the like.
  • the unsubstituted alkynyl group in the present invention refers to an alkynyl group having 2-24 carbon atoms, a linear alkynyl group having 2 to 35 carbon atoms containing a carbon-carbon triple bond, or a linear alkynyl group containing 2 to 35 carbon atoms.
  • branched alkynyl For example: ethynyl, 2-propynyl, etc.
  • the substituted alkynyl group having 2-24 carbon atoms means that at least one hydrogen atom is replaced by a deuterium atom, F, Cl, I, CN, hydroxyl, nitro, amino, and the like.
  • the unsubstituted aryl group in the present invention refers to an aryl group having 6-30 carbon atoms.
  • Aryl refers to an optional functional group or substituent derived from an aromatic carbocyclic ring.
  • the aryl group can be a monocyclic aryl group or a polycyclic aryl group.
  • the aryl group can be a monocyclic aryl group, a condensed ring aryl group, two or more monocyclic aryl groups conjugated by carbon-carbon bonds, A monocyclic aryl group and a fused ring aryl group conjugated by carbon-carbon bonds, and two or more fused ring aryl groups conjugated by a carbon-carbon bond.
  • two or more aromatic groups conjugated through carbon-carbon bonds can also be regarded as aryl groups in the present application.
  • aryl groups for example: phenyl, naphthyl, pyrenyl, dimethylfluorenyl, anthracenyl, phenanthryl, Group, azulenyl, acenaphthylene, biphenyl, benzanthracenyl, spirobifluorenyl, perylene, indenyl, etc.
  • the aryl group can also be terphenyl, tetraphenyl, pentaphenyl, benzo[9,10]phenanthryl, benzofluoranthene.
  • the substituted aryl group with 6-30 carbon atoms means that at least one hydrogen atom is replaced by deuterium, F, Cl, I, CN, hydroxyl, nitro, amino, alkyl, phenyl, biphenyl, terphenyl , Naphthyl, dibenzofuranyl, dibenzothienyl, etc.
  • the total number of carbon atoms on the aryl group and its substituents is 6-30, and the number of carbon atoms in the substituted aryl group can also be 7, 8, 9, 10, 11, 12, 13, 14, 15, 18, or 20, such as naphthyl substituted phenyl, phenyl substituted naphthyl, all are carbon atoms
  • the number is 16 substituted aryl groups.
  • the unsubstituted aralkyl group in the present invention refers to an aralkyl group having 7-30 carbon atoms.
  • an aralkyl group having 7-30 carbon atoms For example: tolyl, dimethyl fluorenyl and so on.
  • the substituted aralkyl group having 7-30 carbon atoms means that at least one hydrogen atom is replaced by a deuterium atom, F, Cl, I, CN, hydroxyl, nitro, amino, etc.
  • the unsubstituted heteroaryl group in the present invention refers to a heteroaryl group having 1-30 carbon atoms.
  • Heteroaryl refers to a monovalent aromatic ring containing at least one heteroatom in the ring or a derivative thereof.
  • the heteroatom may be at least one of B, O, N, P, Si, and S.
  • the heteroaryl group can be a monocyclic heteroaryl group or a polycyclic heteroaryl group.
  • the heteroaryl group can be a single aromatic ring system or multiple aromatic ring systems conjugated by carbon-carbon bonds, and any aromatic
  • the ring system is an aromatic monocyclic ring or an aromatic fused ring.
  • heteroaryl group in this application may include 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 heteroatoms selected from B, O, N, P, Si, Se and S ,
  • the number of carbon atoms can be 1-30.
  • the heteroaryl group can also be N-phenylcarbazolyl.
  • the substituted heteroaryl group with 1-30 carbon atoms means that at least one hydrogen atom is replaced by a deuterium atom, F, Cl, I, CN, hydroxyl, nitro, amino, alkyl, phenyl, biphenyl, terphenyl Substitutions such as dibenzofuranyl, naphthyl, dibenzofuranyl, and dibenzothienyl.
  • the unsubstituted cycloalkyl group in the present invention refers to a cycloalkyl group having 3-20 carbon atoms.
  • the substituted cycloalkyl group having 3-20 carbon atoms means that at least one hydrogen atom is replaced by a deuterium atom, F, Cl, I, CN, hydroxyl, nitro, amino, etc.
  • R 1 and R 3 are the same or different, and are independently selected from single bonds, substituted or unsubstituted arylene groups with 6-25 carbon atoms, substituted or unsubstituted
  • the number of carbon atoms is 5-18 heteroarylene
  • R 2 , R 4 and R 5 are the same or different, and are independently selected from single bonds, substituted or unsubstituted aryl groups with 6-18 carbon atoms, substituted or The number of unsubstituted carbon atoms is 5-18 heteroaryl;
  • the substituents of R 1 , R 2 , R 3 , R 4 and R 5 are the same or different, and are independently selected from deuterium, cyano, nitro, Halogen, hydroxyl, alkyl group with carbon number of 1-10, cycloalkyl group with carbon number of 3-10, aryl group with carbon number of 6-15, carbon number of 3-
  • the substituents are the same or different, and are independently selected from single bonds, substituted or unsubstitute
  • R 1 and R 3 are the same or different from each other, and are each independently selected from the group consisting of groups represented by chemical formula j-1 to chemical formula j-9:
  • M 2 is selected from a single bond or
  • E 1 to E 14 are each independently selected from: hydrogen, deuterium, halogen group, cyano group, heteroaryl group having 3 to 12 carbon atoms, aryl group having 6 to 15 carbon atoms, and 3 carbon atoms -9 trialkylsilyl groups, alkyl groups having 1 to 10 carbon atoms, haloalkyl groups having 1 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, and 1 to 10 carbon atoms ⁇ alkoxy;
  • e 1 to e 14 are represented by e r
  • E 1 to E 14 are represented by E r
  • r is a variable, representing any integer from 1 to 14, and e r is the number of substituents Er ; when r is selected from 1, 2, When 3, 4, 5, 6, 9, 13, or 14, e r is selected from 1, 2, 3 or 4; when r is selected from 7 or 11, e r is selected from 1, 2, 3, 4, 5 or 6; when r is 12, e r is selected from 1, 2, 3, 4, 5, 6 or 7; when r is selected from 8 or 10, e r is selected from 1, 2, 3, 4, 5, 6 , 7 or 8; when e r is greater than 1, any two E r are the same or different;
  • K 3 is selected from O, S, Se, N (E 15 ), C (E 16 E 17 ), Si (E 18 E 19 ); wherein, each of E 15 , E 16 , E 17 , E 18 and E 19 are respectively Independently selected from: hydrogen, aryl groups having 6 to 15 carbon atoms, heteroaryl groups having 3 to 12 carbon atoms, alkyl groups having 1 to 10 carbon atoms, and rings having 3 to 10 carbon atoms Alkyl group, heterocycloalkyl group having 2 to 10 carbon atoms;
  • Each K 4 is independently selected from a single bond, O, S, Se, N (E 20 ), C (E 21 E 22 ), Si (E 23 E 24 ); wherein, each of E 20 , E 21 , E 22 , E 23 and E 24 are each independently selected from: hydrogen, aryl groups having 6 to 15 carbon atoms, heteroaryl groups having 3 to 12 carbon atoms, alkyl groups having 1 to 10 carbon atoms, and carbon atoms It is 3-10 cycloalkyl.
  • R 1 and R 3 are each independently selected from a substituted or unsubstituted group W 1 , and the unsubstituted group W 1 is selected from the following groups:
  • the substituents of W 1 are each independently selected from deuterium, fluorine, chlorine, cyano, methyl, ethyl, propyl, tert-butyl, tri A group consisting of methyl alkylsilyl, phenyl, naphthyl, dibenzofuranyl, dibenzothienyl, and carbazolyl; when the number of substituents of W 1 is more than one, each substituent is the same Or different.
  • R 2 , R 4 and R 5 are the same or different, and are independently selected from substituted or unsubstituted aralkyl groups with 7-30 carbon atoms, substituted or unsubstituted aralkyl groups.
  • R 1 and R 3 are the same or different, and are independently selected from a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted Or unsubstituted terphenylene, substituted or unsubstituted Group, substituted or unsubstituted phenanthrylene group, substituted or unsubstituted naphthylene group, substituted or unsubstituted azurylene ring group, substituted or unsubstituted indenylene group, substituted or unsubstituted pyridylene group, substituted or unsubstituted pyridylene group Substituted pyrimidinylene, substituted or unsubstituted triazinylene, substituted or unsubstituted imidazolylidene.
  • R 1 and R 3 are the same or different, and are each independently selected from: substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted Substituted terphenylene, substituted or unsubstituted anthrylene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted naphthylene, substituted or unsubstituted 9,9-dimethylfluorenylene, A substituted or unsubstituted dibenzofuran subunit, a substituted or unsubstituted dibenzothiophene subunit, a substituted or unsubstituted carbazolylidene group, or two or three of the subunits are connected by a single bond Formed subunit group;
  • substitution means independently substituted by a substituent selected from the following groups: deuterium, cyano, fluorine, chlorine, methyl, ethyl, propyl, tert-butyl, phenyl, naphthyl, carbazolyl , Dibenzofuranyl, dibenzothienyl;
  • each substituent is the same or different.
  • R 1 and R 3 are each independently selected from any one of the following groups:
  • R 2 , R 4 and R 5 are the same or different from each other, and are each independently selected from the group consisting of the groups represented by the chemical formula i-1 to the chemical formula i-11:
  • M 1 is selected from a single bond or
  • D 1 is selected from hydrogen, deuterium, fluorine, chlorine, bromine, cyano, trialkylsilyl groups having 3 to 12 carbon atoms, alkyl groups having 1 to 10 carbon atoms, and those having 1 to 10 carbon atoms A halogenated alkyl group, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkylthio group having 1 to 10 carbon atoms;
  • D 2 to D 9 and D 21 are each independently selected from: hydrogen, deuterium, fluorine, chlorine, bromine, cyano, trialkylsilyl groups having 3 to 12 carbon atoms, and alkane having 1 to 10 carbon atoms Group, a halogenated alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a heteroaryl group having 3 to 12 carbon atoms;
  • D 10 to D 20 are each independently selected from: hydrogen, deuterium, fluorine, chlorine, bromine, cyano, trialkylsilyl having 3 to 12 carbon atoms, alkyl having 1 to 10 carbon atoms, carbon A haloalkyl group having 1 to 10 atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, and 3 carbon atoms ⁇ 12 heteroaryl;
  • d 1 to d 21 are represented by d k
  • D 1 to D 21 are represented by D k
  • k is a variable, which represents any integer from 1 to 21
  • d k represents the number of substituents D k ; wherein, when k is selected from 5 Or when 17, d k is selected from 1, 2 or 3; when k is selected from 2, 7, 8, 12, 15, 16, 18 or 21, d k is selected from 1, 2, 3 or 4; when k is selected When 1, 3, 4, 6, 9 or 14, d k is selected from 1, 2, 3, 4, or 5; when k is 13, d k is selected from 1, 2, 3, 4, 5, or 6; When k is selected from 10 or 19, d k is selected from 1, 2, 3, 4, 5, 6 or 7; when k is 20, d k is selected from 1, 2, 3, 4, 5, 6, 7 Or 8; when k is 11, d k is selected from 1, 2, 3, 4, 5, 6, 7, 8 or 9; and when d k is greater than 1, any two D k are the same or different;
  • K 1 is independently selected from O, S, N (D 22 ), C (D 23 D 24 ), Si (D 25 D 26 ); wherein each of D 22 , D 23 , D 24 , D 25 , and D 26 are respectively Independently selected from: aryl groups having 6 to 15 carbon atoms, heteroaryl groups having 3 to 12 carbon atoms, alkyl groups having 1 to 10 carbon atoms, or cycloalkyl groups having 3 to 10 carbon atoms ;
  • K 2 is selected from a single bond, O, S, N (D 27 ), C (D 28 D 29 ), Si (D 30 D 31 ); wherein, each of D 27 , D 28 , D 29 , D 30 , D 31 They are independently selected from: aryl groups having 6 to 15 carbon atoms, heteroaryl groups having 3 to 12 carbon atoms, alkyl groups having 1 to 10 carbon atoms, or cycloalkanes having 3 to 10 carbon atoms base.
  • R 2 , R 4 and R 5 are the same or different from each other, and are each independently selected from the substituted or unsubstituted group Y 1 , the unsubstituted group Y 1 is selected from the following groups:
  • the substituents of Y 1 are each independently selected from deuterium, fluorine, chlorine, cyano, methyl, ethyl, propyl, isopropyl, tertiary A group consisting of butyl, trimethylsilyl, phenyl, naphthyl, dibenzothienyl, and dibenzofuranyl; when the substituent of Y 1 is more than one, each substituent is the same or different .
  • R 2 , R 4 and R 5 are the same or different, and are each independently selected from: substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or Unsubstituted terphenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted naphthyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted
  • substitution means independently substituted by a substituent selected from the following groups: deuterium, cyano, fluorine, chlorine, methyl, ethyl, propyl, tert-butyl, phenyl, naphthyl, carbazolyl , Dibenzofuranyl, dibenzothienyl;
  • each substituent is the same or different.
  • R 2 , R 4 and R 5 are each independently selected from any one of the following groups:
  • the chemical formula 1 is one of the following structures, but is not limited to this:
  • the present application also provides an organic electroluminescent device.
  • the organic electroluminescent device includes an anode and a cathode disposed oppositely, and an organic layer disposed between the anode and the cathode; the organic layer includes a hole injection layer , Hole transport layer, electron blocking layer, light emitting layer, hole blocking layer, electron transport layer and electron injection layer.
  • the hole transport layer or electron blocking layer contains the above-mentioned compound to improve the voltage characteristics, efficiency characteristics, and lifetime characteristics of the organic electroluminescent device.
  • the organic electroluminescent device may include an anode, a hole transport layer, an electron blocking layer, an organic light emitting layer, a hole blocking layer, an electron transport layer, and a cathode that are sequentially stacked.
  • the compound provided in this application can be applied to the hole transport layer or electron blocking layer of an organic electroluminescent device to increase the life of the organic electroluminescent device, increase the luminous efficiency of the organic electroluminescent device, or reduce the performance of the organic electroluminescent device. Drive voltage.
  • the anode includes an anode material, which is optionally a material with a large work function (work function) that facilitates injection of holes into the functional layer.
  • anode materials include, but are not limited to: metals such as nickel, platinum, vanadium, chromium, copper, zinc and gold or their alloys; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO); combined metals and oxides such as ZnO: Al or SnO 2 : Sb; or conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-di (Oxy)thiophene] (PEDT), polypyrrole and polyaniline. It can optionally include a transparent electrode containing indium tin oxide (ITO) as an anode.
  • ITO indium tin oxide
  • the hole transport layer may include one or more hole transport materials, which may be selected from compounds of the present application, carbazole polymers, carbazole-linked triarylamine compounds or other types of compounds.
  • the organic light-emitting layer may include a host material and a guest material.
  • the holes injected into the organic light-emitting layer and the electrons injected into the organic light-emitting layer can recombine in the organic light-emitting layer to form excitons.
  • the excitons transfer energy to the host material.
  • the material transfers energy to the guest material, which in turn enables the guest material to emit light.
  • the host material is CPB or ADN.
  • the guest material of the organic light-emitting layer can be a compound with a condensed aryl ring or a derivative thereof, a compound with a heteroaryl ring or a derivative thereof, an aromatic amine derivative or other materials, which are not specifically limited in this application .
  • the guest material of the organic light-emitting layer may be Ir(piq) 2 (acac) or the like.
  • the guest material of the organic light-emitting layer may be Ir(ppy) 3 or the like.
  • the electron transport layer may be a single layer structure or a multilayer structure, which may include one or more electron transport materials, which may be selected from, but not limited to, benzimidazole derivatives, Diazole derivatives, quinoxaline derivatives or other electron transport materials.
  • the cathode may include a cathode material, which is a material with a small work function that facilitates injection of electrons into the functional layer.
  • cathode materials include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or their alloys; or multilayer materials such as LiF/Al , Liq/Al, LiO 2 /Al, LiF/Ca, LiF/Al and BaF 2 /Ca.
  • a metal electrode containing aluminum as the cathode.
  • the material of the cathode may be a magnesium-silver alloy.
  • a hole injection layer may also be provided between the anode and the hole transport layer to enhance the ability of injecting holes into the hole transport layer.
