WO2017020831A1 - Compound and organic light-emitting device - Google Patents

Compound and organic light-emitting device Download PDF

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Publication number
WO2017020831A1
WO2017020831A1 PCT/CN2016/093026 CN2016093026W WO2017020831A1 WO 2017020831 A1 WO2017020831 A1 WO 2017020831A1 CN 2016093026 W CN2016093026 W CN 2016093026W WO 2017020831 A1 WO2017020831 A1 WO 2017020831A1
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Prior art keywords
compound
substituted
group
unsubstituted
synthesis
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PCT/CN2016/093026
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French (fr)
Chinese (zh)
Inventor
范洪涛
张向慧
邵爽
任雪艳
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北京鼎材科技有限公司
固安鼎材科技有限公司
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Priority claimed from CN201510472703.9A external-priority patent/CN106432242B/en
Priority claimed from CN201510472766.4A external-priority patent/CN106433614B/en
Application filed by 北京鼎材科技有限公司, 固安鼎材科技有限公司 filed Critical 北京鼎材科技有限公司
Priority to KR1020177034684A priority Critical patent/KR102592175B1/en
Priority to JP2017568412A priority patent/JP6765389B2/en
Publication of WO2017020831A1 publication Critical patent/WO2017020831A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom

Definitions

  • the present invention relates to a novel compound, and to an organic electroluminescent device using the same.
  • the organic materials in the field of OLED mainly include: a hole injecting material, a hole transporting material, a hole blocking material, an electron injecting material, an electron transporting material, an electron blocking material, and a light emitting host material and a light emitting guest (dye).
  • the hole injecting material used in the organic electroluminescent device is generally a derivative having a triarylamine structure (Exit Patent: Publication No. CN1152607C; Baotu Valley Patent: EP0650955A1 and Chemipro Patent: JPH09301934, etc.), as shown in the following figure.
  • the molecular structure of the material generally has a structure such as triarylamine, carbazole or thiophene.
  • a material containing a thiophene group is protected in a light-emitting patent (publication number CN 101506191A, publication date 2009.8.12); and a light-emitting patent (publication number CN102334210A, application date 2012.1.25; publication number: WO 2010/114017 A1, publication date 2010.10) Hole transport materials with carbazole and dibenzofuran structures are protected in .7)), and some representative compounds are shown below:
  • the present invention provides a novel class of compounds for use in an organic electroluminescent device.
  • the compound achieves good host material properties as well as hole injection and transport properties by introducing a novel benzocyclooctenetetrakenylene structure.
  • the compound of the present invention is represented by the following formula (I).
  • Ar is preferably hydrogen, C 6 -C 30 arylamino or heteroarylamino, substituted or unsubstituted C 6 -C 30 aryl, substituted or unsubstituted C 2 -C 30 heteroaryl;
  • R 1 to R 12 are each independently preferably hydrogen, halogen, substituted or unsubstituted C 1 -C 30 alkyl, substituted or unsubstituted C 2 -C 30 alkenyl, substituted or unsubstituted C 2 -C 30 alkyne a substituted or unsubstituted C 3 -C 30 cycloalkyl group, a substituted or unsubstituted C 2 -C 30 heterocycloalkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, substituted or unsubstituted C 2 to C 30 heteroaryl; or R 1 to R 4 and/or R 5 to R 8 may form a ring, respectively.
  • the compound of the present invention can be used as a hole injecting material, can efficiently inject holes from an ITO anode into an organic material, and can also be used as a hole transporting material, and can better have a HOMO level with a host material of a light emitting layer. Matching, which can effectively reduce the operating voltage of the device and improve the luminous efficiency of the device.
  • the compound of the present invention can also be used as a host material of the light-emitting layer, which has relatively uniform electron and hole transport properties, and has an energy level matching the materials of adjacent electron and hole transport layers, and can be sufficient. The energy transfer to the luminescent material achieves high luminous efficiency, thereby reducing device illumination and operating voltage, improving device efficiency, and prolonging device lifetime, and has very important practical significance in the manufacture of organic electroluminescent devices.
  • the expression of Ca- Cb means that the group has a carbon number a to b, and unless otherwise specified, the number of carbon atoms generally does not include the number of carbon atoms of the substituent.
  • the expression of a chemical element includes the concept of a chemically identical isotope, such as the expression "hydrogen”, and also includes the concepts of " ⁇ " and " ⁇ " having the same chemical properties.
  • the compound of the present invention has a structure represented by the following formula (I).
  • Ar may be hydrogen, a C 6 -C 30 arylamino or heteroarylamino group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted C 2 -C 30 heteroaryl group;
  • R 1 to R 12 are each independently hydrogen, halogen, substituted or unsubstituted C 1 -C 30 alkyl, substituted or unsubstituted C 2 -C 30 alkenyl, substituted or unsubstituted C 2 -C 30 alkyne a substituted or unsubstituted C 3 -C 30 cycloalkyl group, a substituted or unsubstituted C 2 -C 30 heterocycloalkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, substituted or unsubstituted C 2 to C 30 heteroaryl;
  • the groups R 1 to R 4 and/or R 5 to R 8 may be bonded to each other to form a cyclic structure, and such a ring structure may be an aliphatic monocyclic or polycyclic, aromatic monocyclic or fused ring. These rings can contain heteroatoms.
  • a ring structure may be an aliphatic monocyclic or polycyclic, aromatic monocyclic or fused ring.
  • These rings can contain heteroatoms.
  • any two adjacent groups of R 1 to R 4 or R 5 to R 8 are bonded to form an aliphatic five-membered ring or a six-membered ring, and the constituent atoms of these rings are in addition to carbon.
  • the atom may be a hetero atom in addition to the atom, and these rings may have a substituent, and the carbon atom constituting the ring may also form a ketone group.
  • the ring include a cyclopentane ring, a cyclohexane ring, a dicyclopentene ring, a tetrahydropyrrole ring, a tetrahydrofuran ring, a piperidine ring, and a carbon in a cyclopentane ring and a cyclohexane ring.
  • An ester ring obtained by substituting an atom with a ketone group or the like.
  • the aromatic monocyclic or fused ring is preferably a C 6 to C 30 monocyclic or fused ring, and examples thereof include a benzene ring and a naphthalene ring; and as a monocyclic or polycyclic ring containing a hetero atom, it is preferably Pyrrole ring, pyridine ring, anthracene ring, N-phenyl substituted anthracene ring.
  • the above aliphatic ring and the aromatic ring and the heteroaryl ring may be combined into a polycyclic ring such as a benzopyrrole ring, a benzofuran ring, a benzothiophene ring, an anthracene ring or the like.
  • the substituted or unsubstituted C 1 -C 30 alkyl group is preferably a C 1 -C 10 alkyl group, more preferably a C 1 -C 6 alkyl group, and examples thereof include a methyl group, an ethyl group, and a n-propyl group. , isopropyl, n-butyl, n-hexyl, n-octyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl and the like.
  • the C 2 -C 30 alkenyl group which is substituted or unsubstituted is preferably a C 2 -C 10 alkenyl group, and examples thereof include a vinyl group, a propenyl group, a propenyl group, a butenyl group, and a pentenyl group. Hexenyl, heptenyl, octenyl, cyclohexenyl and the like.
  • the substituted or unsubstituted C 2 -C 30 alkynyl group is preferably a C 2 -C 10 alkynyl group, and examples thereof include an ethynyl group, a 1-propynyl group, a butynyl group, and a pentynyl group. Hexynyl, heptynyl, octynyl, cyclohexylethynyl and the like.
  • the C 3 -C 30 cycloalkyl group which is substituted or unsubstituted is preferably a C 3 -C 10 cycloalkyl group, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
  • the above substituted or unsubstituted C 2 -C 30 heterocycloalkyl group is preferably a heterocycloalkyl group having 3 to 10 ring skeleton atoms and containing at least one selected from the group consisting of O, S and N, as a preferred example Examples thereof include tetrahydrofuran, pyrrolidine, and tetrahydrothiophene.
  • the above substituted or unsubstituted C 6 -C 30 aryl group preferably has 6 to 20 skeleton carbon atoms, and preferably the aryl group is a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracenyl group, and a phenanthrene group.
  • Base sulfhydryl, fluorenyl and its derivatives, fluoranthene, triphenylene, fluorenyl, fluorenyl, a group in the group consisting of a base and a tetraphenyl group.
  • the biphenyl group is selected from the group consisting of 2-biphenyl, 3-biphenyl and 4-biphenyl
  • the terphenyl includes p-terphenyl-4-yl, p-terphenyl-3- , p-terphenylphenyl-2-yl, m-terphenyl-4-yl, m-triphenyl-3-yl and m-terphenyl-2-yl
  • the naphthyl is 1-naphthalene a group in the group consisting of a 2-naphthyl group
  • the thiol group being selected from the group consisting of a 1-fluorenyl group, a 2-fluorenyl group, and a 9-fluorenyl group
  • the mercapto derivative is selected from 9,9'-
  • the substituted or unsubstituted C 2 -C 30 heteroaryl group it preferably has 5 to 20 skeleton carbon atoms, and preferably the heteroaryl group is a furyl group, a thienyl group, a pyrrolyl group, a benzofuranyl group, a benzothienyl group.
  • the substance is preferably 9-phenylcarbazole, 9-naphthylcarbazole benzoxazole, dibenzoxazole, or indolocarbazole.
  • Examples of the arylamino or heteroarylamino group of C 6 to C 30 include a di(hetero)arylamino group and a tri(hetero)arylamino group, and the expression pattern of the "(hetero)aryl group herein includes an aryl group.
  • heteroaryl group as a specific example, may be selected from the group consisting of diphenylamino, phenylnaphthylamino, 4-triphenylamino, 3-triphenylamino, 4-[N-phenyl-N-(diphenyl) a group in the group consisting of furan-3-yl)]phenylamino and 4-[N-phenyl-N-(dibenzothiophen-3-yl)]phenylamino.
  • the compound has the structure of the following formula (II).
  • Ar 1 and Ar 2 are the same or different and are each independently a C 1 -C 10 alkyl group, a C 6 -C 30 arylamino group or a heteroarylamino group, a substituted or unsubstituted C 6 -C 30 aryl group; , substituted or unsubstituted C 2 -C 30 heteroaryl;
  • R 1 to R 12 are the same or different and are each independently preferably hydrogen, halogen, substituted or unsubstituted C 1 -C 30 alkyl, substituted or unsubstituted C 2 -C 30 alkenyl, substituted or unsubstituted C 2 -C 30 alkynyl, substituted or unsubstituted C 3 -C 30 cycloalkyl, substituted or unsubstituted C 2 -C 30 heterocycloalkyl, substituted or unsubstituted C 6 -C 30 aryl, a substituted or unsubstituted C 2 -C 30 heteroaryl group, a C 6 -C 30 arylamino group or a heteroarylamino group; or, adjacent groups of R 1 to R 4 may be bonded to each other to form a cyclic structure, Such a ring structure may be an aliphatic monocyclic or polycyclic, aromatic monocyclic or fused ring, and these rings may contain
  • the constituent atoms of these rings may be hetero atoms in addition to carbon atoms, and these rings may have a substituent, and the carbon atoms constituting the ring may also be A ketone group is formed.
  • the ring include a cyclopentane ring, a cyclohexane ring, a dicyclopentene ring, a tetrahydropyrrole ring, a tetrahydrofuran ring, a piperidine ring, and a carbon in a cyclopentane ring and a cyclohexane ring.
  • An ester ring obtained by substituting an atom with a ketone group or the like.
  • the aromatic monocyclic or fused ring is preferably a C 6 to C 30 monocyclic or fused ring, and examples thereof include a benzene ring and a naphthalene ring; and as a monocyclic or polycyclic ring containing a hetero atom, it is preferably Pyrrole ring, pyridine ring, anthracene ring, N-phenyl substituted anthracene ring.
  • R 5 to R 8 or an adjacent group of R 9 to R 12 may be bonded to each other to form a cyclic structure, and examples of such a ring structure and a ring structure formed by the adjacent groups of R 1 to R 4 described above The examples are the same and the preferred examples are the same.
  • Ar 1 and Ar 2 may each independently be a substituted or unsubstituted C 6 -C 30 aryl group, and preferably, Ar 1 and Ar 2 are each independently a substituted or unsubstituted C 6 -C 20 More preferably, the aryl group is selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, anthracenyl, fluorenyl and its derivatives, fluoranthenyl, triphenylene, ⁇ , ⁇ , a group in the group consisting of a base and a tetraphenyl group.
  • the biphenyl group is selected from the group consisting of 2-biphenyl, 3-biphenyl and 4-biphenyl
  • the terphenyl includes p-terphenyl-4-yl, p-terphenyl-3 -yl, p-terphenylene-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl
  • the naphthyl group is 1- a group consisting of a naphthyl group and a 2-naphthyl group
  • the fluorenyl group being a group selected from the group consisting of a 1-fluorenyl group, a 2-fluorenyl group, and a 9-fluorenyl group
  • the mercapto derivative is selected
  • Ar 1 and Ar 2 may be a substituted or unsubstituted C 3 -C 30 heteroaryl group, and the hetero atom in the heteroaryl group is preferably one or more selected from the group consisting of O, S and N.
  • the atom, as the heteroaryl group is preferably a substituted or unsubstituted C 5 -C 20 heteroaryl group, and preferred examples of the heteroaryl group herein include a furanyl group, a thienyl group, a pyrrolyl group, and a benzene group.
  • carbazolyl derivative may include, but is not limited to, 9-phenyloxazole, 9-naphthylcarbazole benzoxazole, dibenzoxazole, and anthracene. At least one of carbazoles.
  • Ar 1 and Ar 2 may be a C 6 -C 30 arylamino group or a heteroarylamino group, and specific examples thereof include a di(hetero)arylamino group and a tri(hetero)arylamino group.
  • (hetero)aryl includes both an aryl group and a heteroaryl group, and more specific examples thereof include a diphenylamino group, a phenylnaphthylamino group, a 4-triphenylamino group, and 3- Triphenylamino, 4-[N-phenyl-N-(dibenzofuran-3-yl)]phenylamino, 4-[N-phenyl-N-(dibenzothiophen-3-yl)] a group in the group consisting of phenylamino groups.
  • the compound has the following general formula (III):
  • Ar 3 and Ar 4 are the same or different and are each independently a C 1 -C 10 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted C 2 -C 30 heteroaryl group, An arylamino or heteroarylamino group of C 6 to C 30 ;
  • R 13 to R 24 are the same or different and are each independently preferably hydrogen, halogen, substituted or unsubstituted C 1 -C 30 alkyl, substituted or unsubstituted C 2 -C 30 alkenyl, substituted or unsubstituted C 2 -C 30 alkynyl, substituted or unsubstituted C 3 -C 30 cycloalkyl, substituted or unsubstituted C 2 -C 30 heterocycloalkyl, substituted or unsubstituted C 6 -C 30 aryl, a substituted or unsubstituted C 2 -C 30 heteroaryl group, a C 6 -C 30 arylamino group or a heteroarylamino group; or, adjacent groups of R 13 to R 16 may be bonded to each other to form a cyclic structure, Examples of such a ring structure are the same as those of the ring structure formed by the adjacent groups in the above R 1 to R 4 , and preferred examples
  • Ar 3 and Ar 4 may each independently be a substituted or unsubstituted C 6 -C 30 aryl group, and preferably, Ar 3 and Ar 4 are each independently preferably a substituted or unsubstituted C 6 -C. 20 aryl, substituted or unsubstituted C 3 -C 30 heteroaryl, C 6 -C 30 arylamino or heteroarylamino, as aryl, heteroaryl, arylamino or heteroaryl herein
  • Specific examples and preferred examples of the amino group are the same as those in the above-mentioned structural formula II for the representative examples and preferred examples.
  • the compound of the present invention has a nucleus of a benzocyclooctadecenedioxan structure, and as a representative example, a triplet energy level of a compound of a dibenzocyclooctylenetetrakenylene structure in which Ar is a phenyl group is determined.
  • the germanium structure itself has strong hole injecting ability. Based on such specific electron cloud density and distribution, the present invention is particularly suitable for the light emitting layer host material of the organic electroluminescent element, Hole injection material, and hole transport material.
  • the HOMO and LUMO energy levels of the compounds of the present invention can be adjusted by specific substituent modification, and the conjugated system of cyclooctatetraene can effectively associate various groups to achieve efficient hole injection and hole transport.
  • Performance while ensuring a high triplet energy level, can provide a series of efficient hole injection and transport materials; on the other hand by using electron withdrawing groups, preferably pyridyl, triazine, quinazoline, quinoline
  • the modification of a group such as a oxazolyl group can make the material molecule have both electron and hole transport properties, and by adjusting the number of various groups and the position of the substituent, a high-performance luminescent layer host material can be obtained.
  • Some of the preferred compounds can even exhibit an energy difference of AE ST close to 0, which can significantly reduce the operating voltage of the phosphorescent OLED device using the compound of the present invention as a host material and achieve a long working life.
  • the most important difference between the compounds of the formula (II) and (III) of the compound of the present invention is that the symmetry relationship is different.
  • the symmetrical relationship will have a significant impact on the arrangement of the electron cloud and the crystal growth during film formation.
  • the inventors have intensively studied and found that by adjusting the symmetry relationship and selecting an appropriate substituent, the triplet level and the hole injection transport ability of the compound of the present invention can be finely adjusted, and the electrical properties can be further optimized as needed. And summarized the following rules.
  • Ar 1 to Ar 4 and R 1 to R 24 are a hydrogen atom or a neutral (here, neutral means that the electron-withdrawing property and the pull-electron property are not
  • the compound of the aryl group which is the same as the above), as a neutral aryl group, may, for example, be a phenyl group, a tolyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a triphenylene group, a fluoranthene group, a fluorenyl group or a fluorenyl group.
  • Base, ⁇ and ⁇ base examples of the specific compound include the following compounds A-1 to A-24, but are not limited thereto.
  • the substituent is a neutral group
  • the original parent biguanide is not significantly changed.
  • the electron cloud density and distribution of the cyclooctyltetraenyl group can be used to change the molecular weight of the molecule and adjust the molecular packing mode by changing the substituent, which can be based on the process conditions of vapor deposition film formation in the process of preparing the device.
  • Different types of equipment can adjust the physical and chemical properties of the film-forming molecules, and the degree of freedom of the process is greatly improved. It is also possible to obtain a better vapor-deposited film by adjusting the symmetry and crystallinity of the molecules, thereby improving the luminous efficiency of the organic electroluminescent device. , reduce the drive voltage.
  • a compound of the following formulas II and III in which Ar 1 to Ar 4 and R 1 to R 24 are a hydrogen atom or an electron-donating heteroaryl group is further preferable, and such a heteroaryl group and a parent are Nuclear interactions can fine tune the HOMO energy levels of the compounds of the invention.
  • the HOMO level is 5.4 eV or more as the material of the hole transport layer, the HOMO and the energy level of the host material of the light-emitting layer can be better matched. Thereby improving luminous efficiency.
  • Ar 1 to Ar 4 and R 1 to R 24 can form a compound having a HOMO level of about 5.4 to 5.7, which is very advantageous as a The hole transport material is used.
  • the heteroaryl group having an electron donating property include a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, an indolocarbazolyl group, a benzofurancarbazolyl group, and a benzothienocarbazolyl group. Wait.
  • Specific examples of the compound include the following compounds B-1 to B-30, but are not limited thereto.
  • a compound in which Ar 1 to Ar 4 and R 1 to R 24 are a hydrogen atom or an arylamino group in the formulae II and III, and an arylamino group and a benzocyclooctenetetraene are further preferably used.
  • the two-mother core interaction can significantly improve the electron donating ability of the compound, so that the molecule has a shallow HOMO level and has a strong hole injecting ability.
  • Such a compound is particularly suitable as a material for the hole injecting layer.
  • Specific examples of the diarylamino group include a diphenylamino group and a phenylnaphthylamino group.
  • Ar 1 to Ar 4 and R 1 to R 24 may be a triarylamino group, and specific examples thereof include a 4-triphenylamino group, a 3-triphenylamino group, and a 4-[N-benzene group.
  • the following compounds C-1 to C-15 are preferable, but are not limited thereto.
  • a compound of the following formulas II and III in which Ar 1 to Ar 4 and R 1 to R 24 are hydrogen or a group having an electron withdrawing property is further preferable.
  • a group having a strong electron-trapping ability is attached to a bisindole-cyclooctanetetraene matrix, in addition to maintaining the original hole injection and transport properties, electron injection and transport properties are added to make the molecule At the same time, it has bipolar transmission performance.
  • Such compounds have excellent electron and hole transport properties.
  • As a host material especially for the host material of phosphorescent light-emitting devices, the efficiency of high-brightness is avoided by balanced carrier transport performance.
  • the electron withdrawing group examples include a pyridyl group, a phenylpyridyl group, a quinolyl group, a substituted quinolyl group, a quinazolinyl group, a substituted quinazolinyl group, a quinoxalinyl group, a substituted quinoxaline group, and a pyrimidinyl group.
  • a pyrimidinyl, phenanthroline, triazinyl, substituted triazinyl, benzimidazolyl, oxazolyl and the like Specific examples of such a preferred compound include the following compounds D-1 to D-39, but are not limited thereto.
  • the present invention also provides an organic electroluminescent device using the novel compound of the present invention described above.
  • the organic electroluminescent device structure of the present invention is not different from the known device, and generally includes a first electrode, a second electrode, and one or more organic layers interposed between the first electrode and the second electrode, the characteristics of which are characterized
  • the organic layer comprises the above organic electroluminescent compound.
  • an organic layer such as an electron injecting layer, an electron transporting layer, a light emitting layer, a hole transporting layer, or a hole injecting layer is usually used.
  • the compounds of the present invention can be used, but are not limited to, hole injection materials/hole transport materials and/or luminescent host materials.
  • an organic electroluminescent device using the compounds A-1 to A-24, D-1 to D-39 as a host material of a light-emitting layer, and a compound B-1 to B-30 are organic electroluminescence devices used as a material for a hole transport layer, and organic electroluminescence devices using the above compounds C-1 to C-15 as materials for a hole injection layer.
  • the organic electroluminescent device of the present invention can reduce device brightening and operating voltage, improve device efficiency, and extend device lifetime based on the excellent properties of the compound of the present invention.
  • the preparation method of the representative compound of the present invention is described with reference to the following examples. Since the compounds of the present invention have the same skeleton, based on these preparation methods, those skilled in the art can easily synthesize other compounds of the present invention by a known functional group conversion method. Hereinafter, a method of preparing a light-emitting device comprising the compound and a measurement of luminescent properties are also provided.
  • Various chemicals used in the present invention such as petroleum ether, ethyl acetate, n-hexane, toluene, tetrahydrofuran, dichloromethane, carbon tetrachloride, acetone, 1,2-bis(bromomethyl)benzene, CuI, ortho Phthaloyl chloride, phenylhydrazine hydrochloride, Trifluoroacetic acid, acetic acid, trans-diaminocyclohexane, iodobenzene, cesium carbonate, potassium phosphate, ethylenediamine, benzophenone, cyclopentanone, 9-fluorenone, sodium t-butoxide, methanesulfonic acid , 1-bromo-2-methylnaphthalene, o-dibromobenzene, butyllithium, dibromoethane, o-dibromobenzene, benzoyl peroxide, 1-(2-
  • Analytical detection of the intermediates and compounds in the present invention was performed using an ABSCIEX mass spectrometer (4000QTRAP) and a Bruker nuclear magnetic resonance instrument (400M).
  • Compound A-20 was prepared in the same manner as in Example 29 except that 4-diphenylboronic acid was replaced with an equivalent of 9,9-dimethylindole-2-boronic acid, and after completion of the reaction, 6.24 g of a white solid was obtained. The yield was 68%.
  • Compound A-23 was prepared in the same manner as in Example 23 except that 4-diphenylboronic acid was replaced with an equivalent amount of 6,6,12,12-tetramethyl-6,12-dihydroindole[1, 2-b]indole-2-boronic acid. After completion of the reaction, 6.68 g of a pale yellow solid was obtained.
  • Compound B-4 was prepared in the same manner as in Example 11 except that bromobenzene was replaced by an equivalent of 9-(4-bromophenyl)-9H-carbazole. After completion of the reaction, 6.5 g of a pale yellow solid was obtained. It is 76%.
  • Compound B-5 was prepared in the same manner as in Example 11 except that bromobenzene was replaced by an equivalent of 9-(3-bromophenyl)-9H-carbazole. After completion of the reaction, 6.7 g of a pale yellow solid was obtained. It is 78%.
  • Compound B-6 was prepared in the same manner as in Example 11 except that bromobenzene was replaced with an equivalent of 3-bromo-phenyloxazole, and after completion of the reaction, 6.06 g of a pale yellow solid was obtained, yield 70%. .
  • Compound B-10 was prepared in the same manner as in Example 23 except that the intermediate M2 was replaced with an equivalent of the intermediate M3, and the phenylboronic acid was replaced with an equivalent (4-(9H-carbazol-9-y1) Phenyl)boronic acid. After completion of the reaction, B-10 was obtained as an off-white solid (7.73 g, 76%).
  • Compound B-13 was prepared in the same manner as in Example 25 except that the intermediate M8 was replaced with an equivalent of the intermediate M9, and the 4-biphenylboronic acid was replaced with an equivalent (9-phenyl-9H-carbazol-3). -y1) Boronic acid, after completion of the reaction, B-13 was obtained as a white solid, 6.1 g, yield 78%.
  • Compound B-16 was prepared in the same manner as in Example 49 except that the hydrochloride-9H-carbazole-3-indole was replaced with an equivalent of -9H-carbazole-2-indole hydrochloride.
  • the yellow solid was 29 g, and the yield was 67.1%.
  • Compound B-18 was prepared in the same manner as in Example 51 except that dibenzothiophene-3-boronic acid was replaced with an equivalent amount of dibenzofuran-3-boronic acid. After completion of the reaction, the crude product was separated by column chromatography. A white solid 7.1 g was obtained in a yield of 66%.
  • intermediate compound B-19-2 (10.3 g, 40 mmol), p-bromoiodobenzene (14.2 g, 50 mmol), CuI (1.8 g, 10 mmol), trans-diaminocyclohexane ( A mixture of 4.2 ml, 40 mmol) and cesium carbonate (13 g, 40 mmol) was heated to reflux for 3 hours. Then, the reaction mixture was cooled to room temperature, filtered, and the filter cake was washed with dichloromethane, and the obtained filtrate was subjected to distillation under reduced pressure, and the obtained distillation residue was subjected to column separation to obtain Compound B-19-3 (12.4 g, yield. Rate 75%).
  • intermediate compound B-19-4 45.9 g, 0.1 mol
  • intermediate compound B-19-3 42 g, 0.1 mol
  • CuI 3.3 g, 17.1 mmol
  • cesium carbonate 33.44g, 102.9mmol
  • cyclohexyldiamine 2.3ml, 34.3mmol
  • xylene 500ml
  • Compound B-22 was prepared in the same manner as in Example 11 except that bromobenzene was replaced by an equivalent of 2-bromodibenzo[b,d]thiophene. After completion of the reaction, the crude product was separated by column chromatography to give white solid 4.86 g. The yield was 65%.
  • Compound B-25 was prepared in the same manner as in Example 60 except that the intermediate M13 was replaced with an equivalent of the intermediate M14, and dibenzothiophene-2-boronic acid was replaced with an equivalent of dibenzo[b,d]. After the completion of the reaction, the crude product was purified by column chromatography to afford Compound B-25 as white off solid B-25 (6.4 g, 74%).
  • Compound D-7 was prepared in the same manner as in Example 23 except that the intermediate M2 was replaced with an equivalent of the intermediate M3, and the phenylboronic acid was replaced with an equivalent of the pyridine-2-boronic acid. 5.86 g, yield was 85%.
  • the reaction was carried out at -80 ° C for 1 h, the temperature was raised to room temperature, and the reaction was continued at room temperature for 5 h.
  • the reaction solution was poured into a dilute acid of 100 ml of concentrated hydrochloric acid and 1 L of water, and stirred, and the upper organic phase was separated, and the aqueous phase was 600 ml.
  • the methyl chloride was extracted once. Column chromatography gave 26 g of a white solid in a yield of 90%.
  • OLED device evaluation was performed using the following device structure: ITO/HIL/HTL/EML/ETL/LiF/Al (the above abbreviations correspond to ITO anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer, respectively) /LiF and Al negative, the following abbreviations have the same meaning), the following figure shows the structural formula of the materials used in each functional layer of the device (all materials are purchased from the Belling reagent, purity >99.9%):
  • the glass plate coated with the ITO (150 nm) transparent conductive layer was sonicated in a commercial cleaning agent, rinsed in deionized water, and ultrasonically degreased in an acetone:ethanol mixed solvent (1:1 by volume) in a clean environment. Bake to complete removal of water, wash with UV light and ozone, and bombard the surface with a low energy cation beam from Satella (ULVAC);
  • the above-mentioned glass substrate with an anode was placed in a vacuum chamber, and evacuated to 1 ⁇ 10 -5 to 9 ⁇ 10 -3 Pa, and the compound C-1 was vacuum-deposited on the above anode layer film to form a thickness of 60 nm.
  • Forming an electroluminescent layer on the above hole transport layer specifically: placing CBP [4, 4'-N, N'-dicarbazole-biphenyl] as a main body of the light-emitting layer in a chamber of a vacuum vapor deposition apparatus (piq) 2 Ir(acac)[di-(1-phenylisoquinolinyl)acetylacetonate ruthenium (III)] is placed in another chamber of the vacuum vapor deposition apparatus to be different The rate of evaporation of the two materials simultaneously, (piq) 2 Ir (acac) concentration of 4%, the total thickness of the deposited film is 30nm;
  • the Bphen was vacuum-deposited on the light-emitting layer to form an electron transport layer having a thick film of 20 nm, and the evaporation rate was 0.1 nm/s;
  • LiF LiF was vacuum-deposited on the electron transport layer as an electron injection layer and an Al layer having a thickness of 150 nm as a cathode of the device.
  • the compound of the present invention is used as a hole injecting material
  • An organic electroluminescent device was obtained in the same manner as in Example 1 except that the compound C-1 was replaced with the compound C-3.
  • the compound of the present invention is used as a hole injecting material
  • An organic electroluminescent device was obtained in the same manner as in Example 1 except that the compound C-1 was replaced with the compound C-4.
  • An organic electroluminescent device was obtained in the same manner as in Example 1 except that the compound C-1 was replaced with the compound C-11.
  • the compound of the present invention is used as a hole injecting material
  • An organic electroluminescent device was obtained in the same manner as in Example 1 except that the compound C-1 was replaced with the compound C-12.