  • the hole injection layer can be selected from benzidine derivatives, starburst arylamine compounds, phthalocyanine derivatives or other materials, which are not particularly limited in this application.
  • the hole injection layer may be composed of F4-TCNQ.
  • An electron blocking layer can also be arranged between the hole transport layer and the organic light-emitting layer to block electrons from being transported to the side of the hole transport layer, increase the recombination rate of electrons and holes in the organic light-emitting layer and protect the hole transport layer from electrons The impact.
  • the material of the electron blocking layer can be a compound of the application, a carbazole polymer, a carbazole-linked triarylamine compound, or other feasible structures.
  • An electron injection layer may also be provided between the cathode and the electron transport layer to enhance the ability to inject electrons into the electron transport layer.
  • the electron injection layer may include inorganic materials such as alkali metal sulfides and alkali metal halides, or may include complexes of alkali metals and organic substances.
  • the electron injection layer may include LiQ.
  • MS mass spectrometry
  • Proton nuclear magnetic resonance spectroscopy Bruker 600MHz nuclear magnetic instrument, at room temperature, with CD 2 Cl 2 as the solvent (in ppm), and TMS (0 ppm) as the reference standard. When multiple peaks appear, the following abbreviations will be used: s (singlet), d (doublet), t (triplet, triplet), m (multiplet, multiplet).
  • Phenyl-1-naphthylamine (21.9g, 100mmol), 4-bromo-4'-chlorobiphenyl (26.7g, 100mmol), tris(dibenzylideneacetone) two palladium (0.10g, 0.1mmol), X-PHOS (0.05g, 0.2mmol) and sodium tert-butoxide (1.61g, 150mmol) were added to toluene (200mL), heated to 108°C under nitrogen protection, stirred for 6h; then cooled to room temperature, the reaction solution was washed with water and then added After drying over magnesium sulfate, the filtrate was filtered to remove the solvent under reduced pressure; silica gel column chromatography was performed using n-heptane as the mobile phase to obtain a white intermediate (27.6 g, 68%).
  • Diphenylamine (8.45g, 50mmol), 2-chloro-7-bromo-dibenzothiophene (14.88g, 50mmol), tris(dibenzylideneacetone) two palladium (0.046g, 0.05mmol), X-PHOS (0.048g, 0.1mmol) and sodium tert-butoxide (7.2g, 75mmol) were added to toluene (150mL), heated to 108°C under nitrogen protection, and stirred for 6h; then cooled to room temperature, the reaction solution was washed with water and dried by magnesium sulfate After filtration, the filtrate was decompressed to remove the solvent; using n-heptane as the mobile phase, silica gel column chromatography was used for purification to obtain a white intermediate (13.89 g, 72%).
  • Diphenylamine (8.45g, 50mmol), 2-chloro-4-iodo dibenzofuran (16.42g, 50mmol), tris(dibenzylideneacetone) two palladium (0.046g, 0.05mmol), X-PHOS ( 0.048g, 0.1mmol) and sodium tert-butoxide (7.2g, 75mmol) were added to toluene (150mL), heated to 108°C under nitrogen protection, and stirred for 8h; then cooled to room temperature, the reaction solution was washed with water and dried by adding magnesium sulfate. After filtration, the solvent was removed from the filtrate under reduced pressure; silica gel column chromatography was performed using n-heptane as the mobile phase to obtain a white intermediate (14.05 g, 76%).
  • M-bromoiodobenzene 28.3g 100mmol, intermediate II-C-1 (25.9g, 100mmol), tris(dibenzylideneacetone) two palladium (0.91g, 1mmol), X-Phos (0.95g, 2mmol) and tertiary Sodium butoxide (19.2g, 200mmol) was added to toluene (200mL), heated to 108°C under nitrogen protection, stirred for 6h; then cooled to room temperature, the reaction solution was washed with water and then dried with magnesium sulfate. After filtration, the filtrate was decompressed to remove the solvent ; Use n-heptane as the mobile phase for silica gel column chromatography to obtain a white solid (26.49 g, 64%).
  • the 2-aminobiphenyl (6.77g, 4mmol), 2-bromofluorene (10.4g.3.8mmol), tris(dibenzylideneacetone) two palladium (0.348g, 0.38mmol), 2-dicyclohexylphosphorus -2,4,6-Triisopropylbiphenyl (0.355g, 0.76mmol) and sodium tert-butoxide (5.478g, 5.7mmol) were added to toluene (100mL), heated to 108°C under nitrogen protection, and stirred for 2h; After cooling to room temperature, the reaction solution was washed with water and dried by adding magnesium sulfate.
  • Example 1 Organic electroluminescent device using the compound of the present invention as a hole transport layer
  • the anode is prepared by the following process: the thickness is The ITO substrate (manufactured by Corning) was cut into a size of 40mm ⁇ 40mm ⁇ 0.7mm.
  • the photolithography process was used to prepare an experimental substrate with cathode, anode and insulating layer patterns, and the surface treatment was performed with ultraviolet ozone and O2:N2 plasma , In order to increase the work function of the anode (experimental substrate) and remove scum.
  • M-MTDATA was vacuum evaporated on the experimental substrate (anode) to form a thickness of The hole injection layer (HIL), and the compound 1 is vacuum evaporated on the hole injection layer to form a thickness of The hole transport layer (HTL).
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL Electron blocking layer
  • the light-emitting layer EML
  • DBimiBphen and LiQ were mixed at a weight ratio of 1:1 and evaporated to form Thick electron transport layer (ETL), LiQ is evaporated on the electron transport layer to form a thickness of The electron injection layer (EIL) is then mixed with magnesium (Mg) and silver (Ag) at a deposition rate of 1:9, and then vacuum-evaporated on the electron injection layer to form a thickness of The cathode.
  • ETL Thick electron transport layer
  • Mg magnesium
  • Ag silver
  • N-(4-(9H-carbazol-9-yl)phenyl)-4'-(9H-carbazol-9-yl)-N-phenyl was vapor-deposited on the above cathode with a thickness of 65nm -[1,1'-biphenyl]-4-amine to form a capping layer (CPL) to complete the manufacture of organic light-emitting devices.
  • CPL capping layer
  • the organic electroluminescent device was fabricated in the same manner as in Example 1, except that the compound shown in Table 1 was used to form the hole transport layer (HTL).
  • HTL hole transport layer
  • the device performance is shown in Table 1.
  • Comparative Examples 1 to 2 except that NPB and Compound B were used as the hole transport layer instead of Compound 1, the organic electroluminescence device was manufactured in the same manner as in Example 1. That is, Comparative Example 1 uses NPB to manufacture organic electroluminescent devices, and Comparative Example 2 uses Compound B to manufacture organic electroluminescent devices. The device performance is shown in Table 1.
  • each material used is as follows:
  • Example 1 Compound 1 4.0 6.7 14.3 200 0.140 0.045
  • Example 2 Compound 2 4.1 6.8 14.6 210 0.141 0.044
  • Example 3 Compound 3 3.9 6.9 14.9 198 0.141 0.045
  • Example 4 Compound 4 4.2 7.2 15.1 209 0.141 0.042
  • Example 5 Compound 5 3.8 6.4 14.7 180 0.142 0.044
  • Example 6 Compound 6 3.9 6.6 14.3 176 0.143 0.043
  • Example 7 Compound 7 4.4 6.4 14.4 169 0.142 0.042
  • Example 8 Compound 11 4.1 6.8 14.5 165 0.141 0.044
  • Example 9 Compound 12 4.18 6.7 14.0 168 0.143 0.045
  • Example 10 Compound 13 3.98 6.4 14.4 167 0.142 0.047
  • Example 11 Compound 14 3.93 6.5 13.5 174 0.141 0.046
  • Example 12 Compound 15 4.37
  • the organic electroluminescent device made with the compound of the present invention has a significant reduction in driving voltage (V), and a significant increase in current efficiency (Cd/A) and external quantum efficiency (EQE) It is better than the comparative example, showing a trend of improvement, and the service life (T95) is also significantly increased. Among them, the external quantum efficiency is increased by more than 30%.
  • Example 24 Organic electroluminescent device using the compound of the present invention as an electron blocking layer
  • the anode is prepared by the following process: the thickness is The ITO substrate (manufactured by Corning) was cut into a size of 40mm ⁇ 40mm ⁇ 0.7mm, and a photolithography process was used to prepare it into an experimental substrate with cathode, anode and insulating layer patterns, using ultraviolet ozone and O 2 :N 2 plasma. Surface treatment to increase the work function of the anode (experimental substrate) and remove scum.
  • M-MTDATA was vacuum evaporated on the experimental substrate (anode) to form a thickness of The hole injection layer (HIL), and the compound NPB is vacuum evaporated on the hole injection layer to form a thickness of The hole transport layer (HTL).
  • HIL hole injection layer
  • HTL hole transport layer
  • the compound 8 of the present invention was evaporated on the hole transport layer to form a thickness of The electron blocking layer (EBL).
  • EBL electron blocking layer
  • the light-emitting layer EML
  • DBimiBphen and LiQ were mixed at a weight ratio of 1:1 and evaporated to form Thick electron transport layer (ETL), LiQ is evaporated on the electron transport layer to form a thickness of The electron injection layer (EIL), and then magnesium (Mg) and silver (Ag) are mixed in a ratio of 1:9, and vacuum evaporated on the electron injection layer to form a thickness of The cathode.
  • the thickness of the vapor deposited on the above cathode is N-(4-(9H-carbazol-9-yl)phenyl)-4'-(9H-carbazol-9-yl)-N-phenyl-[1,1'-biphenyl]-4 -Amine to form a capping layer (CPL) to complete the manufacture of organic light-emitting devices.
  • CPL capping layer
  • An organic electroluminescent device was fabricated in the same manner as in Example 24, except that the compounds shown in Table 2 were each used when forming the electron blocking layer (EBL).
  • EBL electron blocking layer
  • Example 25 the compound 9 of the present invention was used to make an organic electroluminescent device, and the Example 26 used the compound 10 of the present invention to make an organic electroluminescent device.
  • Comparative Example 3 uses TCTA to manufacture organic electroluminescent devices
  • Comparative Example 4 uses NPD to manufacture organic electroluminescent devices
  • Comparative Example 5 uses TPD to manufacture organic electroluminescent devices.
  • the device performance is shown in Table 2.
  • each material used is as follows:
  • Compound 8 Compound 8 4.1 6.5 12.1 152 0.141 0.043
  • Example 25 Compound 9 3.7 6.1 14.4 178 0.143 0.043
  • Example 26 Compound 10 4.5 6.1 13.2 186 0.142 0.042
  • Example 27 Compound 19 4.0 6.4 14.6 167 0.141 0.043
  • Example 28 Compound 20 3.8 6.7 14.9 155 0.143 0.042
  • Example 29 Compound 23 3.8 6.5 14.7 168 0.142 0.042
  • Example 30 Compound 26 3.9 6.6.
  • the light-emitting layer uses fluorescent materials, and the fluorescent material emits singlet excitons, and its internal quantum efficiency is up to 25%.
  • the fluorescent material emits singlet excitons, and its internal quantum efficiency is up to 25%.
  • the external quantum efficiency must be lower than 25%, making its efficiency generally low.
  • the device made by using the compound of the present invention has the characteristics of lowering driving voltage, improving luminous efficiency and prolonging service life.
  • the compound of the present invention is used as a hole transport layer or electron blocking layer of an organic electroluminescent device, so that the organic electroluminescent device containing the compound has a lower driving voltage, higher luminous efficiency and more Good life.

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Abstract

本发明提供一种有机电致发光材料及包含所述有机电致发光材料的有机发光器件，该有机电致发光材料的结构式为（I）。相比于含有金刚烷基的单胺类结构，本发明含有的双胺结构有着较高的HOMO能级以及空穴迁移率，可以表现出比单胺类材料器件更高的效率和寿命。包含所述有机电致发光材料的有机发光器件具有较低的驱动电压、较高的发光效率和使用寿命。

Description

一种有机电致发光材料及包含该材料的有机电致发光器件 技术领域
本发明涉及有机电致发光技术领域，具体涉及一种有机电致发光材料及包含该材料的有机电致发光器件。
背景技术
近年来，有机电致发光器件(OLED，Organic electroluminescent device)作为新一代显示技术逐渐进入人们的视野。常见的有机电致发光器件是由阳极、阴极以及在阴极和阳极之间设置一层以上的有机层构成。当阴阳两极施加电压时，两电极产生电场，在电场的作用下，阴极侧的电子向发光层移动，阳极侧的空穴也向发光层移动，两者在发光层结合形成激子，激子处于激发态向外释放能量，从激发态释放能量变为基态释放能量的过程对外发光。因此，提高OLED器件中电子和空穴的再结合性是至关重要的。
为了提高有机电致发光器件的亮度、效率和寿命，通常在器件中使用多层结构。这些多层结构包括：空穴注入层(hole injection layer)、空穴传输层(hole transport layer)、电子阻挡层(electron-bloking layer)、发光层(emitting layer)和电子传输层(electron transport layer)等等。这些有机层具有提高载流子(空穴和电子)在各层界面间的注入效率，平衡载流子在各层之间传输的能力，从而提高器件的亮度和效率。
目前常用的空穴传输材料为NPD，NPD虽然具有优异的空穴传输性能，但是玻璃化转变温度(Tg)只有96℃，这导致在高温条件下，有机电致发光器件在高温下容易结晶，从而降低性能。
关于金刚烷(adamantane)衍生物已记录在很多文献中。例如：
专利文献CN107148408A涉及金刚烷衍生物及其有机电致放光器件，其包括基板、蒸镀在基板上的阴极、阳极，和蒸镀在阴极和阳极之间的有机层，其中有机层包含空穴传输层，其空穴传输层包含如下结构的
Figure PCTCN2020090876-appb-000001
金刚烷衍生物。尽管这些性能优良的有机电致发光材料已被陆续开发出来，但都是单胺类结构，单胺结构空穴传输率低，因此其得到的器件效率和寿命仍然有待提高，如何设计新的性能更好的材料进行调节，以使所有器件能够达到降低电压、提高效率和寿命的效果，一直是本领域技术人员亟待解决的问题。
发明内容
本发明的目的在于提供一种性能优异的有机电致发光材料，可用作有机电致发光器件中的空穴传输层、电子阻挡层等等。本发明的另一目的在于提供一种包含所述有机电致发光材料的有机发光器件， 具有较低的驱动电压、较高的发光效率和使用寿命。
本发明是通过以下技术方案来实现：
一种有机电致发光材料，该材料的结构式如化学式1所示：
Figure PCTCN2020090876-appb-000002
化学式1
其中，R 2、R 4和R 5相同或不同，分别独立地选自取代或未取代的碳原子数为1-20的烷基、取代或未取代的碳原子数为2-20的烯基、取代或未取代的碳原子数为2-24的炔基、取代或未取代的碳原子数为3-20的环烷基、取代或未取代的碳原子数为2-20的杂环烷基、取代或未取代的碳原子数为7-30的芳烷基、取代或未取代的碳原子数为2-30的杂芳烷基、取代或未取代的碳原子数为6-30的芳基、取代或未取代的碳原子数为1-30的杂芳基；
R 1和R 3相同或不同，分别独立地选自单键、取代或未取代碳原子数为1-30的亚芳基、取代或未取代的碳原子数为1-30的亚杂芳基、取代或未取代的碳原子数为7-30的亚芳烷基、取代或未取代的碳原子数为2-30的亚杂芳烷基；
所述R 1、R 2、R 3、R 4和R 5的取代基相同或不同，分别独立地选自氘、氰基、硝基、卤素、羟基、碳原子数为1-40的烷基基团、碳原子数3-40的环烷基基团、碳原子数2-40的烯基基团、碳原子数2-40的炔基基团、碳原子数2-40的杂环烷基基团、碳原子数7-40的芳烷基基团、碳原子数2-40的杂芳烷基基团、碳原子数6-40的芳基基团、碳原子数1-40的杂芳基基团、碳原子数1-40的烷氧基基团、碳原子数1-40的烷氨基基团、碳原子数6-40的芳氨基基团、碳原子数为1-40的烷硫基基团、碳原子数7-40的芳烷氨基基团、碳原子数1-24的杂芳氨基基团、碳原子数为1-45的烷基甲硅烷基基团、碳原子数为6-50的芳基甲硅烷基基团、碳原子数为6-30的芳氧基基团、碳原子数为6-30的芳硫基基团。
本申请还提供一种有机电致发光器件，包括阴极、阳极以及设置在所述阴极和阳极之间的一层以上的有机层，所述有机层至少有一层包含所述的电致发光材料。
优选的，所述有机层包括空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层以及电子注入层。
优选的，所述空穴传输层包含本申请所述的电致发光材料。
优选的，所述电子阻挡层包含本申请所述的电致发光材料。
本申请还提供所述有机电致发光材料在有机电致发光器件中的应用。
与现有技术相比，本发明具有以下有益的技术效果：
相比于含有金刚烷基的单胺类结构，本发明含有的双胺结构有着较高的HOMO能级以及空穴迁移率，可以表现出比单胺类材料器件更高的效率和寿命。由于双胺类材料取代位点较多，通过金刚烷基 在不同位置的取代，也可以对材料空间结构和分子堆叠起到更精细的调节作用；尤其是本发明作为电子阻挡层时，可以起到更佳的空穴传输速率调节作用，从而通过平衡空穴和电子传输效率，进一步增强器件效率和寿命。此外，双胺结构具有高的空穴传输效率，但由于其分子量较小以及对称性高，导致其易于低温下结晶；将双胺结构与金刚烷基相结合，引入了大位阻的金刚烷基后可以大幅度改善此现象，将玻璃态转变温度和结晶温度提高30-50℃，从而有效的抑制了材料的结晶，以及随之引起的发光器件的寿命低下的问题。
包含所述有机电致发光材料的有机发光器件，具有较低的驱动电压、较高的发光效率和使用寿命。
具体实施方式
下面结合具体的实施例对本发明做进一步的详细说明，所述是对本发明的解释而不是限定。
在本申请中，
Figure PCTCN2020090876-appb-000003
是指与其他取代基或结合位置结合的位置。
在本申请中，取代或未取代的芳基的碳原子数指的是芳基及其上的取代基的所有碳原子总数，取代或未取代的杂芳基的碳原子数是指杂芳基及其上的取代基的所有碳原子数。举例而言，若取代或未取代的芳基选自取代的碳原子数为30的芳基，则芳基及其上的取代基的所有碳原子数为30；例如，9,9-二甲基芴基属于碳原子数为15的芳基。若取代或未取代的杂芳基选自取代的碳原子数为12的杂芳基，则杂芳基及其上的取代基的所有碳原子数为12。
在本申请中，“取代或未取代的”这样的术语是指，在该术语后面记载的官能团可以具有或不具有取代基。
在本申请中，当没有另外提供具体的定义时，“杂”是指在一个官能团中包括至少1个B、N、O、S、Se、Si或P等杂原子且其余原子为碳和氢。未取代的烷基可以是没有任何双键或三键的“饱和烷基基团”。
在本申请中所采用的描述方式“各……独立地为”与“……分别独立地为”和“……独立地选自”可以互换，均应做广义理解，其既可以是指在不同基团中，相同符号之间所表达的具体选项之间互相不影响，也可以表示在相同的基团中，相同符号之间所表达的具体选项之间互相不影响。
本申请中，“任选”或者“任选地”意味着随后所描述的事件或者环境可以但不必发生，该说明包括该事情或者环境发生或者不发生的场合。例如，“任选被烷基取代的杂环基团”意味着烷基可以但不必须存在，该说明包括杂环基团被烷基取代的情景和杂环基团不被烷基取代的情景。“任选地，连接于同一原子上的两个取代基之间相互连接以与它们共同连接的原子形成饱和或不饱和的5～18元脂肪族环或5～18元芳香环”意味着连接于同一个原子上的两个取代基可以成环但不必须成环，包括二者相互连接成成饱和或不饱和的5～18元脂肪族环或5～18元芳香环的情景，也包括二者相互独立地存在的情景。
本申请中的不定位连接键，是指从环体系中伸出的单键
Figure PCTCN2020090876-appb-000004
其表示该连接键的一端可以连接该键所贯穿的环体系中的任意位置，另一端连接化合物分子其余部分。例如，下式(X)中所示的，式(X)所表示的萘基通过两个贯穿双环的不定位连接键与分子其他位置连接，其所表示的含义，包括如式(X-1)～式(X-10)所示出的任一可能的连接方式。
Figure PCTCN2020090876-appb-000005
例如，下式(X’)中所示的，式(X’)所表示的菲基通过一个从一侧苯环中间伸出的不定位连接键与分子其他位置连接，其所表示的含义，包括如式(X’-1)～式(X’-4)所示出的任一可能的连接方式。
Figure PCTCN2020090876-appb-000006
本申请中的不定位取代基，指的是通过一个从环体系中央伸出的单键连接的取代基，其表示该取代基可以连接在该环体系中的任何可能位置。例如，下式(Y)中所示的，式(Y)所表示的取代基R基通过一个不定位连接键与喹啉环连接，其所表示的含义，包括如式(Y-1)～式(Y-7)所示出的任一可能的连接方式。
Figure PCTCN2020090876-appb-000007
本申请提供一种有机电致发光材料，该材料的结构式如化学式1所示：
Figure PCTCN2020090876-appb-000008
化学式1
其中，R 2、R 4和R 5相同或不同，分别独立地选自取代或未取代的碳原子数为1-20的烷基、取代或未取代的碳原子数为2-20的烯基、取代或未取代的碳原子数为2-24的炔基、取代或未取代的碳原子数为3-20的环烷基、取代或未取代的碳原子数为2-20的杂环烷基、取代或未取代的碳原子数为7-30的芳烷基、取代或未取代的碳原子数为2-30的杂芳烷基、取代或未取代的碳原子数为6-30的芳基、取代或未取代的碳原子数为1-30的杂芳基；
R 1和R 3相同或不同，分别独立地选自单键、取代或未取代碳原子数为1-30的亚芳基、取代或未取代的碳原子数为1-30的亚杂芳基、取代或未取代的碳原子数为7-30的亚芳烷基、取代或未取代的碳原子数为2-30的亚杂芳烷基；
所述R 1、R 2、R 3、R 4和R 5的取代基相同或不同，分别独立地选自氘、氰基、硝基、卤素、羟基、碳原子数为1-40的烷基基团、碳原子数3-40的环烷基基团、碳原子数2-40的烯基基团、碳原子数2-40的炔基基团、碳原子数2-40的杂环烷基基团、碳原子数7-40的芳烷基基团、碳原子数2-40的杂芳烷基基团、碳原子数6-40的芳基基团、碳原子数1-40的杂芳基基团、碳原子数1-40的烷氧基基团、碳原子数1-40的烷氨基基团、碳原子数6-40的芳氨基基团、碳原子数为1-40的烷硫基基团、碳原子数7-40的芳烷氨基基团、碳原子数1-24的杂芳氨基基团、碳原子数为1-45的烷基甲硅烷基基团、碳原子数为6-50的芳基甲硅烷基基团、碳原子数为6-30的芳氧基基团、碳原子数为6-30芳硫基基团。