  • the compound of the present invention is used as a hole injecting material
  • An organic electroluminescent device was obtained in the same manner as in Example 1 except that the compound C-1 was replaced with the compound C-13.
  • An organic electroluminescent device was obtained in the same manner as in Example 1 except that the compound C-1 was replaced with the compound C-15.
  • the compound of the present invention is used as a hole transporting material
  • An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and NPB was replaced with Compound B-1.
  • the compound of the present invention is used as a hole transporting material
  • An organic electroluminescent device was obtained in the same manner as in Example 1 except that Compound C-1 was replaced with 2-TNATA and NPB was replaced with Compound B-3.
  • An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and NPB was replaced with Compound B-4.
  • An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and NPB was replaced with Compound B-6.
  • An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and NPB was replaced with Compound B-9.
  • An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and NPB was replaced with Compound B-10.
  • An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and NPB was replaced with Compound B-12.
  • An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and NPB was replaced with Compound B-13.
  • An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and NPB was replaced with Compound B-17.
  • An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and NPB was replaced with Compound B-18.
  • An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and NPB was replaced with Compound B-21.
  • An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and NPB was replaced with Compound B-30.
  • the compound of the present invention is used as a red phosphorescent host material
  • An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and CBP was replaced with Compound A-1.
  • the compound of the present invention is used as a red phosphorescent host material
  • An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and CBP was replaced with Compound A-4.
  • An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and CBP was replaced with Compound A-6.
  • An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and CBP was replaced with Compound A-9.
  • An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and CBP was replaced with Compound A-14.
  • An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and CBP was replaced with Compound A-21.
  • An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and CBP was replaced with Compound D-4.
  • An organic electroluminescent device was obtained in the same manner as in Example 1 except that the compound C-1 was replaced with 2-TNATA and the CBP was replaced with the compound D-6.
  • An organic electroluminescent device was obtained in the same manner as in Example 1 except that the compound C-1 was replaced with 2-TNATA and the CBP was replaced with the compound D-10.
  • An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and CBP was replaced with Compound D-25.
  • An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and CBP was replaced with Compound D-27.
  • An organic electroluminescent device was obtained in the same manner as in Example 1 except that Compound C-1 was replaced with 2-TNATA and CBP was replaced with Compound D-33.
  • An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and CBP was replaced with Compound D-37.
  • the compound of the present invention was used as a hole injecting material, a hole transporting material, and a red phosphorescent host material, respectively.
  • An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with C-10, NPB was replaced with Compound B-8, and CBP was replaced with Compound D-25.
  • the compound of the present invention was used as a hole injecting material, a hole transporting material, and a red phosphorescent host material, respectively.
  • An organic electroluminescent device was obtained in the same manner as in Example 1 except that the compound C-1 was replaced with C-13, the NPB was replaced with the compound B-6, and the CBP was replaced with the compound D-37.
  • the compound of the present invention is used as a hole injecting material, a hole transporting material, and a red phosphorescent host material, respectively.
  • An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with C-3, NPB was replaced with Compound B-30, and CBP was replaced with Compound D-4.
  • the compound of the present invention is used as a green phosphorescent host material
  • An organic electroluminescent device was prepared in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, CBP was replaced with Compound D-32, and (piq) 2 Ir(acac) was replaced with Ir(ppy) 3 , the doping concentration was changed to 10%.
  • the compound of the present invention is used as a green phosphorescent host material
  • An organic electroluminescent device was obtained in the same manner as in Example 26 except that the compound D-32 was replaced with D-39.
  • the compounds of the present invention were used as a hole injecting material, a hole transporting material, and a green phosphorescent host material, respectively.
  • An organic electroluminescent device was prepared in the same manner as in Example 1, except that Compound C-1 was replaced with C-3, NPB was replaced with Compound B-8, and CBP was replaced with Compound D-32. Piq) 2 Ir(acac) was replaced by Ir(ppy) 3 and the doping concentration was changed to 10%.
  • the compounds of the present invention were used as a hole injecting material, a hole transporting material, and a green phosphorescent host material, respectively.
  • An organic electroluminescent device was prepared in the same manner as in Example 1, except that Compound C-1 was replaced with C-11, NPB was replaced with Compound B-30, and CBP was replaced with Compound D-39. Piq) 2 Ir(acac) was replaced by Ir(ppy) 3 and the doping concentration was changed to 10%.
  • An organic electroluminescent device was obtained in the same manner as in Example 1 except that the compound C-1 was replaced with 2-TNATA.
  • An organic electroluminescent device was prepared in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, (piq) 2 Ir(acac) was replaced with Ir(ppy) 3 , and doping concentration was used. Change to 10%.
  • the red light device was used to measure the driving voltages of the organic electroluminescent devices prepared in the device examples 1-25 and the comparative example 1 using a Keithley 2602 digital source meter luminance meter (Beijing Normal University Optoelectronic Instrument Factory) at a luminance of 1000 cd/m 2 . And current efficiency, the results are shown in Table 1.
  • the driving voltage of the organic electroluminescent device prepared in the device examples 26-27 and the comparative example 2 was measured using a Keithley 2602 digital source meter luminance meter (Beijing Normal University Optoelectronic Instrument Factory) at a luminance of 2000 cd/m 2 . And current efficiency, the results are shown in Table 1.
  • the C series compound of the present invention replaces the 2-TNATA in the comparative device example 1 as a hole injection. material.
  • the preferred arylamine substituents of the C series compounds enhance the HOMO energy level of the mother nucleus and improve the single carrier performance; the device performance achieves lower driving voltage and higher current efficiency, and improves the luminous efficiency of the light emitting device. It shows that the material of the present invention has more efficient hole injectability.
  • the B series compound of the present invention replaced the NPB in Comparative Device Example 1 as a hole transporting material.
  • the B series compounds are preferably a substituent such as a carbazolyl group, a dibenzofuranyl group or a dibenzothiophenyl group, which slightly raises the HOMO level of the mother core to match the host level, and a relatively higher triplet level. It can simultaneously act as an exciton blocking layer, improve the injection transport performance of single carriers, and has strong hole transport capability, achieving higher current efficiency and lower driving voltage in the same device. Under the structure, the luminous efficiency of the light emitting device is improved.
  • the A and D series compounds of the present invention replaced the CBP in the comparative device Example 1 as a red light host material.
  • the neutral aryl groups of the A series compounds have less influence on the mother nucleus and have good single carrier performance; their devices have lower voltage and higher current efficiency.
  • the D series compounds preferably have a substituent of a pull-electron property such as a pyridyl group, a phenylpyridyl group or a quinolyl group, and have good double carrier performance and a wide composite region, further reducing the operating voltage of the device and higher current efficiency. Excellent carrier transport balance and energy level matching of the materials of the present invention.
  • the D-32, D-39 compound of the present invention replaces the CBP in the second embodiment of the comparative device as the green light body.
  • the material, the current efficiency is increased from 30cd/A to 40cd/A, which has a very significant improvement effect, and the operating voltage is also greatly reduced.

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Abstract

Provided is an organic light-emitting compound shown in a general formula (I) and use thereof in preparation of an organic light-emitting device. The provided organic light-emitting compound is capable of reducing a working voltage of the organic light-emitting device and increasing a luminous efficiency.

Description

化合物及有机电致发光器件Compounds and organic electroluminescent devices 技术领域Technical field
本发明涉及一种新化合物，还涉及使用了该化合物的有机电致发光器件。The present invention relates to a novel compound, and to an organic electroluminescent device using the same.
背景技术Background technique
随着OLED技术在照明和显示两大领域的不断推进，人们对于其高效有机材料的研究更加关注，一个效率好寿命长的有机电致发光器件通常是器件结构与各种有机材料的优化搭配的结果，而往往材料的作用更加显著，可以说材料是OLED技术的根本。OLED领域中的有机材料主要包括：空穴注入材料、空穴传输材料、空穴阻挡材料、电子注入材料、电子传输材料，电子阻挡材料以及发光主体材料和发光客体(染料)等。With the continuous advancement of OLED technology in the two fields of illumination and display, people pay more attention to the research of high-efficiency organic materials. An efficient and long-lived organic electroluminescent device is usually optimized for device structure and various organic materials. As a result, and often the role of materials is more significant, it can be said that materials are fundamental to OLED technology. The organic materials in the field of OLED mainly include: a hole injecting material, a hole transporting material, a hole blocking material, an electron injecting material, an electron transporting material, an electron blocking material, and a light emitting host material and a light emitting guest (dye).
目前，在有机电致发光器件中使用的空穴注入材料一般是具有三芳胺结构的衍生物(出光专利：公开号CN1152607C；保土谷专利：EP0650955A1和Chemipro专利：JPH09301934等)，如下图所示。At present, the hole injecting material used in the organic electroluminescent device is generally a derivative having a triarylamine structure (Exit Patent: Publication No. CN1152607C; Baotu Valley Patent: EP0650955A1 and Chemipro Patent: JPH09301934, etc.), as shown in the following figure.
Figure PCTCN2016093026-appb-000001
Figure PCTCN2016093026-appb-000001
作为空穴传输材料，材料分子结构中一般会带有三芳胺、咔唑或者噻吩等结构。出光专利(公开号CN 101506191A，公开日2009.8.12)中保护了含有噻吩基团的材料；而出光专利(公开号CN102334210A，申请日2012.1.25；公开号：WO 2010/114017 A1，公开日2010.10.7))中保护了具有咔唑和二苯并呋喃结构的空穴传输材料，一些代表性化合物如下图所示： As the hole transporting material, the molecular structure of the material generally has a structure such as triarylamine, carbazole or thiophene. A material containing a thiophene group is protected in a light-emitting patent (publication number CN 101506191A, publication date 2009.8.12); and a light-emitting patent (publication number CN102334210A, application date 2012.1.25; publication number: WO 2010/114017 A1, publication date 2010.10) Hole transport materials with carbazole and dibenzofuran structures are protected in .7)), and some representative compounds are shown below:
Figure PCTCN2016093026-appb-000002
Figure PCTCN2016093026-appb-000002
目前已知的空穴传输材料和空穴注入材料的性能并不理想，业界仍急需开发新的空穴传输材料和空穴注入材料。The properties of hole transport materials and hole injecting materials which are currently known are not satisfactory, and there is still a great need in the industry to develop new hole transport materials and hole injecting materials.
另外，作为常用的发光主体材料CBP(特开2001-313178号公报)，具有良好的空穴传输性能，而在电子传输性能方面较差，导致载流子传输不均衡。而以TAZ作为主体材料(特开2002-352957号公报)则相反，具有很好地电子传输能力，可是空穴传输能力较差，同样也不能实现均衡的载流子传输。开发良好的发光主体材料也是业界迫切需要解决的问题。In addition, as a conventional light-emitting host material CBP (JP-A-2001-313178), it has good hole transport properties and is inferior in electron transport performance, resulting in unbalanced carrier transport. On the other hand, TAZ is used as the main material (JP-A-2002-352957). On the contrary, it has a good electron transporting ability, but the hole transporting ability is poor, and balanced carrier transport cannot be achieved. The development of a good luminescent body material is also an urgent problem to be solved in the industry.
Figure PCTCN2016093026-appb-000003
Figure PCTCN2016093026-appb-000003
发明内容Summary of the invention
为解决上述问题，本发明提供一类新型用于有机电致发光器件的化合物。该化合物通过引入新颖的苯并环辛四烯并二吲哚结构，实现了良好的主体材料性能以及空穴注入、传输性能。本发明的化合物由如下通式(I)表示。In order to solve the above problems, the present invention provides a novel class of compounds for use in an organic electroluminescent device. The compound achieves good host material properties as well as hole injection and transport properties by introducing a novel benzocyclooctenetetrakenylene structure. The compound of the present invention is represented by the following formula (I).
Figure PCTCN2016093026-appb-000004
Figure PCTCN2016093026-appb-000004
其中，环A为
Figure PCTCN2016093026-appb-000005
环，虚线表示与环辛四烯的拼接位置；Where ring A is
Figure PCTCN2016093026-appb-000005
Ring, dashed line indicates the splicing position with cyclooctatetraene;
Ar优选氢，C6～C30的芳基氨基或杂芳基氨基，取代或未取代的C6～C30芳基，取代或未取代的C2～C30杂芳基；Ar is preferably hydrogen, C 6 -C 30 arylamino or heteroarylamino, substituted or unsubstituted C 6 -C 30 aryl, substituted or unsubstituted C 2 -C 30 heteroaryl;
R1至R12各自独立地优选氢、卤素、取代或未取代的C1～C30烷基，取代或未取代的C2～C30烯基，取代或未取代的C2～C30炔基，取代或未取代的C3～C30环烷基，取代或未取代的C2～C30杂环烷基，取代或未取代的C6～C30芳基，取代或未取代的C2～C30杂芳基；或者，R1～R4和/或R5～R8可分别形成环。R 1 to R 12 are each independently preferably hydrogen, halogen, substituted or unsubstituted C 1 -C 30 alkyl, substituted or unsubstituted C 2 -C 30 alkenyl, substituted or unsubstituted C 2 -C 30 alkyne a substituted or unsubstituted C 3 -C 30 cycloalkyl group, a substituted or unsubstituted C 2 -C 30 heterocycloalkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, substituted or unsubstituted C 2 to C 30 heteroaryl; or R 1 to R 4 and/or R 5 to R 8 may form a ring, respectively.
本发明的化合物，能够用作空穴注入材料，能够有效的从ITO阳极将空穴注入到有机材料中，还能够用作空穴传输材料，能够更好地与发光层主体材料的HOMO能级相匹配，从而能够有效降低器件工作电压且提高器件发光效率。另外，本发明的化合物还能作为发光层的主体材料使用，其具有相对较均衡的电子和空穴传输性能，具有与相邻电子及空穴传输层材料相匹配的能级，能将充分的能量转移给发光材料实现高的发光效率，从而能够降低器件起亮和工作电压，提高器件效率，延长器件寿命，在有机电致发光器件的制造中具有非常重要的实际意义。The compound of the present invention can be used as a hole injecting material, can efficiently inject holes from an ITO anode into an organic material, and can also be used as a hole transporting material, and can better have a HOMO level with a host material of a light emitting layer. Matching, which can effectively reduce the operating voltage of the device and improve the luminous efficiency of the device. In addition, the compound of the present invention can also be used as a host material of the light-emitting layer, which has relatively uniform electron and hole transport properties, and has an energy level matching the materials of adjacent electron and hole transport layers, and can be sufficient. The energy transfer to the luminescent material achieves high luminous efficiency, thereby reducing device illumination and operating voltage, improving device efficiency, and prolonging device lifetime, and has very important practical significance in the manufacture of organic electroluminescent devices.
具体实施方式detailed description
本发明中，Ca-Cb的表达方式代表该基团具有的碳原子数为a～b，除非特殊说明，一般而言该碳原子数不包括取代基的碳原子数。In the present invention, the expression of Ca- Cb means that the group has a carbon number a to b, and unless otherwise specified, the number of carbon atoms generally does not include the number of carbon atoms of the substituent.
本发明中，对于化学元素的表述包含化学性质相同的同位素的概念，例如“氢”的表述，也包括化学性质相同的“氘”、“氚”的概念。In the present invention, the expression of a chemical element includes the concept of a chemically identical isotope, such as the expression "hydrogen", and also includes the concepts of "氘" and "氚" having the same chemical properties.
本发明中的杂原子，通常指选自B、N、O、S、P、P(＝O)、Si和Se中的原子或原子团。The hetero atom in the present invention generally means an atom or an atom group selected from the group consisting of B, N, O, S, P, P(=O), Si, and Se.
本发明的化合物具有如下通式(I)表示的结构，The compound of the present invention has a structure represented by the following formula (I).
Figure PCTCN2016093026-appb-000006
Figure PCTCN2016093026-appb-000006
其中，环A为
Figure PCTCN2016093026-appb-000007
虚线是拼接位置；Where ring A is
Figure PCTCN2016093026-appb-000007
The dotted line is the stitching position;
Ar可以为氢、C6～C30的芳基氨基或杂芳基氨基、取代或未取代的C6～C30的芳基、取代或未取代的C2～C30的杂芳基；Ar may be hydrogen, a C 6 -C 30 arylamino or heteroarylamino group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted C 2 -C 30 heteroaryl group;
R1至R12各自独立地为氢、卤素、取代或未取代的C1～C30烷基，取代或未取代的C2～C30烯基，取代或未取代的C2～C30炔基，取代或未取代的C3～C30环烷基，取代或未取代的C2～C30杂环烷基，取代或未取代的C6～C30芳基，取代或未取代的C2～C30杂芳基；R 1 to R 12 are each independently hydrogen, halogen, substituted or unsubstituted C 1 -C 30 alkyl, substituted or unsubstituted C 2 -C 30 alkenyl, substituted or unsubstituted C 2 -C 30 alkyne a substituted or unsubstituted C 3 -C 30 cycloalkyl group, a substituted or unsubstituted C 2 -C 30 heterocycloalkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, substituted or unsubstituted C 2 to C 30 heteroaryl;
另外，R1～R4和/或R5～R8这些基团之间可以互相连接形成环状结构，这样的环结构可以是脂肪族单环或多环、芳香族的单环或稠环，这些环都可以包含杂原子。作为脂肪族单环的例子，例如，R1～R4或R5～R8中任意相邻的两个基团连接形成脂肪族的五元环、六元环，这些环的构成原子除了碳原子之外还可以是杂原子，这些环可以具有取代基，构成环的碳原子也可以形成酮基。作为这些环的例子，可举出环戊烷环、环己烷环、二环戊烯环、四氢吡咯环、四氢呋喃环、哌啶环、以及环戊烷环和环己烷环中的碳原子被酮基取代得到的酯环等。作为芳香族的单环或稠环，优选为C6～C30的单环或稠环，作为例子可举出苯环、萘环等；作为包含杂原子的单环或多环，优选的是吡咯环、吡啶环、吲哚环、N-苯基取代吲哚环。上述脂肪族环和芳香族环、杂芳环之间可以组合为多环，例如苯并吡咯环、苯并呋喃环、苯并噻吩环、芴环等。Further, the groups R 1 to R 4 and/or R 5 to R 8 may be bonded to each other to form a cyclic structure, and such a ring structure may be an aliphatic monocyclic or polycyclic, aromatic monocyclic or fused ring. These rings can contain heteroatoms. As an example of the aliphatic monocyclic ring, for example, any two adjacent groups of R 1 to R 4 or R 5 to R 8 are bonded to form an aliphatic five-membered ring or a six-membered ring, and the constituent atoms of these rings are in addition to carbon. The atom may be a hetero atom in addition to the atom, and these rings may have a substituent, and the carbon atom constituting the ring may also form a ketone group. Examples of the ring include a cyclopentane ring, a cyclohexane ring, a dicyclopentene ring, a tetrahydropyrrole ring, a tetrahydrofuran ring, a piperidine ring, and a carbon in a cyclopentane ring and a cyclohexane ring. An ester ring obtained by substituting an atom with a ketone group or the like. The aromatic monocyclic or fused ring is preferably a C 6 to C 30 monocyclic or fused ring, and examples thereof include a benzene ring and a naphthalene ring; and as a monocyclic or polycyclic ring containing a hetero atom, it is preferably Pyrrole ring, pyridine ring, anthracene ring, N-phenyl substituted anthracene ring. The above aliphatic ring and the aromatic ring and the heteroaryl ring may be combined into a polycyclic ring such as a benzopyrrole ring, a benzofuran ring, a benzothiophene ring, an anthracene ring or the like.
作为上述取代或未取代的C1～C30烷基，优选C1～C10的烷基，更优选C1～C6的烷基，例如可举出：甲基、乙基、正丙基、异丙基、正丁基、正己基、正辛基、异丁基、叔丁基、环戊基、环己基等。The substituted or unsubstituted C 1 -C 30 alkyl group is preferably a C 1 -C 10 alkyl group, more preferably a C 1 -C 6 alkyl group, and examples thereof include a methyl group, an ethyl group, and a n-propyl group. , isopropyl, n-butyl, n-hexyl, n-octyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl and the like.
作为上述取代或未取代的C2～C30烯基，优选C2～C10的烯基，作为其例子，例如可举出乙烯基，丙烯基，丙烯基，丁烯基，戊烯基，己烯基，庚烯基，辛烯基，环己烯基等。The C 2 -C 30 alkenyl group which is substituted or unsubstituted is preferably a C 2 -C 10 alkenyl group, and examples thereof include a vinyl group, a propenyl group, a propenyl group, a butenyl group, and a pentenyl group. Hexenyl, heptenyl, octenyl, cyclohexenyl and the like.
作为上述取代或未取代的C2～C30炔基，优选C2～C10的炔基，作为其例子，例如可举出乙炔基，1-丙炔基，丁炔基，戊炔基，己炔基，庚炔基，辛炔基，环己基乙炔基等。The substituted or unsubstituted C 2 -C 30 alkynyl group is preferably a C 2 -C 10 alkynyl group, and examples thereof include an ethynyl group, a 1-propynyl group, a butynyl group, and a pentynyl group. Hexynyl, heptynyl, octynyl, cyclohexylethynyl and the like.
作为上述取代或未取代的C3～C30环烷基，优选C3～C10的环烷基、例如可举出环丙基、环丁基、环戊基、环己基等。 The C 3 -C 30 cycloalkyl group which is substituted or unsubstituted is preferably a C 3 -C 10 cycloalkyl group, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
作为上述取代或未取代的C2～C30杂环烷基，优选地为具有3-10个环骨架原子且包含至少一个选自O、S和N中的杂环烷基，作为优选的例子可以举出四氢呋喃、吡咯烷和四氢噻吩等。The above substituted or unsubstituted C 2 -C 30 heterocycloalkyl group is preferably a heterocycloalkyl group having 3 to 10 ring skeleton atoms and containing at least one selected from the group consisting of O, S and N, as a preferred example Examples thereof include tetrahydrofuran, pyrrolidine, and tetrahydrothiophene.
作为上述取代或未取代的C6～C30芳基，优选具有6-20个骨架碳原子，优选所述芳基为由苯基、联苯基、三联苯基、萘基、蒽基、菲基、茚基、芴基及其衍生物、荧蒽基、三亚苯基、芘基、苝基、
Figure PCTCN2016093026-appb-000008
基和并四苯基所组成的组中的基团。所述联苯基为选自由2-联苯基、3-联苯基和4-联苯基，所述三联苯基包括对-三联苯基-4-基、对-三联苯基-3-基、对-三联苯基-2-基、间-三联苯基-4-基、间-三联苯基-3-基和间-三联苯基-2-基；所述萘基为1-萘基和2-萘基所组成的组中的基团；所述蒽基选自由1-蒽基、2-蒽基和9-蒽基所组成的组中的基团；所述芴基选自由1-芴基、2-芴基、3-芴基、4-芴基和9-芴基所组成的组中的基团；所述芴基衍生物选自由9，9’-二甲基芴，9，9’-螺二芴和苯并芴所组成的组中的基团；所述芘基选自由1-芘基、2-芘基和4-芘基所组成的组中的基团；所述并四苯基选自由1-并四苯基、2-并四苯基和9-并四苯基所组成的组中的基团。The above substituted or unsubstituted C 6 -C 30 aryl group preferably has 6 to 20 skeleton carbon atoms, and preferably the aryl group is a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracenyl group, and a phenanthrene group. Base, sulfhydryl, fluorenyl and its derivatives, fluoranthene, triphenylene, fluorenyl, fluorenyl,
Figure PCTCN2016093026-appb-000008
a group in the group consisting of a base and a tetraphenyl group. The biphenyl group is selected from the group consisting of 2-biphenyl, 3-biphenyl and 4-biphenyl, and the terphenyl includes p-terphenyl-4-yl, p-terphenyl-3- , p-terphenylphenyl-2-yl, m-terphenyl-4-yl, m-triphenyl-3-yl and m-terphenyl-2-yl; the naphthyl is 1-naphthalene a group in the group consisting of a 2-naphthyl group; the thiol group being selected from the group consisting of a 1-fluorenyl group, a 2-fluorenyl group, and a 9-fluorenyl group; a group in the group consisting of 1-indenyl, 2-indenyl, 3-indenyl, 4-indenyl and 9-fluorenyl; the mercapto derivative is selected from 9,9'-dimethylindole a group in the group consisting of 9,9'-spirobifluorene and benzopyrene; the thiol group is selected from the group consisting of a 1-mercapto group, a 2-fluorenyl group and a 4-fluorenyl group. The tetracylphenyl group is selected from the group consisting of 1-tetraphenyl, 2-tetraphenyl and 9-tetraphenyl.
作为取代或未取代的C2～C30杂芳基，优选具有5-20个骨架碳原子，优选所述杂芳基为呋喃基、噻吩基、吡咯基、苯并呋喃基、苯并噻吩基、异苯并呋喃基、吲哚基、二苯并呋喃基、二苯并噻吩基、咔唑基及其衍生物或苯并间二氧杂环戊烯基，其中，所述咔唑基衍生物优选为9-苯基咔唑、9-萘基咔唑苯并咔唑、二苯并咔唑、或吲哚并咔唑。As the substituted or unsubstituted C 2 -C 30 heteroaryl group, it preferably has 5 to 20 skeleton carbon atoms, and preferably the heteroaryl group is a furyl group, a thienyl group, a pyrrolyl group, a benzofuranyl group, a benzothienyl group. , isobenzofuranyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, oxazolyl and derivatives thereof or benzodioxolyl, wherein the carbazolyl derivative The substance is preferably 9-phenylcarbazole, 9-naphthylcarbazole benzoxazole, dibenzoxazole, or indolocarbazole.
作为C6～C30的芳基氨基或杂芳基氨基，可举出二(杂)芳基氨基、三(杂)芳基氨基，此处“(杂)芳基”的表达方式包含芳基和杂芳基两者，作为具体例子可举出选自二苯氨基、苯基萘基氨基、4-三苯氨基、3-三苯氨基、4-[N-苯基-N-(二苯并呋喃-3-基)]苯基氨基、4-[N-苯基-N-(二苯并噻吩-3-基)]苯基氨基所组成的组中的基团。 Examples of the arylamino or heteroarylamino group of C 6 to C 30 include a di(hetero)arylamino group and a tri(hetero)arylamino group, and the expression pattern of the "(hetero)aryl group herein includes an aryl group. And a heteroaryl group, as a specific example, may be selected from the group consisting of diphenylamino, phenylnaphthylamino, 4-triphenylamino, 3-triphenylamino, 4-[N-phenyl-N-(diphenyl) a group in the group consisting of furan-3-yl)]phenylamino and 4-[N-phenyl-N-(dibenzothiophen-3-yl)]phenylamino.
作为本发明的一个优选的化合物，该化合物具有如下通式(II)的结构。As a preferred compound of the present invention, the compound has the structure of the following formula (II).
Figure PCTCN2016093026-appb-000009
Figure PCTCN2016093026-appb-000009
其中，Ar1、Ar2相同或不同，分别独立地为C1-C10烷基、C6～C30的芳基氨基或杂芳基氨基、取代或未取代的C6-C30芳基、取代或未取代的C2-C30杂芳基；Wherein, Ar 1 and Ar 2 are the same or different and are each independently a C 1 -C 10 alkyl group, a C 6 -C 30 arylamino group or a heteroarylamino group, a substituted or unsubstituted C 6 -C 30 aryl group; , substituted or unsubstituted C 2 -C 30 heteroaryl;
其中，R1至R12相同或不同，各自独立地优选氢、卤素、取代或未取代的C1-C30烷基、取代或未取代的C2-C30烯基、取代或未取代的C2-C30炔基、取代或未取代的C3-C30环烷基、取代或未取代的C2-C30杂环烷基、取代或未取代的C6-C30芳基、取代或未取代的C2-C30杂芳基、C6～C30的芳基氨基或杂芳基氨基；或者，R1～R4的相邻的基团可以互相连接形成环状结构，这样的环结构可以是脂肪族单环或多环、芳香族的单环或稠环，这些环中可以包含杂原子，其中，作为脂肪族单环的例子，例如，R1～R4中任意相邻的两个基团连接形成脂肪族的五元环、六元环，这些环的构成原子除了碳原子之外还可以是杂原子，这些环可以具有取代基，构成环的碳原子也可以形成酮基。作为这些环的例子，可举出环戊烷环、环己烷环、二环戊烯环、四氢吡咯环、四氢呋喃环、哌啶环、以及环戊烷环和环己烷环中的碳原子被酮基取代得到的酯环等。作为芳香族的单环或稠环，优选为C6～C30的单环或稠环，作为例子可举出苯环、萘环等；作为包含杂原子的单环或多环，优选的是吡咯环、吡啶环、吲哚环、N-苯基取代吲哚环。R5～R8，或者R9～R12中的相邻的基团可以互相连接形成环状结构，这样的环结构的例子与上述R1～R4的相邻基团形成的环结构的例子相同，优选例子也相同。Wherein R 1 to R 12 are the same or different and are each independently preferably hydrogen, halogen, substituted or unsubstituted C 1 -C 30 alkyl, substituted or unsubstituted C 2 -C 30 alkenyl, substituted or unsubstituted C 2 -C 30 alkynyl, substituted or unsubstituted C 3 -C 30 cycloalkyl, substituted or unsubstituted C 2 -C 30 heterocycloalkyl, substituted or unsubstituted C 6 -C 30 aryl, a substituted or unsubstituted C 2 -C 30 heteroaryl group, a C 6 -C 30 arylamino group or a heteroarylamino group; or, adjacent groups of R 1 to R 4 may be bonded to each other to form a cyclic structure, Such a ring structure may be an aliphatic monocyclic or polycyclic, aromatic monocyclic or fused ring, and these rings may contain a hetero atom, wherein, as an example of the aliphatic monocyclic ring, for example, any of R 1 to R 4 The two adjacent groups are bonded to form an aliphatic five-membered ring or a six-membered ring. The constituent atoms of these rings may be hetero atoms in addition to carbon atoms, and these rings may have a substituent, and the carbon atoms constituting the ring may also be A ketone group is formed. Examples of the ring include a cyclopentane ring, a cyclohexane ring, a dicyclopentene ring, a tetrahydropyrrole ring, a tetrahydrofuran ring, a piperidine ring, and a carbon in a cyclopentane ring and a cyclohexane ring. An ester ring obtained by substituting an atom with a ketone group or the like. The aromatic monocyclic or fused ring is preferably a C 6 to C 30 monocyclic or fused ring, and examples thereof include a benzene ring and a naphthalene ring; and as a monocyclic or polycyclic ring containing a hetero atom, it is preferably Pyrrole ring, pyridine ring, anthracene ring, N-phenyl substituted anthracene ring. R 5 to R 8 or an adjacent group of R 9 to R 12 may be bonded to each other to form a cyclic structure, and examples of such a ring structure and a ring structure formed by the adjacent groups of R 1 to R 4 described above The examples are the same and the preferred examples are the same.