本发明中的未取代烷基，指的是碳原子数为1-20的直链的烷基，或包含碳原子数为1-13的支链的烷基。在又一些实施方案中，烷基基团含有1-4个碳原子；还在一些实施方案中，烷基基团含有1-3个碳原子。所述烷基基团可以任选地被一个或多个本发明描述的取代基所取代。例如，甲基、乙基、丙基、异丁基、仲丁基、戊基、异戊基、已基等。取代的碳原子数为1-20的烷基是指至少一个氢原子被氘原子、F、Cl、I、CN、羟基、硝基、氨基、苯基、联苯基、三联苯基、萘基、二苯并呋喃基、二苯并噻吩基等取代。
本发明中的未取代的烯基，指的是的碳原子数为2-20的烯基，包含碳碳双键的碳原子数为2-20的直链的烯基，或包含碳原子数为1-13的支链的烯基。例如：乙烯基、丙烯基、烯丙基、异丙烯基、2-丁烯基等。取代的碳原子数为2-20的烯基是指至少一个氢原子被氘原子、F、Cl、I、CN、羟基、硝基、氨基等取代。
本发明中的未取代的炔基，指的是的碳原子数为2-24的炔基，包含碳碳三键的碳原子数为2-35的直链的炔基，或包含碳原子数为1-10的支链的炔基。例如：乙炔基、2-丙炔基等。取代的碳原子数为2-24的炔基是指至少一个氢原子被氘原子、F、Cl、I、CN、羟基、硝基、氨基等取代。
本发明中的未取代的芳基，指的是的碳原子数为6-30的芳基。芳基指的是衍生自芳香碳环的任选官能团或取代基。芳基可以是单环芳基或多环芳基，换言之，芳基可以是单环芳基、稠环芳基、通过碳碳键共轭连接的两个或者更多个单环芳基、通过碳碳键共轭连接的单环芳基和稠环芳基、通过碳碳键共轭连接的两个或者更多个稠环芳基。即，通过碳碳键共轭连接的两个或者更多个芳香基团也可以视为本申请的芳基。例如：苯基、萘基、芘基、二甲基芴基、蒽基、菲基、
Figure PCTCN2020090876-appb-000009
基、甘菊环基、 苊基、联苯基、苯并蒽基、螺二芴基、苝基、茚基等。芳基还可以是三联苯基、四联苯基、五联苯基、苯并[9,10]菲基、苯并荧蒽基。
取代的碳原子数为6-30的芳基是指至少一个氢原子被氘原子、F、Cl、I、CN、羟基、硝基、氨基、烷基、苯基、联苯基、三联苯基、萘基、二苯并呋喃基、二苯并噻吩基等取代，其中芳基及其取代基上的总碳原子数为6-30，取代的芳基的碳原子数还可以是7个、8个、9个、10个、11个、12个、13个、14个、15个，18个、或20个，例如萘基取代的苯基、苯基取代的萘基，均为碳原子数为16的取代的芳基。
本发明中未取代的芳烷基，指的是碳原子数为7-30的芳烷基。例如：甲苯基、二甲基芴基等等。取代的碳原子数为7-30的芳烷基是指至少一个氢原子被氘原子、F、Cl、I、CN、羟基、硝基、氨基等取代。
本发明中未取代的杂芳基，指的是碳原子数为1-30的杂芳基。杂芳基是指环中包含至少一个杂原子的一价芳香环或其衍生物，杂原子可以是B、O、N、P、Si和S中的至少一种。杂芳基可以是单环杂芳基或多环杂芳基，换言之，杂芳基可以是单个芳香环体系，也可以是通过碳碳键共轭连接的多个芳香环体系，且任一芳香环体系为一个芳香单环或者一个芳香稠环。本申请中的“杂芳基”可以包括1、2、3、4、5、6、7、8、9或10个任选自B、O、N、P、Si、Se和S的杂原子，碳原子数可以是1-30个。例如：吡啶基、吡嗪基、嘧啶基、哒嗪基、三嗪基、喹啉基、吲哚基、咔唑基、二苯并呋喃基、二苯并噻吩基、二苯并硒吩基等。杂芳基还可以是N-苯基咔唑基。
取代的碳原子数为1-30的杂芳基是指至少一个氢原子被氘原子、F、Cl、I、CN、羟基、硝基、氨基、烷基、苯基、联苯基、三联苯基、萘基、二苯并呋喃基、二苯并噻吩基等取代。
在本申请中，对芳基的解释可应用于亚芳基，对杂芳基的解释同样应用于亚杂芳基，对烷基的解释可应用于亚烷基，对环烷基的解释可应用于亚环烷基。本发明中未取代的环烷基，指的是碳原子数为3-20的环烷基。例如：环丙基、环丁基、环戊基、环己基、降冰片基、金刚烷基等等。取代的碳原子数为3-20的环烷基是指至少一个氢原子被氘原子、F、Cl、I、CN、羟基、硝基、氨基等取代。
在本申请的一种可选的实施方式中，R 1和R 3相同或不同，分别独立地选自单键、取代或未取代碳原子数为6-25的亚芳基、取代或未取代的碳原子数为5-18亚杂芳基，R 2、R 4和R 5相同或不同，分别独立地选自单键、取代或未取代碳原子数为6-18的芳基、取代或未取代的碳原子数为5-18杂芳基；所述R 1、R 2、R 3、R 4和R 5的取代基相同或不同，分别独立地选自氘、氰基、硝基、卤素、羟基、碳原子数为1-10的烷基基团、碳原子数为3-10的环烷基基团、碳原子数为6-15的芳基基团、碳原子数为3-12的杂芳基基团，当取代基多于一个时，各取代基相同或不同。
在本申请的一种可选的实施方式中，R 1和R 3彼此相同或不同，各自独立地选自化学式j-1至化学式j-9所示的基团所组成的组：
Figure PCTCN2020090876-appb-000010
其中，M 2选自单键或者
Figure PCTCN2020090876-appb-000011
E 1～E 14分别独立地选自：氢、氘、卤素基团、氰基、碳原子数为3～12的杂芳基、碳原子数为6～15的芳基、碳原子数为3～9的三烷基硅基、碳原子数为1～10的烷基、碳原子数为1～10的卤代烷基、碳原子数为3～10的环烷基、碳原子数为1～10的烷氧基；
e 1～e 14以e r表示，E 1～E 14以E r表示，r为变量，表示1～14的任意整数，e r表示取代基E r的数量；当r选自1、2、3、4、5、6、9、13或14时，e r选自1、2、3或者4；当r选自7或11时，e r选自1、2、3、4、5或者6；当r为12时，e r选自1、2、3、4、5、6或者7；当r选自8或10时，e r选自1、2、3、4、5、6、7或者8；当e r大于1时，任意两个E r相同或者不相同；
K 3选自O、S、Se、N(E 15)、C(E 16E 17)、Si(E 18E 19)；其中，各E 15、E 16、E 17、E 18和E 19分别独立地选自：氢、碳原子数为6～15的芳基、碳原子数为3～12的杂芳基、碳原子数为1～10的烷基、碳原子数为3～10的环烷基、碳原子数为2～10的杂环烷基；
各K 4独立地选自单键、O、S、Se、N(E 20)、C(E 21E 22)、Si(E 23E 24)；其中，各E 20、E 21、E 22、E 23、E 24分别独立地选自：氢、碳原子数为6～15的芳基、碳原子数为3～12的杂芳基、碳原子数为1～10的烷基、碳原子数为3～10的环烷基。
在本申请的一种可选的实施方式中，R 1和R 3各自独立地选自取代或未取代的基团W 1，所述未取代的基团W 1选自如下基团：
Figure PCTCN2020090876-appb-000012
Figure PCTCN2020090876-appb-000013
所述W 1基团被一个或多个取代基所取代时，W 1的取代基各自独立地选自由氘、氟、氯、氰基、甲基、乙基、丙基、叔丁基、三甲基烷硅基、苯基、萘基、二苯并呋喃基、二苯并噻吩基、咔唑基所组成的组；所述W 1的取代基数目多于1个时，各个取代基相同或不同。
在本申请的一种可选的实施方式中，R 2、R 4和R 5相同或不同，分别独立地选自取代或未取代的碳原子数为7-30的芳烷基、取代或未取代的碳原子数为2-30的杂芳烷基、取代或未取代的碳原子数为6-30的芳基、取代或未取代的碳原子数为1-30的杂芳基。
在本申请的一种可选的实施方式中，R 1和R 3相同或不同，分别独立地选自单键、取代或未取代的亚苯基、取代或未取代的亚联苯基、取代或未取代的亚三联苯基、取代或未取代的亚
Figure PCTCN2020090876-appb-000014
基、取代或未取代的亚菲基、取代或未取代的亚萘基、取代或未取代的亚甘菊环基、取代或未取代的亚茚基、取代或未取代的亚吡啶基、取代或未取代的亚嘧啶基、取代或未取代的亚三嗪基、取代或未取代的亚咪唑基。
在本申请的一种可选的实施方式中，R 1和R 3相同或不同，分别独立地选自：取代或未取代的亚苯基、取代或未取代的亚联苯基、取代或未取代的亚三联苯基、取代或未取代的亚蒽基、取代或未取代的亚菲基、取代或未取代的亚萘基、取代或未取代的9,9-二甲基芴亚基、取代或未取代的二苯并呋喃亚基、取代或未取代的二苯并噻吩亚基、取代或未取代的亚咔唑基，或所述亚基中两者或三者通过单键连接所形成的亚基基团；
所述取代是指独立地被选自以下基团的取代基所取代：氘、氰基、氟、氯、甲基、乙基、丙基、叔丁基、苯基、萘基、咔唑基、二苯并呋喃基、二苯并噻吩基；
当取代基有多个时，各取代基相同或不同。
在本申请的一种可选的实施方式中，R 1和R 3各自独立地选自如下基团中的任意一个：
Figure PCTCN2020090876-appb-000015
在本申请的一种可选的实施方式中，R 2、R 4和R 5彼此相同或不同，各自独立地选自化学式i-1至化学式i-11所示的基团所组成的组：
Figure PCTCN2020090876-appb-000016
Figure PCTCN2020090876-appb-000017
其中，M 1选自单键或者
Figure PCTCN2020090876-appb-000018
D 1选自氢、氘、氟、氯、溴、氰基、碳原子数为3～12的三烷基硅基、碳原子数为1～10的烷基、碳原子数为1～10的卤代烷基、碳原子数为3～10的环烷基、碳原子数为1～10的烷氧基、碳原子数为1～10的烷硫基；
D 2～D 9、D 21各自独立地选自：氢、氘、氟、氯、溴、氰基、碳原子数为3～12的三烷基硅基、碳原子数为1～10的烷基、碳原子数为1～10的卤代烷基、碳原子数为3～10的环烷基、碳原子数为1～10的烷氧基、碳原子数为3～12的杂芳基；
D 10～D 20各自独立地选自：氢、氘、氟、氯、溴、氰基、碳原子数为3～12的三烷基硅基、碳原子数为1～10的烷基、碳原子数为1～10的卤代烷基、碳原子数为3～10的环烷基、碳原子数为1～10的烷氧基、碳原子数为6～15的芳基、碳原子数为3～12的杂芳基；
d 1～d 21以d k表示，D 1～D 21以D k表示，k为变量，表示1～21的任意整数，d k表示取代基D k的个数；其中，当k选自5或者17时，d k选自1、2或者3；当k选自2、7、8、12、15、16、18或者21时，d k选自1、2、3或者4；当k选自1、3、4、6、9或者14时，d k选自1、2、3、4或者5；当k为13时，d k选自1、2、3、4、5或者6；当k选自10或者19时，d k选自1、2、3、4、5、6或者7；当k为20时，d k选自1、2、3、4、5、6、7或者8；当k为11时，d k选自1、2、3、4、5、6、7、8或9；且当d k大于1时，任意两个D k相同或者不相同；
K 1独立地选自O、S、N(D 22)、C(D 23D 24)、Si(D 25D 26)；其中，各D 22、D 23、D 24、D 25、D 26分别独立地选自：碳原子数为6～15的芳基、碳原子数为3～12的杂芳基、碳原子数为1～10的烷基或碳原子数 为3～10的环烷基；
K 2选自单键、O、S、N(D 27)、C(D 28D 29)、Si(D 30D 31)；其中，各D 27、D 28、D 29、D 30、D 31分别独立地选自：碳原子数为6～15的芳基、碳原子数为3～12的杂芳基、碳原子数为1～10的烷基或碳原子数为3～10的环烷基。
在本申请的一种可选的实施方式中，R 2、R 4和R 5彼此相同或不同，且分别独立地选自取代或未取代的基团Y 1，所述未取代的基团Y 1选自如下基团：
Figure PCTCN2020090876-appb-000019
所述Y 1基团被一个或多个取代基所取代时，Y 1的取代基各自独立地选自由氘、氟、氯、氰基、甲基、乙基、丙基、异丙基、叔丁基、三甲基硅基、苯基、萘基、二苯并噻吩基、二苯并呋喃基所组成的组；所述Y 1的取代基多于1个时，各个取代基相同或不同。
在本申请的一种可选的实施方式中，R 2、R 4和R 5相同或不同，分别独立地选自：取代或未取代的苯基、取代或未取代的联苯基、取代或未取代的三联苯基、取代或未取代的蒽基、取代或未取代的菲基、取代或未取代的萘基、取代或未取代的9,9-二甲基芴基、取代或未取代的二苯并呋喃基、取代或 未取代的二苯并噻吩基、取代或未取代的咔唑基，或为所述基团中两者或三者通过单键连接所形成的基团；
所述取代是指独立地被选自以下基团的取代基所取代：氘、氰基、氟、氯、甲基、乙基、丙基、叔丁基、苯基、萘基、咔唑基、二苯并呋喃基、二苯并噻吩基；
当取代基有多个时，各取代基相同或不同。
在本申请的一种可选的实施方式中，R 2、R 4和R 5各自独立地选自如下基团中的任意一个：
Figure PCTCN2020090876-appb-000020
在本申请的一种可选的实施方式中，所述化学式1为如下结构中的一种，但不仅限于此：
Figure PCTCN2020090876-appb-000021
Figure PCTCN2020090876-appb-000022
Figure PCTCN2020090876-appb-000023
Figure PCTCN2020090876-appb-000024
Figure PCTCN2020090876-appb-000025
Figure PCTCN2020090876-appb-000026
Figure PCTCN2020090876-appb-000027
本申请还提供一种有机电致发光器件，有机电致发光器件包括相对设置的阳极和阴极，以及设置于所述阳极和所述阴极之间的有机层；所述有机层包含空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层以及电子注入层。
本申请的有机电致发光器件中，所述空穴传输层或电子阻挡层包含上述化合物，以改善有机电致发光器件的电压特性、效率特性和寿命特性。
举例而言，有机电致发光器件可以包括依次层叠设置的阳极、空穴传输层、电子阻挡层、有机发光层、空穴阻挡层、电子传输层和阴极。本申请提供的化合物可以应用于有机电致发光器件的空穴传输层或电子阻挡层，以提高有机电致发光器件的寿命、提高有机电致发光器件的发光效率或者降低有机电致发光器件的驱动电压。
可选地，阳极包括阳极材料，其可选地为有助于空穴注入至功能层中的具有大逸出功(功函数，work function)的材料。阳极材料的具体实例包括但不限于：金属如镍、铂、钒、铬、铜、锌和金或它们的合金；金属氧化物如氧化锌、氧化铟、氧化铟锡(ITO)和氧化铟锌(IZO)；组合的金属和氧化物如ZnO:Al或SnO 2:Sb；或导电聚合物如聚(3-甲基噻吩)、聚[3,4-(亚乙基-1,2-二氧基)噻吩](PEDT)、聚吡咯和聚苯胺。可选包括包含氧化铟锡(铟锡氧化物，indium tin oxide)(ITO)作为阳极的透明电极。
可选地，空穴传输层可以包括一种或者多种空穴传输材料，空穴传输材料可以选自本申请化合物，咔唑多聚体、咔唑连接三芳胺类化合物或者其他类型的化合物。
可选地，有机发光层可以包括主体材料和客体材料，注入有机发光层的空穴和注入有机发光层的电子可以在有机发光层复合而形成激子，激子将能量传递给主体材料，主体材料将能量传递给客体材料，进而使得客体材料能够发光。在本申请的一种实施方式中，主体材料为CPB或ADN。
有机发光层的客体材料可以为具有缩合芳基环的化合物或其衍生物、具有杂芳基环的化合物或其衍生物、芳香族胺衍生物或者其他材料，本申请对此不做特殊的限制。在本申请的一种实施方式中，有机发光层的客体材料可以为Ir(piq) 2(acac)等。在本申请的另一种实施方式中，有机发光层的客体材料可以为Ir(ppy) 3等。
可选地，电子传输层可以为单层结构，也可以为多层结构，其可以包括一种或者多种电子传输材料，电子传输材料可以选自，但不限于，苯并咪唑衍生物、恶二唑衍生物、喹喔啉衍生物或者其他电子传输材料。
可选地，阴极可以包括阴极材料，其是有助于电子注入至功能层中的具有小逸出功的材料。阴极材料的具体实例包括但不限于，金属如镁、钙、钠、钾、钛、铟、钇、锂、钆、铝、银、锡和铅或它们的合金；或多层材料如LiF/Al、Liq/Al、LiO 2/Al、LiF/Ca、LiF/Al和BaF 2/Ca。可选包括包含铝的金属电极作为阴极。在本申请的一种实施方式中，阴极的材料可以为镁银合金。
在阳极和空穴传输层之间还可以设置有空穴注入层，以增强向空穴传输层注入空穴的能力。空穴注入层可以选用联苯胺衍生物、星爆状芳基胺类化合物、酞菁衍生物或者其他材料，本申请对此不做特殊的限制。例如，空穴注入层可以由F4-TCNQ组成。
空穴传输层和有机发光层之间还可以设置有电子阻挡层，以阻挡电子向空穴传输层侧传输，提高电子和空穴在有机发光层的复合率并保护空穴传输层免受电子的冲击。电子阻挡层的材料可以为本申请化合物、咔唑多聚体、咔唑连接三芳胺类化合物或者其他可行的结构。
在阴极和电子传输层之间还可以设置有电子注入层，以增强向电子传输层注入电子的能力。电子注入层可以包括有碱金属硫化物、碱金属卤化物等无机材料，或者可以包括碱金属与有机物的络合物。例如，电子注入层可以包括LiQ。
合成例：
以下，通过实施例对本发明进一步详细说明。但是，下述实施例仅是本发明的例示，而并非限定本发明。
下面所描述的合成例中，除非另有声明，否则所有的温度的单位为摄氏度。部分试剂购买于商品供应商如Aldrich Chemical Company,Arco Chemical Company and Alfa ChemicalCompany，除非另有声明， 否则使用时都没有经过进一步纯化。
在各个合成例中，低分辨率质谱(MS)数据的测定条件是：Agilent 6120四级杆HPLC-M(柱子型号：Zorbax SB-C18,2.1×30mm,3.5微米,6min,流速为0.6mL/min。流动相：5％-95％(含0.1％甲酸的乙腈)在(含0.1％甲酸的水)中的比例)，采用电喷雾电离(ESI)，在210nm/254nm下，用UV检测。
核磁共振氢谱：布鲁克(Bruker)600MHz核磁仪，室温条件下，以CD 2Cl 2为溶剂(以ppm为单位)，用TMS(0ppm)作为参照标准。当出现多重峰的时候，将使用下面的缩写：s(singlet，单峰)、d(doublet，双峰)、t(triplet，三重峰)、m(multiplet，多重峰)。
合成例1
化合物1的合成
Figure PCTCN2020090876-appb-000028
将1-金刚烷醇(50.0g，328.4mmol)、溴苯(51.6g，328.4mmol)、二氯甲烷(500mL)加入圆底烧瓶中，氮气保护下降温至-5-0℃、下滴加三氟甲磺酸(73.9g，492.6mmol)，保温搅拌3h；向反应液中加入去离子水(300mL)水洗至pH＝7，加入二氯甲烷(100mL)进行萃取，合并有机相，使用无水硫酸镁进行干燥，过滤，减压除去溶剂；所得粗品使用正庚烷为流动相进行硅胶柱色谱提纯，得到白色固体中间体I-A-1(53.1g，55.4％)。
Figure PCTCN2020090876-appb-000029