在结构式II中，Ar1、Ar2可以各自独立地为取代或未取代的C6-C30芳基，优选地，Ar1和Ar2各自独立地为取代或未取代的C6-C20芳基；作为该芳基更优选为选自由苯基、联苯基、三联苯基、萘基、蒽基、菲基、茚基、芴基及其衍生物、荧蒽基、三亚苯基、芘基、苝基、
Figure PCTCN2016093026-appb-000010
基和并四苯基所组成的组中的基团。所述联苯基为选自由2-联苯基、3-联苯基和4-联苯基，所述为三联苯基包括对-三联苯基-4-基、对-三联苯基-3-基、对-三联苯基-2-基、间-三联苯基-4-基、间-三联苯基-3-基和间-三联苯基-2-基；所述萘基为1-萘基和2-萘基所组成的组中；所述蒽基为选自由1-蒽基、2-蒽基和9-蒽基所组成的组中的基团；所述芴基为选自由1-芴基、2-芴基、3-芴基、4-芴基和9-芴基所组成的组中的基团；所述芴基衍生物为选自由9，9’-二甲基芴，9，9’-螺二芴和苯并芴所组成的组中的基团；所述芘基为选自由1-芘基、2-芘基和4-芘基所组成的组中的基团；所述并四苯基选自由1-并四苯基、2-并四苯基和9-并四苯基所组成的组中的基团。In Structural Formula II, Ar 1 and Ar 2 may each independently be a substituted or unsubstituted C 6 -C 30 aryl group, and preferably, Ar 1 and Ar 2 are each independently a substituted or unsubstituted C 6 -C 20 More preferably, the aryl group is selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, anthracenyl, fluorenyl and its derivatives, fluoranthenyl, triphenylene,芘基,苝基,
Figure PCTCN2016093026-appb-000010
a group in the group consisting of a base and a tetraphenyl group. The biphenyl group is selected from the group consisting of 2-biphenyl, 3-biphenyl and 4-biphenyl, and the terphenyl includes p-terphenyl-4-yl, p-terphenyl-3 -yl, p-terphenylene-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group is 1- a group consisting of a naphthyl group and a 2-naphthyl group; the fluorenyl group being a group selected from the group consisting of a 1-fluorenyl group, a 2-fluorenyl group, and a 9-fluorenyl group; a group in the group consisting of 1-nonyl, 2-indenyl, 3-indenyl, 4-indenyl and 9-fluorenyl; the mercapto derivative is selected from 9,9'-dimethyl a group in the group consisting of 9,9'-spirobifluorene and benzopyrene; the fluorenyl group is selected from the group consisting of 1-indenyl, 2-indenyl and 4-indenyl a group; the tetracyl group is selected from the group consisting of 1-tetraphenyl, 2-tetraphenyl, and 9-tetraphenyl.
在结构式II中，Ar1和Ar2可以为取代或未取代的C3-C30杂芳基，作为该杂芳基中的杂原子优选为一个或多个选自O、S和N的杂原子，作为该杂芳基优选为取代或 未取代的C5-C20杂芳基，作为此处的杂芳基的优选的例子，可举出选自由呋喃基、噻吩基、吡咯基、苯并呋喃基、苯并噻吩基、异苯并呋喃基、吲哚基、二苯并呋喃基、二苯并噻吩基、咔唑基及其衍生物和苯并间二氧杂环戊烯基组成的组中的至少一种，其中，所述咔唑基衍生物可以包括但不限于9-苯基咔唑、9-萘基咔唑苯并咔唑、二苯并咔唑、和吲哚并咔唑中的至少一种。In Structural Formula II, Ar 1 and Ar 2 may be a substituted or unsubstituted C 3 -C 30 heteroaryl group, and the hetero atom in the heteroaryl group is preferably one or more selected from the group consisting of O, S and N. The atom, as the heteroaryl group, is preferably a substituted or unsubstituted C 5 -C 20 heteroaryl group, and preferred examples of the heteroaryl group herein include a furanyl group, a thienyl group, a pyrrolyl group, and a benzene group. And furyl, benzothienyl, isobenzofuranyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, oxazolyl and its derivatives and benzodioxolyl At least one of the group, wherein the carbazolyl derivative may include, but is not limited to, 9-phenyloxazole, 9-naphthylcarbazole benzoxazole, dibenzoxazole, and anthracene. At least one of carbazoles.
在结构式II中，Ar1和Ar2可以为C6～C30的芳基氨基或杂芳基氨基，作为其具体例，可举出二(杂)芳基氨基、三(杂)芳基氨基，此处“(杂)芳基”的表达方式包含芳基和杂芳基两者，作为更具体例子可举出选自二苯氨基、苯基萘基氨基、4-三苯氨基、3-三苯氨基、4-[N-苯基-N-(二苯并呋喃-3-基)]苯基氨基、4-[N-苯基-N-(二苯并噻吩-3-基)]苯基氨基所组成的组中的基团。In Structural Formula II, Ar 1 and Ar 2 may be a C 6 -C 30 arylamino group or a heteroarylamino group, and specific examples thereof include a di(hetero)arylamino group and a tri(hetero)arylamino group. Here, the expression of "(hetero)aryl" includes both an aryl group and a heteroaryl group, and more specific examples thereof include a diphenylamino group, a phenylnaphthylamino group, a 4-triphenylamino group, and 3- Triphenylamino, 4-[N-phenyl-N-(dibenzofuran-3-yl)]phenylamino, 4-[N-phenyl-N-(dibenzothiophen-3-yl)] a group in the group consisting of phenylamino groups.
作为本发明的一种优选化合物，该化合物具有如下通式(III)：As a preferred compound of the invention, the compound has the following general formula (III):
Figure PCTCN2016093026-appb-000011
Figure PCTCN2016093026-appb-000011
其中，Ar3、Ar4相同或不同，分别独立地为C1-C10烷基、取代或未取代的C6-C30芳基、取代或未取代的C2-C30杂芳基、C6～C30的芳基氨基或杂芳基氨基；Wherein, Ar 3 and Ar 4 are the same or different and are each independently a C 1 -C 10 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted C 2 -C 30 heteroaryl group, An arylamino or heteroarylamino group of C 6 to C 30 ;
其中，R13至R24相同或不同，各自独立地优选氢、卤素、取代或未取代的C1-C30烷基、取代或未取代的C2-C30烯基、取代或未取代的C2-C30炔基、取代或未取代的C3-C30环烷基、取代或未取代的C2-C30杂环烷基、取代或未取代的C6-C30芳基、取代或未取代的C2-C30杂芳基、C6～C30的芳基氨基或杂芳基氨基；或者，R13～R16的相邻的基团可以互相连接形成环状结构，这样的环结构的例子与上述R1～R4中的相邻基团形成的环结构的例子相同，优选例子也相同；R17～R20中的相邻的基团可以互相连接形成环状结构，这样的环结构的例子与上述R1～R4的相邻基团形成的环结构的例子相同，优选例子也相同。Wherein R 13 to R 24 are the same or different and are each independently preferably hydrogen, halogen, substituted or unsubstituted C 1 -C 30 alkyl, substituted or unsubstituted C 2 -C 30 alkenyl, substituted or unsubstituted C 2 -C 30 alkynyl, substituted or unsubstituted C 3 -C 30 cycloalkyl, substituted or unsubstituted C 2 -C 30 heterocycloalkyl, substituted or unsubstituted C 6 -C 30 aryl, a substituted or unsubstituted C 2 -C 30 heteroaryl group, a C 6 -C 30 arylamino group or a heteroarylamino group; or, adjacent groups of R 13 to R 16 may be bonded to each other to form a cyclic structure, Examples of such a ring structure are the same as those of the ring structure formed by the adjacent groups in the above R 1 to R 4 , and preferred examples are also the same; adjacent groups of R 17 to R 20 may be bonded to each other to form a ring. The structure, examples of such a ring structure are the same as the examples of the ring structure formed by the adjacent groups of the above R 1 to R 4 , and preferred examples are also the same.
在结构式III中，Ar3、Ar4可以各自独立地为取代或未取代的C6-C30芳基，优选地，Ar3和Ar4各自独立地优选为取代或未取代的C6-C20芳基、取代或未取代的C3-C30杂芳基、C6～C30的芳基氨基或杂芳基氨基，作为此处的芳基、杂芳基、芳基氨基或杂芳基氨基的具体的例子和优选的例子，与上述结构式II中的对于对应基团所举出的 代表例、优选例相同。In Structural Formula III, Ar 3 and Ar 4 may each independently be a substituted or unsubstituted C 6 -C 30 aryl group, and preferably, Ar 3 and Ar 4 are each independently preferably a substituted or unsubstituted C 6 -C. 20 aryl, substituted or unsubstituted C 3 -C 30 heteroaryl, C 6 -C 30 arylamino or heteroarylamino, as aryl, heteroaryl, arylamino or heteroaryl herein Specific examples and preferred examples of the amino group are the same as those in the above-mentioned structural formula II for the representative examples and preferred examples.
本发明化合物具有苯并环辛四烯并二吲哚结构的母核，作为代表例，测定了Ar为苯基的二苯并环辛四烯并二吲哚结构的化合物的三线态能级约为2.8(如下图)，另外吲哚结构本身具有较强的空穴注入能力，基于这样的特定的电子云密度和分布，本发明特别适合用于有机电致发光元件的发光层主体材料、空穴注入材料、和空穴传输材料。The compound of the present invention has a nucleus of a benzocyclooctadecenedioxan structure, and as a representative example, a triplet energy level of a compound of a dibenzocyclooctylenetetrakenylene structure in which Ar is a phenyl group is determined. 2.8 (as shown in the figure below), in addition, the germanium structure itself has strong hole injecting ability. Based on such specific electron cloud density and distribution, the present invention is particularly suitable for the light emitting layer host material of the organic electroluminescent element, Hole injection material, and hole transport material.
Figure PCTCN2016093026-appb-000012
Figure PCTCN2016093026-appb-000012
另外，通过特定的取代基修饰，可以调节本发明化合物的HOMO以及LUMO能级，而且环辛四烯的共轭体系可以将各个基团有效的联系起来，从而实现高效空穴注入和空穴传输性能，同时保证了较高的三线态能级，能够提供出一系列高效的空穴注入和传输材料；另一方面通过用拉电子基团，优选吡啶基、三嗪、喹唑啉、喹啉基、噁唑基等基团的的修饰，可以使得材料分子同时具有电子和空穴传输性，并且通过各种基团数目和取代基位置的调整，能够得到高性能的发光层主体材料，某些优选化合物甚至能显示出接近0的AEST的能量差，能够显著地降低使用本发明化合物作为主体材料的磷光发光OLED器件的工作电压以及实现长的工作寿命。In addition, the HOMO and LUMO energy levels of the compounds of the present invention can be adjusted by specific substituent modification, and the conjugated system of cyclooctatetraene can effectively associate various groups to achieve efficient hole injection and hole transport. Performance, while ensuring a high triplet energy level, can provide a series of efficient hole injection and transport materials; on the other hand by using electron withdrawing groups, preferably pyridyl, triazine, quinazoline, quinoline The modification of a group such as a oxazolyl group can make the material molecule have both electron and hole transport properties, and by adjusting the number of various groups and the position of the substituent, a high-performance luminescent layer host material can be obtained. Some of the preferred compounds can even exhibit an energy difference of AE ST close to 0, which can significantly reduce the operating voltage of the phosphorescent OLED device using the compound of the present invention as a host material and achieve a long working life.
另外，本发明化合物的式(II)和(III)的化合物最主要的差别是对称关系不同。对称关系将会对电子云的排布、成膜时的结晶生长产生明显影响。在此基础上，本发明人锐意研究，发现通过对称关系的调整、并选择适当的取代基，可以对本发明的化合物的三线态能级、空穴注入传输能力进行微调，进一步根据需要优化电学性能，并总结了如下规律。Further, the most important difference between the compounds of the formula (II) and (III) of the compound of the present invention is that the symmetry relationship is different. The symmetrical relationship will have a significant impact on the arrangement of the electron cloud and the crystal growth during film formation. On the basis of this, the inventors have intensively studied and found that by adjusting the symmetry relationship and selecting an appropriate substituent, the triplet level and the hole injection transport ability of the compound of the present invention can be finely adjusted, and the electrical properties can be further optimized as needed. And summarized the following rules.
具体而言，作为本发明的化合物，进一步优选在通式II、III中Ar1～Ar4、R1～R24为氢原子或中性(此处中性是指推电子和拉电子性能不明显，以下同)的芳基的化合物，作为中性的芳基，例如可举出苯基、甲苯基、联苯基、萘基、菲基、三亚苯基、荧蒽基、屈基、芴基、茚并芴基等。作为具体的化合物的例子，可以举出以下A-1～A-24的化合物，但并不限于这些化合物。 Specifically, as the compound of the present invention, it is more preferred that in the formulae II and III, Ar 1 to Ar 4 and R 1 to R 24 are a hydrogen atom or a neutral (here, neutral means that the electron-withdrawing property and the pull-electron property are not The compound of the aryl group which is the same as the above), as a neutral aryl group, may, for example, be a phenyl group, a tolyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a triphenylene group, a fluoranthene group, a fluorenyl group or a fluorenyl group. Base, 茚 and 芴 base. Examples of the specific compound include the following compounds A-1 to A-24, but are not limited thereto.
Figure PCTCN2016093026-appb-000013
Figure PCTCN2016093026-appb-000013
作为上述优选的化合物，由于取代基为中性基团，不会明显的改变原母体双吲哚 并环辛四烯基团的电子云密度以及分布，可以非常好的发挥通过取代基的变化改变分子的分子量并调整分子的堆积方式，可以根据制备器件的过程中蒸镀成膜的工艺条件、设备种类的不同要求来调整成膜分子的理化性质，工艺自由度大幅提升；也可以通过调整分子的对称性、结晶性等来获得更好的蒸镀膜，从而提高有机电致发光器件的发光效率，降低驱动电压。As the above preferred compound, since the substituent is a neutral group, the original parent biguanide is not significantly changed. The electron cloud density and distribution of the cyclooctyltetraenyl group can be used to change the molecular weight of the molecule and adjust the molecular packing mode by changing the substituent, which can be based on the process conditions of vapor deposition film formation in the process of preparing the device. Different types of equipment can adjust the physical and chemical properties of the film-forming molecules, and the degree of freedom of the process is greatly improved. It is also possible to obtain a better vapor-deposited film by adjusting the symmetry and crystallinity of the molecules, thereby improving the luminous efficiency of the organic electroluminescent device. , reduce the drive voltage.
作为本发明的化合物，还进一步优选下列在通式II、III中Ar1～Ar4、R1～R24为氢原子或给电子性质的杂芳基的化合物，通过这样的杂芳基与母核相互作用，可以微调本发明化合物的HOMO能级。经本发明人研究发现，在有机电致发光器件中，作为空穴传输层的材料如果HOMO能级在5.4eV或者以上，则能更好地与发光层主体材料的HOMO、能级相匹配，从而提高发光效率。通过利用在通式II、III中Ar1～Ar4、R1～R24为给电子性质的杂芳基的化合物，能使形成的化合物的HOMO能级为5.4-5.7左右，非常有利于作为空穴传输材料使用。作为给电子性质的杂芳基，可举出咔唑基、二苯并呋喃基、二苯并噻吩基、吲哚并咔唑基、苯并呋喃并咔唑基、苯并噻吩并咔唑基等。作为具体的化合物的例子，可以例举以下B-1～B-30的化合物，但并不限于这些化合物。Further, as the compound of the present invention, a compound of the following formulas II and III in which Ar 1 to Ar 4 and R 1 to R 24 are a hydrogen atom or an electron-donating heteroaryl group is further preferable, and such a heteroaryl group and a parent are Nuclear interactions can fine tune the HOMO energy levels of the compounds of the invention. According to the study by the present inventors, in the organic electroluminescent device, if the HOMO level is 5.4 eV or more as the material of the hole transport layer, the HOMO and the energy level of the host material of the light-emitting layer can be better matched. Thereby improving luminous efficiency. By using a compound having a heteroaryl group of electron-donating properties in the general formulae II and III, Ar 1 to Ar 4 and R 1 to R 24 can form a compound having a HOMO level of about 5.4 to 5.7, which is very advantageous as a The hole transport material is used. Examples of the heteroaryl group having an electron donating property include a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, an indolocarbazolyl group, a benzofurancarbazolyl group, and a benzothienocarbazolyl group. Wait. Specific examples of the compound include the following compounds B-1 to B-30, but are not limited thereto.
Figure PCTCN2016093026-appb-000014
Figure PCTCN2016093026-appb-000014
Figure PCTCN2016093026-appb-000015
Figure PCTCN2016093026-appb-000015
Figure PCTCN2016093026-appb-000016
Figure PCTCN2016093026-appb-000016
作为本发明的化合物，还进一步优选下列在通式II、III中Ar1～Ar4、R1～R24为氢原子或芳基氨基的化合物，通过芳基氨基与苯并环辛四烯并二吲哚母核相互作用，能够显著提高化合物的给电子能力，使得分子具有较浅的HOMO能级并具有很强的空穴注入能力，这样的化合物特别适合作为空穴注入层的材料来使用。作为二芳基氨基的具体例子，可以举出二苯氨基、苯基萘基氨基等。Ar1～Ar4、R1～R24中的一个或多个还可以为三芳基氨基，作为具体例子可举出选自由4-三苯氨基、3-三苯氨基、4-[N-苯基-N-(二苯并呋喃-3-基)]苯基氨基、4-[N-苯基-N-(二苯并噻吩-3-基)]苯基氨基。作为这样的适合用作空穴注入层材料化合物的具体例，优选以下C-1～C-15的化合物，但并不限于这些化合物。Further, as the compound of the present invention, a compound in which Ar 1 to Ar 4 and R 1 to R 24 are a hydrogen atom or an arylamino group in the formulae II and III, and an arylamino group and a benzocyclooctenetetraene are further preferably used. The two-mother core interaction can significantly improve the electron donating ability of the compound, so that the molecule has a shallow HOMO level and has a strong hole injecting ability. Such a compound is particularly suitable as a material for the hole injecting layer. . Specific examples of the diarylamino group include a diphenylamino group and a phenylnaphthylamino group. One or more of Ar 1 to Ar 4 and R 1 to R 24 may be a triarylamino group, and specific examples thereof include a 4-triphenylamino group, a 3-triphenylamino group, and a 4-[N-benzene group. Base-N-(dibenzofuran-3-yl)]phenylamino, 4-[N-phenyl-N-(dibenzothiophen-3-yl)]phenylamino. As a specific example of such a compound suitable as a material for the hole injection layer, the following compounds C-1 to C-15 are preferable, but are not limited thereto.
Figure PCTCN2016093026-appb-000017
Figure PCTCN2016093026-appb-000017
Figure PCTCN2016093026-appb-000018
Figure PCTCN2016093026-appb-000018
作为本发明的化合物，还进一步优选下列在通式II、III中Ar1～Ar4、R1～R24为氢、或者具有拉电子性质的基团的化合物。在双吲哚并环辛四烯母体上连接具有较强拉电子能力的基团时，除了能在保持原有的空穴注入以及传输的性能外，附加了电子的注入和传输性能，使得分子同时具有双极传输性能，这样的化合物由于电子和空穴的传输性能都优异，作为主体材料，特别是磷光发光器件的主体材料时，凭借均衡的载流子传输性能避免在高亮度下的效率滚降，从而降低器件起亮和工作电压，提高器件效率，延长器件寿命。作为拉电子基团可举出吡啶基、苯基吡啶基、喹啉基、取代喹啉基、喹唑啉基、取代喹唑啉基、喹喔啉基、取代喹喔啉基、嘧啶基、取代嘧啶基、邻菲啰啉基、三嗪基、取代三嗪基、苯并咪唑基、噁唑基等。作为这样的优选化合物的具体的例子，可以举出以下D-1～D-39的化合物，但并不限于这些化合物。Further, as the compound of the present invention, a compound of the following formulas II and III in which Ar 1 to Ar 4 and R 1 to R 24 are hydrogen or a group having an electron withdrawing property is further preferable. When a group having a strong electron-trapping ability is attached to a bisindole-cyclooctanetetraene matrix, in addition to maintaining the original hole injection and transport properties, electron injection and transport properties are added to make the molecule At the same time, it has bipolar transmission performance. Such compounds have excellent electron and hole transport properties. As a host material, especially for the host material of phosphorescent light-emitting devices, the efficiency of high-brightness is avoided by balanced carrier transport performance. Roll-off, which reduces device illumination and operating voltage, increases device efficiency, and extends device life. Examples of the electron withdrawing group include a pyridyl group, a phenylpyridyl group, a quinolyl group, a substituted quinolyl group, a quinazolinyl group, a substituted quinazolinyl group, a quinoxalinyl group, a substituted quinoxaline group, and a pyrimidinyl group. Substituted pyrimidinyl, phenanthroline, triazinyl, substituted triazinyl, benzimidazolyl, oxazolyl and the like. Specific examples of such a preferred compound include the following compounds D-1 to D-39, but are not limited thereto.
Figure PCTCN2016093026-appb-000019
Figure PCTCN2016093026-appb-000019
Figure PCTCN2016093026-appb-000020
Figure PCTCN2016093026-appb-000020
Figure PCTCN2016093026-appb-000021
Figure PCTCN2016093026-appb-000021
有机电致发光器件Organic electroluminescent device
本发明还提供了使用上述本发明新颖的化合物的有机电致发光器件。本发明的有机电致发光器件结构与公知的器件并无不同，一般包括第一电极、第二电极和插入所述第一电极和第二电极之间的一层或多成有机层，其特征在于，所述有机层包含上述有机电致发光化合物。作为第一电极和第二电极之间的有机层，通常有电子注入层、电子传输层、发光层、空穴传输层、空穴注入层等有机层。本发明的化合物可以用作但不限于空穴注入材料/空穴传输材料和/或发光主体材料。The present invention also provides an organic electroluminescent device using the novel compound of the present invention described above. The organic electroluminescent device structure of the present invention is not different from the known device, and generally includes a first electrode, a second electrode, and one or more organic layers interposed between the first electrode and the second electrode, the characteristics of which are characterized The organic layer comprises the above organic electroluminescent compound. As the organic layer between the first electrode and the second electrode, an organic layer such as an electron injecting layer, an electron transporting layer, a light emitting layer, a hole transporting layer, or a hole injecting layer is usually used. The compounds of the present invention can be used, but are not limited to, hole injection materials/hole transport materials and/or luminescent host materials.
其中，作为本发明的有机电致发光器件的优选例子，可举出将化合物A-1～A-24，D-1～D-39用作发光层主体材料的有机电致发光器件，将化合物B-1～B-30用作空穴传输层材料的有机电致发光器件，以及将上述化合物C-1～C-15用作空穴注入层的材料的有机电致发光器件。本发明的有机电致发光器件基于本发明化合物的优异性能，能够降低器件起亮和工作电压，提高器件效率，延长器件寿命。In a preferred example of the organic electroluminescent device of the present invention, an organic electroluminescent device using the compounds A-1 to A-24, D-1 to D-39 as a host material of a light-emitting layer, and a compound B-1 to B-30 are organic electroluminescence devices used as a material for a hole transport layer, and organic electroluminescence devices using the above compounds C-1 to C-15 as materials for a hole injection layer. The organic electroluminescent device of the present invention can reduce device brightening and operating voltage, improve device efficiency, and extend device lifetime based on the excellent properties of the compound of the present invention.
实施例Example
参照以下实施例描述了本发明的代表化合物的制备方法。由于本发明化合物具有相同的骨架，本领域人员基于这些制备方法，可以通过已知的官能团转换方法、容易的合成其他本发明的化合物。以下，还提供包含所述化合物的发光器件的制备方法和发光性质测定。The preparation method of the representative compound of the present invention is described with reference to the following examples. Since the compounds of the present invention have the same skeleton, based on these preparation methods, those skilled in the art can easily synthesize other compounds of the present invention by a known functional group conversion method. Hereinafter, a method of preparing a light-emitting device comprising the compound and a measurement of luminescent properties are also provided.
合成实施例Synthesis example
以下简要说明本发明代表化合物的合成方法。The synthesis method of the representative compound of the present invention is briefly explained below.
本发明中所用的各种化学药品如石油醚、乙酸乙酯、正己烷、甲苯、四氢呋喃、二氯甲烷、四氯化碳、丙酮、1，2-双(溴甲基)苯、CuI、邻苯二甲酰氯、盐酸苯肼、 三氟乙酸、乙酸、反式-二氨基环己烷、碘苯、碳酸铯、磷酸钾、乙二胺、二苯甲酮、环戊酮、9-芴酮、叔丁醇钠、甲烷磺酸、1-溴-2-甲基萘、邻二溴苯、丁基锂、二溴乙烷、邻二溴苯、过氧化苯甲酰、1-(2-溴苯基)-2-甲基萘、N-溴代丁二酰亚胺、甲氧甲基三甲基氯化鏻、三(二亚苄基丙酮)二钯、四(三苯基膦)钯、1，3-双二苯基膦丙烷氯化镍、咔唑、3，6-二甲基咔唑、3-(2-萘基)-6-苯基咔唑、N-苯基咔唑-3-硼酸、9-(2-萘基)咔唑-3-硼酸等基础化工原料均可在国内化工产品市场买到。Various chemicals used in the present invention such as petroleum ether, ethyl acetate, n-hexane, toluene, tetrahydrofuran, dichloromethane, carbon tetrachloride, acetone, 1,2-bis(bromomethyl)benzene, CuI, ortho Phthaloyl chloride, phenylhydrazine hydrochloride, Trifluoroacetic acid, acetic acid, trans-diaminocyclohexane, iodobenzene, cesium carbonate, potassium phosphate, ethylenediamine, benzophenone, cyclopentanone, 9-fluorenone, sodium t-butoxide, methanesulfonic acid , 1-bromo-2-methylnaphthalene, o-dibromobenzene, butyllithium, dibromoethane, o-dibromobenzene, benzoyl peroxide, 1-(2-bromophenyl)-2-methyl Naphthalene, N-bromosuccinimide, methoxymethyltrimethylphosphonium chloride, tris(dibenzylideneacetone)dipalladium, tetrakis(triphenylphosphine)palladium, 1,3-bisdiphenyl Phosphonium chloride, carbazole, 3,6-dimethylcarbazole, 3-(2-naphthyl)-6-phenyloxazole, N-phenylcarbazole-3-boronic acid, 9-( Basic chemical raw materials such as 2-naphthyl)carbazole-3-boronic acid can be purchased in the domestic chemical product market.
本发明中的中间体和化合物的分析检测使用ABSCIEX质谱仪(4000QTRAP)和布鲁克核磁共振仪(400M)。Analytical detection of the intermediates and compounds in the present invention was performed using an ABSCIEX mass spectrometer (4000QTRAP) and a Bruker nuclear magnetic resonance instrument (400M).
有机电致发光化合物的制备：Preparation of organic electroluminescent compounds:
合成实施例1.中间体M1的合成：Synthesis Example 1. Synthesis of Intermediate M1:
Figure PCTCN2016093026-appb-000022
Figure PCTCN2016093026-appb-000022
向1升三口瓶中加入1，2-双(溴甲基)苯(26.4g，0.1mol)和500毫升的无水四氢呋喃(THF)，充氮气保护下，加入经过活化的锌粉(13g，0.2mol)，反应2小时，制成双锌试剂。加入CuI(2g，10mmol)和邻苯二甲酰氯(20g，0.1mol)，先在室温下反应1小时，再在回流条件下反应10小时。反应完毕后，缓慢加入饱和氯化铵水溶液淬灭反应，然后用100ml乙酸乙酯萃取三次，合并得到的有机相，无水MgSO4干燥，减压除去有机溶剂后，对剩余物进行柱分离，得到中间体化合物M(18.5g，收率78.4％)。To a 1 liter three-necked flask, 1,2-bis(bromomethyl)benzene (26.4 g, 0.1 mol) and 500 ml of anhydrous tetrahydrofuran (THF) were added, and under activated nitrogen, activated zinc powder (13 g, 0.2 mol), reacted for 2 hours to prepare a double zinc reagent. CuI (2 g, 10 mmol) and phthaloyl chloride (20 g, 0.1 mol) were added, and the mixture was reacted at room temperature for 1 hour, and then reacted under reflux for 10 hours. After completion of the reaction, the reaction mixture was quenched with saturated aqueous ammonium chloride, and then extracted three times with ethyl acetate (100 ml). Intermediate Compound M (18.5 g, yield 78.4%).
向1升三口瓶中加入盐酸苯肼(63.6g，0.44mol)，中间体化合物M(47.2g，0.2mol)，乙醇400毫升，3min内滴加2.1g浓硫酸，在65℃反应下反应4小时，反应结束后，冷却至室温，过滤，然后依次用乙醇、石油醚洗涤滤饼，得白色固体M1-1(83g，收率82.9％)。To a 1 liter three-necked flask was added phenylhydrazine hydrochloride (63.6 g, 0.44 mol), intermediate compound M (47.2 g, 0.2 mol), ethanol 400 ml, 2.1 g of concentrated sulfuric acid was added dropwise over 3 min, and the reaction was carried out at 65 ° C. After the completion of the reaction, the mixture was cooled to room temperature and filtered, and then the filter cake was washed with ethanol and petroleum ether to give white solid M1-1 (83 g, yield 82.9%).
向1升三口瓶中加入上述M1-1(49g，0.1mol)，乙酸650g，三氟乙酸65g，在72℃下回流反应15小时，冷却至室温，过滤，然后依次用乙酸、石油醚洗涤滤饼，得到中间体化合物M1(25g，65％)，为白色固体。The above M1-1 (49 g, 0.1 mol), 650 g of acetic acid, and 65 g of trifluoroacetic acid were added to a 1-liter three-necked flask, and the mixture was refluxed at 72 ° C for 15 hours, cooled to room temperature, filtered, and then washed with acetic acid and petroleum ether. The title compound gave the title compound M1 (25 g, 65%).
M1的核磁波普数据：M1 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.76(s，1H)，8.42(s，2H)，8.14(d，J＝45.0Hz， 3H)，7.40(s，1H)，7.19(d，J＝10.0Hz，2H). 1 H NMR (500MHz, Chloroform) δ8.76 (s, 1H), 8.42 (s, 2H), 8.14 (d, J = 45.0Hz, 3H), 7.40 (s, 1H), 7.19 (d, J = 10.0 Hz, 2H).