将中间体I-A-1(7.0g,24.04mmol)，苯胺(2.69g,28.84mmol)，三(二亚苄基丙酮)二钯(0.22g,0.24mmol)，2-二环己基磷-2’,4’,6’-三异丙基联苯(0.23g,0.48mmol)以及叔丁醇钠(3.46g,36.05mmol)加入甲苯(60mL)中，氮气保护下加热至108℃，搅拌3h；而后冷却至室温，反应液使用去离子水洗后加入无水硫酸镁干燥，过滤后将滤液通过短硅胶柱，减压除去溶剂；使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到浅绿色固体中间体I-A(5.83g,79.9％)。
Figure PCTCN2020090876-appb-000030
将二苯胺(3.80g,22.45mmol)，4-溴-4’-碘联苯(10.48g,29.19mmol)，三(二亚苄基丙酮)二钯(0.21g,0.22mmol)，三叔丁基膦(0.10g,0.44mmol)以及叔丁醇钠(3.24g,33.68mmol)加入甲苯(100mL)中，氮气保护下加热至108℃，搅拌10h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液减压除去溶剂；使用正庚烷为流动相进行硅胶柱色谱提纯，得到白色固体中间体II-A(3.6g,40.06％)。
Figure PCTCN2020090876-appb-000031
将中间体I-A(3g,9.89mmol)，中间体II-A(3.55g,9.89mmol)，三(二亚苄基丙酮)二钯(0.09g,0.10mmol)，2-二环己基磷-2’,6’-二甲氧基联苯(0.08g,0.20mmol)以及叔丁醇钠(1.43g,14.83mmol)加入甲苯(30mL)中，氮气保护下加热至108℃，搅拌1h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；使用二氯甲烷/正庚烷(1:1)为流动相进行硅胶柱色谱提纯，之后用二氯甲烷/乙酸乙酯体系对粗品进行重结晶提纯，得到白色固体化合物1(5.15g,83.74％)。质谱：m/z＝623.3(M+H) +
合成例2
化合物2的合成
Figure PCTCN2020090876-appb-000032
将N-苯基-4-联苯胺(5.00g,20.38mmol)，4-溴-4’-碘联苯(9.15g,25.48mmol)，三(二亚苄基丙酮)二钯(0.19g,0.20mmol)，三叔丁基膦(0.08g,0.41mmol)以及叔丁醇钠(2.94g,30.57mmol)加入甲苯(80mL)中，氮气保护下加热至108℃，搅拌16h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液减压除去溶剂；使用正庚烷为流动相进行硅胶柱色谱提纯，得到中间体II-B(5.55g,57.16％)。
Figure PCTCN2020090876-appb-000033
将上述合成例1中的中间体I-A(4.70g,15.49mmol)，中间体II-B(5.55g,15.49mmol)，三(二亚苄基丙酮)二钯(0.14g,0.15mmol)，2-二环己基磷-2’,6’-二甲氧基联苯(0.13g,0.31mmol)以及叔丁醇钠(2.23g,23.23mmol)加入甲苯(50mL)中，氮气保护下加热至108℃，搅拌1h；而后冷却至室温， 反应液过滤后将滤液减压除去溶剂；使用二氯甲烷/正庚烷(1:1)为流动相进行硅胶柱色谱提纯，之后用二氯甲烷/乙酸乙酯体系对粗品进行重结晶提纯，得到白色固体化合物2(7.34g,67.78％)。质谱：m/z＝699.4(M+H) +
合成例3
化合物3的合成
Figure PCTCN2020090876-appb-000034
将3-溴二苯并呋喃(10.0g,40.47mmol)，苯胺(4.15g,44.52mmol)，三(二亚苄基丙酮)二钯(0.37g,0.40mmol)，2-二环己基磷-2,4,6-三异丙基联苯(0.39g,0.81mmol)以及叔丁醇钠(5.84g,60.71mmol)加入甲苯(100mL)中，氮气保护下加热至108℃，搅拌1h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液通过短硅胶柱，过柱液减压除去溶剂；使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到灰色固体中间体II-C-1(8.2g,78.17％)。
Figure PCTCN2020090876-appb-000035
将3-溴-4’氯-1，1’-联苯(8.00g,29.90mmol)，中间体II-C-1(5.17g,19.93mmol)，三(二亚苄基丙酮)二钯(0.18g,0.20mmol)，三叔丁基膦(0.10g,0.40mmol)以及叔丁醇钠(2.87g,29.90mmol)加入甲苯(70mL)中，氮气保护下加热至108℃，搅拌12h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液减压除去溶剂；使用正庚烷为流动相进行硅胶柱色谱提纯，得到灰色固体中间体II-C(4.82g,54.28％)。
Figure PCTCN2020090876-appb-000036
将上述合成例1中的中间体I-A(3.00g,9.89mmol)，中间体II-C(4.41g,9.89mmol)，三(二亚苄基丙酮)二钯(0.10g,0.10mmol)，2-二环己基磷-2’,6’-二甲氧基联苯(0.09g,0.20mmol)以及叔丁醇钠(1.43g,14.83mmol)加入甲苯(50mL)中，氮气保护下加热至108℃，搅拌2h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；使用二氯甲烷/正庚烷(1:3)为流动相进行硅胶柱色谱提纯，之后用二氯甲烷/乙酸乙酯体系对粗品进行重结晶提纯，得到白色固体化合物3(5.35g,76.14％)。质谱：m/z＝713.3(M+H) +
合成例4
化合物4的合成
Figure PCTCN2020090876-appb-000037
将苯胺(10.0g,107.38mmol)，3-溴二苯并噻吩(26.91.0g,102.26mmol)，三(二亚苄基丙酮)二钯(0.94g,1.02mmol)，2-二环己基磷-2,4,6-三异丙基联苯(0.98g,2.05mmol)以及叔丁醇钠(14.74g,153.40mmol)加入甲苯(180mL)中，氮气保护下加热至108℃，搅拌2h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液通过短硅胶柱，过柱液减压除去溶剂；使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到白色固体中间体II-D-1(21.69g,77.02％)。
Figure PCTCN2020090876-appb-000038
将中间体II-D-1(5.90g,21.43mmol)，4-溴-4’-碘联苯(10g,27.85mmol)，三(二亚苄基丙酮)二钯(0.19g,0.21mmol)，三叔丁基膦(0.20g,0.13mmol)以及叔丁醇钠(3.09g,32.14mmol)加入甲苯(80mL)中，氮气保护下加热至108℃，搅拌7h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；使用正庚烷为流动相进行硅胶柱色谱提纯，之后用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到白色固体中间体II-D(6.07g,55.95％)。
Figure PCTCN2020090876-appb-000039
将上述合成例1中的中间体I-A(3.60g,11.86mmol)，中间体II-D(6.07g,11.86mmol)，三(二亚苄基丙酮)二钯(0.11g,0.12mmol)，2-二环己基磷-2’,6’-二甲氧基联苯(0.11g,0.24mmol)以及叔丁醇钠(1.71g,17.80mmol)加入甲苯(50mL)中，氮气保护下加热至108℃，搅拌1h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到白色固体化合物4(7.12g,56.62％)。质谱：m/z＝729.3(M+H) +
合成例5
化合物5的合成
Figure PCTCN2020090876-appb-000040
将1-金刚烷醇(10.0g,65.69mmol)、4-溴联苯(15.31g,65.69mmol)、加入盛有(150mL)二氯甲烷的圆底烧瓶中，氮气保护下降温至(-20)-(-10)℃下滴加三氟甲磺酸(14.7g,98.53mmol)，保温搅拌6h；向反应液中加入去离子水(100mL)水洗至pH＝7，加入MC(100mL)进行萃取，合并有机相，使用无水硫酸镁进行干燥，过滤，减压除去溶剂；所得粗品使用正庚烷为流动相进行硅胶柱色谱提纯，得到白色固体中间体I-E-1(9.80g，40.61％)。
Figure PCTCN2020090876-appb-000041
将中间体I-E-1(9.50g,25.89mmol)，4-氨基联苯(4.60g,27.18mmol)，三(二亚苄基丙酮)二钯(0.24g,0.26mmol)，2-二环己基磷-2’,4’,6’-三异丙基联苯(0.25g,0.52mmol)以及叔丁醇钠(3.73g,38.83mmol)加入甲苯(100mL)中，氮气保护下加热至108℃，搅拌3h；而后冷却至室温，反应液使用去离子水洗后加入无水硫酸镁干燥，过滤后将滤液通过短硅胶柱，减压除去溶剂；使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到浅绿色固体中间体I-E(8.71g,73.88％)。
Figure PCTCN2020090876-appb-000042
将2-溴,4-氯联苯(50.00g,180.69mmol)、苯硼酸(20.17g,170.79mmol)、四三苯基膦钯(4.1g,0.36mmol)、碳酸钾(54.0g,390.16mmol)、四丁基氯化铵(.9.9g,35.6mmol)、甲苯(400mL)、乙醇(100mL)和去离子水(100mL)加入圆底烧瓶中，氮气保护下升温至78℃，搅拌8小时；将反应液冷却至室温，加入甲苯(1000mL)进行萃取，合并有机相，使用无水硫酸镁进行干燥，过滤，减压除去溶剂；所得粗品使用二氯甲烷/正庚烷(1：8)为流动相进行硅胶柱色谱提纯，之后用二氯甲烷/乙醇体系进行重结晶提纯，得到浅黄色固体中间体II-E-1(38.0g，80.85％)。
Figure PCTCN2020090876-appb-000043
将中间体II-E-1(3.80g,14.35mmol)，4-氨基联苯(2.55g,15.07mmol)，三(二亚苄基丙酮)二钯 (0.29g,0.31mmol)，2-二环己基磷-2’,4’,6’-三异丙基联苯(0.26g,0.63mmol)以及叔丁醇钠(2.26g,23.5mmol)加入甲苯(30mL)中，氮气保护下加热至108℃，搅拌5h；而后冷却至室温，反应液使用去离子水洗后加入无水硫酸镁干燥，过滤后将滤液通过短硅胶柱，减压除去溶剂；使用二氯乙烷对粗品进行重结晶提纯，得到浅绿色片状固体中间体II-E-2(4.7g,82.31％)。
Figure PCTCN2020090876-appb-000044
将II-E-2(4.50g,11.14mmol)，4-溴-4’-碘联苯(6.00g,16.7mmol)，三(二亚苄基丙酮)二钯(0.10g,0.11mmol)，三叔丁基磷(0.05g,0.22mmol)以及叔丁醇钠(1.61g,16.71mmol)加入甲苯(50mL)中，氮气保护下加热至108℃，搅拌16h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液减压除去溶剂；使用正庚烷为流动相进行硅胶柱色谱提纯，得到白色中间体II-E(3.2g,45.71％)。
Figure PCTCN2020090876-appb-000045
将中间体I-E(2.30g,5.05mmol)，中间体II-E(3.2g,5.05mmol)，三(二亚苄基丙酮)二钯(0.10g,0.11mmol)，2-二环己基磷-2’,6’-二甲氧基联苯(0.08g,0.22mmol)以及叔丁醇钠(0.73g,7.58mmol)加入甲苯(30mL)中，氮气保护下加热至108℃，搅拌2h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；使用二氯甲烷/正庚烷(1:1)为流动相进行硅胶柱色谱提纯，之后用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到白色固体化合物5(2.12g,41.9％)。质谱：m/z＝1003.5(M+H) +
合成例6
化合物6的合成
Figure PCTCN2020090876-appb-000046
将3-溴-N,N-双(4-甲基苯基)苯胺(10.0g,30.74mmol)、4'-溴-4-联苯硼酸(5.68g,20.50mmol)、四三苯基膦钯(0.47g,0.41mmol)、碳酸钾(6.22g,45.09mmol)、四丁基氯化铵(1.14g,4.10mmol)、甲苯(80mL)、乙醇(20mL)和去离子水(20mL)加入圆底烧瓶中，氮气保护下升温至78℃，搅拌8小时；将反应液冷却至室温，加入甲苯(100mL)进行萃取，合并有机相，使用无水硫酸镁进行干燥，过滤，减压除去溶剂；所得粗品使用正庚烷为流动相进行硅胶柱色谱提纯，之后用二氯甲烷/乙酸乙酯体系进行重结晶提纯，得到白色固体中间体II-F(3.69g，35.69％)。
Figure PCTCN2020090876-appb-000047
将上述合成例4中的中间体I-D(3.50g,7.68mmol)，中间体II-F(3.8g,7.68mmol)，三(二亚苄基丙酮)二钯(0.14g,0.15mmol)，2-二环己基磷-2’,6’-二甲氧基联苯(0.13g,0.31mmol)以及叔丁醇钠(1.11g,11.52mmol)加入甲苯(30mL)中，氮气保护下加热至108℃，搅拌3h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到白色固体化合物6(4.17g,61.33％)。质谱：m/z＝879.5(M+H) +
合成例7
化合物7的合成
Figure PCTCN2020090876-appb-000048
将1-金刚烷醇(10.0g,65.69mmol)、1-溴代萘(12.95g,62.56mmol)、二氯甲烷(120mL)加入圆底烧瓶中，氮气保护下降温至(-20)-(-10)℃、下滴加三氟甲磺酸(14.08g,93.84mmol)，保温搅拌6h；向反应液中加入去离子水(300mL)水洗至pH＝7，加入MC(50mL)进行萃取，合并有机相，使用无水硫酸镁进行干燥，过滤后滤液减压除去溶剂；所得粗品使用正庚烷为流动相进行硅胶柱色谱提纯，得到白色固体中间体I-G-1(12.58g，58.92％)。
Figure PCTCN2020090876-appb-000049
将中间体I-G-1(10g,29.30mmol)，苯胺(2.87g,30.77mmol)，三(二亚苄基丙酮)二钯(0.27g,0.29mmol)，2-二环己基磷-2’,4’,6’-三异丙基联苯(0.28g,0.59mmol)以及叔丁醇钠(4.22g,43.95mmol)加入甲苯(80mL)中，氮气保护下加热至108℃，搅拌3h；而后冷却至室温，反应液使用去离子水洗后加入无水硫酸镁干燥，过滤后将滤液通过短硅胶柱，减压除去溶剂；使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到橙色固体中间体I-G(7.63g,73.65％)。
Figure PCTCN2020090876-appb-000050
将苯胺(3.00g,32.69mmol)，9-(4-溴苯基)-咔唑(10.00g,31.13mmol)，三(二亚苄基丙酮)二钯(0.29g,0.31mmol)，2-二环己基磷-2’,4’,6’-三异丙基联苯(0.29g,0.63mmol)以及叔丁醇钠(4.49g,46.70mmol)加入甲苯(80mL)中，氮气保护下加热至108℃，搅拌6h；而后冷却至室温，反应液使用去离子水洗后加入无水硫酸镁干燥，过滤后将滤液通过短硅胶柱，减压除去溶剂；使用二氯甲烷/正庚烷(1:3)为流动相进行硅胶柱色谱提纯，之后用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到白色固体中间体II-G-1(8.54g,82.05％)。
Figure PCTCN2020090876-appb-000051
将中间体II-G-1(5.00g,14.95mmol)，4-溴-4’-碘联苯(8.05g,22.43mmol)，三(二亚苄基丙酮)二钯(0.14g,0.15mmol)，2-二环己基磷-2’,6’-二甲氧基联苯(0.14g,0.30mmol)以及叔丁醇钠(2.16g,22.43mmol)加入甲苯(80mL)中，氮气保护下加热至108℃，搅拌16h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；所得粗品使用正庚烷为流动相进行硅胶柱色谱提纯，之后用正庚烷对粗品进行重结晶提纯，得到黄色固体中间体II-G(3.52g,41.61％)。
Figure PCTCN2020090876-appb-000052
将中间体I-G(2.20g,6.22mmol)，中间体II-G(3.52g,6.22mmol)，三(二亚苄基丙酮)二钯(0.06g,0.06mmol)，2-二环己基磷-2’,6’-二甲氧基联苯(0.05g,0.12mmol)以及叔丁醇钠(0.90g,9.34mmol)加入甲苯(30mL)中，氮气保护下加热至108℃，搅拌2h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；使用二氯甲烷/乙酸乙酯体系对粗品进行重结晶提纯，得到白色固体化合物7(2.31g,44.25％)。质谱：m/z＝838.4(M+H) +
合成例8
化合物8的合成
Figure PCTCN2020090876-appb-000053
将1-金刚烷醇(10.0g,65.69mmol)、邻溴甲苯(11.23g,65.69mmol)、二氯甲烷(120mL)加入圆底烧瓶中，氮气保护下降温至(-45)-(-35)℃℃下滴加三氟甲磺酸(14.78g,98.53mmol)，保温搅拌5h；向反应液中加入去离子水(300mL)水洗至pH＝7，加入MC(50mL)进行萃取，合并有机相，使用无水硫酸镁进行干燥，过滤，减压除去溶剂；所得粗品使用正庚烷为流动相进行硅胶柱色谱提纯，得到白色固体中间体I-H-1(12.84g，63.94％)。
Figure PCTCN2020090876-appb-000054
将中间体I-H-1(10.0g,32.76mmol)，4-氨基对三联苯(8.28g,33.74mmol)，三(二亚苄基丙酮)二钯(0.30g,0.33mmol)，2-二环己基磷-2’,4’,6’-三异丙基联苯(0.31g,0.66mmol)以及叔丁醇钠(4.72g,49.14mmol)加入甲苯(100mL)中，氮气保护下加热至108℃，搅拌5h；而后冷却至室温，反应液使用去离子水洗后加入无水硫酸镁干燥，过滤后将滤液通过短硅胶柱，减压除去溶剂；所得粗品使用二氯甲烷/正庚烷(1:5)为流动相进行硅胶柱色谱提纯，之后用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到灰白色固体中间体I-H(10.96g,71.22％)。
Figure PCTCN2020090876-appb-000055
将2-溴-7-碘-9,9-二甲基芴(10.0g,25.06mmol)，N-(4-(-1-萘基)苯基)-4-联苯胺(6.39g,17.21mmol)，三(二亚苄基丙酮)二钯(0.15g,0.16mmol)，三叔丁基膦(0.07g,0.33mmol)以及叔丁醇钠(2.41g,23.5mmol)加入甲苯(100mL)中，氮气保护下加热至18℃，搅拌16h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；所得粗品使用正庚烷为流动相进行硅胶柱色谱提纯，之后用正庚烷对粗品进行重结晶提纯，得到淡黄色固体中间体II-H(3.07g,28.58％)。
Figure PCTCN2020090876-appb-000056
将中间体I-H(2.20g,4.68mmol)，中间体II-H(3.00g,4.68mmol)，三(二亚苄基丙酮)二钯(0.09g,0.09mmol)，2-二环己基磷-2’,6’-二甲氧基联苯(0.08g,0.19mmol)以及叔丁醇钠(0.68g,7.03mmol)加入甲苯(30mL)中，氮气保护下加热至108℃，搅拌4h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；使用二氯甲烷/乙酸乙酯体系对粗品进行重结晶提纯，得到白色固体化合物8(2.18g,45.13％)。质谱：m/z＝1031.5(M+H) +
合成例9
化合物9的合成
Figure PCTCN2020090876-appb-000057
将3-氨基-4’-甲基联苯(5.00g,27.29mmol)，3-溴-5'-苯基-1,1':3',1”-三联苯(10.21g,26.49mmol)，三(二亚苄基丙酮)二钯(0.49g,0.53mmol)，2-二环己基磷-2’,4’,6’-三异丙基联苯(0.50g,1.06mmol)以及叔丁醇钠(3.82g,39.74mmol)加入甲苯(100mL)中，氮气保护下加热至108℃，搅拌6h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；所得粗品使用二氯甲烷/正庚烷对粗品进行重结晶提纯，得到白色固体中间体II-I-1(8.69g,69.41％)。
Figure PCTCN2020090876-appb-000058
将中间体II-I-1(5.00g,10.25mmol)，1-溴-4-碘萘(5.12g,15.38mmol)，三(二亚苄基丙酮)二钯(0.19g,0.21mmol)，三叔丁基膦(0.08g,0.41mmol)以及叔丁醇钠(1.48g,15.38mmol)加入甲苯(50mL)中，氮气保护下加热至108℃，搅拌7h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；所得粗品使用二氯甲烷/正庚烷(1：8)为流动相进行硅胶柱色谱提纯，之后用二氯甲烷/正庚烷对粗品进行重结晶提纯，得到灰白色固体中间体II-I(3.61g,54.86％)
Figure PCTCN2020090876-appb-000059
将上述合成例1中的中间体I-A(1.70g,5.60mmol)，中间体II-I(3.60g,5.60mmol)，三(二亚苄基丙酮)二钯(0.10g,0.11mmol)，2-二环己基磷-2’,6’-二甲氧基联苯(0.09g,0.22mmol)以及叔丁醇钠(0.81g,8.4mmol)加入甲苯(30mL)中，氮气保护下加热至108℃，搅拌4h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；使用二氯甲烷/乙酸乙酯体系对粗品进行重结晶提纯，得到白色固体化合物9(2.04g,39.84％)。质谱：m/z＝915.5(M+H) +
合成例10
化合物10的合成
Figure PCTCN2020090876-appb-000060
将上述合成例1中的中间体I-A-1(5.00g,17.17mmol)，2-氨基-9，9二甲基芴(3.70g,17.68mmol)，三(二亚苄基丙酮)二钯(0.31g,0.34mmol)，2-二环己基磷-2’,4’,6’-三异丙基联苯(0.32g,0.69mmol)以及叔丁醇钠(2.47g,25.75mmol)加入甲苯(50mL)中，氮气保护下加热至108℃，搅拌3h；而后冷却至室温，反应液使用去离子水洗后加入无水硫酸镁干燥，过滤后将滤液通过短硅胶柱，减压除去溶剂；使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到白色固体中间体I-J(5.85g,81.25％)。
Figure PCTCN2020090876-appb-000061
将N,9-二苯基-9H-咔唑-3-胺(5.00g,14.95mmol)，4-溴-4’-碘联苯(8.05g,22.43mmol)，三(二亚苄基丙酮)二钯(0.27g,0.30mmol)，三叔丁基膦(0.12g,0.60mmol)以及叔丁醇钠(2.16g,22.43mmol)加入甲苯(80mL)中，氮气保护下加热至108℃，搅拌6h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；所得粗品使用正庚烷为流动相进行硅胶柱色谱提纯，之后二氯甲烷/正庚烷对粗品进行重结晶提纯，得到黄色固体中间体II-J(3.10g,36.64％)
Figure PCTCN2020090876-appb-000062
将中间体I-J(2.30g,5.48mmol)，中间体II-J(3.10g,5.48mmol)，三(二亚苄基丙酮)二钯(0.10g,0.11mmol)，2-二环己基磷-2’,6’-二甲氧基联苯(0.09g,0.22mmol)以及叔丁醇钠(0.79g,8.22mmol)加入甲苯(30mL)中，氮气保护下加热至108℃，搅拌2h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到白色固体化合物10(2.36g,47.58％)。质谱：m/z＝904.5(M+H) +
合成例11:
化合物11的合成
除了使用5.64g(15mmol)4-氨基-4’-甲基联苯代替苯胺，用5.23g(16.5mmol)中间体II-E-2代替二苯胺之外，与合成例1相同的方法合成了化合物11。质谱：m/z＝942.3(M+H) +
Figure PCTCN2020090876-appb-000063
合成例12:
化合物12的合成
除了使用5.42g(15mmol)2-萘胺代替苯胺，用5.33g(16.5mmol)中间体II-E-2代替二苯胺之外，与合成例1相同的方法合成了化合物12。质谱：m/z＝901.4(M+H) +
Figure PCTCN2020090876-appb-000064
合成例13:
化合物13的合成
除了使用3.11g(15mmol)对甲苯胺代替4-胺基联苯，用4-溴-N,N-双(4-甲基苯基)苯胺代替3-溴-N,N-双(4-甲基苯基)苯胺，5.06g(16.5mmol)4-溴-2,3-二甲基苯基苯硼酸代替4'-溴-4-联苯硼酸，与合成例6相同的方法合成了化合物13。质谱：m/z＝770.1(M+H) +
Figure PCTCN2020090876-appb-000065
合成例14:
化合物14的合成
除了使用4.96g(15mmol)2-溴联苯代替溴苯之外，使用与中间体Ⅰ-A相同的合成路线制备中间体Ⅰ-S，再使用Ⅰ-S代替Ⅰ-A，与合成例3相同的方法合成了化合物14。质谱：m/z＝790.0(M+H) +
Figure PCTCN2020090876-appb-000066
合成例15:
化合物15的合成
除了使用5.73g(15mmol)3-氨基联苯代替苯胺之外，与合成例1相同的方法合成了化合物15。质谱m/z＝699.9(M+H) +
Figure PCTCN2020090876-appb-000067
合成例16:
化合物16的合成
除了使用5.64g(15mmol)3-溴-4’-碘联苯代替4-溴-4’-碘联苯之外，与合成例1相同的方法合成了化合物16。质谱：m/z＝623.9(M+H)质谱：m/z＝623.9(M+H) +
Figure PCTCN2020090876-appb-000068
合成例17:
化合物17的合成
除了使用4.45g(15mmol)1-(3-溴苯基)金刚烷代替中间体I-A之外，与合成例1相同的方法合成了化合物17。质谱m/z＝623.9M+H) +
Figure PCTCN2020090876-appb-000069
合成例18:
化合物18的合成
除了使用5.28g(15mmol)4-氨基联苯、5.35g(16.5mmol)4溴-4’甲基联苯和4.29g(13.5mmol)对氯苯硼酸代替3-溴-N,N-双(4-甲基苯基)苯胺和4'-溴-4-联苯硼酸之外，与合成例6相同的方法合成了化合物18。质谱m/z＝1017.5(M+H) +
Figure PCTCN2020090876-appb-000070
合成例19:
化合物19的合成
除了使用9-(4-溴苯基)咔唑、苯胺和对氯苯硼酸代替3-溴-N,N-双(4-甲基苯基)苯胺和4'-溴-4-联苯硼酸之外，与合成例6相同的方法合成了化合物19。质谱m/z＝1016.5(M+H) +
Figure PCTCN2020090876-appb-000071
合成例20:
化合物20的合成
除了使用5.17g(15mmol)二苯胺5.81g(16.5mmol)4-溴-4'-碘-联苯和4.29g(13.5mmol)间氯苯硼酸之后，与合成例5相同的方法合成了化合物22。质谱：m/z＝775.4(M+H) +
Figure PCTCN2020090876-appb-000072
合成例21:
化合物21的合成
除了使用4氯联苯-4’硼酸和4-氨基联苯代替二苯胺和苯胺之后，与合成例1相同的方法合成了化合物21。质谱：m/z＝851.5(M+H) +
Figure PCTCN2020090876-appb-000073
合成例22:
化合物22的合成
除了使用4氯联苯-3’硼酸和2-氨基-9,9-二甲基芴代替二苯胺和苯胺之后，与合成例1相同的方法 合成了化合物22。质谱：m/z＝891.5(M+H) +
Figure PCTCN2020090876-appb-000074
合成例23:
化合物23的合成
除了使用3-二苯并噻吩和3-溴二苯并呋喃合成的中间体代替二苯胺之后，与合成例1相同的方法合成了化合物23。质谱：m/z＝819.3(M+H) +
Figure PCTCN2020090876-appb-000075
合成例24
化合物24的合成
Figure PCTCN2020090876-appb-000076
将苯基-1-萘胺(21.9g,100mmol)，4-溴-4’-氯联苯(26.7g,100mmol)，三(二亚苄基丙酮)二钯(0.10g,0.1mmol)，X-PHOS(0.05g,0.2mmol)以及叔丁醇钠(1.61g,150mmol)加入甲苯(200mL)中，氮气保护下加热至108℃，搅拌6h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液减压除去溶剂；使用正庚烷为流动相进行硅胶柱色谱提纯，得到白色中间体(27.6g,68％)。
Figure PCTCN2020090876-appb-000077
将上述合成的中间体(8.12g,20mmol)，中间体II-C(7.58g,20mmol)，三(二亚苄基丙酮)二钯(0.018g,0.02mmol)，2-二环己基磷-2’,4’,6’-三异丙基联苯(0.019g,0.04mmol)以及叔丁醇钠(2.88g,30mmol)加入甲苯(100mL)中，氮气保护下加热至108℃，搅拌2h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；使用二氯甲烷/正庚烷(1:3)为流动相进行硅胶柱色谱提纯，之后用二氯甲烷 /乙酸乙酯体系对粗品进行重结晶提纯，得到白色固体化合物(7.79g,52％)。质谱：m/z＝749.3(M+H) +
1HNMR(400MHz,CD 2Cl 2):7.97(d,1H),7.92(d,1H),7.82(d,1H),7.54-7.36(m,14H),7.36(t,2H),7.21(t,2H),7.15-7.12(m,6H),7.07-7.04(m,5H),6.96(t,1H),2.11-2.10(m,3H),1.96-1.95(m,6H),1.83-1.77(m,6H).
合成例25
化合物25的合成
Figure PCTCN2020090876-appb-000078
将N-苯基二苯并噻吩-2-胺(13.75g,50mmol)，4-溴-4’-氯联苯(13.35g,50mmol)，三(二亚苄基丙酮)二钯(0.046g,0.05mmol)，X-PHOS(0.048g,0.1mmol)以及叔丁醇钠(7.2g,75mmol)加入甲苯(150mL)中，氮气保护下加热至108℃，搅拌6h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液减压除去溶剂；使用正庚烷为流动相进行硅胶柱色谱提纯，得到白色中间体(15.24g,66％)。
Figure PCTCN2020090876-appb-000079
将上述合成的中间体(9.24g,20mmol)，中间体I-A(6.04g,20mmol)，三(二亚苄基丙酮)二钯(0.018g,0.02mmol)，2-二环己基磷-2’,4’,6’-三异丙基联苯(0.019g,0.04mmol)以及叔丁醇钠(2.88g,30mmol)加入甲苯(100mL)中，氮气保护下加热至108℃，搅拌2h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；使用二氯甲烷/正庚烷(1:3)为流动相进行硅胶柱色谱提纯，之后用二氯甲烷/乙酸乙酯体系对粗品进行重结晶提纯，得到白色固体化合物(8.45g,58％)。质谱：m/z＝729.3(M+H) +
1HNMR(400MHz,CD 2Cl 2):7.99(d,1H),7.94(s,1H),7.85(d,1H),7.77(d,1H),7.47-7.39(m,6H),7.30-7.24(m,7H),7.16-7.00(m,12H),2.08-2.09(m,3H),1.91-1.90(m,6H),1.81-1.75(dd,6H).
合成例26
化合物26的合成
Figure PCTCN2020090876-appb-000080
4-溴苯硫醇(18.9g100mmol)，4-氯-2-氟硝基苯(17.5g100mmol)，DMF 100ml混合，开启搅拌，使体系溶清，加入碳酸钾(17.94g 130mmol)，升温至80℃～90℃保温反应18h，反应完成。将反应液降至20℃～30℃，加入20L水充分搅拌过滤，滤饼用水水洗3次至中性，20℃～30℃乙醇打浆，常温过 滤，烘料(T＝50-60℃)，烘干得浅黄色固体(31.01g，收率90％).
Figure PCTCN2020090876-appb-000081
加入上一步所得硝基中间体(17.23g 50mmol)，乙醇100ml，开启搅拌，加入还原铁粉(9.8g175mmol)，开启升温T＝50～60℃，滴加5mL浓盐酸(稀释10倍加入)，T＝50-60℃保温反应小时，反应完成。反应液降至20～25℃，过氧化铝的短柱过滤，滤饼用THF淋洗，滤饼暂放。合并滤液加入水和二氯乙烷萃取搅拌10min，静置1h，分液，水相用二氯乙烷萃取一次，合并有机相，水洗至PH＝6-7，有机相加入无水硫酸钠干燥1h，过滤，滤饼用二氯乙烷淋洗，滤液合并浓干(50～65℃，-0.075MPa～-0.09MPa)，浓缩至不出溶剂时加入石油醚充分搅拌，降温至0～5℃，析出固体，过滤，收集滤饼烘干(鼓风烘箱，40～45℃，约6h)得产物13.37g，收率85％。
Figure PCTCN2020090876-appb-000082
加入上面氨基中间体18.87g 60mmol，加入100ml的二氯乙烷溶解透亮后，加入三氟乙酸13.68g120mmol，无水硫酸镁3.6g,30mmol搅拌10min，分批加入亚硝酸钠8.48g 132mmo，严格控制温度在40-50℃，40-50℃保温反应反应完成，将反应液降温至20-30℃，过硅胶漏斗,滤饼用二氯乙烷淋洗,合并滤液。滤液用水水洗3～4次至中性，分液，有机相用无水硫酸钠干燥。过滤，滤饼用的二氯乙烷淋洗无水硫酸钠滤饼，合并滤液，浓缩(50～65℃，-0.075MPa～-0.09MPa)。浓干加入石油醚45～50℃煮洗两次。固体用甲苯溶解，常温过柱，过柱液浓缩(65～80℃，-0.08MPa～-0.09MPa)，降温重结晶，T＝-5～0℃过滤。滤固烘干，用二氯乙烷回流溶解透亮重结晶，降温至-5～0℃过滤，50～60℃烘料。得到8.03克，收率45％。
Figure PCTCN2020090876-appb-000083
将二苯胺(8.45g,50mmol)，2-氯-7-溴-二苯并噻吩(14.88g,50mmol)，三(二亚苄基丙酮)二钯(0.046g,0.05mmol)，X-PHOS(0.048g,0.1mmol)以及叔丁醇钠(7.2g,75mmol)加入甲苯(150mL)中，氮气保护下加热至108℃，搅拌6h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液减压除去溶剂；使用正庚烷为流动相进行硅胶柱色谱提纯，得到白色中间体(13.89g,72％)。
Figure PCTCN2020090876-appb-000084
将上述合成例1中的中间体(7.72g,20mmol)，中间体I-A(6.04g,20mmol)，三(二亚苄基丙酮)二钯(0.018g,0.02mmol)，2-二环己基磷-2’,4’,6’-三异丙基联苯(0.019g,0.04mmol)以及叔丁醇钠(2.88g, 30mmol)加入甲苯(100mL)中，氮气保护下加热至108℃，搅拌2h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；使用二氯甲烷/正庚烷(v:v＝1:3)为流动相进行硅胶柱色谱提纯，之后用二氯甲烷/乙酸乙酯体系对粗品进行重结晶提纯，得到白色固体化合物(8.22g,63％)。质谱：m/z＝653.3(M+H) +
合成例27
化合物27的合成
Figure PCTCN2020090876-appb-000085