合成实施例2.中间体M2的合成Synthesis Example 2. Synthesis of Intermediate M2
Figure PCTCN2016093026-appb-000023
Figure PCTCN2016093026-appb-000023
向1升三口瓶中加入3-溴苯肼盐酸盐(92.8g，0.415mol)，二酮中间体M(49g，0.207mol，乙醇(400毫升)，搅拌条件下，3min内滴加2g浓硫酸，在65℃下反应4小时，反应结束后，冷却至室温，过滤，依次用乙醇、石油醚洗涤滤饼，得到中间体化合物M2-1(122g，91％)。To a 1 liter three-necked flask was added 3-bromophenylhydrazine hydrochloride (92.8 g, 0.415 mol), diketone intermediate M (49 g, 0.207 mol, ethanol (400 ml), and 2 g thick was added dropwise over 3 min. Sulfuric acid was reacted at 65 ° C for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, filtered, and the filter cake was washed with ethanol and petroleum ether to give intermediate compound M2-1 (122 g, 91%).
向1升三口瓶中加入化合物M2-1(48.4g，74.8mmol)，乙酸(650g)和三氟乙酸(65g，0.57mol)，在72℃下回流反应15小时，冷却至室温，过滤，依次用乙酸、石油醚洗涤滤饼，得中间体化合物M2-2(35g，85％)。Compound M2-1 (48.4 g, 74.8 mmol), acetic acid (650 g) and trifluoroacetic acid (65 g, 0.57 mol) were added to a 1-liter three-necked flask, and the mixture was refluxed at 72 ° C for 15 hours, cooled to room temperature, and filtered. The filter cake was washed with acetic acid and petroleum ether to give intermediate compound M2-2 (35 g, 85%).
将二甲苯(100毫升)、M2-2(5.4g，10mmol)，碘苯(5.1g，25mmol)，CuI(0.9g，5mmol)，反式-二氨基环己烷(2.1毫升，20mmol)和碳酸铯(6.5g，20mmol)混合，回流反应3小时，反应结束后，冷却至室温，过滤，然后用二氯甲烷洗涤滤饼，合并滤液，干燥，然后减压除去溶剂，将得到的蒸馏剩余物进行柱分离(洗脱液∶体积比为1∶2的二氯甲烷和石油醚的混合溶液)，得到中间体化合物M2，为白色固体(5.88g，产率85％)。Xylene (100 ml), M2-2 (5.4 g, 10 mmol), iodobenzene (5.1 g, 25 mmol), CuI (0.9 g, 5 mmol), trans-diaminocyclohexane (2.1 ml, 20 mmol) and The cesium carbonate (6.5 g, 20 mmol) was mixed and refluxed for 3 hours. After the reaction was completed, it was cooled to room temperature, filtered, and then the filter cake was washed with dichloromethane, and the filtrate was combined, and then the solvent was removed under reduced pressure, and the obtained distillation was left. Column separation (mixed solution of dichloromethane and petroleum ether in an eluent: 1:2 ratio) afforded intermediate compound M2 as white solid (5.88 g, yield 85%).
M2的核磁波普数据：M2 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.72(s，1H)，8.41(s，2H)，8.09(s，2H)，7.88(s，1H)，7.59(d，J＝20.0Hz，3H)，7.49(s，2H)，7.38(s，1H). 1 H NMR (500 MHz, Chloroform) δ 8.72 (s, 1H), 8.41 (s, 2H), 8.09 (s, 2H), 7.78 (s, 1H), 7.59 (d, J = 20.0 Hz, 3H), 7.49 (s, 2H), 7.38 (s, 1H).
合成实施例3.中间体M3的合成Synthesis Example 3. Synthesis of Intermediate M3
Figure PCTCN2016093026-appb-000024
Figure PCTCN2016093026-appb-000024
向1升三口瓶中加入4-溴苯肼盐酸盐(92.8g，0.415mol)，二酮中间体M(49g， 0.207mol，乙醇(400毫升)，搅拌条件下，3min内滴加2g浓硫酸，在65℃下反应4小时，反应结束后，冷却至室温，过滤，依次用乙醇、石油醚洗涤滤饼，得到中间体化合物M3-1(113g，收率84％)。To a 1 liter three-necked flask was added 4-bromophenylhydrazine hydrochloride (92.8 g, 0.415 mol), diketone intermediate M (49 g, 0.207mol, ethanol (400ml), 2g concentrated sulfuric acid was added dropwise under stirring for 3 hours, and reacted at 65 ° C for 4 hours. After the reaction was completed, it was cooled to room temperature, filtered, and the filter cake was washed with ethanol and petroleum ether in order to obtain Intermediate compound M3-1 (113 g, yield 84%).
向1升三口瓶中加入化合物M3-1(65g，0.1mol)，乙酸(650g)和三氟乙酸(65g，0.57mol)，在72℃下回流反应15小时，冷却至室温，过滤，依次用乙酸、石油醚洗涤滤饼，得中间体化合物M3-2(42g，收率77％)。Compound M3-1 (65 g, 0.1 mol), acetic acid (650 g) and trifluoroacetic acid (65 g, 0.57 mol) were added to a 1-liter three-necked flask, and the mixture was refluxed at 72 ° C for 15 hours, cooled to room temperature, filtered, and sequentially used. The filter cake was washed with acetic acid and petroleum ether to give Intermediate Compound M3-2 (42 g, yield 77%).
将二甲苯(100毫升)、M3-2(5.4g，10mmol)，碘苯(5.1g，25mmol)，CuI(0.9g，5mmol)，反式-二氨基环己烷(2.1毫升，20mmol)和碳酸铯(6.5g，20mmol)混合，回流反应3小时，反应结束后，冷却至室温，过滤，然后用二氯甲烷洗涤滤饼，合并滤液，干燥，然后减压除去溶剂，将得到的蒸馏剩余物进行柱分离(洗脱液：体积比为1∶2的二氯甲烷和石油醚的混合溶液)，得到中间体化合物M3，为白色固体(4.92g，产率71％)。Xylene (100 ml), M3-2 (5.4 g, 10 mmol), iodobenzene (5.1 g, 25 mmol), CuI (0.9 g, 5 mmol), trans-diaminocyclohexane (2.1 ml, 20 mmol) and The cesium carbonate (6.5 g, 20 mmol) was mixed and refluxed for 3 hours. After the reaction was completed, it was cooled to room temperature, filtered, and then the filter cake was washed with dichloromethane, and the filtrate was combined, and then the solvent was removed under reduced pressure, and the obtained distillation was left. Column separation (eluent: a mixture of dichloromethane and petroleum ether in a volume ratio of 1:2) gave Intermediate Compound M3 as a white solid (4.92 g, yield 71%).
M3的核磁波普数据：M3's nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.42(s，1H)，8.10(s，1H)，7.89(s，1H)，7.62(s，1H)，7.58(s，1H)，7.50(s，1H)，7.43(d，J＝17.9Hz，1H). 1 H NMR (500 MHz, Chloroform) δ 8.42 (s, 1H), 8.10 (s, 1H), 7.89 (s, 1H), 7.62 (s, 1H), 7.58 (s, 1H), 7.50 (s, 1H) ), 7.43 (d, J = 17.9 Hz, 1H).
合成实施例4.中间体M4的合成Synthesis Example 4. Synthesis of Intermediate M4
Figure PCTCN2016093026-appb-000025
Figure PCTCN2016093026-appb-000025
采用与合成实施例1相同的合成方法，不同在于，将苯肼盐酸盐置换为等当量的2-萘肼盐酸盐，经过三步合成反应，得到中间体M4，白色固体34.2g，最后一步合成收率为71％。The same synthesis method as in Synthesis Example 1 was employed except that phenylhydrazine hydrochloride was replaced with an equivalent amount of 2-naphthoquinone hydrochloride, and a three-step synthesis reaction was carried out to obtain Intermediate M4, white solid, 34.2 g, and finally. The one-step synthesis yield was 71%.
M4的核磁波普数据：M4 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.76(s，1H)，8.42(s，2H)，8.30(d，J＝16.0Hz，2H)，8.14(s，1H)，8.10(s，2H)，7.84(s，1H)，7.75(s，1H)，7.48(s，1H). 1 H NMR (500 MHz, Chloroform) δ 8.76 (s, 1H), 8.42 (s, 2H), 8.30 (d, J = 16.0 Hz, 2H), 8.14 (s, 1H), 8.10 (s, 2H), 7.84(s,1H), 7.75(s,1H), 7.48(s,1H).
合成实施例5.中间体M5的合成Synthesis Example 5. Synthesis of Intermediate M5
Figure PCTCN2016093026-appb-000026
Figure PCTCN2016093026-appb-000026
采用与合成实施例1相同的合成方法，不同在于，将苯肼盐酸盐置换为等当量的1-萘肼盐酸盐，经过三步合成反应，得到中间体M5，白色固体31g，最后一步合成收率为67％。The same synthesis method as in Synthesis Example 1 was employed except that phenylhydrazine hydrochloride was replaced with an equivalent amount of 1-naphthoquinone hydrochloride, and a three-step synthesis reaction was carried out to obtain Intermediate M5, white solid 31 g, and the next step. The synthesis yield was 67%.
M5的核磁波普数据：1H NMR(500MHz，Chloroform)δ9.60(s，1H)，8.51(s，1H)，8.42(s，2H)，8.11(d，J＝5.0Hz，3H)，7.72(s，1H)，7.67(s，1H)，7.63(s，1H)，7.08(s，1H).NMR data of M5: 1 H NMR (500 MHz, Chloroform) δ 9.60 (s, 1H), 8.51 (s, 1H), 8.42 (s, 2H), 8.11 (d, J = 5.0 Hz, 3H), 7.72(s,1H), 7.67(s,1H), 7.63(s,1H),7.08(s,1H).
合成实施例6.中间体M6的合成：Synthesis Example 6. Synthesis of Intermediate M6:
Figure PCTCN2016093026-appb-000027
Figure PCTCN2016093026-appb-000027
向1升三口瓶中加入盐酸苯肼(60g，0.415mol)，二苯并[a，e]-5，11-环辛二烯(6H，12H)-二酮(49g，0.207mol)和乙醇(400毫升)，搅拌条件下，3min内滴加2.1g浓硫酸，在65℃下反应4小时，反应结束后，冷却至室温，过滤，依次用乙醇、石油醚洗涤滤饼，得到固体M6-1(56g)。To a 1 liter three-necked flask was added phenylhydrazine hydrochloride (60 g, 0.415 mol), dibenzo[a,e]-5,11-cyclooctadiene (6H,12H)-dione (49 g, 0.207 mol) and ethanol. (400 ml), under stirring, 2.1 g of concentrated sulfuric acid was added dropwise in 3 min, and reacted at 65 ° C for 4 hours. After the reaction was completed, it was cooled to room temperature, filtered, and the filter cake was washed successively with ethanol and petroleum ether to obtain a solid M6- 1 (56g).
向1升三口瓶中加入48g M6-1，650g乙酸和65g三氟乙酸，在72℃下回流反应15小时，冷却至室温，过滤，依次用乙酸、石油醚洗涤滤饼，得化合物M6(29g，65％)。48 g of M6-1, 650 g of acetic acid and 65 g of trifluoroacetic acid were added to a 1-liter three-necked flask, and the mixture was refluxed at 72 ° C for 15 hours, cooled to room temperature, filtered, and the filter cake was washed successively with acetic acid and petroleum ether to obtain compound M6 (29 g). , 65%).
M6的核磁波普数据：M6 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.75(s，1H)，8.42(s，2H)，8.14(d，J＝45.0Hz，3H)，7.40(s，1H)，7.19(d，J＝10.0Hz，2H). 1 H NMR (500MHz, Chloroform) δ8.75 (s, 1H), 8.42 (s, 2H), 8.14 (d, J = 45.0Hz, 3H), 7.40 (s, 1H), 7.19 (d, J = 10.0 Hz, 2H).
合成实施例7.中间体M7的合成Synthesis Example 7. Synthesis of Intermediate M7
Figure PCTCN2016093026-appb-000028
Figure PCTCN2016093026-appb-000028
将中间体M7(38.6g，0.1mol)、1-溴-4-碘苯(56.7g，0.2mol)、CuI(3.3g，17.1mmol)、K3PO4(21.8g，102.9mmol)、乙二胺(2.3毫升，34.3mmol)和甲苯(500毫升)混合，在 回流条件下搅拌1天，反应结束后，冷却至室温，用乙酸乙酯萃取有机层并减压蒸馏，对得到的蒸馏剩余物进行柱分离(洗脱液：二氯甲烷/己烷)，得到化合物(48.3g，70.1％)。Intermediate M7 (38.6 g, 0.1 mol), 1-bromo-4-iodobenzene (56.7 g, 0.2 mol), CuI (3.3 g, 17.1 mmol), K3PO4 (21.8 g, 102.9 mmol), ethylenediamine ( 2.3 ml, 34.3 mmol) and toluene (500 ml) are mixed in The mixture was stirred under reflux for 1 day. After the reaction was completed, the mixture was cooled to room temperature. The organic layer was extracted with ethyl acetate and evaporated under reduced pressure, and the obtained distillation residue was subjected to column separation (eluent: dichloromethane/hexane). Compound (48.3 g, 70.1%).
M7的核磁波普数据：M7 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.47(d，J＝64.9Hz，46H)，8.38-8.37(m，1H)，8.08(s，26H)，7.77(s，33H)，7.55(d，J＝49.9Hz，46H)，7.14(s，9H)，7.09(s，13H). 1 H NMR (500MHz, Chloroform) δ8.47 (d, J = 64.9Hz, 46H), 8.38-8.37 (m, 1H), 8.08 (s, 26H), 7.77 (s, 33H), 7.55 (d, J =49.9 Hz, 46H), 7.14 (s, 9H), 7.09 (s, 13H).
合成实施例8.中间体M8的合成Synthesis Example 8. Synthesis of Intermediate M8
Figure PCTCN2016093026-appb-000029
Figure PCTCN2016093026-appb-000029
采用与合成实施例1相同的合成方法，不同在于，将邻苯二甲酰氯置换为等当量的4-溴邻苯二甲酰氯，经过三步合成反应，得到中间体M8，白色固体34.6g，三步总收率为75％。The same synthesis method as in Synthesis Example 1 was employed except that phthaloyl chloride was replaced with an equivalent amount of 4-bromophthaloyl chloride, and after three-step synthesis, Intermediate M8 was obtained as a white solid (34.6 g). The total yield in three steps was 75%.
M8的核磁波普数据：M8 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.76(d，J＝15.0Hz，2H)，8.42(s，2H)，8.14(d，J＝45.0Hz，4H)，7.38(t，J＝27.5Hz，4H)，7.19(d，J＝10.0Hz，4H)，7.11(s，1H). 1 H NMR (500 MHz, Chloroform) δ 8.76 (d, J = 15.0 Hz, 2H), 8.42 (s, 2H), 8.14 (d, J = 45.0 Hz, 4H), 7.38 (t, J = 27.5 Hz, 4H), 7.19 (d, J = 10.0 Hz, 4H), 7.11 (s, 1H).
合成实施例9.中间体M9的合成Synthesis Example 9. Synthesis of Intermediate M9
Figure PCTCN2016093026-appb-000030
Figure PCTCN2016093026-appb-000030
采用与合成实施例6相同的合成方法，不同在于，将二苯并[a，e]-5，11-环辛二烯(6H，12H)-二酮置换为等当量的2-溴二苯并[a，e]-5，11-环辛二烯(6H，12H)-二酮，经过二步合成反应，得到中间体M9，白色固体37g，三步总收率为80％。The same synthesis method as in Synthesis Example 6 was employed except that the dibenzo[a,e]-5,11-cyclooctadiene (6H,12H)-dione was replaced with an equivalent amount of 2-bromodiphenyl. And [a,e]-5,11-cyclooctadiene (6H,12H)-dione, after two-step synthesis, to obtain intermediate M9, white solid 37g, the total yield of three steps is 80%.
M9的核磁波普数据：M9's nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.74(d，J＝8.5Hz，2H)，8.42(s，2H)，8.14(d，J＝45.0 Hz，4H)，7.38(t，J＝27.5Hz，4H)，7.19(d，J＝10.0Hz，4H)，7.11(s，1H). 1 H NMR (500 MHz, Chloroform) δ 8.74 (d, J = 8.5 Hz, 2H), 8.42 (s, 2H), 8.14 (d, J = 45.0 Hz, 4H), 7.38 (t, J = 27.5 Hz, 4H), 7.19 (d, J = 10.0 Hz, 4H), 7.11 (s, 1H).
合成实施例10.中间体M10的合成Synthesis Example 10. Synthesis of Intermediate M10
Figure PCTCN2016093026-appb-000031
Figure PCTCN2016093026-appb-000031
采用与合成实施例1相同的合成方法，不同在于，将邻二溴苄置换为等当量的4-溴邻二溴苄，经过三步合成反应，得到中间体M108，白色固体32g，三步总收率为71％。The same synthesis method as in Synthesis Example 1 was employed except that o-dibromobenzyl was replaced with an equivalent amount of 4-bromo-o-bromobenzyl, and a three-step synthesis reaction was carried out to obtain Intermediate M108, white solid 32 g, three-step total The yield was 71%.
M10的核磁波普数据：M10 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.76(d，J＝8.5Hz，2H)，8.42(s，2H)，8.14(d，J＝45.0Hz，4H)，7.38(t，J＝27.5Hz，4H)，7.19(d，J＝10.0Hz，4H)，7.11(s，1H). 1 H NMR (500MHz, Chloroform) δ8.76 (d, J = 8.5Hz, 2H), 8.42 (s, 2H), 8.14 (d, J = 45.0Hz, 4H), 7.38 (t, J = 27.5Hz, 4H), 7.19 (d, J = 10.0 Hz, 4H), 7.11 (s, 1H).
合成实施例11.化合物A-1的合成Synthesis Example 11. Synthesis of Compound A-1
Figure PCTCN2016093026-appb-000032
Figure PCTCN2016093026-appb-000032
将中间体M6(38.2g，0.1mol)、溴苯(31.5g，0.2mol)、CuI(3.3g，17.1mmol)、K3PO4(21.8g，102.9mmol)、乙二胺(2.3毫升，34.3mmol)和甲苯(500毫升)混合，在回流条件下搅拌反应1天，反应结束后，冷却至室温，用乙酸乙酯萃取有机层并减压蒸馏，对得到的蒸馏剩余物进行柱分离(洗脱液：二氯甲烷/己烷)，得到化合物A-1(37.3g，70.1％)。Intermediate M6 (38.2 g, 0.1 mol), bromobenzene (31.5 g, 0.2 mol), CuI (3.3 g, 17.1 mmol), K3PO4 (21.8 g, 102.9 mmol), ethylenediamine (2.3 ml, 34.3 mmol) It was mixed with toluene (500 ml), and the reaction was stirred under reflux for 1 day. After the reaction was completed, the mixture was cooled to room temperature, and the organic layer was extracted with ethyl acetate and distilled under reduced pressure, and the obtained distillation residue was subjected to column separation (eluent) : dichloromethane/hexane) gave Compound A-1 (37.3 g, 70.1%).
A-1的核磁波普数据：Nuclear Magnetic Pop Data for A-1:
1H NMR(500MHz，Chloroform)δ8.54(s，4H)，8.41(s，6H)，8.09(s，6H)，7.59(d，J＝20.0Hz，11H)，7.50(d，J＝10.0Hz，10H)，7.15(s，2H)，7.10(s，3H). 1 H NMR (500MHz, Chloroform) δ8.54 (s, 4H), 8.41 (s, 6H), 8.09 (s, 6H), 7.59 (d, J = 20.0Hz, 11H), 7.50 (d, J = 10.0 Hz, 10H), 7.15 (s, 2H), 7.10 (s, 3H).
合成实施例12.化合物A-2的合成 Synthesis Example 12. Synthesis of Compound A-2
Figure PCTCN2016093026-appb-000033
Figure PCTCN2016093026-appb-000033
采用与实施例11中化合物A-1相同的合成方法，不同在于，将溴苯置换为等当量的对溴甲苯，反应完全后处理得到白色固体45.6g，收率81％。The same synthesis method as in the compound A-1 of Example 11 was employed, except that bromobenzene was replaced with an equivalent amount of p-bromotoluene, and the reaction was completed to give 45.6 g of a white solid, yield 81%.
合成实施例13.化合物A-3的合成Synthesis Example 13. Synthesis of Compound A-3
Figure PCTCN2016093026-appb-000034
Figure PCTCN2016093026-appb-000034
采用与实施例11中化合物A-1相同的合成方法，不同在于，将溴苯置换为等当量的2-溴萘，反应完成后，得到白色固体48.3g，收率76％。The same synthesis method as in the compound A-1 of Example 11 was employed, except that bromobenzene was replaced with an equivalent amount of 2-bromonaphthalene, and after completion of the reaction, 48.3 g of a white solid was obtained, yield 76%.
合成实施例14.化合物A-4的合成Synthesis Example 14. Synthesis of Compound A-4
Figure PCTCN2016093026-appb-000035
Figure PCTCN2016093026-appb-000035
采用与实施例11中化合物A-1相同的合成方法，不同在于，将溴苯置换为等当量的3-溴菲，反应完成后，得到白色固体58.8g，收率80％。The same synthesis method as in the compound A-1 of Example 11 was employed, except that bromobenzene was replaced with an equivalent amount of 3-bromophenanthrene, and after completion of the reaction, 58.8 g of a white solid was obtained, yield 80%.
A-4的核磁波普数据：Nuclear magnetic pop data for A-4:
1H NMR(500MHz，Chloroform)δ9.40(s，1H)，8.84(s，1H)，8.55(s，1H)，8.42(s，2H)，8.25(s，1H)，8.12(d，J＝18.2Hz，3H)，7.90(s，1H)，7.75(s，2H)，7.68(s，1H)，7.63(s，1H)，7.52(s，1H)，7.16(s，1H)，7.11(s，1H). 1 H NMR (500MHz, Chloroform) δ9.40 (s, 1H), 8.84 (s, 1H), 8.55 (s, 1H), 8.42 (s, 2H), 8.25 (s, 1H), 8.12 (d, J = 18.2 Hz, 3H), 7.90 (s, 1H), 7.75 (s, 2H), 7.68 (s, 1H), 7.63 (s, 1H), 7.52 (s, 1H), 7.16 (s, 1H), 7.11 (s, 1H).
合成实施例15.化合物A-5的合成 Synthesis Example 15. Synthesis of Compound A-5
Figure PCTCN2016093026-appb-000036
Figure PCTCN2016093026-appb-000036
采用与实施例11中化合物A-1的合成方法，不同在于，将溴苯置换为等当量的8-溴荧蒽，得到黄色固体52.3g，收率67％。The synthesis method of the compound A-1 of Example 11 was used, except that bromobenzene was replaced with an equivalent amount of 8-bromofluoranthene to obtain 52.3 g of a yellow solid in a yield of 67%.
合成实施例16.化合物A-6的合成Synthesis Example 16. Synthesis of Compound A-6
Figure PCTCN2016093026-appb-000037
Figure PCTCN2016093026-appb-000037
采用与实施例11中化合物A-1相同的合成方法，不同在于，将溴苯置换为等当量的3-溴荧蒽，后处理得到淡黄色固体49.5g，收率为60％。The same synthesis method as in the compound A-1 of Example 11 was used, except that bromobenzene was replaced with an equivalent amount of 3-bromofluoranthene, and then worked up to give a pale yellow solid, 49.5 g, yield 60%.
A-6的核磁波普数据：A-6 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.55(s，13H)，8.42(s，46H)，8.32(s，37H)，8.10(s，25H)，8.02(d，J＝49.0Hz，7H)，7.94(s，14H)，7.75(d，J＝55.0Hz，28H)，7.54(d，J＝15.0Hz，27H)，7.16(s，8H)，7.11(s，11H). 1 H NMR (500MHz, Chloroform) δ8.55 (s, 13H), 8.42 (s, 46H), 8.32 (s, 37H), 8.10 (s, 25H), 8.02 (d, J = 49.0Hz, 7H), 7.94 (s, 14H), 7.75 (d, J = 55.0 Hz, 28H), 7.54 (d, J = 15.0 Hz, 27H), 7.16 (s, 8H), 7.11 (s, 11H).
合成实施例17.化合物A-7的合成Synthesis Example 17. Synthesis of Compound A-7
Figure PCTCN2016093026-appb-000038
Figure PCTCN2016093026-appb-000038
采用与实施例11中化合物A-1相同的合成方法，不同在于，将溴苯置换为等当量的3-溴
Figure PCTCN2016093026-appb-000039
后处理得到淡黄色固体53.4g，收率为64％。The same synthesis method as in the compound A-1 of Example 11 was employed except that bromobenzene was replaced with an equivalent amount of 3-bromo.
Figure PCTCN2016093026-appb-000039
Work-up gave 53.4 g of a pale yellow solid in a yield of 64%.
合成实施例18.化合物A-8的合成 Synthesis Example 18. Synthesis of Compound A-8
Figure PCTCN2016093026-appb-000040
Figure PCTCN2016093026-appb-000040
采用与实施例11中化合物A-1相同的合成方法，不同在于，将溴苯置换为等当量的2-溴-9，9-二甲基芴，得到淡黄色固体60.6g，收率79％。The same synthesis method as in the compound A-1 of Example 11 was employed, except that bromobenzene was replaced by an equivalent amount of 2-bromo-9,9-dimethylhydrazine to give 60.6 g of a pale yellow solid, yield 79%. .
合成实施例19.化合物A-9的合成Synthesis Example 19. Synthesis of Compound A-9
采用与实施例11中化合物A-1相同的合成方法，不同在于，将溴苯置换为等当量的3-溴-9，9-双甲基芴，得到淡黄色固体54g，收率76％。The same synthesis method as in the compound A-1 of Example 11 was used, except that bromobenzene was replaced with an equivalent amount of 3-bromo-9,9-bismethylhydrazine to obtain 54 g of a pale yellow solid, yield 76%.
A-9的核磁波普数据：A-9 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.55(s，2H)，8.42(s，4H)，8.19(s，2H)，8.10(s，4H)，7.98(d，J＝1.4Hz，1H)，7.94(d，J＝37.7Hz，3H)，7.78(s，2H)，7.57(s，2H)，7.52(s，2H)，7.34(s，2H)，7.24(s，2H)，7.16(s，2H)，7.11(s，2H)，1.69(s，12H). 1 H NMR (500 MHz, Chloroform) δ 8.55 (s, 2H), 8.42 (s, 4H), 8.19 (s, 2H), 8.10 (s, 4H), 7.98 (d, J = 1.4 Hz, 1H), 7.94 (d, J = 37.7 Hz, 3H), 7.78 (s, 2H), 7.57 (s, 2H), 7.52 (s, 2H), 7.34 (s, 2H), 7.24 (s, 2H), 7.16 (s) , 2H), 7.11 (s, 2H), 1.69 (s, 12H).
合成实施例20.化合物A-10的合成Synthesis Example 20. Synthesis of Compound A-10
采用与实施例11中化合物A-1相同的合成方法，不同在于，将溴苯置换为等当量的3-溴-11，11-二甲基苯并[b]芴，得到黄色固体47.7g，收率55％。The same synthesis method as in the compound A-1 of Example 11 was employed, except that bromobenzene was replaced with an equivalent amount of 3-bromo-11,11-dimethylbenzo[b]indole to obtain a yellow solid 47.7 g. The yield was 55%.
合成实施例21.化合物A-11的合成Synthesis Example 21. Synthesis of Compound A-11
Figure PCTCN2016093026-appb-000041
Figure PCTCN2016093026-appb-000041
将中间体M1(38.2g，0.1mol)、溴苯(31.5g，0.2mol)、CuI(3.3g，17.1mmol)、K3PO4(21.8g，102.9mmol)和乙二胺(2.3毫升，34.3mmol)与甲苯(500毫升)混合，在回流条件下搅拌1天，冷却到室温，加去离子水淬灭反应。用100ml乙酸乙酯萃取上述反应体系三次，合并得到的有机相，并用无水MgSO4干燥，过滤后将有机相进行减压除去溶剂，对得到的蒸馏剩余物进行柱分离(洗脱液：二氯甲烷/正己烷)，得到白色化合物A-11(37.4g，收率70％)。Intermediate M1 (38.2 g, 0.1 mol), bromobenzene (31.5 g, 0.2 mol), CuI (3.3 g, 17.1 mmol), K 3 PO 4 (21.8 g, 102.9 mmol) and ethylenediamine (2.3 ml, 34.3 mmol) was mixed with toluene (500 ml), stirred under reflux for 1 day, cooled to room temperature and quenched with deionized water. The reaction system was extracted three times with 100 ml of ethyl acetate. The obtained organic phase was combined and dried over anhydrous MgSO 4 filtered, and the organic phase was evaporated to remove solvent, and the obtained distillation residue was subjected to column separation (eluent: Methyl chloride / n-hexane) gave white compound A-11 (37.4 g, yield 70%).
合成实施例22.化合物A-12的合成 Synthesis Example 22. Synthesis of Compound A-12
Figure PCTCN2016093026-appb-000042
Figure PCTCN2016093026-appb-000042
将中间体M1(38.2g，0.1mol)、4-溴联苯(46.6g，0.2mol)、CuI(3.3g，17.1mmol)、K3PO4(21.8g，102.9mmol)和乙二胺(2.3毫升，34.3mmol)与甲苯(500毫升)混合，在回流条件下搅拌1天，冷却到室温，加去离子水淬灭反应。用100ml乙酸乙酯萃取上述反应体系三次，合并得到的有机相，并用无水MgSO4干燥，过滤后将有机相进行减压除去溶剂，对得到的蒸馏剩余物进行柱分离(洗脱液：二氯甲烷/正己烷)，得到白色化合物A-12(52.2g，收率76％)。Intermediate M1 (38.2 g, 0.1 mol), 4-bromobiphenyl (46.6 g, 0.2 mol), CuI (3.3 g, 17.1 mmol), K 3 PO 4 (21.8 g, 102.9 mmol) and ethylenediamine ( 2.3 ml, 34.3 mmol) was mixed with toluene (500 ml), stirred under reflux for 1 day, cooled to room temperature and quenched with deionized water. The reaction system was extracted three times with 100 ml of ethyl acetate. The obtained organic phase was combined and dried over anhydrous MgSO 4 filtered, and the organic phase was evaporated to remove solvent, and the obtained distillation residue was subjected to column separation (eluent: Methyl chloride / n-hexane) gave white compound A-12 (52.2 g, yield 76%).