二苯并呋喃(16.8g，100mmol)、DMF 150ml，NCS(13.3g,100mmol)，开启搅拌和加热，在40-50℃保温反应，开始时反应液为棕色，随着反应的进行体系会变为黄色。反应7h完成。反应液倒入水中，析出固体，固体用正庚烷(m/v＝1/3)重结晶，加热到95-98℃溶解，自然降温至25-30℃过滤，按此操作重结晶，共重结晶4次，烘干得到白固体3-氯二苯并呋喃7.67g，收率38％,纯度HPLC＝98.54％。
Figure PCTCN2020090876-appb-000086
3-氯二苯并呋喃(20.2g,100mmol)，四氢呋喃200mL，通氮气开搅拌，用液氮降温至－45～－35℃，滴加120mmol LDA(1mol/L的THF溶液,)，40min滴完，保温1h，反应液用液氮降温至－95～－85℃，滴加碘溶液(100毫升THF溶解29.4g，120mmol碘)，60min滴完，保温40min后反应完成，反应完成后向反应液中加入亚硫酸氢钠的水溶液，搅拌10min使反应液褪色，静置10min，分液，水相用2L/次的乙酸乙酯萃取2次，有机相合并后用无水硫酸钠干燥60min后在0.07MPa,60～85℃下浓缩，得到油状粗品，向该油状物中加入正庚烷，加热至95～98℃搅拌60min，降温至15～20℃，析出固体，过滤，得到粗品。
重结晶：1g粗品：4ml乙酸乙酯在75～80℃下溶解，自然降温至20～25℃，析出固体，过滤，滤饼鼓风烘箱60～65℃下烘12h，得到130.00g类白色固体，LC＝99.08％。母液回收，得到的固体重结晶两次，得到13.79g固体，总收率42％。
Figure PCTCN2020090876-appb-000087
将二苯胺(8.45g,50mmol)，2-氯-4-碘二苯并呋喃(16.42g,50mmol)，三(二亚苄基丙酮)二钯(0.046g,0.05mmol)，X-PHOS(0.048g,0.1mmol)以及叔丁醇钠(7.2g,75mmol)加入甲苯(150mL)中，氮气保护下加热至108℃，搅拌8h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液减压除去溶剂；使用正庚烷为流动相进行硅胶柱色谱提纯，得到白色中间体(14.05g,76％)。
Figure PCTCN2020090876-appb-000088
将上述合成例的中间体(7.40g,20mmol)，中间体I-G(7.06g,20mmol)，三(二亚苄基丙酮)二钯(0.018g,0.02mmol)，2-二环己基磷-2’,4’,6’-三异丙基联苯(0.019g,0.04mmol)以及叔丁醇钠(2.88g,30mmol)加入甲苯(100mL)中，氮气保护下加热至108℃，搅拌2h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；使用二氯甲烷/正庚烷(1:3)为流动相进行硅胶柱色谱提纯，之后用二氯甲烷/乙酸乙酯体系对粗品进行重结晶提纯，得到白色固体化合物(9.61g,70％)。质谱：m/z＝687.3(M+H) +
合成例28
化合物28的合成
Figure PCTCN2020090876-appb-000089
将中间体I-A(7.0g,24.04mmol)，1,1’联苯-4-胺(4.87g,28.84mmol)，三(二亚苄基丙酮)二钯(0.22g,0.24mmol)，2-二环己基磷-2’,4’,6’-三异丙基联苯(0.23g,0.48mmol)以及叔丁醇钠(3.46g,36.05mmol)加入甲苯(70mL)中，氮气保护下加热至108℃，搅拌3h；而后冷却至室温，反应液使用去离子水洗后加入无水硫酸镁干燥，过滤后将滤液通过短硅胶柱，减压除去溶剂；使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到浅绿色固体中间体I-K(7.30g,80％)。
Figure PCTCN2020090876-appb-000090
2-溴-6氯-萘(24.1g,100mmol),中间体I-K(37.9g,100mmol),三(二亚苄基丙酮)二钯(0.91g,1mmol)，X-Phos(0.95g,2mmol)以及叔丁醇钠(19.2g,200mmol)加入甲苯(200mL)中，氮气保护下加热至108℃，搅拌6h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液减压除去溶剂；使用正庚烷为流动相进行硅胶柱色谱提纯，得到白色中间体(28.13g,54％)。
Figure PCTCN2020090876-appb-000091
将上述合成的中间体(27g,50mmol)，苯基联苯胺(12.25g,50mmol)，三(二亚苄基丙酮)二钯(0.49g,0.5mmol)，2-二环己基磷-2’,4’,6’-三异丙基联苯(0.47g,1mmol)以及叔丁醇钠(9.6g,100mmol)加入甲苯(200mL)中，氮气保护下加热至108℃，搅拌2h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；使用二氯甲烷/正庚烷(v/v＝1:3)为流动相进行硅胶柱色谱提纯，之后用二氯甲烷/乙酸乙酯体系对粗品进行重结晶提纯，得到白色固体化合物(16.10g,43％)。质谱：m/z＝749.3(M+H) +
合成例29
化合物29的合成
Figure PCTCN2020090876-appb-000092
间溴碘苯28.3克100mmol,中间体II-C-1(25.9g,100mmol),三(二亚苄基丙酮)二钯(0.91g,1mmol)，X-Phos(0.95g,2mmol)以及叔丁醇钠(19.2g,200mmol)加入甲苯(200mL)中，氮气保护下加热至108℃，搅拌6h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液减压除去溶剂；使用正庚烷为流动相进行硅胶柱色谱提纯，得到白色固体(26.49g,64％)。
Figure PCTCN2020090876-appb-000093
将上述合成的中间体(20.7g,50mmol)，中间体I-K(18.95g,50mmol)，三(二亚苄基丙酮)二钯(0.49g,0.5mmol)，2-二环己基磷-2’,4’,6’-三异丙基联苯(0.47g,1mmol)以及叔丁醇钠(9.6g,100mmol)加入甲苯(200mL)中，氮气保护下加热至108℃，搅拌2h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；使用二氯甲烷/正庚烷(v:v＝1:3)为流动相进行硅胶柱色谱提纯，之后用二氯甲烷/乙酸乙酯体系对粗品进行重结晶提纯，得到白色固体化合物(20.67g,58％)。质谱：m/z＝713.4(M+H) +。
合成例30
化合物30的合成
Figure PCTCN2020090876-appb-000094
将中间体I-A(13.6g,4.5mmol)，间氯碘苯(1068g,4.5mmol)，三(二亚苄基丙酮)二钯(0.41g,0.45mmol)，2-二环己基磷-2’,6’-二甲氧基联苯(0.3674g,0.9mmol)以及叔丁醇钠(5.16g,5.3mmol)加入甲苯(136mL)中，氮气保护下加热至108℃，搅拌1h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；使用二氯甲烷/正庚烷(1:5)为流动相进行硅胶柱色谱提纯，之后用二氯甲烷/乙酸乙酯体系对粗品进行重结晶提纯，得到白色固体化合物30-1(15g,25％)。
Figure PCTCN2020090876-appb-000095
将苯胺(3.72g,4mmol)，2-溴二苯并噻吩(10g.3.8mmol)，三(二亚苄基丙酮)二钯(0.348g,0.38mmol)，2-二环己基磷-2,4,6-三异丙基联苯(0.355g,0.76mmol)以及叔丁醇钠(5.478g,5.7mmol)加入甲苯(100mL)中，氮气保护下加热至108℃，搅拌2h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液通过短硅胶柱，过柱液减压除去溶剂；使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到白色固体中间体30-2(7.2g,72％)。
Figure PCTCN2020090876-appb-000096
将上述合成的中间体34-1(6.2g,15mmol)，中间体34-2(4.13g,15mmol)，三(二亚苄基丙酮)二钯(0.14g,0.15mmol)，2-二环己基磷-2’,4’,6’-三异丙基联苯(0.13g,0.3mmol)以及叔丁醇钠(2.16g,22.5mmol)加入甲苯(60mL)中，氮气保护下加热至108℃，搅拌2h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；使用二氯甲烷/正庚烷(v:v＝1:5)为流动相进行硅胶柱色谱提纯，之后用二氯甲烷/乙酸乙酯体系对粗品进行重结晶提纯，得到白色固体化合物30(6.9,71％)。质谱：m/z＝653.3(M+H) +。
合成例31
化合物31的合成
Figure PCTCN2020090876-appb-000097
将中间体I-k(17.1g,4.5mmol)，对氯碘苯(10.7g,4.5mmol)，三(二亚苄基丙酮)二钯(0.41g,0.45mmol)，2-二环己基磷-2’,6’-二甲氧基联苯(0.3674g,0.9mmol)以及叔丁醇钠(5.16g,5.3mmol)加入甲苯(150mL)中，氮气保护下加热至108℃，搅拌1h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；使用甲苯/正庚烷(1:8)为流动相进行硅胶柱色谱提纯，之后用甲苯/乙酸乙酯体系对粗品进行重结晶提纯，得到白色固体化合物31-1(16.6g,51％)。
Figure PCTCN2020090876-appb-000098
将4-胺基联苯(6.77g,4mmol)，3-溴二苯并噻吩(10g.3.8mmol)，三(二亚苄基丙酮)二钯(0.348g,0.38mmol)，2-二环己基磷-2,4,6-三异丙基联苯(0.355g,0.76mmol)以及叔丁醇钠(5.478g,5.7mmol)加入甲苯(100mL)中，氮气保护下加热至108℃，搅拌2h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液通过短硅胶柱，过柱液减压除去溶剂；使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到白色固体中间体31-2(10g,75％)。
Figure PCTCN2020090876-appb-000099
将上述合成的中间体31-1(7.14g,15mmol)，中间体31-2(5.3g,15mmol)，三(二亚苄基丙酮)二钯(0.14g,0.15mmol)，2-二环己基磷-2’,4’,6’-三异丙基联苯(0.13g,0.3mmol)以及叔丁醇钠(2.16g,22.5mmol)加入甲苯(60mL)中，氮气保护下加热至108℃，搅拌2h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；使用甲苯/正庚烷(v:v＝1:5)为流动相进行硅胶柱色谱提纯，之后用甲苯/乙酸乙酯体系对粗品进行重结晶提纯，得到白色固体化合物(7.8,65％)。质谱：m/z＝805.3(M+H) +。
合成例32
化合物32的合成
Figure PCTCN2020090876-appb-000100
将中间体I-A(13.6g,4.5mmol)，对氯碘苯(10.68g,4.5mmol)，三(二亚苄基丙酮)二钯(0.41g,0.45mmol)，2-二环己基磷-2’,6’-二甲氧基联苯(0.3674g,0.9mmol)以及叔丁醇钠(5.16g,5.3mmol)加入甲苯(136mL)中，氮气保护下加热至108℃，搅拌1h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；使用二氯甲烷/正庚烷(1:5)为流动相进行硅胶柱色谱提纯，之后用二氯甲烷/乙酸乙酯体系对粗品进行重结晶提纯，得到白色固体化合物32-1(17g,75％)。
Figure PCTCN2020090876-appb-000101
将2-胺基联苯(6.77g,4mmol)，2-溴芴(10.4g.3.8mmol)，三(二亚苄基丙酮)二钯(0.348g,0.38mmol)，2-二环己基磷-2,4,6-三异丙基联苯(0.355g,0.76mmol)以及叔丁醇钠(5.478g,5.7mmol)加入甲苯(100mL)中，氮气保护下加热至108℃，搅拌2h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液通过短硅胶柱，过柱液减压除去溶剂；使用甲苯/正庚烷体系对粗品进行重结晶提纯，得到白色固体中间体32-2(10.43g,76％)。
Figure PCTCN2020090876-appb-000102
将上述合成的中间体32-1(6.2g,15mmol)，中间体36-2(5.4g,15mmol)，三(二亚苄基丙酮)二钯(0.14g,0.15mmol)，2-二环己基磷-2’,4’,6’-三异丙基联苯(0.13g,0.3mmol)以及叔丁醇钠(2.16g,22.5mmol)加入甲苯(60mL)中，氮气保护下加热至108℃，搅拌2h；而后冷却至室温，反应液过滤后将滤液减压除去溶剂；使用甲苯/正庚烷(v:v＝1:5)为流动相进行硅胶柱色谱提纯，之后用甲苯/乙酸乙酯体系对粗品进行重结晶提纯，得到白色固体化合物32(8.2,73％)。质谱：m/z＝739.4(M+H) +。
制作有机电致发光器件
实施例1：使用本发明化合物作为空穴传输层的有机电致发光器件
通过以下过程制备阳极：将厚度为
Figure PCTCN2020090876-appb-000103
的ITO基板(康宁制造)切割成40mm×40mm×0.7mm的尺寸，采用光刻工序，将其制备成具有阴极、阳极以及绝缘层图案的实验基板，利用紫外臭氧以及 O2:N2等离子进行表面处理，以增加阳极(实验基板)的功函数的和清除浮渣。
在实验基板(阳极)上真空蒸镀m-MTDATA以形成厚度为
Figure PCTCN2020090876-appb-000104
的空穴注入层(HIL)，并且在空穴注入层上真空蒸镀化合物1，以形成厚度为
Figure PCTCN2020090876-appb-000105
的空穴传输层(HTL)。
在空穴传输层上蒸镀TCTA，形成厚度为
Figure PCTCN2020090876-appb-000106
的电子阻挡层(EBL)
将α,β-AND作为主体，同时掺杂4,4'-(3,8-二苯基芘-1,6-二基双(N,N-二苯基苯胺)，形成了厚度为
Figure PCTCN2020090876-appb-000107
的发光层(EML)。
将DBimiBphen和LiQ以1:1的重量比进行混合并蒸镀形成了
Figure PCTCN2020090876-appb-000108
厚的电子传输层(ETL)，将LiQ蒸镀在电子传输层上以形成厚度为
Figure PCTCN2020090876-appb-000109
的电子注入层(EIL)，然后将镁(Mg)和银(Ag)以1:9的蒸镀速率混合，真空蒸镀在电子注入层上，形成厚度为
Figure PCTCN2020090876-appb-000110
的阴极。
此外，在上述阴极上蒸镀了厚度为65nm的N-(4-(9H-咔唑-9-基)苯基)-4'-(9H-咔唑-9-基)-N-苯基-[1,1'-联苯]-4-胺，形成覆盖层(CPL)，从而完成有机发光器件的制造。
实施例2-23
除了在形成空穴传输层(HTL)使用表1中所示的化合物以外，利用与实施例1相同的方法制作有机电致发光器件。
器件性能见表1。
比较例1～比较例2
在所述比较例1～比较例2中，除了使用了NPB和化合物B作为空穴传输层替代化合物1之外，用与实施例1相同的方法制造有机电致发光器件。即比较例1采用NPB制造有机电致发光器件，比较例2采用化合物B制造有机电致发光器件，器件性能见表1。
其中，在制备电致发光器件时，所使用的各个材料的结构如下：
Figure PCTCN2020090876-appb-000111
对上述制得的有机电致发光器件，在20mA/cm 2的条件下分析了器件的性能，其结果示于下表1。
Figure PCTCN2020090876-appb-000112
化合物B
表1
实施例 化合物 Volt(V) Cd/A EQE(％) T95(hrs) CIEx CIEy
实施例1 化合物1 4.0 6.7 14.3 200 0.140 0.045
实施例2 化合物2 4.1 6.8 14.6 210 0.141 0.044
实施例3 化合物3 3.9 6.9 14.9 198 0.141 0.045
实施例4 化合物4 4.2 7.2 15.1 209 0.141 0.042
实施例5 化合物5 3.8 6.4 14.7 180 0.142 0.044
实施例6 化合物6 3.9 6.6 14.3 176 0.143 0.043
实施例7 化合物7 4.4 6.4 14.4 169 0.142 0.042
实施例8 化合物11 4.1 6.8 14.5 165 0.141 0.044
实施例9 化合物12 4.18 6.7 14.0 168 0.143 0.045
实施例10 化合物13 3.98 6.4 14.4 167 0.142 0.047
实施例11 化合物14 3.93 6.5 13.5 174 0.141 0.046
实施例12 化合物15 4.37 6.5 13.3 172 0.140 0.045
实施例13 化合物16 4.28 6.8 14.2 198 0.141 0.048
实施例14 化合物17 3.98 6.4 13.8 194 0.141 0.045
实施例15 化合物18 4.02 6.8 13.3 174 0.141 0.042
实施例16 化合物21 4.14 6.8 13.2 203 0.140 0.045
实施例17 化合物22 3.98 6.8 13.2 172 0.141 0.046
实施例18 化合物24 3.97 6.7 14.6 205 0.141 0.046
实施例19 化合物25 4.07 6.7 14.3 205 0.142 0.044
实施例20 化合物28 4.03 6.6 14.1 193 0.141 0.046
实施例21 化合物30 3.92 6.7 14.5 183 0.141 0.047
实施例22 化合物32 4.02 6.4 13.7 198 0.143 0.045
实施例23 化合物31 4.1 6.8 14.5 195 0.141 0.044
比较例1 NPB 5.0 4.0 6.4 80 0.142 0.043
比较例2 化合物B 4.4 5.9 10 160 0.141 0.043