合成实施例22.化合物A-13的合成Synthesis Example 22. Synthesis of Compound A-13
Figure PCTCN2016093026-appb-000043
Figure PCTCN2016093026-appb-000043
将中间体M1(38.2g，0.1mol)、2-溴萘(41.4g，0.2mol)、CuI(3.3g，17.1mmol)、K3PO4(21.8g，102.9mmol)和乙二胺(2.3毫升，34.3mmol)与甲苯(500毫升)混合，在回流条件下搅拌1天，冷却到室温，加去离子水淬灭反应。用100ml乙酸乙酯萃取上述反应体系三次，合并得到的有机相，并用无水MgSO4干燥，过滤后将有机相进行减压除去溶剂，对得到的蒸馏剩余物进行柱分离(洗脱液：二氯甲烷/正己烷)，得到白色化合物A-13(43.2g，收率68％)。Intermediate M1 (38.2 g, 0.1 mol), 2-bromonaphthalene (41.4 g, 0.2 mol), CuI (3.3 g, 17.1 mmol), K 3 PO 4 (21.8 g, 102.9 mmol) and ethylenediamine (2.3) ML, 34.3 mmol) was mixed with toluene (500 mL), stirred under reflux for 1 day, cooled to room temperature and quenched with deionized water. The reaction system was extracted three times with 100 ml of ethyl acetate. The obtained organic phase was combined and dried over anhydrous MgSO 4 filtered, and the organic phase was evaporated to remove solvent, and the obtained distillation residue was subjected to column separation (eluent: Methyl chloride / n-hexane) gave white compound A-13 (43.2 g, yield 68%).
合成实施例23.化合物A-14的合成Synthesis Example 23. Synthesis of Compound A-14
Figure PCTCN2016093026-appb-000044
Figure PCTCN2016093026-appb-000044
将中间体M2(6.92g，10mmol)、苯硼酸(3.05g，25mmol)、Pd(PPh3)4(0.58g，0.5mmol)、Na2CO3(5.3g，50mmol)、甲苯(60mL)和EtOH(20mL)和蒸馏水(20mL)混合，然后在回流下搅拌反应2小时。反应完成后，蒸馏水洗涤反应体系，然后用100ml乙酸乙酯萃取三次，合并得到的有机层，用MgSO4干燥有机层，并用旋转蒸发器除 去溶剂，对除去溶剂的剩余物进行柱分离，得到化合物A-14，为白色固体(5.63g，84％)。Intermediate M2 (6.92 g, 10 mmol), phenylboronic acid (3.05 g, 25 mmol), Pd(PPh 3 ) 4 (0.58 g, 0.5 mmol), Na 2 CO 3 (5.3 g, 50 mmol), toluene (60 mL) EtOH (20 mL) was mixed with distilled water (20 mL), and then the mixture was stirred under reflux for 2 hr. After completion of the reaction, the reaction system was washed with distilled water, and then extracted three times with 100 ml of ethyl acetate. The obtained organic layer was combined, and the organic layer was dried with MgSO 4 , and the solvent was removed by a rotary evaporator, and the residue of the solvent was subjected to column separation to obtain a compound. A-14, as a white solid (5.63 g, 84%).
A-14的核磁波普数据：A-14 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.42(s，21H)，8.38-7.82(m，51H)，8.07-7.82(m，2H)，7.79(s，14H)，7.75(s，23H)，7.62(s，20H)，7.58(s，15H)，7.49(d，J＝5.0Hz，46H)，7.41(s，7H). 1 H NMR (500MHz, Chloroform) δ8.42 (s, 21H), 8.38-7.82 (m, 51H), 8.07-7.82 (m, 2H), 7.79 (s, 14H), 7.75 (s, 23H), 7.62 (s, 20H), 7.58 (s, 15H), 7.49 (d, J = 5.0 Hz, 46H), 7.41 (s, 7H).
合成实施例24.化合物A-15的合成Synthesis Example 24. Synthesis of Compound A-15
采用与合成实施例21相同的合成方法，不同在于，将溴苯置换为等当量的2-溴-9，9-二甲基芴，反应完成后得到化合物A-15为白色固体(59.8g，收率78％)。The same synthesis method as in Synthesis Example 21 was employed, except that bromobenzene was replaced with an equivalent amount of 2-bromo-9,9-dimethylhydrazine, and after completion of the reaction, Compound A-15 was obtained as a white solid (59.8 g, Yield 78%).
合成实施例25.化合物A-16的合成Synthesis Example 25. Synthesis of Compound A-16
Figure PCTCN2016093026-appb-000045
Figure PCTCN2016093026-appb-000045
N2保护下，三口瓶中加入碘苯22g(0.11mol)，中间体M846.1g(O.1mol)，氯化亚铜2g(20mmol)，水合1，10-菲啰啉4g(20mmol)，氢氧化钾16.8g(0.3mol)，二甲苯300ml。反应体系保持回流反应20h，反应完全，蒸馏水洗涤反应体系，然后用100ml乙酸乙酯萃取三次，合并得到的有机层，用MgSO4干燥有机层，并用旋转蒸发器除去溶剂，对除去溶剂的剩余物进行柱分离，得到中间体化合物A-16-1，为白色固体(52.3g，86％)。Under N2 protection, 22g (0.11mol) of iodobenzene, intermediate M846.1g (0.11mol), cuprous chloride 2g (20mmol), hydrated 1,10-phenanthroline 4g (20mmol), hydrogen Potassium oxide 16.8 g (0.3 mol), xylene 300 ml. The reaction system was kept under reflux for 20 hours, and the reaction was completed. The reaction mixture was washed with distilled water, and then extracted three times with 100 ml of ethyl acetate. The organic layer obtained was combined, dried over MgSO 4 and solvent was evaporated to remove solvent. Column separation gave intermediate compound A-16-1 as a white solid (52.3 g, 86%).
将中间体A-16-1(6.14g，10mmol)、联苯硼酸(22g，11mmol)、Pd(PPh3)4(0.58g，0.5mmol)、Na2CO3(5.3g，50mmol)、甲苯(60mL)和EtOH(20mL)和蒸馏水(20mL)混合，然后在回流下搅拌反应2小时。反应完成后，蒸馏水洗涤反应体系，然后用100ml乙酸乙酯萃取三次，合并得到的有机层，用MgSO4干燥有机层，并用旋转蒸发器除去溶剂，对除去溶剂的剩余物进行柱分离，得到化合物A-16，为白色固体(5.97g，87％)。Intermediate A-16-1 (6.14 g, 10 mmol), biphenylboronic acid (22 g, 11 mmol), Pd(PPh 3 ) 4 (0.58 g, 0.5 mmol), Na 2 CO 3 (5.3 g, 50 mmol), toluene (60 mL) and EtOH (20 mL) and distilled water (20 mL) were mixed, and then the mixture was stirred under reflux for 2 hours. After completion of the reaction, the reaction system was washed with distilled water, and then extracted three times with 100 ml of ethyl acetate. The obtained organic layer was combined, and the organic layer was dried with MgSO 4 , and the solvent was removed by a rotary evaporator, and the residue of the solvent was subjected to column separation to obtain a compound. A-16, as a white solid (5.97 g, 87%).
合成实施例26.化合物A-17的合成Synthesis Example 26. Synthesis of Compound A-17
采用与合成实施例25相同的合成方法，不同在于，将中间体M8置换为等当量的中间体M9，将联苯硼酸置换为等当量的2-三亚苯硼酸，反应完成后得到化合物A-17为白色固体。The same synthesis method as in Synthesis Example 25 was employed except that the intermediate M8 was replaced with an equivalent of the intermediate M9, and the biphenylboronic acid was replaced with an equivalent amount of 2-triphenylbenzeneboronic acid. After the completion of the reaction, the compound A-17 was obtained. It is a white solid.
合成实施例27.化合物A-18的合成 Synthesis Example 27. Synthesis of Compound A-18
Figure PCTCN2016093026-appb-000046
Figure PCTCN2016093026-appb-000046
向1升三口瓶中加入3-苯基盐酸苯肼(91.6g，0.415mol)，二苯并[a，e]-5，11-环辛二烯(6H，12H)-二酮(49g，0.207mol)，乙醇(400毫升)，搅拌条件下，3min内滴加2g浓硫酸，在65℃下反应4小时，反应结束后，冷却至室温，过滤，依次用乙醇、石油醚洗涤滤饼，得到化合物A-18-1(120g，90％)。To a 1 liter three-necked flask was added 3-phenylhydrazine hydrochloride (91.6 g, 0.415 mol), dibenzo[a,e]-5,11-cyclooctadiene (6H,12H)-dione (49 g, 0.207mol), ethanol (400ml), 2g concentrated sulfuric acid was added dropwise under stirring for 3 hours, and reacted at 65 ° C for 4 hours. After the reaction was completed, it was cooled to room temperature, filtered, and the filter cake was washed with ethanol and petroleum ether in order. Compound A-18-1 (120 g, 90%) was obtained.
向1升三口瓶中加入化合物C-19-1(48g，74.8mmol)，乙酸(650g)和三氟乙酸(65g，0.57mol)，在72℃下回流反应15小时，冷却至室温，过滤，依次用乙酸、石油醚洗涤滤饼，得化合物A-18-2(33g，82％)。Compound C-19-1 (48 g, 74.8 mmol), acetic acid (650 g) and trifluoroacetic acid (65 g, 0.57 mol) were added to a 1 liter three-necked flask, and the mixture was refluxed at 72 ° C for 15 hours, cooled to room temperature, and filtered. The filter cake was washed successively with acetic acid and petroleum ether to give Compound A-18-2 (33 g, 82%).
将二甲苯(100毫升)、C-19-2(5.4g，10mmol)，溴苯(3.9g，25mmol)，CuI(0.9g，5mmol)，反式-二氨基环己烷(2.1毫升，20mmol)和碳酸铯(6.5g，20mmol)混合，回流反应3小时，反应结束后，冷却至室温，过滤，然后用二氯甲烷(二氯甲烷)洗涤滤饼，滤液进行减压蒸馏，将得到的蒸馏剩余物进行柱分离(洗脱液：DCM/PE＝1/2，v/v(体积比为1∶2的二氯甲烷和石油醚的混合溶液))，得到化合物A-18，为白色固体(5.0g，产率72％)。Xylene (100 ml), C-19-2 (5.4 g, 10 mmol), bromobenzene (3.9 g, 25 mmol), CuI (0.9 g, 5 mmol), trans-diaminocyclohexane (2.1 ml, 20 mmol) The mixture was mixed with cesium carbonate (6.5 g, 20 mmol), and refluxed for 3 hours. After the reaction was completed, it was cooled to room temperature, filtered, and then the filter cake was washed with dichloromethane (dichloromethane), and the filtrate was distilled under reduced pressure. The residue was distilled for column separation (eluent: DCM/PE = 1/2, v/v (mixed solution of dichloromethane and petroleum ether in a volume ratio of 1:2)) to give compound A-18 as white Solid (5.0 g, yield 72%).
合成实施例28.中间体M11的合成Synthesis Example 28. Synthesis of Intermediate M11
Figure PCTCN2016093026-appb-000047
Figure PCTCN2016093026-appb-000047
向1升三口瓶中加入3-溴苯肼盐酸盐(92.8g，0.415mol)，二苯并[a，e]-5，11-环辛二烯(6H，12H)-二酮(49g，0.207mol)，乙醇(400毫升)，搅拌条件下，3min内滴加2g浓硫酸，在65℃下反应4小时，反应结束后，冷却至室温，过滤，依次用乙醇、石油醚洗涤滤饼，得到中间体化合物M11-1(122g，91％)。To a 1 liter three-necked flask was added 3-bromophenylhydrazine hydrochloride (92.8 g, 0.415 mol), dibenzo[a,e]-5,11-cyclooctadiene (6H,12H)-dione (49 g) , 0.207mol), ethanol (400ml), under stirring, add 2g concentrated sulfuric acid in 3min, react at 65 ° C for 4 hours, after the reaction is finished, cool to room temperature, filter, wash the filter cake with ethanol, petroleum ether The intermediate compound M11-1 (122 g, 91%) was obtained.
向1升三口瓶中加入化合物M11-1(48.4g，74.8mmol)，乙酸(650g)和三氟乙酸(65g，0.57mol)，在72℃下回流反应15小时，冷却至室温，过滤，依次用乙酸、 石油醚洗涤滤饼，得中间体化合物M11-2(35g，85％)。Compound M11-1 (48.4 g, 74.8 mmol), acetic acid (650 g) and trifluoroacetic acid (65 g, 0.57 mol) were added to a 1-liter three-necked flask, and the mixture was refluxed at 72 ° C for 15 hours, cooled to room temperature, and filtered. With acetic acid, The filter cake was washed with petroleum ether to give the intermediate compound M11-2 (35 g, 85%).
将二甲苯(100毫升)、M11-2(5.4g，10mmol)，碘苯(5.1g，25mmol)，CuI(0.9g，5mmol)，反式-二氨基环己烷(2.1毫升，20mmol)和碳酸铯(6.5g，20mmol)混合，回流反应3小时，反应结束后，冷却至室温，过滤，然后用二氯甲烷(二氯甲烷)洗涤滤饼，合并滤液，干燥，然后减压除去溶剂，将得到的蒸馏剩余物进行柱分离(DCM/PE＝1/2，v/v(体积比为1∶2的二氯甲烷和石油醚的混合溶液))，得到中间体化合物M11，为白色固体(5.88g，产率85％)。Xylene (100 ml), M11-2 (5.4 g, 10 mmol), iodobenzene (5.1 g, 25 mmol), CuI (0.9 g, 5 mmol), trans-diaminocyclohexane (2.1 ml, 20 mmol) and The cesium carbonate (6.5 g, 20 mmol) was mixed and refluxed for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, filtered, and then the filter cake was washed with dichloromethane (dichloromethane), and the filtrate was dried. The obtained distillation residue was subjected to column separation (DCM/PE = 1/2, v/v (mixed solution of dichloromethane and petroleum ether in a volume ratio of 1:2)) to give the intermediate compound M11 as a white solid. (5.88 g, yield 85%).
合成实施例29.化合物A-19的合成Synthesis Example 29. Synthesis of Compound A-19
Figure PCTCN2016093026-appb-000048
Figure PCTCN2016093026-appb-000048
将中间体M11(6.92g，10mmol)、4-联苯硼酸(4.95g，25mmol)、Pd(PPh3)4(0.58g，0.5mmol)、Na2CO3(5.3g，50mmol)、甲苯(60mL)和EtOH(20mL)和蒸馏水(20mL)混合，然后在回流下搅拌反应2小时。反应完成后，蒸馏水洗涤反应体系，然后用乙酸乙酯萃取，得到有机层，用MgSO4干燥有机层，并用旋转蒸发器除去溶剂，对除去溶剂的剩余物进行柱分离，得到化合物A-19，为白色固体(7.0g，81％)。Intermediate M11 (6.92 g, 10 mmol), 4-biphenylboronic acid (4.95 g, 25 mmol), Pd(PPh 3 ) 4 (0.58 g, 0.5 mmol), Na 2 CO 3 (5.3 g, 50 mmol), toluene ( 60 mL) and EtOH (20 mL) and distilled water (20 mL) were mixed, and then the reaction was stirred under reflux for 2 hours. After completion of the reaction, the reaction system was washed with distilled water, and then extracted with ethyl acetate to give an organic layer. The organic layer was dried with MgSO 4 and evaporated to remove solvent. It was a white solid (7.0 g, 81%).
合成实施例30.化合物A-20的合成Synthesis Example 30. Synthesis of Compound A-20
采用与实施例29相同的方法制备化合物A-20，不同在于将4-联苯硼酸替换为等当量的9，9-二甲基芴-2-硼酸，反应完成后，分离得到白色固体6.24g，收率为68％。Compound A-20 was prepared in the same manner as in Example 29 except that 4-diphenylboronic acid was replaced with an equivalent of 9,9-dimethylindole-2-boronic acid, and after completion of the reaction, 6.24 g of a white solid was obtained. The yield was 68%.
合成实施例31.化合物A-21的合成Synthesis Example 31. Synthesis of Compound A-21
Figure PCTCN2016093026-appb-000049
Figure PCTCN2016093026-appb-000049
采用与合成实施例21相同的合成方法，不同在于，将中间体M1置换为等当量的中间体M4，反应完成后，得到白色固体4.32g，收率为68％。The same synthesis method as in Synthesis Example 21 was employed, except that the intermediate M1 was replaced with an equivalent of the intermediate M4, and after completion of the reaction, 4.32 g of a white solid was obtained, yield 68%.
A-21的核磁波普数据：A-21 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.61(s，1H)，8.43(d，J＝6.0Hz，3H)，8.28(s，1H)， 8.10(s，2H)，7.84(s，1H)，7.75(s，1H)，7.62(s，2H)，7.58(s，1H)，7.49(d，J＝10.0Hz，3H). 1 H NMR (500 MHz, Chloroform) δ 8.61 (s, 1H), 8.43 (d, J = 6.0 Hz, 3H), 8.28 (s, 1H), 8.10 (s, 2H), 7.84 (s, 1H), 7.75 (s, 1H), 7.62 (s, 2H), 7.58 (s, 1H), 7.49 (d, J = 10.0 Hz, 3H).
合成实施例32.化合物A-22的合成Synthesis Example 32. Synthesis of Compound A-22
采用与合成实施例29相同的合成方法，不同在于，将4-联苯硼酸换为等当量的9，9-二甲基-2-芴硼酸，反应完成后，得到淡黄色固体7.08g，收率为77％。The same synthesis method as in Synthesis Example 29 was employed, except that 4-diphenylboronic acid was changed to an equivalent amount of 9,9-dimethyl-2-indoleboric acid, and after completion of the reaction, a pale yellow solid was obtained. The rate is 77%.
合成实施例33.化合物A-23的合成Synthesis Example 33. Synthesis of Compound A-23
采用与实施例23相同的方法制备化合物A-23，不同在于将4-联苯硼酸替换为等当量的6，6，12，12-四甲基-6，12-二氢茚并[1，2-b]芴-2-硼酸，反应完成后，分离得到淡黄色固体6.68g，收率为58％。Compound A-23 was prepared in the same manner as in Example 23 except that 4-diphenylboronic acid was replaced with an equivalent amount of 6,6,12,12-tetramethyl-6,12-dihydroindole[1, 2-b]indole-2-boronic acid. After completion of the reaction, 6.68 g of a pale yellow solid was obtained.
合成实施例34.化合物A-24的合成Synthesis Example 34. Synthesis of Compound A-24
Figure PCTCN2016093026-appb-000050
Figure PCTCN2016093026-appb-000050
将中间体M5(48.2g，0.1mol)、2-溴萘(41.4g，0.2mol)、CuI(3.3g，17.1mmol)、K3PO4(21.8g，102.9mmol)和乙二胺(2.3毫升，34.3mmol)与甲苯(500毫升)混合，在回流条件下搅拌1天，冷却到室温，加去离子水淬灭反应。用100ml乙酸乙酯萃取上述反应体系三次，合并得到的有机相，并用无水MgSO4干燥，过滤后将有机相进行减压除去溶剂，对得到的蒸馏剩余物进行柱分离(洗脱液：二氯甲烷/正己烷)，得到白色化合物A-24(49.9g，收率68％)。Intermediate M5 (48.2 g, 0.1 mol), 2-bromonaphthalene (41.4 g, 0.2 mol), CuI (3.3 g, 17.1 mmol), K 3 PO 4 (21.8 g, 102.9 mmol) and ethylenediamine (2.3) ML, 34.3 mmol) was mixed with toluene (500 mL), stirred under reflux for 1 day, cooled to room temperature and quenched with deionized water. The reaction system was extracted three times with 100 ml of ethyl acetate. The obtained organic phase was combined and dried over anhydrous MgSO 4 filtered, and the organic phase was evaporated to remove solvent, and the obtained distillation residue was subjected to column separation (eluent: Methyl chloride / n-hexane) gave white compound A-24 (49.9 g, yield 68%).
合成实施例35.化合物B-1的合成Synthesis Example 35. Synthesis of Compound B-1
Figure PCTCN2016093026-appb-000051
Figure PCTCN2016093026-appb-000051
将中间体M2(69.6g，0.1mol)、溴苯(31.5g，0.2mol)、CuI(3.3g，17.1mmol)、K3PO4(21.8g，102.9mmol)和乙二胺(2.3毫升，34.3mmol)与甲苯(500毫升)混合，在回流条件下搅拌1天，冷却到室温，加去离子水淬灭反应。用100ml乙酸乙酯萃取上述反应体系三次，合并得到的有机相，并用无水MgSO4干燥，过滤后将有机相进行减压除去溶剂，对得到的蒸馏剩余物进行柱分离(洗脱液：二氯甲烷/正己烷)，得到 淡黄色化合物B-1(55.4g，收率64％)。Intermediate M2 (69.6 g, 0.1 mol), bromobenzene (31.5 g, 0.2 mol), CuI (3.3 g, 17.1 mmol), K 3 PO 4 (21.8 g, 102.9 mmol) and ethylenediamine (2.3 ml, 34.3 mmol) was mixed with toluene (500 ml), stirred under reflux for 1 day, cooled to room temperature and quenched with deionized water. The reaction system was extracted three times with 100 ml of ethyl acetate. The obtained organic phase was combined and dried over anhydrous MgSO 4 filtered, and the organic phase was evaporated to remove solvent, and the obtained distillation residue was subjected to column separation (eluent: Methyl chloride/n-hexane) gave pale yellow compound B-1 (55.4 g, yield: 64%).
B-1的核磁波普数据：Nuclear magnetic pop data of B-1:
1H NMR(500MHz，Chloroform)δ8.43-8.37(m，1H)，8.36-8.29(m，1H)，8.22-8.12(m，1H)，8.09-7.97(m，2H)，7.96-7.78(m，2H)，7.64-7.54(m，2H)，7.54-7.24(m，4H). 1 H NMR (500 MHz, Chloroform) δ 8.43 - 8.37 (m, 1H), 8.36 - 8.29 (m, 1H), 8.22 - 8.12 (m, 1H), 8.09 - 7.97 (m, 2H), 7.96 - 7.78 ( m, 2H), 7.64 - 7.54 (m, 2H), 7.54 - 7.24 (m, 4H).
合成实施例36.化合物B-2的合成Synthesis Example 36. Synthesis of Compound B-2
Figure PCTCN2016093026-appb-000052
Figure PCTCN2016093026-appb-000052
将盐酸9-苯基咔唑-3肼(30.98g，0.1mol)，中间体M(47.2g，0.2mol)和400毫升的乙醇混合，搅拌条件下，3min内滴加2.1g浓硫酸，在65℃下反应4小时，反应结束后，冷却至室温，过滤，依次用乙醇、石油醚洗涤滤饼，得固体B-2-1(68g，收率83％)。Mix 9-phenyloxazole-3 hydrazine hydrochloride (30.98 g, 0.1 mol), intermediate M (47.2 g, 0.2 mol) and 400 ml of ethanol, and add 2.1 g of concentrated sulfuric acid in 3 min under stirring. The reaction was carried out at 65 ° C for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, filtered, and the filter cake was washed with ethanol and petroleum ether to give solid B-2-1 (68 g, yield 83%).
将述固体B-2-1(68g，0.083mol)、600毫升乙酸和60毫升三氟乙酸混合，在72℃下，回流反应15小时，冷却至室温，过滤，依次用乙酸、石油醚洗涤滤饼，得化合物B-2-2(32g，收率54％)。The solid B-2-1 (68 g, 0.083 mol), 600 ml of acetic acid and 60 ml of trifluoroacetic acid were mixed, refluxed at 72 ° C for 15 hours, cooled to room temperature, filtered, and washed with acetic acid and petroleum ether. The cake obtained Compound B-2-2 (32 g, yield 54%).
将中间体B-2-2(35.84g，50mmol)、溴苯(39.2g，250mol)、CuI(1g，5.3mmol)、K3PO4(7g，35mmol)、二氨基环己烷(6毫升，34.3mmol)和二甲苯(500毫升)混合，在回流条件下搅拌反应1天，反应结束后，冷却至室温，用乙酸乙酯萃取有机层，对分离得到的有机层进行减压蒸馏，对得到的蒸馏剩余物进行柱分离(洗脱液：二氯甲烷/己烷)，得到白色化合物B-2(29.8g，收率62％)。Intermediate B-2-2 (35.84 g, 50 mmol), bromobenzene (39.2 g, 250 mol), CuI (1 g, 5.3 mmol), K 3 PO 4 (7 g, 35 mmol), diaminocyclohexane (6 ml) , 34.3 mmol) and xylene (500 ml) were mixed, and the reaction was stirred under reflux for 1 day. After the reaction was completed, the mixture was cooled to room temperature, and the organic layer was extracted with ethyl acetate. The obtained distillation residue was subjected to column chromatography (eluent: dichloromethane /hexane) to afford white compound B-2 (29.8 g, yield 62%).
合成实施例37.化合物B-3的合成Synthesis Example 37. Synthesis of Compound B-3
Figure PCTCN2016093026-appb-000053
Figure PCTCN2016093026-appb-000053
将中间体M7(6.9g，10mmol)、9-苯基-[9H]-咔唑-3-硼酸(7.2g，25mmol)、Pd(PPh3)4(0.58g，0.5mmol)、K2CO3(5.3g，50mmol)、甲苯(60mL)和EtOH(20mL)和蒸 馏水(20mL)混合，然后在120℃下搅拌反应2小时。反应完成后，蒸馏水洗涤反应体系，然后用乙酸乙酯萃取，得到有机层，用MgSO4干燥有机层，并用旋转蒸发器除去溶剂，对除去溶剂的剩余物进行柱分离，得到化合物B-3，为淡黄色固体(8.8g，87％)。Intermediate M7 (6.9 g, 10 mmol), 9-phenyl-[9H]-carbazole-3-boronic acid (7.2 g, 25 mmol), Pd(PPh 3 ) 4 (0.58 g, 0.5 mmol), K 2 CO 3 (5.3 g, 50 mmol), toluene (60 mL) and EtOH (20 mL) and distilled water (20 mL) were mixed, and then the mixture was stirred at 120 ° C for 2 hours. After completion of the reaction, the reaction system was washed with distilled water, and then extracted with ethyl acetate to give an organic layer. The organic layer was dried with MgSO 4 and evaporated to remove solvent. It was a pale yellow solid (8.8 g, 87%).
B-3的核磁波普数据：B-3 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ9.81-9.75(m，2H)，9.37(dd，J＝7.5，1.4Hz，1H)，8.85(dd，J＝7.5，2.0Hz，2H)，8.49-8.41(m，4H)，8.17(dd，J＝7.4，1.6Hz，1H)，8.05-7.84(m，9H)，7.60(t，J＝7.5Hz，4H)，7.56-7.22(m，14H)，7.07(dt，J＝7.5，2.2Hz，2H)，6.76(td，J＝7.5，2.0Hz，2H)，6.64(tdt，J＝7.3，4.9，2.2Hz，2H). 1 H NMR (500 MHz, Chloroform) δ 9.81 - 9.75 (m, 2H), 9.37 (dd, J = 7.5, 1.4 Hz, 1H), 8.85 (dd, J = 7.5, 2.0 Hz, 2H), 8.49-8.41 (m, 4H), 8.17 (dd, J = 7.4, 1.6 Hz, 1H), 8.05-7.84 (m, 9H), 7.60 (t, J = 7.5 Hz, 4H), 7.56-7.22 (m, 14H), 7.07 (dt, J = 7.5, 2.2 Hz, 2H), 6.76 (td, J = 7.5, 2.0 Hz, 2H), 6.64 (tdt, J = 7.3, 4.9, 2.2 Hz, 2H).
合成实施例38.化合物B-4的合成Synthesis Example 38. Synthesis of Compound B-4
采用与实施例11相同的方法制备化合物B-4，不同在于将溴苯替换为等当量的9-(4-bromophenyl)-9H-carbazole，反应完成后，分离得到淡黄色固体6.5g，收率为76％。Compound B-4 was prepared in the same manner as in Example 11 except that bromobenzene was replaced by an equivalent of 9-(4-bromophenyl)-9H-carbazole. After completion of the reaction, 6.5 g of a pale yellow solid was obtained. It is 76%.
B-4的核磁波普数据：Nuclear magnetic pop data of B-4:
1H NMR(500MHz，Chloroform)δ8.45-8.31(m，1H)，8.22-8.07(m，1H)，8.06-7.91(m，2H)，7.91-7.78(m，1H)，7.56-7.29(m，3H). 1 H NMR (500 MHz, Chloroform) δ 8.45-8.31 (m, 1H), 8.22-8.07 (m, 1H), 8.06-7.91 (m, 2H), 7.91-7.78 (m, 1H), 7.56-7.29 ( m, 3H).
合成实施例39.化合物B-5的合成Synthesis Example 39. Synthesis of Compound B-5
采用与实施例11相同的方法制备化合物B-5，不同在于将溴苯替换为等当量的9-(3-bromophenyl)-9H-carbazole，反应完成后，分离得到淡黄色固体6.7g，收率为78％。Compound B-5 was prepared in the same manner as in Example 11 except that bromobenzene was replaced by an equivalent of 9-(3-bromophenyl)-9H-carbazole. After completion of the reaction, 6.7 g of a pale yellow solid was obtained. It is 78%.
合成实施例40.化合物B-6的合成Synthesis Example 40. Synthesis of Compound B-6
采用与实施例11相同的方法制备化合物B-6，不同在于将溴苯替换为等当量的3-溴-苯基咔唑，反应完成后，分离得到淡黄色固体6.06g，收率为70％。Compound B-6 was prepared in the same manner as in Example 11 except that bromobenzene was replaced with an equivalent of 3-bromo-phenyloxazole, and after completion of the reaction, 6.06 g of a pale yellow solid was obtained, yield 70%. .
B-6的核磁波普数据：B-6 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.62(dd，J＝16.8，1.4Hz，1H)，8.51(ddd，J＝14.0，7.6，1.5Hz，1H)，8.42(dt，J＝7.4，1.8Hz，1H)，8.21(ddd，J＝7.3，5.9，1.5Hz，1H)，8.14-8.02(m，1H)，8.06-7.95(m，1H)，7.95(dd，J＝7.8，2.1Hz，1H)，7.89(ddd，J＝7.5，4.1，2.0Hz，1H)，7.79(dd，J＝24.9，7.4Hz，1H)，7.70(ddd，J＝19.2，7.5，1.5Hz，1H)，7.60(t，J＝7.4Hz，2H)，7.54-7.24(m，7H). 1 H NMR (500 MHz, Chloroform) δ 8.62 (dd, J = 16.8, 1.4 Hz, 1H), 8.51 (ddd, J = 14.0, 7.6, 1.5 Hz, 1H), 8.42 (dt, J = 7.4, 1.8 Hz) , 1H), 8.21 (ddd, J = 7.3, 5.9, 1.5 Hz, 1H), 8.14 - 8.02 (m, 1H), 8.06-7.95 (m, 1H), 7.95 (dd, J = 7.8, 2.1 Hz, 1H) ), 7.89 (ddd, J = 7.5, 4.1, 2.0 Hz, 1H), 7.79 (dd, J = 24.9, 7.4 Hz, 1H), 7.70 (ddd, J = 19.2, 7.5, 1.5 Hz, 1H), 7.60 ( t, J = 7.4 Hz, 2H), 7.54 - 7.24 (m, 7H).
合成实施例41.化合物B-7的合成Synthesis Example 41. Synthesis of Compound B-7
采用与实施例21相同的方法制备化合物B-7，不同在于将溴苯替换为等当量的9-(4-bromophenyl)-9H-carbazole，反应完成后，分离得到白色固体B-7(4.7g，产率54％)。Compound B-7 was prepared in the same manner as in Example 21 except that bromobenzene was replaced by an equivalent of 9-(4-bromophenyl)-9H-carbazole. After completion of the reaction, a white solid B-7 (4.7 g) was obtained. , yield 54%).
合成实施例42.化合物B-8的合成Synthesis Example 42. Synthesis of Compound B-8
采用与实施例21相同的方法制备化合物B-8，不同在于将溴苯替换为等当量的9-(3-bromophenyl)-9H-carbazole，反应完成后，分离得到B-8，为白色固体5.5g，收率 为61％。Compound B-8 was prepared in the same manner as in Example 21 except that bromobenzene was replaced by an equivalent of 9-(3-bromophenyl)-9H-carbazole. After completion of the reaction, B-8 was obtained as a white solid. g, yield It is 61%.
合成实施例43.化合物B-9的合成Synthesis Example 43. Synthesis of Compound B-9
采用与实施例23相同的方法制备化合物B-9，不同在于将苯硼酸替换为等当量的(9-phenyl-9H-carbazol-3-yl)boronic acid，反应完成后，分离得到B-9，为淡黄色固体8.44g，收率为83％。Compound B-9 was prepared in the same manner as in Example 23 except that phenylboronic acid was replaced with an equivalent amount of (9-phenyl-9H-carbazol-3-yl)boronic acid. After completion of the reaction, B-9 was isolated. It was 8.44 g of a pale yellow solid in a yield of 83%.
B-9的核磁波普数据：B-9 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ9.01(d，J＝1.4Hz，1H)，8.97-8.91(m，2H)，8.42(dd，J＝7.3，1.5Hz，1H)，8.32(d，J＝7.5Hz，1H)，8.26-8.08(m，10H)，7.97(dd，J＝7.5，2.0Hz，2H)，7.90(dd，J＝7.7，2.0Hz，2H)，7.84(ddd，J＝7.5，5.9，1.6Hz，2H)，7.64-7.47(m，10H)，7.43(td，J＝7.5，1.6Hz，1H)，7.37-7.27(m，4H)，7.31-7.24(m，4H)，7.17(dd，J＝7.3，2.3Hz，1H)，7.09(ddd，J＝13.6，5.7，3.9Hz，2H)，6.69(dtd，J＝19.6，7.4，2.2Hz，2H)，6.60(dd，J＝5.7，3.8Hz，2H). 1 H NMR (500 MHz, Chloroform) δ 9.01 (d, J = 1.4 Hz, 1H), 8.97-8.91 (m, 2H), 8.42 (dd, J = 7.3, 1.5 Hz, 1H), 8.32 (d, J) = 7.5 Hz, 1H), 8.26-8.08 (m, 10H), 7.97 (dd, J = 7.5, 2.0 Hz, 2H), 7.90 (dd, J = 7.7, 2.0 Hz, 2H), 7.84 (ddd, J = 7.5, 5.9, 1.6 Hz, 2H), 7.64-7.47 (m, 10H), 7.43 (td, J = 7.5, 1.6 Hz, 1H), 7.37-7.27 (m, 4H), 7.31-7.24 (m, 4H) , 7.17 (dd, J = 7.3, 2.3 Hz, 1H), 7.09 (ddd, J = 13.6, 5.7, 3.9 Hz, 2H), 6.69 (dtd, J = 19.6, 7.4, 2.2 Hz, 2H), 6.60 (dd , J = 5.7, 3.8 Hz, 2H).
合成实施例44.化合物B-10的合成Synthesis Example 44. Synthesis of Compound B-10
采用与实施例23相同的方法制备化合物B-10，不同在于将中间体M2替换为等当量的中间体M3，同时将苯硼酸置换为等当量的(4-(9H-carbazol-9-y1)phenyl)boronic acid，反应完成后，分离得到B-10，为类白色固体(7.73g，76％)。Compound B-10 was prepared in the same manner as in Example 23 except that the intermediate M2 was replaced with an equivalent of the intermediate M3, and the phenylboronic acid was replaced with an equivalent (4-(9H-carbazol-9-y1) Phenyl)boronic acid. After completion of the reaction, B-10 was obtained as an off-white solid (7.73 g, 76%).
B-10的核磁波普数据：B-10 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ9.15-9.09(m，1H)，8.55-8.39(m，4H)，8.40-8.29(m，2H)，8.20-8.13(m，1H)，8.00-7.90(m，2H)，7.90(dt，J＝7.7，3.0Hz，2H)，7.72-7.55(m，4H)，7.50-7.38(m，2H)，7.35-7.24(m，2H)，7.19(ddd，J＝12.7，7.4，2.1Hz，1H)，6.69(ddtd，J＝50.7，23.4，7.5，2.2Hz，2H). 1 H NMR (500 MHz, Chloroform) δ 9.15-9.09 (m, 1H), 8.55-8.39 (m, 4H), 8.40-8.29 (m, 2H), 8.20-8.13 (m, 1H), 8.00-7.90 ( m, 2H), 7.90 (dt, J = 7.7, 3.0 Hz, 2H), 7.72 - 7.55 (m, 4H), 7.50 - 7.38 (m, 2H), 7.35 - 7.24 (m, 2H), 7.19 (ddd, J=12.7, 7.4, 2.1 Hz, 1H), 6.69 (ddtd, J=50.7, 23.4, 7.5, 2.2 Hz, 2H).
合成实施例45.化合物B-11的合成Synthesis Example 45. Synthesis of Compound B-11
采用与实施例21相同的方法制备化合物B-11，不同在于将溴苯替换为等当量的3-bromo-9-ethyl-9H-carbazole，反应完成后，分离得到B-11为类白色固体5.5g，收率为72％。Compound B-11 was prepared in the same manner as in Example 21 except that bromobenzene was replaced by an equivalent of 3-bromo-9-ethyl-9H-carbazole. After completion of the reaction, B-11 was isolated as a white solid. g, the yield was 72%.
合成实施例46.化合物B-12的合成Synthesis Example 46. Synthesis of Compound B-12
采用与实施例21相同的方法制备化合物B-12，不同在于将溴苯替换为等当量的3-bromo-9-phenyl-9H-carbazole，反应完成后，分离得到B-12，为淡黄色固体5.8g，收率为67％。Compound B-12 was prepared in the same manner as in Example 21 except that bromobenzene was replaced with an equivalent of 3-bromo-9-phenyl-9H-carbazole. After completion of the reaction, B-12 was obtained as a pale yellow solid. 5.8 g, yield 67%.
B-12的核磁波普数据：B-12 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.33(dddd，J＝13.1，11.6，7.0，1.8Hz，2H)，8.24-8.09(m，2H)，8.09-8.02(m，1H)，8.02-7.85(m，3H)，7.86-7.75(m，1H)，7.73-7.61(m，1H)，7.64-7.56(m，2H)，7.53-7.42(m，2H)，7.41-7.24(m，4H). 1 H NMR (500 MHz, Chloroform) δ 8.33 (dddd, J = 13.1, 11.6, 7.0, 1.8 Hz, 2H), 8.24-8.09 (m, 2H), 8.09-8.02 (m, 1H), 8.02-7.85 ( m, 3H), 7.86-7.75 (m, 1H), 7.73-7.61 (m, 1H), 7.64-7.56 (m, 2H), 7.53-7.42 (m, 2H), 7.41-7.24 (m, 4H).
合成实施例47.化合物B-13的合成 Synthesis Example 47. Synthesis of Compound B-13
采用与实施例25相同的方法制备化合物B-13，不同在于将中间体M8替换为等当量的中间体M9，将4-联苯硼酸置换为等当量的(9-phenyl-9H-carbazol-3-y1)boronic acid，反应完成后，分离得到B-13，为白色固体6.1g，收率为78％。Compound B-13 was prepared in the same manner as in Example 25 except that the intermediate M8 was replaced with an equivalent of the intermediate M9, and the 4-biphenylboronic acid was replaced with an equivalent (9-phenyl-9H-carbazol-3). -y1) Boronic acid, after completion of the reaction, B-13 was obtained as a white solid, 6.1 g, yield 78%.
B-13的核磁波普数据：B-13 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.50-8.43(m，3H)，8.36(dd，J＝7.5，1.4Hz，1H)，8.16(d，J＝1.0Hz，1H)，8.10(dt，J＝7.5，1.9Hz，3H)，8.03(dd，J＝7.4，2.1Hz，1H)，7.96-7.83(m，8H)，7.77(dd，J＝7.4，1.4Hz，1H)，7.67(d，J＝1.1Hz，2H)，7.60(t，J＝7.4Hz，6H)，7.54-7.47(m，2H)，7.49-7.37(m，3H)，7.37-7.24(m，7H). 1 H NMR (500 MHz, Chloroform) δ 8.50-8.43 (m, 3H), 8.36 (dd, J = 7.5, 1.4 Hz, 1H), 8.16 (d, J = 1.0 Hz, 1H), 8.10 (dt, J) = 7.5, 1.9 Hz, 3H), 8.03 (dd, J = 7.4, 2.1 Hz, 1H), 7.96-7.83 (m, 8H), 7.77 (dd, J = 7.4, 1.4 Hz, 1H), 7.67 (d, J=1.1 Hz, 2H), 7.60 (t, J=7.4 Hz, 6H), 7.54-7.47 (m, 2H), 7.49-7.37 (m, 3H), 7.37-7.24 (m, 7H).
合成实施例48.化合物B-14的合成Synthesis Example 48. Synthesis of Compound B-14
采用与实施例25相同的方法制备化合物B-14，不同在于将中间体M8替换为等当量的中间体M10，将4-联苯硼酸置换为等当量的(9-phenyl-9H-carbazol-3-yl)boronicacid，反应完成后，分离得到B-14，为白色固体6.5g，收率为85％。Compound B-14 was prepared in the same manner as in Example 25 except that the intermediate M8 was replaced with an equivalent of the intermediate M10, and the 4-biphenylboronic acid was replaced with an equivalent (9-phenyl-9H-carbazol-3). -yl)boronic acid, after completion of the reaction, B-14 was isolated as a white solid 6.5 g, yield: 85%.
合成实施例49.化合物B-15的合成Synthesis Example 49. Synthesis of Compound B-15
Figure PCTCN2016093026-appb-000054
Figure PCTCN2016093026-appb-000054
将盐酸-9H-咔唑-3-肼(103g，0.44mol)，二苯并[a，e]-5，11-环辛二烯(6H，12H)-二酮(49g，0.207mol)和400毫升的乙醇混合，搅拌条件下，3min内滴加2.1g浓硫酸，在65℃下反应4小时，反应结束后，冷却至室温，过滤，依次用乙醇、石油醚洗涤滤饼，得棕色固体150g。9H-indazole-3-indole hydrochloride (103 g, 0.44 mol), dibenzo[a,e]-5,11-cyclooctadiene (6H,12H)-dione (49 g, 0.207 mol) and 400 ml of ethanol was mixed, and 2.1 g of concentrated sulfuric acid was added dropwise under stirring for 3 hours, and reacted at 65 ° C for 4 hours. After the reaction was completed, it was cooled to room temperature, filtered, and the filter cake was washed with ethanol and petroleum ether to obtain a brown solid. 150g.
将150g上述固体、600毫升乙酸和60毫升三氟乙酸混合，在72℃下，回流反应15小时，冷却至室温，过滤，依次用乙酸、石油醚洗涤滤饼，得到中间体化合物M12，为白色固体(84.6g，75％)。150 g of the above solid, 600 ml of acetic acid and 60 ml of trifluoroacetic acid were mixed, refluxed at 72 ° C for 15 hours, cooled to room temperature, filtered, and the filter cake was washed successively with acetic acid and petroleum ether to give the intermediate compound M12 as white. Solid (84.6 g, 75%).
将中间体M12(28g，50mmol)、碘苯(51g，250mol)、CuI(1g，5.3mmol)、Cs2CO3(7g，35mmol)、乙二胺(10毫升，34.3mmol)和二甲苯(500毫升)混合，在回流条件下搅拌反应1天，反应结束后，冷却至室温，用乙酸乙酯萃取有机层，对分离得到的有机层进行减压蒸馏，对得到的蒸馏剩余物进行柱分离(洗脱液∶二氯甲烷/己烷)，得到化合物B-15，为淡黄色固体(26.8g，62％)。Intermediate M12 (28 g, 50 mmol), iodobenzene (51 g, 250 mol), CuI (1 g, 5.3 mmol), Cs 2 CO 3 (7 g, 35 mmol), ethylenediamine (10 ml, 34.3 mmol) and xylene ( 500 ml) were mixed, and the reaction was stirred under reflux for 1 day. After the reaction was completed, the mixture was cooled to room temperature, and the organic layer was extracted with ethyl acetate. The separated organic layer was subjected to distillation under reduced pressure, and the obtained distillation residue was subjected to column separation. (Eluent: methylene chloride / hexane) gave Compound B-15 as pale yellow solid (26.8 g, 62%).
合成实施例50.化合物B-16的合成 Synthesis Example 50. Synthesis of Compound B-16
采用与实施例49相同的方法制备化合物B-16，不同在于将盐酸-9H-咔唑-3-肼替换为等当量的盐酸-9H-咔唑-2-肼，经过三步反应，得到淡黄色固体29g，收率67.1％。Compound B-16 was prepared in the same manner as in Example 49 except that the hydrochloride-9H-carbazole-3-indole was replaced with an equivalent of -9H-carbazole-2-indole hydrochloride. The yellow solid was 29 g, and the yield was 67.1%.
合成实施例51.化合物B-17的合成Synthesis Example 51. Synthesis of Compound B-17
Figure PCTCN2016093026-appb-000055
Figure PCTCN2016093026-appb-000055
将2-溴硝基苯(46g，230mmol)、二苯并噻吩-3-硼酸(63，276mmol)、Pd(PPh3)4(5g，4.6mmol)、K2CO3(61g，575mmol)、600mL甲苯和200mL EtOH混合，向该混合物中加入200mL蒸馏水，然后在120℃下搅拌反应2小时。反应完成后，用蒸馏水洗涤反应体系，用乙酸乙酯萃取得到有机层，用MgSO4干燥有机层，并旋蒸除去溶剂。最后，对除去溶剂的剩余物进行柱分离，得到化合物B-17-1(61g，87％)。2-Bromonitrobenzene (46 g, 230 mmol), dibenzothiophene-3-boronic acid (63,276 mmol), Pd(PPh3)4 (5 g, 4.6 mmol), K 2 CO 3 (61 g, 575 mmol), 600 mL Toluene was mixed with 200 mL of EtOH, and 200 mL of distilled water was added to the mixture, followed by stirring at 120 ° C for 2 hours. After completion of the reaction, the reaction system was washed with distilled water, the organic layer was dried over MgSO 4 to obtain an organic layer was extracted with ethyl acetate, and the solvent was removed by rotary evaporation. Finally, the residue of the solvent was subjected to column separation to give Compound B-17-1 (61 g, 87%).
将化合物B-17-1(3.05g，10mmol)、30mL P(OEt)3和30mL 1，2-二氯苯混合后，在150℃下搅拌反应8小时，反应完毕后，除去溶剂，对除去溶剂的剩余物进行柱分离，得到化合物B-17-2(1.2g，48％)。After compound B-17-1 (3.05 g, 10 mmol), 30 mL of P(OEt) 3 and 30 mL of 1,2-dichlorobenzene were mixed, the reaction was stirred at 150 ° C for 8 hours. After completion of the reaction, the solvent was removed and removed. The residue of the solvent was subjected to column separation to give Compound B-17-2 (1.2 g, 48%).
将100毫升的二甲苯中、化合物M7(6.9g，10mmol)、化合物B-17-2(6.2g，25mmol)、CuI(0.9g，5mmol)、反式-二氨基环己烷(2.1毫升，20mmol)和碳酸铯(6.5g，20mmol)混合，搅拌回流3小时。反应完毕后，冷却至室温后，过滤，用二氯甲烷(二氯甲烷)洗涤滤饼，合并滤液，进行减压蒸馏除去溶剂，对得到的蒸馏剩余物进行柱分离，得到化合物B-17(5.6g，产率52％)，为淡黄色固体。100 ml of xylene, compound M7 (6.9 g, 10 mmol), compound B-17-2 (6.2 g, 25 mmol), CuI (0.9 g, 5 mmol), trans-diaminocyclohexane (2.1 ml, 20 mmol) and cesium carbonate (6.5 g, 20 mmol) were mixed and stirred under reflux for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, filtered, and the cake was washed with dichloromethane (dichloromethane), and the filtrate was combined. The solvent was evaporated under reduced pressure, and the obtained distillation residue was subjected to column separation to obtain Compound B-17 ( 5.6 g, yield 52%), as a pale yellow solid.
B-17的核磁波普数据：B-17 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ9.73(d，J＝7.5Hz，2H)，9.21(dd，J＝7.5，1.5Hz，1H)，8.69-8.57(m，5H)，8.47(dd，J＝7.3，1.5Hz，1H)，8.38-8.28(m，3H)，8.20(dt，J＝7.5，1.7Hz，2H)，8.12-7.99(m，5H)，7.98-7.93(m，2H)，7.80(td，J＝7.5，1.5Hz，1H)，7.74-7.60(m，3H)，7.54-7.36(m，4H)，7.37-7.29(m，4H)，7.32-7.20(m，4H)，7.07(td，J＝7.7，1.8Hz，2H)，6.77(dddd，J＝14.8，12.5，7.4，2.1Hz，3H)，6.63(td，J＝7.5，2.1Hz，1H). 1 H NMR (500 MHz, Chloroform) δ 9.73 (d, J = 7.5 Hz, 2H), 9.21. (dd, J = 7.5, 1.5 Hz, 1H), 8.69-8.57 (m, 5H), 8.47 (dd, J = 7.3, 1.5 Hz, 1H), 8.38-8.28 (m, 3H), 8.20 (dt, J = 7.5, 1.7 Hz, 2H), 8.12-7.99 (m, 5H), 7.98-7.93 (m, 2H), 7.80 (td, J=7.5, 1.5 Hz, 1H), 7.74-7.60 (m, 3H), 7.54-7.36 (m, 4H), 7.37-7.29 (m, 4H), 7.32-7.20 (m, 4H), 7.07 (td, J = 7.7, 1.8 Hz, 2H), 6.77 (dddd, J = 14.8, 12.5, 7.4, 2.1 Hz, 3H), 6.63 (td, J = 7.5, 2.1 Hz, 1H).
合成实施例52.化合物B-18的合成Synthesis Example 52. Synthesis of Compound B-18
采用与实施例51相同的方法制备化合物B-18，不同在于将二苯并噻吩-3-硼酸替换为等当量的二苯并呋喃-3-硼酸，反应完成后，经柱色谱分离粗产品，得到白色固体7.1g，收率为66％。Compound B-18 was prepared in the same manner as in Example 51 except that dibenzothiophene-3-boronic acid was replaced with an equivalent amount of dibenzofuran-3-boronic acid. After completion of the reaction, the crude product was separated by column chromatography. A white solid 7.1 g was obtained in a yield of 66%.
B-18的核磁波普数据：B-18 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.33(dd，J＝7.5，1.7Hz，2H)，7.98(dd，J＝7.5，1.5Hz，2H)，7.88(dd，J＝5.6，3.9Hz，2H)，7.64-7.56(m，2H)，7.53(s，4H)，7.44(td，J＝7.5，1.6Hz，1H)，7.39-7.20(m，7H)，7.16(td，J＝7.5，1.6Hz，2H). 1 H NMR (500 MHz, Chloroform) δ 8.33 (dd, J = 7.5, 1.7 Hz, 2H), 7.98 (dd, J = 7.5, 1.5 Hz, 2H), 7.88 (dd, J = 5.6, 3.9 Hz, 2H ), 7.64 - 7.56 (m, 2H), 7.53 (s, 4H), 7.44 (td, J = 7.5, 1.6 Hz, 1H), 7.39-7.20 (m, 7H), 7.16 (td, J = 7.5, 1.6) Hz, 2H).
合成实施例53.化合物B-19的合成Synthesis Example 53. Synthesis of Compound B-19
Figure PCTCN2016093026-appb-000056
Figure PCTCN2016093026-appb-000056
化合物B-19-1的制备Preparation of Compound B-19-1
二苯并[b，d]呋喃-3-硼酸(106g，0.5mol)、2-溴-硝基苯(101g，0.5mol)、四三苯基膦钯(1.15g，1mmol)、碳酸钾(138g，1mol)、甲苯(1L)、乙醇(0.5L)和蒸馏水(0.3L)混合，在110℃下搅拌反应2h。反应完成后蒸馏水洗涤反应体系，然后用200ml乙酸乙酯萃取三次，合并得到有机层，用无水MgSO4干燥有机相，并用旋转蒸 发器除去溶剂，将除去溶剂的剩余物进行柱分离，得到中间体化合物B-19-1(130g，收率89％)。Dibenzo[b,d]furan-3-boronic acid (106 g, 0.5 mol), 2-bromo-nitrobenzene (101 g, 0.5 mol), tetrakistriphenylphosphine palladium (1.15 g, 1 mmol), potassium carbonate ( 138 g, 1 mol), toluene (1 L), ethanol (0.5 L) and distilled water (0.3 L) were mixed, and the reaction was stirred at 110 ° C for 2 h. After the completion of the reaction, the reaction system was washed with distilled water, and then extracted three times with 200 ml of ethyl acetate. The organic layer was combined, and the organic phase was dried over anhydrous MgSO 4 and the solvent was removed on a rotary evaporator. Compound B-19-1 (130 g, yield 89%).
化合物B-19-2的制备Preparation of Compound B-19-2
2L反应瓶中，向中间体化合物B-19-1(100g，0.34mol)里加入1000ml亚磷酸三乙酯，在150℃搅拌6小时后，冷却到室温，用300ml乙酸乙酯萃取三次，合并得到的有机相，用500ml去离子水清洗有机相三次，有机相用无水MgSO4去除有机相中的水分，然后对有机相进行减压蒸馏，对得到的蒸馏剩余物进行柱分离，得到化合物B-19-2(56g，收率64％)。In a 2 L reaction flask, 1000 ml of triethyl phosphite was added to the intermediate compound B-19-1 (100 g, 0.34 mol), and the mixture was stirred at 150 ° C for 6 hours, cooled to room temperature, and extracted three times with 300 ml of ethyl acetate. The obtained organic phase was washed three times with 500 ml of deionized water, and the organic phase was washed with anhydrous MgSO 4 to remove water in the organic phase, and then the organic phase was subjected to distillation under reduced pressure, and the obtained distillation residue was subjected to column separation to obtain a compound. B-19-2 (56 g, yield 64%).
化合物B-19-3的制备Preparation of Compound B-19-3
在250ml三口瓶中，将中间体化合物B-19-2(10.3g，40mmol)、对溴碘苯(14.2g，50mmol)、CuI(1.8g，10mmol)，反式-二氨基环己烷(4.2ml，40mmol)和碳酸铯(13g，40mmol)形成的混合物加热回流3小时。然后将反应混合物冷却至室温，过滤，用二氯甲烷洗涤滤饼，然后对得到的滤液进行减压蒸馏，对得到的蒸馏剩余物进行柱分离，得到化合物B-19-3(12.4g，产率75％)。In a 250 ml three-necked flask, intermediate compound B-19-2 (10.3 g, 40 mmol), p-bromoiodobenzene (14.2 g, 50 mmol), CuI (1.8 g, 10 mmol), trans-diaminocyclohexane ( A mixture of 4.2 ml, 40 mmol) and cesium carbonate (13 g, 40 mmol) was heated to reflux for 3 hours. Then, the reaction mixture was cooled to room temperature, filtered, and the filter cake was washed with dichloromethane, and the obtained filtrate was subjected to distillation under reduced pressure, and the obtained distillation residue was subjected to column separation to obtain Compound B-19-3 (12.4 g, yield. Rate 75%).
化合物B-19-4的制备Preparation of Compound B-19-4
在1L反应瓶中，将中间体M6(38.2g，0.1mol)、溴苯(16g，0.1mol)、CuI(3.3g，17.1mmol)、碳酸铯(33.44g，102.9mmol)、环己基二胺(2.3ml，34.3mmol)和二甲苯(500ml)混合，在回流条件下搅拌反应1天，反应结束后，冷却至室温，用250ml乙酸乙酯萃取，有机层经无水硫酸镁后减压蒸馏除去溶剂，对得到的蒸馏剩余物进行柱分离(洗脱液：二氯甲烷/己烷)，得到化合物B-19-4(25.7g，收率56％)。Intermediate M6 (38.2 g, 0.1 mol), bromobenzene (16 g, 0.1 mol), CuI (3.3 g, 17.1 mmol), cesium carbonate (33.44 g, 102.9 mmol), cyclohexyldiamine in a 1 L reaction flask (2.3 ml, 34.3 mmol) and xylene (500 ml) were mixed, and the reaction was stirred under reflux for 1 day. After completion of the reaction, the mixture was cooled to room temperature and extracted with ethyl acetate (250 ml). The solvent was removed, and the obtained distillation residue was subjected to column chromatography (eluent: dichloromethane/hexane) to afford Compound B-19-4 (25.7 g, yield 56%).
化合物A-19的制备Preparation of Compound A-19
在1L反应瓶中，将中间体化合物B-19-4(45.9g，0.1mol)、中间体化合物B-19-3(42g，0.1mol)、CuI(3.3g，17.1mmol)、碳酸铯(33.44g，102.9mmol)、环己基二胺(2.3ml，34.3mmol)和二甲苯(500ml)混合，在回流条件下搅拌反应1天，反应结束后，冷却至室温，用250ml乙酸乙酯萃取，有机层经无水硫酸镁后减压蒸馏除去溶剂，对得到的蒸馏剩余物进行柱分离(洗脱液：二氯甲烷/己烷)，得到淡黄色化合物B-19(67.2g，收率85％)。In a 1 L reaction flask, intermediate compound B-19-4 (45.9 g, 0.1 mol), intermediate compound B-19-3 (42 g, 0.1 mol), CuI (3.3 g, 17.1 mmol), cesium carbonate ( 33.44g, 102.9mmol), cyclohexyldiamine (2.3ml, 34.3mmol) and xylene (500ml) were mixed, and the reaction was stirred under reflux for 1 day. After the reaction was completed, it was cooled to room temperature and extracted with 250 ml of ethyl acetate. The organic layer was evaporated over anhydrous magnesium sulfate and evaporated, evaporated, evaporated, evaporated. %).
合成实施例54.化合物B-20的合成 Synthesis Example 54. Synthesis of Compound B-20
Figure PCTCN2016093026-appb-000057
Figure PCTCN2016093026-appb-000057
中间体化合物B-20-1的制备Preparation of intermediate compound B-20-1
将500毫升甲苯、邻碘硝基苯(30g，120.4mmol)、4-溴苯基硼酸(26g，132.5mmol)、Pd(PPh3)4(6.9g，6.02mmol)和150毫升Na2CO3(浓度为2M)混合，在100℃下反应4小时，反应完毕后，冷却至室温，并用乙酸乙酯萃取，得到有机相，然后用蒸馏水洗涤有机相，用MgSO4去除有机相中的水分，对有机相进行减压蒸馏，对得到的蒸馏剩余物进行柱分离，得到中间体化合物B-20-1(28g，83.3％)。500 ml of toluene, o-iodonitrobenzene (30 g, 120.4 mmol), 4-bromophenylboronic acid (26 g, 132.5 mmol), Pd(PPh 3 ) 4 (6.9 g, 6.02 mmol) and 150 ml of Na 2 CO 3 (concentration: 2M), the mixture was reacted at 100 ° C for 4 hours. After completion of the reaction, it was cooled to room temperature and extracted with ethyl acetate to give an organic phase. The organic phase was washed with distilled water, and the organic phase was removed with MgSO 4 . The organic phase was subjected to distillation under reduced pressure, and the obtained distillation residue was subjected to column separation to obtain Intermediate Compound B-20-1 (28 g, 83.3%).
中间体化合物B-20-2的制备Preparation of intermediate compound B-20-2
向300毫升亚磷酸三乙酯中加入28g化合物B-20-1(0.1mol)，并在150℃下搅拌6小时，冷却至室温，并用乙酸乙酯萃取，得到有机相，然后用蒸馏水洗涤有机相，用无水MgSO4干燥去除有机相中的水分，有机相进行减压蒸馏蒸除掉有机溶剂，对得到的蒸馏剩余物进行柱分离，得到中间体化合物B-20-2(11g，44.4％)。To 300 ml of triethyl phosphite, 28 g of compound B-20-1 (0.1 mol) was added, and the mixture was stirred at 150 ° C for 6 hours, cooled to room temperature, and extracted with ethyl acetate to give an organic phase, which was then washed with distilled water. The phase was dried over anhydrous MgSO 4 to remove the water in the organic phase, and the organic phase was distilled off under reduced pressure to remove the organic solvent, and the obtained distillation residue was subjected to column separation to obtain intermediate compound B-20-2 (11 g, 44.4). %).
中间体化合物B-20-3的制备Preparation of intermediate compound B-20-3
将中间体化合物B-20-2(24.6g，0.1mol)、碘苯(41.3g，0.2mol)、CuI(9.6g，50mmol)、Cs2CO3(82.5g，0.25mol)以及甲苯600毫升混合，并在50℃下反应，然后向混合物中加入乙二胺(6.8ml，0.1mol)，回流反应14小时，反应完毕，在室温下冷却，并向其中加入蒸馏水，并用乙酸乙酯萃取，得到有机相，用无水MgSO4干燥去除有机相中的水分，对有机相进行减压蒸馏，对得到的蒸馏剩余物进行柱分离，得到中间体化合物B-20-3(24g，收率75％)。 Intermediate compound B-20-2 (24.6 g, 0.1 mol), iodobenzene (41.3 g, 0.2 mol), CuI (9.6 g, 50 mmol), Cs 2 CO 3 (82.5 g, 0.25 mol) and toluene 600 ml After mixing, and reacting at 50 ° C, ethylenediamine (6.8 ml, 0.1 mol) was added to the mixture, and the reaction was refluxed for 14 hours. The reaction was completed, cooled at room temperature, and distilled water was added thereto, and extracted with ethyl acetate. The organic phase is obtained, and the organic phase is dried over anhydrous MgSO 4 to remove the organic phase. The organic phase is subjected to distillation under reduced pressure, and the obtained distillation residue is subjected to column separation to obtain intermediate compound B-20-3 (24 g, yield 75). %).