参见上述表1器件评价结果可知，实施例1-7将本发明的化合物用作空穴传输层(HTL)的情况下，与比较例1-2中的化合物相比，在色坐标CIEy相差不大的情况下，在相同电流密度下进行测试，用本发明的化合物制作的有机电致发光器件，驱动电压(V)明显降低，电流效率(Cd/A)和外量子效率(EQE)提升明显优于比较例，呈现出提升的趋势，而使用寿命(T95)也显著增加，其中，外量子效率提升达到30％以上。
实施例24:使用本发明化合物作为电子阻挡层的有机电致发光器件
通过以下过程制备阳极：将厚度为
Figure PCTCN2020090876-appb-000113
的ITO基板(康宁制造)切割成40mm×40mm×0.7mm的尺寸，采用光刻工序，将其制备成具有阴极、阳极以及绝缘层图案的实验基板，利用紫外臭氧以及O 2:N 2等离子进行表面处理，以增加阳极(实验基板)的功函数的和清除浮渣。
在实验基板(阳极)上真空蒸镀m-MTDATA以形成厚度为
Figure PCTCN2020090876-appb-000114
的空穴注入层(HIL)，并且在空穴注入层上真空蒸镀化合物NPB，以形成厚度为
Figure PCTCN2020090876-appb-000115
的空穴传输层(HTL)。
在空穴传输层上蒸镀本发明化合物8形成厚度为
Figure PCTCN2020090876-appb-000116
的电子阻挡层(EBL)。
将α,β-AND作为主体，同时掺杂4,4'-(3,8-二苯基芘-1,6-二基双(N，N-二苯基苯胺)，形成了厚度为
Figure PCTCN2020090876-appb-000117
的发光层(EML)。
将DBimiBphen和LiQ以1:1的重量比进行混合并蒸镀形成了
Figure PCTCN2020090876-appb-000118
厚的电子传输层(ETL)，将LiQ蒸镀在电子传输层上以形成厚度为
Figure PCTCN2020090876-appb-000119
的电子注入层(EIL)，然后将镁(Mg)和银(Ag)以1:9的比例混合，真空蒸镀在电子注入层上，形成厚度为
Figure PCTCN2020090876-appb-000120
的阴极。
此外，在上述阴极上作为蒸镀了厚度为
Figure PCTCN2020090876-appb-000121
的N-(4-(9H-咔唑-9-基)苯基)-4'-(9H-咔唑-9-基)-N-苯基-[1,1'-联苯]-4-胺，形成覆盖层(CPL)，从而完成有机发光器件的制造。
实施例24-35
除了在形成电子阻挡层(EBL)时各自使用表2中所示的化合物以外，利用与实施例24相同的方法制作有机电致发光器件。
即实施例25采用本发明化合物9制作有机电致发光器件，实施例26采用本发明化合物10制作有机电致发光器件。
器件性能见表2
比较例3～比较例5
在所述比较例3～比较例5中，除了使用了TCTA、NPD、TPD作为电子阻挡层替代化合物8之外，用与实施例24相同的方法制造有机电致发光器件。
即比较例3采用TCTA制造有机电致发光器件，比较例4采用NPD制造有机电致发光器件，比较例5采用TPD制造有机电致发光器件，器件性能见表2。
其中，在制备电致发光器件时，所使用的各材料的结构如下：
Figure PCTCN2020090876-appb-000122
对上述制得的有机电致发光器件，在20mA/cm 2的条件下分析了器件的性能，其结果示于下表2。
表2
实施例 化合物 Volt(V) Cd/A EQE(％) T95(hrs) CIEx CIEy
实施例24 化合物8 4.1 6.5 12.1 152 0.141 0.043
实施例25 化合物9 3.7 6.1 14.4 178 0.143 0.043
实施例26 化合物10 4.5 6.1 13.2 186 0.142 0.042
实施例27 化合物19 4.0 6.4 14.6 167 0.141 0.043
实施例28 化合物20 3.8 6.7 14.9 155 0.143 0.042
实施例29 化合物23 3.8 6.5 14.7 168 0.142 0.042
实施例30 化合物26 3.9 6.6. 14.7 175 0.143 0.043
实施例31 化合物27 4.1 6.3 14.4 176 0.143 0.044
实施例32 化合物29 4.0 6.5 14.5 183 0.142 0.042
实施例33 化合物30 4.1 6.4 14.4 188 0.143 0.043
实施例34 化合物31 3.9 6.3 14.2 185 0.143 0.043
实施例35 化合物32 4.1 6.4 13.5 189 0.142 0.042
比较例3 TCTA 5.0 5.1 8.3 75 0.141 0.044
比较例4 NPD 6.5 4.2 8.7 68 0.140 0.043
比较例5 TPD 5.7 4.9 9.5 59 0.144 0.045
参见上述表2器件评价结果可知，实施例24～35将本发明的化合物用作电子阻挡层(EBL)的情况下，与比较例3～5中的化合物相比，在色坐标CIEy相差不大的情况下，在相同电流密度下进行测试，用本发明的化合物制作的有机电致发光器件，驱动电压(V)明显降低，电流效率(Cd/A)和外量子效率(EQE)提升明显优于比较例，呈现出提升的趋势，而使用寿命(T95)也显著增加。
从表2可知，本发明化合物用于蓝光器件的电子阻挡层时，与比较例相比，外量子效率提高了20％以上，这对蓝光器件而言，是非常显著的提升。对于OLED器件(即有机电致发光器件)来说，对其效果(例如EQE方面)的改善即使在数据上看来只有百分之几，但是，这种改善也是非常显著的。
具体地说，外量子效率(EQE)可以按照如下公式计算，例如EQE＝射出组件的光子数目/注入电子数目；又例如EQE＝出光率*内部量子效率(出光率小于1)。
对于蓝光器件而言，发光层用的是荧光材料，而荧光材料是单线态激子发光，其内部量子效率最高为25％。而对外发光时，由于耦合等器件结构所导致的光的损失等其他原因，因为只能利用25％的激子，导致外量子效率一定低于25％，使得其效率通常较低。
因此，使用本发明化合物制作的器件，具有降低驱动电压、提高发光效率以及延长使用寿命的特性。
综上所述，将本发明化合物用作有机电致发光器件的空穴传输层或电子阻挡层，使得包含该化合物的有机电致发光器件具有更低的驱动电压、更高的发光效率和更好的寿命。
以上实施例只是对本发明的化合物的进一步说明，本发明的发明要求保护范围并不限定于此。对本发明所属领域的普通技术人员而言，在不脱离发明要求保护范围中所记载的本发明的技术思想的范围下，对本发明进行的各种补充及变形也属于本发明的保护范围。

Claims (16)

  1. 一种有机电致发光材料，该材料的结构式如化学式1所示：
    Figure PCTCN2020090876-appb-100001
    其中，R 2、R 4和R 5相同或不同，分别独立地选自取代或未取代的碳原子数为1-20的烷基、取代或未取代的碳原子数为2-20的烯基、取代或未取代的碳原子数为2-24的炔基、取代或未取代的碳原子数为3-20的环烷基、取代或未取代的碳原子数为2-20的杂环烷基、取代或未取代的碳原子数为7-30的芳烷基、取代或未取代的碳原子数为2-30的杂芳烷基、取代或未取代的碳原子数为6-30的芳基、取代或未取代的碳原子数为1-30的杂芳基；
    R 1和R 3相同或不同，分别独立地选自单键、取代或未取代碳原子数为1-30的亚芳基、取代或未取代的碳原子数为1-30的亚杂芳基、取代或未取代的碳原子数为7-30的亚芳烷基、取代或未取代的碳原子数为2-30的亚杂芳烷基；
    所述R 1、R 2、R 3、R 4和R 5的取代基相同或不同，分别独立地选自氘、氰基、硝基、卤素、羟基、碳原子数为1-40的烷基基团、碳原子数3-40的环烷基基团、碳原子数2-40的烯基基团、碳原子数2-40的炔基基团、碳原子数2-40的杂环烷基基团、碳原子数7-40的芳烷基基团、碳原子数2-40的杂芳烷基基团、碳原子数6-40的芳基基团、碳原子数1-40的杂芳基基团、碳原子数1-40的烷氧基基团、碳原子数1-40的烷氨基基团、碳原子数6-40的芳氨基基团、碳原子数为1-40的烷硫基基团、碳原子数7-40的芳烷氨基基团、碳原子数1-24的杂芳氨基基团、碳原子数为1-45的烷基甲硅烷基基团、碳原子数为6-50的芳基甲硅烷基基团、碳原子数为6-30的芳氧基基团、碳原子数为6-30的芳硫基基团。
  2. 根据权利要求1所述的有机电致发光材料，其中，R 1和R 3相同或不同，分别独立地选自单键、取代或未取代碳原子数为6-25的亚芳基、取代或未取代的碳原子数为5-18的亚杂芳基，R 2、R 4和R 5相同或不同，分别独立地选自单键、取代或未取代碳原子数为6-18的芳基、取代或未取代的碳原子数为5-18的杂芳基；
    所述R 1、R 2、R 3、R 4和R 5的取代基相同或不同，分别独立地选自氘、氰基、硝基、卤素、羟基、碳原子数为1-10的烷基基团、碳原子数为3-10的环烷基基团、碳原子数为6-15的芳基基团、碳原子数为3-12的杂芳基基团，当取代基多于一个时，各取代基相同或不同。
  3. 根据权利要求1所述的有机电致发光材料，其中，R 1和R 3彼此相同或不同，各自独立地选自化学式j-1至化学式j-9所示的基团所组成的组：
    Figure PCTCN2020090876-appb-100002
    其中，M 2选自单键或者
    Figure PCTCN2020090876-appb-100003
    E 1～E 14分别独立地选自：氢、氘、卤素基团、氰基、碳原子数为3～12的杂芳基、碳原子数为6～15的芳基、碳原子数为3～9的三烷基硅基、碳原子数为1～10的烷基、碳原子数为1～10的卤代烷基、碳原子数为3～10的环烷基、碳原子数为1～10的烷氧基；
    e 1～e 14以e r表示，E 1～E 14以E r表示，r为变量，表示1～14的任意整数，e r表示取代基E r的数量；当r选自1、2、3、4、5、6、9、13或14时，e r选自1、2、3或者4；当r选自7或11时，e r选自1、2、3、4、5或者6；当r为12时，e r选自1、2、3、4、5、6或者7；当r选自8或10时，e r选自1、2、3、4、5、6、7或者8；当e r大于1时，任意两个E r相同或者不相同；
    K 3选自O、S、Se、N(E 15)、C(E 16E 17)、Si(E 18E 19)；其中，各E 15、E 16、E 17、E 18和E 19分别独立地选自：氢、碳原子数为6～15的芳基、碳原子数为3～12的杂芳基、碳原子数为1～10的烷基、碳原子数为3～10的环烷基、碳原子数为2～10的杂环烷基；
    各K 4独立地选自单键、O、S、Se、N(E 20)、C(E 21E 22)、Si(E 23E 24)；其中，各E 20、E 21、E 22、E 23、E 24分别独立地选自：氢、碳原子数为6～15的芳基、碳原子数为3～12的杂芳基、碳原子数为1～10的烷基、碳原子数为3～10的环烷基。
  4. 根据权利要求1所述的有机电致发光材料，其中，R 1和R 3各自独立地选自取代或未取代的基团W 1，所述未取代的基团W 1选自如下基团：
    Figure PCTCN2020090876-appb-100004
    Figure PCTCN2020090876-appb-100005
    所述W 1基团被一个或多个取代基所取代时，W 1的取代基各自独立地选自由氘、氟、氯、氰基、甲基、乙基、丙基、叔丁基、三甲基烷硅基、苯基、萘基、二苯并呋喃基、二苯并噻吩基、咔唑基所组成的组；所述W 1的取代基数目多于1个时，各个取代基相同或不同。
  5. 根据权利要求1所述的有机电致发光材料，其中，R 1和R 3相同或不同，分别独立地选自单键、取代或未取代的亚苯基、取代或未取代的亚联苯基、取代或未取代的亚三联苯基、取代或未取代的亚
    Figure PCTCN2020090876-appb-100006
    基、取代或未取代的亚菲基、取代或未取代的亚萘基、取代或未取代的亚甘菊环基、取代或未取代的亚茚基、取代或未取代的亚吡啶基、取代或未取代的亚嘧啶基、取代或未取代的亚三嗪基、取代或未取代的亚咪唑基。
  6. 根据权利要求1所述的有机电致发光材料，其中，R 1和R 3相同或不同，分别独立地选自取代或未取代的亚苯基、取代或未取代的亚联苯基、取代或未取代的亚三联苯基、取代或未取代的亚蒽基、取代或未取代的亚菲基、取代或未取代的亚萘基、取代或未取代的9,9-二甲基芴亚基、取代或未取代的亚二苯并呋喃基、取代或未取代的亚二苯并噻吩基、取代或未取代的亚咔唑基，或所述亚基中两者或三者通过单键连接所形成的亚基基团；
    所述取代是指独立地被选自以下基团的取代基所取代：氘、氰基、氟、氯、甲基、乙基、丙基、叔丁基、苯基、萘基、咔唑基、二苯并呋喃基、二苯并噻吩基；
    当取代基有多个时，各取代基相同或不同。
  7. 根据权利要求1所述的有机电致发光材料，其中，R 2、R 4和R 5彼此相同或不同，各自独立地选自化学式i-1至化学式i-11所示的基团所组成的组：
    Figure PCTCN2020090876-appb-100007
    其中，M 1选自单键或者
    Figure PCTCN2020090876-appb-100008
    D 1选自氢、氘、氟、氯、溴、氰基、碳原子数为3～12的三烷基硅基、碳原子数为1～10的烷基、碳原子数为1～10的卤代烷基、碳原子数为3～10的环烷基、碳原子数为1～10的烷氧基、碳原子数为1～10的烷硫基；
    D 2～D 9、D 21各自独立地选自：氢、氘、氟、氯、溴、氰基、碳原子数为3～12的三烷基硅基、碳原子数为1～10的烷基、碳原子数为1～10的卤代烷基、碳原子数为3～10的环烷基、碳原子数为1～10的烷氧基、碳原子数为3～12的杂芳基；
    D 10～D 20各自独立地选自：氢、氘、氟、氯、溴、氰基、碳原子数为3～12的三烷基硅基、碳原子数为1～10的烷基、碳原子数为1～10的卤代烷基、碳原子数为3～10的环烷基、碳原子数为1～10的烷氧基、碳原子数为6～15的芳基、碳原子数为3～12的杂芳基；
    d 1～d 21以d k表示，D 1～D 21以D k表示，k为变量，表示1～21的任意整数，d k表示取代基D k的个数；其中，当k选自5或者17时，d k选自1、2或者3；当k选自2、7、8、12、15、16、18或者21时，d k选自1、2、3或者4；当k选自1、3、4、6、9或者14时，d k选自1、2、3、4或者5；当k为13 时，d k选自1、2、3、4、5或者6；当k选自10或者19时，d k选自1、2、3、4、5、6或者7；当k为20时，d k选自1、2、3、4、5、6、7或者8；当k为11时，d k选自1、2、3、4、5、6、7、8或9；且当d k大于1时，任意两个D k相同或者不相同；
    K 1独立地选自O、S、N(D 22)、C(D 23D 24)、Si(D 25D 26)；其中，各D 22、D 23、D 24、D 25、D 26分别独立地选自：碳原子数为6～15的芳基、碳原子数为3～12的杂芳基、碳原子数为1～10的烷基或碳原子数为3～10的环烷基；
    K 2选自单键、O、S、N(D 27)、C(D 28D 29)、Si(D 30D 31)；其中，各D 27、D 28、D 29、D 30、D 31分别独立地选自：碳原子数为6～15的芳基、碳原子数为3～12的杂芳基、碳原子数为1～10的烷基或碳原子数为3～10的环烷基。
  8. 根据权利要求1所述的有机电致发光材料，其中，R 2、R 4和R 5彼此相同或不同，且分别独立地选自取代或未取代的基团Y 1，所述未取代的基团Y 1选自如下基团：
    Figure PCTCN2020090876-appb-100009
    Figure PCTCN2020090876-appb-100010
    所述Y 1基团被一个或多个取代基所取代时，Y 1的取代基各自独立地选自由氘、氟、氯、氰基、甲基、乙基、丙基、异丙基、叔丁基、三甲基硅基、苯基、萘基、二苯并噻吩基、二苯并呋喃基所组成的组；所述Y 1的取代基多于1个时，各个取代基相同或不同。
  9. 根据权利要求1所述的有机电致发光材料，其中，R 2、R 4和R 5相同或不同，分别独立地选自取代或未取代的苯基、取代或未取代的联苯基、取代或未取代的三联苯基、取代或未取代的蒽基、取代或未取代的菲基、取代或未取代的萘基、取代或未取代的9,9-二甲基芴基、取代或未取代的二苯并呋喃基、取代或未取代的二苯并噻吩基、取代或未取代的咔唑基，或为所述基团中两者或三者通过单键连接所形成的基团；
    所述取代是指独立地被选自以下基团的取代基所取代：氘、氰基、氟、氯、甲基、乙基、丙基、叔丁基、苯基、萘基、咔唑基、二苯并呋喃基、二苯并噻吩基；
    当取代基有多个时，各取代基相同或不同。
  10. 根据权利要求1所述的有机电致发光材料，其中，所述R 1、R 2、R 3、R 4和R 5的取代基相同或不同，分别独立地选自氘、氟、氯、氰基、碳原子数为1～4的烷基、碳原子数为5～10的环烷基、碳原子数为1～4的烷氧基、碳原子数为3～9的三烷基硅基、碳原子数为6～15的芳基、碳原子数为3～12的杂芳基、三苯基甲硅烷基。
  11. 根据权利要求1所述的有机电致发光材料，其中，所述R 1、R 2、R 3、R 4和R 5的取代基相同或不同，分别独立地选自氘、氟、氯、溴、氰基、甲基、乙基、丙基、异丙基、叔丁基、环戊基、甲氧基、乙氧基、三甲基硅烷基、苯基、吡啶基、9,9-二甲基芴基、二苯并呋喃基、二苯并噻吩基、吡啶基、嘧啶基、三嗪基、三苯基甲硅烷基。
  12. 根据权利要求1所述的有机电致发光材料，选自如下化合物：
    Figure PCTCN2020090876-appb-100011
    Figure PCTCN2020090876-appb-100012
    Figure PCTCN2020090876-appb-100013
    Figure PCTCN2020090876-appb-100014
    Figure PCTCN2020090876-appb-100015
    Figure PCTCN2020090876-appb-100016
    Figure PCTCN2020090876-appb-100017
    Figure PCTCN2020090876-appb-100018
  13. 一种有机电致发光器件，其特征在于，包括阴极、阳极以及设置在所述阴极和阳极之间的一层以上的有机层，所述有机层至少有一层包含权利要求1～12所述的电致发光材料。
  14. 根据权利要求13所述的有机电致发光器件，其特征在于，所述有机层包括空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层以及电子注入层。
  15. 根据权利要求14所述的有机电致发光器件，其特征在于，所述空穴传输层包含权利要求1～12所述的电致发光材料，或者所述电子阻挡层包含权利要求1～12所述的电致发光材料。
  16. 权利要求1～12任一项所述的有机电致发光材料在有机电致发光器件中的应用。
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