中间体化合物B-20-4的制备Preparation of intermediate compound B-20-4
将化合物B-20-3(21g，86mmol)溶于300毫升THF，并在-78℃向混合物中缓慢加入正丁基锂(38ml，95mmol，2.5M己烷溶液)。在-78℃下保持1小时后，向混合物中加入硼酸三甲酯(12.4ml，112mmol)。然后缓慢升温至室温，并在室温下搅拌反应12小时。向经过搅拌的混合物中加入饱和氯化铵水溶液淬灭反应，并用乙酸乙酯萃取三次，合并有机相，有机相用无水MgSO4干燥去除有机相中的水分。对有机相进行减压蒸馏，对得到的蒸馏剩余物进行柱分离，得到中间体化合物B-20-4(20g，收率81％)。Compound B-20-3 (21 g, 86 mmol) was dissolved in 300 mL of THF and n-butyl lithium (38 ml, 95 mmol, 2.5 M hexanes) was slowly added to the mixture at -78 °C. After maintaining at -78 ° C for 1 hour, trimethyl borate (12.4 ml, 112 mmol) was added to the mixture. Then, the temperature was slowly raised to room temperature, and the reaction was stirred at room temperature for 12 hours. To a stirred mixture of saturated aqueous ammonium chloride was added to quench the reaction, and extracted three times with ethyl acetate, the combined organic phases, the organic phase was dried over anhydrous MgSO 4 the organic phase to remove moisture. The organic phase was subjected to distillation under reduced pressure, and the obtained distillation residue was subjected to column separation to obtain Intermediate Compound B-20-4 (20 g, yield 81%).
中间体化合物B-20-5的制备Preparation of intermediate compound B-20-5
将化合物B-20-4(20g，70mmol)、1-溴-2-硝基苯(14.3g，71mmol)、Pd(PPh3)4(4.3g，2.4mmol)、75毫升2M Na2CO3溶液、甲苯300ml以及乙醇70ml混合，回流搅拌5小时后，冷却到室温，向混合物中加入200ml去离子水，然后用100ml乙酸乙酯萃取三次，合并有机相，用无水MgSO4干燥去除有机相中的水分，并对有机相进行减压蒸馏，对得到的蒸馏剩余物进行柱分离，得到中间体化合物B-20-5(20.6g，收率81.％)。Compound B-20-4 (20 g, 70 mmol), 1-bromo-2-nitrobenzene (14.3 g, 71 mmol), Pd(PPh 3 ) 4 (4.3 g, 2.4 mmol), 75 mL 2M Na 2 CO 3 The solution, 300 ml of toluene and 70 ml of ethanol were mixed, stirred under reflux for 5 hours, cooled to room temperature, 200 ml of deionized water was added to the mixture, and then extracted three times with 100 ml of ethyl acetate. The organic phase was combined and dried over anhydrous MgSO 4 to remove organic phase. The organic phase was subjected to vacuum distillation, and the obtained distillation residue was subjected to column separation to obtain Intermediate Compound B-20-5 (20.6 g, yield 81.%).
中间体化合物B-20-6的制备Preparation of intermediate compound B-20-6
在向化合物B-20-5(20g，55mmol)加入200毫升亚磷酸三乙酯，在150℃搅拌6小时后，在室温下冷却，用乙酸乙酯萃取，得到有机相，蒸馏水清洗有机相后，用无水MgSO4干燥去除有机相中的水分，然后对有机相进行减压蒸馏，对得到的蒸馏剩余物进行柱分离，得到化合物B-20-6(7g，收率38％)。After adding 200 ml of triethyl phosphite to the compound B-20-5 (20 g, 55 mmol), and stirring at 150 ° C for 6 hours, it was cooled at room temperature, and extracted with ethyl acetate to obtain an organic phase, and the organic phase was washed with distilled water. The water in the organic phase was removed by drying with anhydrous MgSO 4 , and then the organic phase was subjected to distillation under reduced pressure, and the obtained distillation residue was subjected to column separation to obtain Compound B-20-6 (7 g, yield 38%).
化合物B-20的制备Preparation of Compound B-20
向100毫升的二甲苯中加入化合物M7(6.9g，10mmol)，中间体化合物C-31-6(8.3g，25mmol)，CuI(0.9g，5mmol)，反式-二氨基环己烷(2.1毫升，20mmol)和碳酸铯(6.5g，20mmol)，将该混合物回流3小时。然后将反应混合物冷却至室温，过滤，用二氯甲烷(二氯甲烷)洗涤滤饼，然后对得到的滤液进行减压蒸馏，对得到的蒸馏剩余物进行柱分离，得到化合物B-20为黄色固体(5.4g，产率45％)。Compound 100 (6.9 g, 10 mmol), intermediate compound C-31-6 (8.3 g, 25 mmol), CuI (0.9 g, 5 mmol), trans-diaminocyclohexane (2.1) was added to 100 ml of xylene. Milliliter, 20 mmol) and cesium carbonate (6.5 g, 20 mmol), and the mixture was refluxed for 3 hr. Then, the reaction mixture was cooled to room temperature, filtered, and the filter cake was washed with dichloromethane (dichloromethane), and then the obtained filtrate was subjected to distillation under reduced pressure, and the obtained distillation residue was subjected to column separation to obtain Compound B-20 in yellow. Solid (5.4 g, yield 45%).
合成实施例55.化合物B-21的合成Synthesis Example 55. Synthesis of Compound B-21
采用与实施例11相同的方法制备化合物B-21，不同在于将溴苯替换为等当量的2-bromodibenzo[b，d]furan，反应完成后，经柱色谱分离粗产品，得到白色固体4.36g，收率为61％。Compound B-21 was prepared in the same manner as in Example 11 except that bromobenzene was replaced with an equivalent of 2-bromodibenzo[b,d]furan. After completion of the reaction, the crude product was separated by column chromatography to give white solid 4.36 g. The yield was 61%.
B-21的核磁波普数据： B-21 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.66-8.50(m，3H)，8.24-8.13(m，2H)，8.09-7.96(m，3H)，7.89(ddd，J＝16.9，7.4，2.0Hz，1H)，7.67-7.44(m，4H)，7.43-7.24(m，3H). 1 H NMR (500MHz, Chloroform) δ8.66-8.50 (m, 3H), 8.24-8.13 (m, 2H), 8.09-7.96 (m, 3H), 7.89 (ddd, J = 16.9,7.4,2.0Hz, 1H), 7.67-7.44 (m, 4H), 7.43 - 7.24 (m, 3H).
合成实施例56.化合物B-22的合成Synthesis Example 56. Synthesis of Compound B-22
采用与实施例11相同的方法制备化合物B-22，不同在于将溴苯替换为等当量的2-bromodibenzo[b，d]thiophene，反应完成后，经柱色谱分离粗产品，得到白色固体4.86g，收率为65％。Compound B-22 was prepared in the same manner as in Example 11 except that bromobenzene was replaced by an equivalent of 2-bromodibenzo[b,d]thiophene. After completion of the reaction, the crude product was separated by column chromatography to give white solid 4.86 g. The yield was 65%.
合成实施例57.化合物B-23的合成Synthesis Example 57. Synthesis of Compound B-23
采用与实施例21相同的方法制备化合物B-23，不同在于将溴苯替换为等当量的2-bromodibenzo[b，d]thiophene，反应完成后，经柱色谱分离粗产品，得到类白色固体5.9g，收率为79％。Compound B-23 was prepared in the same manner as in Example 21 except that bromobenzene was replaced with an equivalent of 2-bromodibenzo[b,d]thiophene. After completion of the reaction, the crude product was separated by column chromatography to afford white solid 5.9. g, yield was 79%.
合成实施例58.化合物M13的合成Synthesis Example 58. Synthesis of Compound M13
Figure PCTCN2016093026-appb-000058
Figure PCTCN2016093026-appb-000058
将中间体M1(38.6g，0.1mol)、1-溴-4-碘苯(56.7g，0.2mol)、CuI(3.3g，17.1mmol)、K3PO4(21.8g，102.9mmol)、乙二胺(2.3毫升，34.3mmol)和甲苯(500毫升)混合，在回流条件下搅拌1天，反应结束后，冷却至室温，用乙酸乙酯萃取有机层并减压蒸馏，对得到的蒸馏剩余物进行柱分离(洗脱液：二氯甲烷/己烷)，得到中间体化合物M13(48.3g，70.1％)Intermediate M1 (38.6 g, 0.1 mol), 1-bromo-4-iodobenzene (56.7 g, 0.2 mol), CuI (3.3 g, 17.1 mmol), K 3 PO 4 (21.8 g, 102.9 mmol), B The diamine (2.3 ml, 34.3 mmol) and toluene (500 ml) were mixed and stirred under reflux for 1 day. After the reaction was completed, the mixture was cooled to room temperature, and the organic layer was extracted with ethyl acetate and distilled under reduced pressure. Column separation (eluent: dichloromethane / hexane) gave intermediate compound M13 (48.3 g, 70.1%)
合成实施例59.化合物M14的合成Synthesis Example 59. Synthesis of Compound M14
采用与实施例58相同的方法制备化合物M14，不同在于将对溴碘苯替换为等当量的3-溴碘苯，反应完成后，经柱色谱分离粗产品，得到中间体M14为白色固体52.5g，收率为75％。Compound M14 was prepared in the same manner as in Example 58 except that the bromoiodobenzene was replaced with an equivalent of 3-bromoiodobenzene. After the reaction was completed, the crude product was separated by column chromatography to afford Intermediate M14 as a white solid 52.5 g. The yield is 75%.
合成实施例60.化合物B-24的合成 Synthesis Example 60. Synthesis of Compound B-24
Figure PCTCN2016093026-appb-000059
Figure PCTCN2016093026-appb-000059
将中间体M13(6.9g，10mmol)、二苯并噻吩-2-硼酸(5.7g，25mmol)、Pd(PPh3)4(0.58g，0.5mmol)、Na2CO3(5.3g，50mmol)、60mL甲苯和20mL EtOH混合，向该混合物中加入蒸馏水20mL，然后在120℃下搅拌反应2小时。反应完成后，用蒸馏水洗涤反应体系，然后用50ml乙酸乙酯萃取三次，合并得到的有机层，用MgSO4干燥有机层，并旋蒸除去溶剂，最后，对除去溶剂的剩余物进行柱分离，得到化合物B-24(7.3g，81％)，为类白色固体。Intermediate M13 (6.9 g, 10 mmol), dibenzothiophene-2-boronic acid (5.7 g, 25 mmol), Pd(PPh 3 ) 4 (0.58 g, 0.5 mmol), Na 2 CO 3 (5.3 g, 50 mmol) 60 mL of toluene and 20 mL of EtOH were mixed, and 20 mL of distilled water was added to the mixture, followed by stirring at 120 ° C for 2 hours. After completion of the reaction, the reaction system was washed with distilled water, and then extracted three times with 50 ml of ethyl acetate. The organic layer obtained was combined, dried over MgSO 4 and evaporated to remove solvent. Compound B-24 (7.3 g, 81%) was obtained as an off white solid.
合成实施例61.化合物B-25的合成Synthesis Example 61. Synthesis of Compound B-25
采用与实施例60相同的方法制备化合物B-25，不同在于将中间体M13替换为等当量的中间体M14，同时将二苯并噻吩-2-硼酸置换为等当量的dibenzo[b，d]furan-2-ylboronic acid，反应完成后，经柱色谱分离粗产品，得到化合物B-25为类白色固体B-25(6.4g，74％)。Compound B-25 was prepared in the same manner as in Example 60 except that the intermediate M13 was replaced with an equivalent of the intermediate M14, and dibenzothiophene-2-boronic acid was replaced with an equivalent of dibenzo[b,d]. After the completion of the reaction, the crude product was purified by column chromatography to afford Compound B-25 as white off solid B-25 (6.4 g, 74%).
合成实施例62.化合物B-26的合成Synthesis Example 62. Synthesis of Compound B-26
采用与合成实施例23相同的合成方法，不同在于，将苯硼酸换为等当量的2-二苯并噻吩硼酸，反应完成后，得到淡黄色固体8.1g，收率为80％。The same synthesis method as in Synthesis Example 23 was employed, except that phenylboronic acid was changed to an equivalent amount of 2-dibenzothiopheneboronic acid, and after completion of the reaction, 8.1 g of a pale yellow solid was obtained, yield: 80%.
合成实施例63.化合物B-27的合成Synthesis Example 63. Synthesis of Compound B-27
Figure PCTCN2016093026-appb-000060
Figure PCTCN2016093026-appb-000060
将中间体M3-2(6.9g，10mmol)、苯硼酸(3.05g，25mmol)、Pd(PPh3)4(0.58g，0.5mmol)、Na2CO3(5.3g，50mmol)、60mL甲苯和20mL EtOH混合，向该混合物中加入蒸馏水20mL，然后在120℃下搅拌反应2小时。反应完成后，用蒸馏水洗涤反应体系，然后用乙酸乙酯萃取，得到有机层，用MgSO4干燥有机层，并旋蒸除去溶剂，最后，对除去溶剂的剩余物进行柱分离，得到中间体化合物B-27-1(4.5g，84％)， 为白色固体。Intermediate M3-2 (6.9 g, 10 mmol), phenylboronic acid (3.05 g, 25 mmol), Pd (PPh 3 ) 4 (0.58 g, 0.5 mmol), Na 2 CO 3 (5.3 g, 50 mmol) 20 mL of EtOH was mixed, and 20 mL of distilled water was added to the mixture, followed by stirring at 120 ° C for 2 hours. After completion of the reaction, the reaction system was washed with distilled water, and then extracted with ethyl acetate to give an organic layer. The organic layer was dried with MgSO 4 and evaporated to remove solvent, and the residue of the solvent was subjected to column separation to obtain intermediate compound B. -27-1 (4.5 g, 84%), as a white solid.
将中间体化合物B-27-1(5.35g，10mmol)，2-溴二苯并噻吩(5.4g，20mmol)、CuI(1g，5mmol)、Cs2CO3(8.3g，25mmol)以及甲苯100毫升混合，并在50℃下反应，然后向混合物中加入乙二胺(0.7ml，10mmol)，回流反应14小时，反应完毕，在室温下冷却，并向其中加入蒸馏水，并用乙酸乙酯萃取，得到有机相，用无水MgSO4干燥去除有机相中的水分，对有机相进行减压蒸馏，对得到的蒸馏剩余物进行柱分离，得到淡黄色固体的目标化合物B-27(5.84g，收率65％)。Intermediate compound B-27-1 (5.35 g, 10 mmol), 2-bromodibenzothiophene (5.4 g, 20 mmol), CuI (1 g, 5 mmol), Cs 2 CO 3 (8.3 g, 25 mmol) and toluene 100 The mixture was mixed and reacted at 50 ° C, then ethylenediamine (0.7 ml, 10 mmol) was added to the mixture, and the reaction was refluxed for 14 hours. The reaction was completed, cooled at room temperature, and distilled water was added thereto and extracted with ethyl acetate. The organic phase was obtained, and the organic phase was dried over anhydrous MgSO 4 , and the organic phase was distilled under reduced pressure. The obtained residue was subjected to column separation to give the title compound B-27 (5.84 g, Rate 65%).
合成实施例64.化合物B-28的合成Synthesis Example 64. Synthesis of Compound B-28
采用与合成实施例34相同的合成方法，不同在于将溴苯置换为等当量的2-bromodibenzo[b，d]thiophene，反应完成后，得到白色固体4.32g，收率为68％。The same synthesis method as in Synthesis Example 34 was employed except that bromobenzene was replaced by an equivalent amount of 2-bromodibenzo[b,d]thiophene, and after completion of the reaction, 4.32 g of a white solid was obtained, yield 68%.
合成实施例65.化合物B-29的合成Synthesis Example 65. Synthesis of Compound B-29
采用与合成实施例25相同的合成方法，不同在于将4-联苯硼酸置换为等当量的dibenzo[b，d]thiophen-2-ylboronic acid，反应完成后，得到白色固体4.15g，两步总收率为58％。The same synthesis method as in Synthesis Example 25 was employed except that 4-diphenylboronic acid was replaced with an equivalent amount of dibenzo[b,d]thiophen-2-ylboronic acid, and after completion of the reaction, 4.15 g of a white solid was obtained. The yield was 58%.
合成实施例66.化合物B-30的合成Synthesis Example 66. Synthesis of Compound B-30
Figure PCTCN2016093026-appb-000061
Figure PCTCN2016093026-appb-000061
将中间体M7(6.9g，10mmol)、二苯并噻吩-2-硼酸(5.7g，25mmol)、Pd(PPh3)4(0.58g，0.5mmol)、K2CO3(5.3g，50mmol)、60mL甲苯和20mL EtOH混合，向该混合物中加入蒸馏水20mL，然后在120℃下搅拌反应2小时。反应完成后，用蒸馏水洗涤反应体系，然后用乙酸乙酯萃取，得到有机层，用MgSO4干燥有机层，并旋蒸除去溶剂，最后，对除去溶剂的剩余物进行柱分离，得到化合物B-30(6.8g，76％)，为白色固体。Intermediate M7 (6.9 g, 10 mmol), dibenzothiophene-2-boronic acid (5.7 g, 25 mmol), Pd(PPh 3 ) 4 (0.58 g, 0.5 mmol), K 2 CO 3 (5.3 g, 50 mmol) 60 mL of toluene and 20 mL of EtOH were mixed, and 20 mL of distilled water was added to the mixture, followed by stirring at 120 ° C for 2 hours. After completion of the reaction, the reaction system was washed with distilled water, and then extracted with ethyl acetate to give an organic layer. The organic layer was dried with MgSO 4 and evaporated to remove solvent, and the residue of the solvent was subjected to column separation to give compound B- 30 (6.8 g, 76%) as a white solid.
B-30的核磁波普数据：B-30 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.39(dt，J＝7.5，1.8Hz，1H)，8.23-8.16(m，2H)，8.19-8.12(m，1H)，8.15-8.04(m，2H)，8.01(dt，J＝7.4，2.2Hz，1H)，7.92-7.79(m，2H)，7.83-7.72(m，3H)，7.57-7.24(m，7H). 1 H NMR (500 MHz, Chloroform) δ 8.39 (dt, J = 7.5, 1.8 Hz, 1H), 8.23-8.16 (m, 2H), 8.19-8.12 (m, 1H), 8.15-8.04 (m, 2H) , 8.01 (dt, J = 7.4, 2.2 Hz, 1H), 7.92-7.79 (m, 2H), 7.83-7.72 (m, 3H), 7.57-7.24 (m, 7H).
合成实施例67.化合物B-31的合成Synthesis Example 67. Synthesis of Compound B-31
采用与合成实施例66相同的合成方法，不同在于将 dibenzo[b，d]thiophen-2-ylboronic acid置换为等当量的dibenzo[b，d]furan-2-ylboronic acid，反应完成后，得到白色固体7.1g，收率为66％。The same synthesis method as in Synthesis Example 66 was employed, except that Dibenzo[b,d]thiophen-2-ylboronic acid was replaced with an equivalent amount of dibenzo[b,d]furan-2-ylboronic acid. After completion of the reaction, 7.1 g of a white solid was obtained, yield 66%.
合成实施例68.化合物C-1的合成Synthesis Example 68. Synthesis of Compound C-1
Figure PCTCN2016093026-appb-000062
Figure PCTCN2016093026-appb-000062
向100毫升的二甲苯中加入化合物M6(3.86g，10mmol)，4-溴三苯基胺(9.7g，30mmol)，CuI(0.9g，5mmol)，反式-二氨基环己烷(2.1毫升，20mmol)和碳酸铯(6.5g，20mmol)，将该混合物物回流3小时。将反应混合物冷却至室温后，过滤，然后用二氯甲烷洗涤滤饼，滤液进行减压蒸馏除去溶解，对得到的蒸馏剩余物进行柱分离，得到淡黄色固体化合物C-1(6.25g，产率72％)。To 100 ml of xylene was added compound M6 (3.86 g, 10 mmol), 4-bromotriphenylamine (9.7 g, 30 mmol), CuI (0.9 g, 5 mmol), trans-diaminocyclohexane (2.1 ml) 20 mmol) and cesium carbonate (6.5 g, 20 mmol), and the mixture was refluxed for 3 hr. After the reaction mixture was cooled to room temperature, it was filtered, and then the filter cake was washed with dichloromethane, and the filtrate was evaporated under reduced pressure to dissolve, and the obtained distillation residue was subjected to column separation to obtain a pale yellow solid compound C-1 (6.25 g. Rate 72%).
C-1的核磁波普数据：Nuclear magnetic pop data of C-1:
1H NMR(500MHz，Chloroform)δ8.50(s，12H)，8.37(s，17H)，8.05(s，17H)，7.64(s，21H)，7.47(s，10H)，7.32-7.03(m，105H)，7.12(s，6H)，7.15-7.03(m，44H)，7.05(d，J＝14.9Hz，54H)，6.96(s，14H). 1 H NMR (500MHz, Chloroform) δ8.50 (s, 12H), 8.37 (s, 17H), 8.05 (s, 17H), 7.64 (s, 21H), 7.47 (s, 10H), 7.32-7.03 (m , 105H), 7.12 (s, 6H), 7.15-7.03 (m, 44H), 7.05 (d, J = 14.9 Hz, 54H), 6.96 (s, 14H).
合成实施例69.化合物C-2的合成Synthesis Example 69. Synthesis of Compound C-2
采用与化合物C-1相同的合成方法，不同在于，将4-溴三苯基胺置换为等当量的三苯基胺-3-溴化物，反应完成后，得到淡黄色固体5.8g C-2，收率为68％。The same synthesis method as the compound C-1 was employed except that 4-bromotriphenylamine was replaced with an equivalent amount of triphenylamine-3-bromide, and after completion of the reaction, 5.8 g of a pale yellow solid was obtained. The yield was 68%.
合成实施例70.化合物C-3的合成Synthesis Example 70. Synthesis of Compound C-3
采用与化合物C-1相同的合成方法，不同在于，将三苯基胺-4-溴化物置换为等当量的N-苯基-N-(4-溴苯)基-2-萘胺，反应得到淡黄色固体5.23g，收率为55％。The same synthesis method as the compound C-1 was employed except that the triphenylamine-4-bromide was replaced with an equivalent amount of N-phenyl-N-(4-bromophenyl)-2-naphthylamine. Obtained 5.23 g of a pale yellow solid in a yield of 55%.
C-3的核磁波普数据：Nuclear magnetic pop data for C-3:
1H NMR(500MHz，Chloroform)δ8.49(d，J＝65.0Hz，46H)，8.39(s，2H)，8.10(s，26H)，7.88-7.60(m，61H)，7.53(d，J＝10.0Hz，30H)，7.43(d，J＝15.0Hz，33H)，7.38(s，11H)，7.32(s，27H)，7.24(s，31H)，7.19-7.06(m，72H)，7.00(s，14H). 1 H NMR (500MHz, Chloroform) δ8.49 (d, J = 65.0Hz, 46H), 8.39 (s, 2H), 8.10 (s, 26H), 7.88-7.60 (m, 61H), 7.53 (d, J =10.0 Hz, 30H), 7.43 (d, J = 15.0 Hz, 33H), 7.38 (s, 11H), 7.32 (s, 27H), 7.24 (s, 31H), 7.19-7.06 (m, 72H), 7.00 (s, 14H).
合成实施例71.化合物C-4的合成 Synthesis Example 71. Synthesis of Compound C-4
Figure PCTCN2016093026-appb-000063
Figure PCTCN2016093026-appb-000063
在250mL三口瓶中，通N2保护。将4.22g(25mmol)二苯基胺，6.92g(10mmol)中间体M11，0.27g(0.5mmol)Pd(dba)2，6.2g(125mmol)叔丁醇钠，1.04mL(0.5mmol)三叔丁基膦，150mL甲苯置于三口瓶内，反应混合物在回流状态下反应2小时，TLC检测反应完全，停止反应。混合物降到室温后，加入去离子水淬灭反应，并用甲苯萃取三次，合并有机相，有机相用无水硫酸镁干燥，过硅胶短柱，滤液旋干，残留物经柱色谱分离得到黄色固体7.04g，收率81％。In a 250 mL three-necked bottle, it was protected by N 2 . 4.22 g (25 mmol) of diphenylamine, 6.92 g (10 mmol) of intermediate M11, 0.27 g (0.5 mmol) of Pd(dba) 2 , 6.2 g (125 mmol) of sodium tert-butoxide, 1.04 mL (0.5 mmol) Butylphosphine, 150 mL of toluene was placed in a three-necked flask, and the reaction mixture was reacted under reflux for 2 hours, and the reaction was completed by TLC, and the reaction was stopped. After the mixture was cooled to room temperature, the reaction was quenched with deionized water and extracted with toluene three times. The organic phase was combined and dried over anhydrous magnesium sulfate, dried over silica gel, and the filtrate was evaporated to dryness. 7.04 g, yield 81%.
C-4的核磁波普数据：Nuclear magnetic pop data for C-4:
1H NMR(500MHz，Chloroform)δ8.42(s，2H)，8.10(s，2H)，8.01(s，1H)，7.60(d，J＝20.0Hz，3H)，7.49(d，J＝10.0Hz，3H)，7.24(s，4H)，7.08(s，4H)，7.00(s，2H)，6.48(s，1H). 1 H NMR (500 MHz, Chloroform) δ 8.42 (s, 2H), 8.10 (s, 2H), 8.1 (s, 1H), 7.60 (d, J = 20.0 Hz, 3H), 7.49 (d, J = 10.0) Hz, 3H), 7.24 (s, 4H), 7.08 (s, 4H), 7.00 (s, 2H), 6.48 (s, 1H).
合成实施例72.化合物C-5的合成Synthesis Example 72. Synthesis of Compound C-5
采用与化合物C-4相同的合成方法，不同在于，将中间体M11置换为等当量的中间体M13，反应得到黄色固体7.1g，收率82％。The same synthesis method as the compound C-4 was employed, except that the intermediate M11 was replaced with an equivalent of the intermediate M13 to give a yellow solid 7.1 g, yield 82%.
合成实施例73.化合物C-6的合成Synthesis Example 73. Synthesis of Compound C-6
采用与化合物C-5相同的合成方法，不同在于，将二苯基胺置换为等当量的苯基萘基胺，反应得到黄色固体7.5g，收率84％。The same synthesis method as the compound C-5 was employed except that diphenylamine was replaced with an equivalent amount of phenylnaphthylamine, and 7.5 g of a yellow solid was obtained in a yield of 84%.
合成实施例74.化合物C-7的合成Synthesis Example 74. Synthesis of Compound C-7
Figure PCTCN2016093026-appb-000064
Figure PCTCN2016093026-appb-000064
将中间体M1(38.6g，0.1mol)、1-溴-3-碘苯(56.7g，0.2mol)、CuI(3.3g，17.1mmol)、K3PO4(21.8g，102.9mmol)、乙二胺(2.3毫升，34.3mmol)和甲苯(500毫升)混合，在回流条件下搅拌1天，反应结束后，冷却至室温，用乙酸乙酯萃取有机层并减压蒸馏， 对得到的蒸馏剩余物进行柱分离(洗脱液：二氯甲烷/己烷)，得到中间体化合物M14(48.3g，70.1％)Intermediate M1 (38.6 g, 0.1 mol), 1-bromo-3-iodobenzene (56.7 g, 0.2 mol), CuI (3.3 g, 17.1 mmol), K3PO4 (21.8 g, 102.9 mmol), ethylenediamine ( 2.3 ml, 34.3 mmol) and toluene (500 ml) were mixed, and stirred under reflux for 1 day. After the reaction was completed, the mixture was cooled to room temperature, and the organic layer was extracted with ethyl acetate. The obtained distillation residue was subjected to column separation (eluent: dichloromethane/hexane) to afford intermediate compound M14 (48.3 g, 70.1%)
在250mL三口瓶中，通N2保护。将4.22g(25mmol)二苯基胺，6.92g(10mmol)中间体M14，0.27g(0.5mmol)Pd(dba)2，6.2g(125mmol)叔丁醇钠，1.04mL(0.5mmol)三叔丁基膦，150mL甲苯置于三口瓶内，反应混合物在回流状态下反应2小时，TLC检测反应完全，停止反应。混合物降到室温后，加入去离子水淬灭反应，并用甲苯萃取三次，合并有机相，有机相用无水硫酸镁干燥，过硅胶短柱，滤液旋干，残留物经柱色谱分离得到化合物C-7为黄色固体7.5g，收率85％。In a 250 mL three-necked bottle, it was protected by N 2 . 4.22 g (25 mmol) of diphenylamine, 6.92 g (10 mmol) of intermediate M14, 0.27 g (0.5 mmol) of Pd(dba) 2 , 6.2 g (125 mmol) of sodium tert-butoxide, 1.04 mL (0.5 mmol) Butylphosphine, 150 mL of toluene was placed in a three-necked flask, and the reaction mixture was reacted under reflux for 2 hours, and the reaction was completed by TLC, and the reaction was stopped. After the mixture was cooled to room temperature, the reaction was quenched by the addition of deionized water, and extracted with toluene three times. The organic phase was combined, and then the organic phase was dried over anhydrous magnesium sulfate, and the filtrate was evaporated to dryness. -7 was a yellow solid 7.5 g, yield 85%.
合成实施例75.化合物C-8的合成Synthesis Example 75. Synthesis of Compound C-8
Figure PCTCN2016093026-appb-000065
Figure PCTCN2016093026-appb-000065
采用与实施例63中化合物B-27相同的合成方法，不同在于，将中间体2-溴二苯并噻吩置换为等当量的4-溴三苯胺，反应得到淡黄色固体7.0g，收率75％。The same synthesis procedure as in the compound B-27 of Example 63 was employed, except that the intermediate 2-bromodibenzothiophene was replaced with an equivalent of 4-bromotriphenylamine to give a pale yellow solid (yield: 7.0 g). %.
合成实施例76.化合物C-9的合成Synthesis Example 76. Synthesis of Compound C-9
采用与化合物C-4相同的合成方法，不同在于，将中间体M11置换为等当量的中间体M3，反应得到黄色固体7.04g，收率81％。The same synthesis method as the compound C-4 was used, except that the intermediate M11 was replaced with an equivalent of the intermediate M3, and the reaction gave a white solid (yield: 7.04 g, yield: 81%).
合成实施例77.化合物C-10的合成Synthesis Example 77. Synthesis of Compound C-10
采用与化合物C-4相同的合成方法，不同在于，将中间体M11置换为等当量的中间体M2，反应得到黄色固体7.1g，收率82％。The same synthesis method as the compound C-4 was employed, except that the intermediate M11 was replaced with an equivalent of the intermediate M2 to give a yellow solid 7.1 g, yield 82%.
合成实施例78.化合物C-11的合成Synthesis Example 78. Synthesis of Compound C-11
采用与化合物C-4相同的合成方法，不同在于，将中间体二苯基胺置换为等当量的苯基-2-萘基胺，反应得到淡黄色固体7.2g，收率为74％The same synthesis method as the compound C-4 was employed, except that the intermediate diphenylamine was replaced with an equivalent amount of phenyl-2-naphthylamine, and the reaction gave 7.2 g of a pale yellow solid, yield 74%.
C-11的核磁波普数据：Nuclear magnetic pop data for C-11:
1H NMR(500MHz，Chloroform)δ8.42(s，19H)，8.23(s，11H)，8.13(d，J＝6.6Hz，2H)，8.03(d，J＝70.0Hz，34H)，7.73(t，J＝3.3Hz，5H)，7.71(s，10H)，7.66(d，J＝45.0Hz，35H)，7.72-7.52(m，64H)，7.50(s，12H)，7.43(d，J＝15.0Hz，33H)，7.38(s，8H)，7.24(s，22H)，7.10(d，J＝15.0Hz，31H)，7.00(s，10H)，6.40(s，11H). 1 H NMR (500MHz, Chloroform) δ8.42 (s, 19H), 8.23 (s, 11H), 8.13 (d, J = 6.6Hz, 2H), 8.03 (d, J = 70.0Hz, 34H), 7.73 ( t, J = 3.3 Hz, 5H), 7.71 (s, 10H), 7.66 (d, J = 45.0 Hz, 35H), 7.72 - 7.52 (m, 64H), 7.50 (s, 12H), 7.43 (d, J) =15.0 Hz, 33H), 7.38 (s, 8H), 7.24 (s, 22H), 7.10 (d, J = 15.0 Hz, 31H), 7.00 (s, 10H), 6.40 (s, 11H).
合成实施例79.化合物C-12的合成 Synthesis Example 79. Synthesis of Compound C-12
Figure PCTCN2016093026-appb-000066
Figure PCTCN2016093026-appb-000066
化合物C-12-1的制备Preparation of Compound C-12-1
将中间体M7(34.5g，50mmol)、N-苯基-二苯并[b，d]呋喃-3-胺(7.8g，30mmol)、Pd2(dba)3(0.27g，0.3mmol)、叔丁醇钠(5.8g，60mmol)和甲苯(200mL)混合，然后在110℃下搅拌反应2小时。反应完成后，蒸馏水洗涤反应体系，然后用100ml乙酸乙酯萃取三次，合并得到的有机层，用无水MgSO4干燥有机层，并用旋转蒸发器除去溶剂，最后，对除去溶剂的剩余物进行柱分离，得到化合物C-12-1(16g，收率61.5％)。Intermediate M7 (34.5 g, 50 mmol), N-phenyl-dibenzo[b,d]furan-3-amine (7.8 g, 30 mmol), Pd 2 (dba) 3 (0.27 g, 0.3 mmol), Sodium tert-butoxide (5.8 g, 60 mmol) and toluene (200 mL) were mixed, and then the reaction was stirred at 110 ° C for 2 hours. After the completion of the reaction, the reaction system was washed with distilled water, and then extracted three times with 100 ml of ethyl acetate. The organic layer obtained was combined, dried over anhydrous MgSO 4 and evaporated, and evaporated. Separation gave Compound C-12-1 (16 g, yield: 61.5%).
化合物C-12的制备Preparation of Compound C-12
将化合物C-12-1(17g，20mmol)、N-苯基-二苯并[b，d]噻吩-3-胺(7.7g，30mmol)、Pd2(dba)3(0.27g，0.3mmol)、叔丁醇钠(5.8g，60mmol)和甲苯(200mL)混合，然后在110℃下搅拌反应2小时。反应完成后，蒸馏水洗涤反应体系，然后用100ml乙酸乙酯萃取三次，合并得到的有机层，用无水MgSO4干燥有机层，并用旋转蒸发器除去溶剂，最后，对除去溶剂的剩余物进行柱分离，得到化合物C-12，为黄色化合物(18.9g，89％)。Compound C-12-1 (17 g, 20 mmol), N-phenyl-dibenzo[b,d]thiophen-3-amine (7.7 g, 30 mmol), Pd 2 (dba) 3 (0.27 g, 0.3 mmol The sodium tert-butoxide (5.8 g, 60 mmol) and toluene (200 mL) were mixed, and then the reaction was stirred at 110 ° C for 2 hours. After the completion of the reaction, the reaction system was washed with distilled water, and then extracted three times with 100 ml of ethyl acetate. The organic layer obtained was combined, dried over anhydrous MgSO 4 and evaporated, and evaporated. Isolated to give compound C-12 as a yellow compound (18.9 g, 89%).
C-12的核磁波普数据：Nuclear magnetic pop data of C-12:
1H NMR(500MHz，Chloroform)δ8.56-8.38(m，50H)，8.08(s，25H)，8.05-8.03(m，1H)，7.99(t，J＝12.5Hz，23H)，8.03-7.71(m，38H)，7.57(dd，J＝39.9，34.9Hz，54H)，7.51(s，12H)，7.38(s，8H)，7.33-7.26(m，51H)，7.23(s，28H)，7.15(s，9H)，7.08(d，J＝15.0Hz，43H)，7.00(d，J＝15.0Hz，20H). 1 H NMR (500MHz, Chloroform) δ8.56-8.38 (m, 50H), 8.08 (s, 25H), 8.05-8.03 (m, 1H), 7.99 (t, J = 12.5Hz, 23H), 8.03-7.71 (m, 38H), 7.57 (dd, J = 39.9, 34.9 Hz, 54H), 7.51 (s, 12H), 7.38 (s, 8H), 7.33-7.26 (m, 51H), 7.23 (s, 28H), 7.15 (s, 9H), 7.08 (d, J = 15.0 Hz, 43H), 7.00 (d, J = 15.0 Hz, 20H).
合成实施例80.化合物C-13的合成 Synthesis Example 80. Synthesis of Compound C-13
Figure PCTCN2016093026-appb-000067
Figure PCTCN2016093026-appb-000067
中间体化合物C-13-1的制备Preparation of intermediate compound C-13-1
将中间体M7(34.5g，50mmol)、二苯胺(5.7g，30mmol)、Pd2(dba)3(0.27g，0.3mmol)、叔丁醇钠(5.8g，60mmol)和甲苯(200mL)混合，然后在110℃下搅拌反应2小时。反应完成后，蒸馏水洗涤反应体系，然后用100ml乙酸乙酯萃取三次，合并得到的有机层，用无水MgSO4干燥有机层，并用旋转蒸发器除去溶剂，最后，对除去溶剂的剩余物进行柱分离，得到单取代中间体化合物C-13-1(21g，90％)。Mix intermediate M7 (34.5 g, 50 mmol), diphenylamine (5.7 g, 30 mmol), Pd 2 (dba) 3 (0.27 g, 0.3 mmol), sodium tert-butoxide (5.8 g, 60 mmol) and toluene (200 mL) Then, the reaction was stirred at 110 ° C for 2 hours. After the completion of the reaction, the reaction system was washed with distilled water, and then extracted three times with 100 ml of ethyl acetate. The organic layer obtained was combined, dried over anhydrous MgSO 4 and evaporated, and evaporated. Separation gave the monosubstituted intermediate compound C-13-1 (21 g, 90%).
化合物C-13的制备Preparation of Compound C-13
将化合物C-13-1(21g，27mmol)、N-苯基-二苯并[b，d]噻吩-3-胺(7.7g，30mmol)、Pd2(dba)3(0.27g，0.3mmol)、叔丁醇钠(5.8g，60mmol)和甲苯(200mL)混合，然后在120℃下搅拌反应2小时。反应完成后，蒸馏水洗涤反应体系，然后用100ml乙酸乙酯萃取三次，合并得到的有机层，用无水MgSO4干燥有机层，并用旋转蒸发器除去溶剂，最后，对除去溶剂的剩余物进行柱分离，得到化合物C-13，为黄色固体(23.7g，90％)。Compound C-13-1 (21 g, 27 mmol), N-phenyl-dibenzo[b,d]thiophen-3-amine (7.7 g, 30 mmol), Pd 2 (dba) 3 (0.27 g, 0.3 mmol The sodium tert-butoxide (5.8 g, 60 mmol) and toluene (200 mL) were mixed, and then the reaction was stirred at 120 ° C for 2 hours. After the completion of the reaction, the reaction system was washed with distilled water, and then extracted three times with 100 ml of ethyl acetate. The organic layer obtained was combined, dried over anhydrous MgSO 4 and evaporated, and evaporated. Isolated to give compound C-13 as a yellow solid (23.7 g, 90%).
C-13的核磁波普数据：Nuclear magnetic pop data for C-13:
1H NMR(500MHz，Chloroform)δ8.67-8.21(m，259H)，8.37(s，13H)，8.08(s，122H)，8.05(s，5H)，8.03(d，J＝21.7Hz，6H)，8.01-7.70(m，112H)，7.61(d，J＝64.9Hz，190H)，7.51(s，59H)，7.30(d，J＝5.0Hz，178H)，7.23(s，226H)，7.15(s，39H)，7.08(d，J＝15.0Hz，299H)，7.00(d，J＝15.0Hz，126H). 1 H NMR (500MHz, Chloroform) δ8.67-8.21 (m, 259H), 8.37 (s, 13H), 8.08 (s, 122H), 8.05 (s, 5H), 8.03 (d, J = 21.7Hz, 6H ), 8.01-7.70 (m, 112H), 7.61 (d, J = 64.9 Hz, 190H), 7.51 (s, 59H), 7.30 (d, J = 5.0 Hz, 178H), 7.23 (s, 226H), 7.15 (s, 39H), 7.08 (d, J = 15.0 Hz, 299H), 7.00 (d, J = 15.0 Hz, 126H).
合成实施例81.化合物C-14的合成Synthesis Example 81. Synthesis of Compound C-14
采用与实施例25制备化合物A-16的相同的方法制备化合物C-14，不同在于将中间体M8替换为等当量的中间体M9，将4-联苯硼酸置换为等当量的(4-(diphenylamino)phenyl)boronic acid，反应完成后，分离得到B-13，为白色固体6.6g，收率为85％。Compound C-14 was prepared in the same manner as in the preparation of compound A-16 of Example 25, except that intermediate M8 was replaced with an equivalent of intermediate M9, and 4-biphenylboronic acid was replaced with an equivalent (4-( Diphenylamino)phenyl)boronic acid, after completion of the reaction, B-13 was obtained as a white solid 6.6 g, yield: 85%.
合成实施例82.化合物C-15的合成Synthesis Example 82. Synthesis of Compound C-15
采用与实施例25制备化合物A-16的相同的方法制备化合物C-14，不同在于将中间体M8替换为等当量的中间体M9，将4-联苯硼酸置换为等当量的(4-(diphenylamino)phenyl)boronic acid，反应完成后，分离得到B-13，为白色固体6.6g， 收率为85％。Compound C-14 was prepared in the same manner as in the preparation of compound A-16 of Example 25, except that intermediate M8 was replaced with an equivalent of intermediate M9, and 4-biphenylboronic acid was replaced with an equivalent (4-( Diphenylamino)phenyl)boronic acid, after completion of the reaction, B-13 was isolated as a white solid 6.6 g. The yield was 85%.
C-15的核磁波普数据：Nuclear magnetic pop data for C-15:
1H NMR(500MHz，Chloroform)δ8.51(s，17H)，8.38(s，13H)，8.06(s，13H)，7.56(d，J＝19.9Hz，46H)，7.48(d，J＝10.0Hz，42H)，7.36(s，7H)，7.21(s，31H)，7.14(d，J＝10.0Hz，19H)，7.06(d，J＝14.9Hz，43H)，6.97(s，9H)，6.90(s，9H). 1 H NMR (500MHz, Chloroform) δ8.51 (s, 17H), 8.38 (s, 13H), 8.06 (s, 13H), 7.56 (d, J = 19.9Hz, 46H), 7.48 (d, J = 10.0 Hz, 42H), 7.36 (s, 7H), 7.21 (s, 31H), 7.14 (d, J = 10.0 Hz, 19H), 7.06 (d, J = 14.9 Hz, 43H), 6.97 (s, 9H), 6.90 (s, 9H).
合成实施例83.化合物C-16的合成Synthesis Example 83. Synthesis of Compound C-16
Figure PCTCN2016093026-appb-000068
Figure PCTCN2016093026-appb-000068
N2保护下，三口瓶中加入碘苯22g(0.11mol)，中间体M946.1g(0.1mol)，氯化亚铜2g(20mmol)，水合1，10-菲啰啉4g(20mmol)，氢氧化钾16.8g(0.3mol)，二甲苯300ml。反应体系保持回流反应20h，反应完全，蒸馏水洗涤反应体系，然后用100ml乙酸乙酯萃取三次，合并得到的有机层，用MgSO4干燥有机层，并用旋转蒸发器除去溶剂，对除去溶剂的剩余物进行柱分离，得到中间体化合物为白色固体(46.1g，75％)。Under N2 protection, 22g (0.11mol) of iodobenzene, intermediate M946.1g (0.1mol), cuprous chloride 2g (20mmol), hydrated 1,10-phenanthroline 4g (20mmol), hydroxide Potassium was 16.8 g (0.3 mol) and xylene was 300 ml. The reaction system was kept under reflux for 20 hours, and the reaction was completed. The reaction mixture was washed with distilled water, and then extracted three times with 100 ml of ethyl acetate. The organic layer obtained was combined, dried over MgSO 4 and solvent was evaporated to remove solvent. Column separation gave the intermediate compound as a white solid (46.1 g, 75%).
将中间体C-16-1(6.14g，10mmol)、二苯基胺(1.7g，10mmol)、Pd2(dba)3(0.03g，0.03mmol)、叔丁醇钠(1.9g，20mmol)和甲苯(100mL)混合，然后在120℃下搅拌反应2小时。反应完成后，蒸馏水洗涤反应体系，然后用100ml乙酸乙酯萃取三次，合并得到的有机层，用无水MgSO4干燥有机层，并用旋转蒸发器除去溶剂，最后，对除去溶剂的剩余物进行柱分离，得到化合物C-16，为黄色固体(6.25g，89％)。Intermediate C-16-1 (6.14 g, 10 mmol), diphenylamine (1.7 g, 10 mmol), Pd 2 (dba) 3 (0.03 g, 0.03 mmol), sodium tert-butoxide (1.9 g, 20 mmol) It was mixed with toluene (100 mL), and then the reaction was stirred at 120 ° C for 2 hours. After the completion of the reaction, the reaction system was washed with distilled water, and then extracted three times with 100 ml of ethyl acetate. The organic layer obtained was combined, dried over anhydrous MgSO 4 and evaporated, and evaporated. Isolated to give compound C-16 as a yellow solid (6.25 g, 89%).
合成实施例84.化合物D-1的合成Synthesis Example 84. Synthesis of Compound D-1
Figure PCTCN2016093026-appb-000069
Figure PCTCN2016093026-appb-000069
在250ml三口瓶中，将中间体化合物M6(19.1g，50mmol)、2-溴吡啶(18.9g，120mmol)、CuI(1.8g，10mmol)，反式-二氨基环己烷(5.4ml，50mmol)和碳酸铯(16g，50mmol)形成的混合物加热回流3小时。然后将反应混合物冷却至室温，过滤，用二 氯甲烷洗涤滤饼，得到的有机相用去离子水充分洗涤，然后用无水硫酸钠干燥。将干燥后的有机相进行减压除去溶剂，得到的残余物进行柱分离，得到淡黄色化合物D-1(23.1g，产率86％)。In a 250 ml three-necked flask, intermediate compound M6 (19.1 g, 50 mmol), 2-bromopyridine (18.9 g, 120 mmol), CuI (1.8 g, 10 mmol), trans-diaminocyclohexane (5.4 ml, 50 mmol) The mixture formed with cesium carbonate (16 g, 50 mmol) was heated to reflux for 3 hours. Then the reaction mixture was cooled to room temperature, filtered, and used The filter cake was washed with methyl chloride, and the obtained organic phase was washed thoroughly with deionized water and then dried over anhydrous sodium sulfate. The organic phase after drying was evaporated under reduced pressure, and the residue obtained was purified, mjjjjjjjj
合成实施例85.化合物D-2的合成Synthesis Example 85. Synthesis of Compound D-2
采用与合成实施例84相同的合成方法，不同在于，将2-溴吡啶用等当量的5-溴-2-苯基吡啶代替，反应后得到淡黄色固体27.1g，收率为79％。The same synthesis method as in Synthesis Example 84 was employed, except that 2-bromopyridine was replaced with an equivalent of 5-bromo-2-phenylpyridine to give 27.1 g of a pale yellow solid.
合成实施例86.化合物D-3的合成Synthesis Example 86. Synthesis of Compound D-3
采用与合成实施例84相同的合成方法，不同在于，将2-溴吡啶用等当量的2-(4-溴苯基)吡啶代替，反应后得到淡黄色固体29g，收率为84％。The same synthesis method as in Synthesis Example 84 was employed, except that 2-bromopyridine was replaced with an equivalent of 2-(4-bromophenyl)pyridine to give a pale yellow solid (yield: 84%).
合成实施例87.化合物D-4的合成Synthesis Example 87. Synthesis of Compound D-4
采用与合成实施例84相同的合成方法，不同在于，将2-溴吡啶用等当量的3-(4-溴苯基)吡啶代替，反应后得到淡黄色固体24.5g，收率为71％。The same synthesis method as in Synthesis Example 84 was employed, except that 2-bromopyridine was replaced with an equivalent of 3-(4-bromophenyl)pyridine to give a pale yellow solid (24.5 g, yield 71%).
D-4的核磁波普数据：D-4 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ9.24(s，21H)，8.70(s，11H)，8.49(d，J＝δ5.0Hz，74H)，8.39(s，3H)，8.33(s，19H)，8.10(s，35H)，7.91(d，J＝5.0Hz，84H)，7.49(d，J＝25.0Hz，39H)，7.44(s，2H)，7.16(s，12H)，7.11(s，17H). 1 H NMR (500 MHz, Chloroform) δ 9.24 (s, 21H), 8.70 (s, 11H), 8.49 (d, J = δ 5.0 Hz, 74H), 8.39 (s, 3H), 8.33 (s, 19H) , 8.10 (s, 35H), 7.91 (d, J = 5.0 Hz, 84H), 7.49 (d, J = 25.0 Hz, 39H), 7.44 (s, 2H), 7.16 (s, 12H), 7.11 (s, 17H).
合成实施例88.化合物D-5的合成Synthesis Example 88. Synthesis of Compound D-5
Figure PCTCN2016093026-appb-000070
Figure PCTCN2016093026-appb-000070
采用与实施例21中化合物A-11相同的合成方法，不同在于，将中间体溴苯置换为等当量的5-bromo-2-phenylpyridine，反应得到黄色固体5.65g，收率为82％。The same synthesis method as the compound A-11 of Example 21 was used, except that the intermediate bromobenzene was replaced by an equivalent of 5-bromo-2-phenylpyridine, and the reaction gave 5.65 g of a yellow solid.
合成实施例89.化合物D-6的合成Synthesis Example 89. Synthesis of Compound D-6
Figure PCTCN2016093026-appb-000071
Figure PCTCN2016093026-appb-000071
采用与实施例63中化合物B-27相同的合成方法，不同在于，将中间体2-溴二 苯并噻吩置换为等当量的4-溴三苯胺，反应得到淡黄色固体7.0g，收率75％。The same synthetic procedure as in the compound B-27 of Example 63 was employed, except that the intermediate 2-bromo The benzothiophene was replaced with an equivalent amount of 4-bromotriphenylamine, and the reaction gave 7.0 g of a pale yellow solid, yield 75%.
D-6的核磁波普数据：D-6 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.43(d，J＝5.0Hz，42H)，8.20(s，15H)，8.11(d，J＝10.0Hz，41H)，7.92(t，J＝45.0Hz，45H)，7.79-7.57(m，60H)，7.54(s，12H)，7.49(s，28H)，7.41(s，8H). 1 H NMR (500MHz, Chloroform) δ8.43 (d, J = 5.0Hz, 42H), 8.20 (s, 15H), 8.11 (d, J = 10.0Hz, 41H), 7.92 (t, J = 45.0Hz, 45H), 7.79-7.57 (m, 60H), 7.54 (s, 12H), 7.49 (s, 28H), 7.41 (s, 8H).
合成实施例90.化合物D-7的合成Synthesis Example 90. Synthesis of Compound D-7
采用与实施例23相同的方法制备化合物D-7，不同在于将中间体M2替换为等当量的中间体M3，同时将苯硼酸置换为等当量的吡啶-2-硼酸，反应完成后得到黄色固体5.86g，收率为85％。Compound D-7 was prepared in the same manner as in Example 23 except that the intermediate M2 was replaced with an equivalent of the intermediate M3, and the phenylboronic acid was replaced with an equivalent of the pyridine-2-boronic acid. 5.86 g, yield was 85%.
合成实施例91.化合物D-8的合成Synthesis Example 91. Synthesis of Compound D-8
采用与合成实施例84相同的合成方法制备化合物D-8，不同在于，将2-溴吡啶用等当量的2-溴喹啉啶代替，反应后得到黄色化合物26.8g，产率84％。Compound D-8 was prepared by the same synthetic procedure as in the the the the the the the the the the the the the the the the the
合成实施例92.中间体化合物M15的合成Synthesis Example 92. Synthesis of Intermediate Compound M15
Figure PCTCN2016093026-appb-000072
Figure PCTCN2016093026-appb-000072
向1升三口瓶中加入4-溴苯肼盐酸盐(92.8g，0.415mol)，二苯并[a，e]-5，11-环辛二烯(6H，12H)-二酮(49g，0.207mol)，乙醇(400毫升)，搅拌条件下，3min内滴加2g浓硫酸，在65℃下反应4小时，反应结束后，冷却至室温，过滤，依次用乙醇、石油醚洗涤滤饼，得到中间体化合物M15-1(110g，85％)。To a 1 liter three-necked flask was added 4-bromophenylhydrazine hydrochloride (92.8 g, 0.415 mol), dibenzo[a,e]-5,11-cyclooctadiene (6H,12H)-dione (49 g) , 0.207mol), ethanol (400ml), under stirring, add 2g concentrated sulfuric acid in 3min, react at 65 ° C for 4 hours, after the reaction is finished, cool to room temperature, filter, wash the filter cake with ethanol, petroleum ether The intermediate compound M15-1 (110 g, 85%) was obtained.
向1升三口瓶中加入化合物M15-1(48.4g，74.8mmol)，乙酸(650g)和三氟乙酸(65g，0.57mol)，在72℃下回流反应15小时，冷却至室温，过滤，依次用乙酸、石油醚洗涤滤饼，得中间体化合物M15-2(32g，80％)。Compound M15-1 (48.4 g, 74.8 mmol), acetic acid (650 g) and trifluoroacetic acid (65 g, 0.57 mol) were added to a 1-liter three-necked flask, and the mixture was refluxed at 72 ° C for 15 hours, cooled to room temperature, and filtered. The filter cake was washed with acetic acid and petroleum ether to give intermediate compound M15-2 (32 g, 80%).
将二甲苯(100毫升)、M15-2(5.4g，10mmol)，碘苯(5.1g，25mmol)，CuI(0.9g，5mmol)，反式-二氨基环己烷(2.1毫升，20mmol)和碳酸铯(6.5g，20mmol)混合，回流反应3小时，反应结束后，冷却至室温，过滤，然后用二氯甲烷(二氯甲烷)洗涤滤饼，合并滤液，干燥，然后减压除去溶剂，将得到的蒸馏剩余物进行柱分离(DCM/PE＝1/2，v/v(体积比为1∶2的二氯甲烷和石油醚的混合溶液))，得到中间体化 合物M15，为白色固体(5.5g，产率82％)。Xylene (100 ml), M15-2 (5.4 g, 10 mmol), iodobenzene (5.1 g, 25 mmol), CuI (0.9 g, 5 mmol), trans-diaminocyclohexane (2.1 ml, 20 mmol) and The cesium carbonate (6.5 g, 20 mmol) was mixed and refluxed for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, filtered, and then the filter cake was washed with dichloromethane (dichloromethane), and the filtrate was dried. The obtained distillation residue was subjected to column separation (DCM/PE=1/2, v/v (mixed solution of dichloromethane and petroleum ether in a volume ratio of 1:2)) to obtain an intermediate. Compound M15 was a white solid (5.5 g, yield 82%).
合成实施例93.化合物D-9的合成Synthesis Example 93. Synthesis of Compound D-9
Figure PCTCN2016093026-appb-000073
Figure PCTCN2016093026-appb-000073
在氮气保护下，将中间体M15(6.9g，10mmol)、3-吡啶硼酸(3.08g，25mmol)、Pd(PPh3)4(0.58g，0.5mmol)、Na2CO3(5.3g，50mmol)、60mL甲苯和20mL EtOH混合，向该混合物中加入蒸馏水20mL，然后在110℃下搅拌反应2小时。反应完成后，用蒸馏水洗涤反应体系，然后用100ml乙酸乙酯萃取三次，合并得到的有机层，用MgSO4干燥有机层，并旋蒸除去溶剂，最后，对除去溶剂的剩余物进行柱分离，得到黄色固体化合物D-9(5.2g，75％)。Intermediate M15 (6.9 g, 10 mmol), 3-pyridineboronic acid (3.08 g, 25 mmol), Pd(PPh 3 ) 4 (0.58 g, 0.5 mmol), Na 2 CO 3 (5.3 g, 50 mmol) 60 mL of toluene and 20 mL of EtOH were mixed, and 20 mL of distilled water was added to the mixture, followed by stirring at 110 ° C for 2 hours. After the completion of the reaction, the reaction system was washed with distilled water, and then extracted three times with 100 ml of ethyl acetate. The organic layer obtained was combined, dried over MgSO 4 and evaporated to remove solvent. The yellow solid compound D-9 (5.2 g, 75%) was obtained.
合成实施例94.化合物D-10的合成Synthesis Example 94. Synthesis of Compound D-10
采用与合成实施例84相同的合成方法，不同在于，将2-溴吡啶用等当量的5-溴-1，10菲罗啉代替，反应后得到淡黄色固体29.9g，收率为81％。The same synthesis method as in Synthesis Example 84 was employed, except that 2-bromopyridine was replaced with an equivalent of 5-bromo-1,10 phenanthroline to give a pale yellow solid (29.9 g, yield: 81%).
D-10的核磁波普数据：D-10 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.80(s，2H)，8.55(s，1H)，8.43(d，J＝6.3Hz，3H)，8.12(d，J＝20.0Hz，4H)，7.52(s，1H)，7.39(s，2H)，7.16(s，1H)，7.11(s，1H). 1 H NMR (500 MHz, Chloroform) δ 8.80 (s, 2H), 8.55 (s, 1H), 8.43 (d, J = 6.3 Hz, 3H), 8.12 (d, J = 20.0 Hz, 4H), 7.52 ( s, 1H), 7.39 (s, 2H), 7.16 (s, 1H), 7.11 (s, 1H).
合成实施例95.化合物D-11的合成Synthesis Example 95. Synthesis of Compound D-11
Figure PCTCN2016093026-appb-000074
Figure PCTCN2016093026-appb-000074
干燥的1L三口烧瓶中加入中间体M6(22.9g，50mmol)并用200mL无水DMF溶解，室温，氮气保护，磁力搅拌下分批加入60％NaH(4g，0.1mol)，有大量气体产生，加完后继续室温搅拌1小时。然后在室温下，通过恒压滴液漏斗加入2-氯-4，6-二苯基嘧啶(32g，120mmol)的150mL无水DMF溶液，约1.5小时滴加完毕。加完继续室温搅拌3小时，然后慢慢滴加水淬灭反应，淬灭后加入300mL乙酸乙酯和 200mL水搅拌30分钟，体系呈悬浊状态。抽滤，固体用二氯甲烷溶解，饱和食盐水洗，无水硫酸钠干燥，用5cm硅胶柱抽滤，减压旋干。柱色谱分离得到化合物D-11，为黄色粉末状固体36.7g，收率87％。Intermediate M6 (22.9 g, 50 mmol) was added to a dry 1 L three-necked flask and dissolved in 200 mL of anhydrous DMF. At room temperature, under nitrogen atmosphere, 60% NaH (4 g, 0.1 mol) was added in batches with magnetic stirring, and a large amount of gas was produced. After completion, the mixture was stirred at room temperature for 1 hour. Then, a solution of 2-chloro-4,6-diphenylpyrimidine (32 g, 120 mmol) in 150 mL of anhydrous DMF was added at room temperature through a constant pressure dropping funnel, and the addition was completed over about 1.5 hours. After the addition was completed, stirring was continued at room temperature for 3 hours, and then the reaction was quenched by dropwise addition of water, and after quenching, 300 mL of ethyl acetate and After stirring for 200 minutes in 200 mL of water, the system was suspended. After suction filtration, the solid was dissolved in dichloromethane, washed with saturated brine and dried over anhydrous sodium sulfate. Column chromatography gave Compound D-11 as a yellow powdery solid (36.7 g, yield: 87%).
合成实施例96.化合物D-12的合成Synthesis Example 96. Synthesis of Compound D-12
采用与合成实施例95相同的合成方法，不同在于，将2-氯-4，6-二苯基嘧啶用等当量的2-氯-4-苯基喹唑啉代替，反应后得到黄色固体32.4g，收率为82％。The same synthesis method as in Synthesis Example 95 was employed, except that 2-chloro-4,6-diphenylpyrimidine was replaced with an equivalent of 2-chloro-4-phenyl quinazoline to give a yellow solid. g, the yield was 82%.
合成实施例97.化合物D-13的合成Synthesis Example 97. Synthesis of Compound D-13
采用与合成实施例95相同的合成方法，不同在于，将2-氯-4，6-二苯基嘧啶用等当量的2-氯-喹喔啉代替，反应后得到黄色固体25g，收率为75％。The same synthesis method as in Synthesis Example 95 was employed, except that 2-chloro-4,6-diphenylpyrimidine was replaced with an equivalent amount of 2-chloro-quinoxaline, and 25 g of a yellow solid was obtained. 75%.
合成实施例98.化合物D-14的合成Synthesis Example 98. Synthesis of Compound D-14
采用与合成实施例95相同的合成方法，不同在于，将2-氯-4，6-二苯基嘧啶用等当量的2-chloroquinazoline代替，反应后得到黄色固体22.7g，收率为71％。The same synthesis method as in Synthesis Example 95 was employed, except that 2-chloro-4,6-diphenylpyrimidine was replaced with an equivalent of 2-chloroquinazoline, and 22.7 g of a yellow solid was obtained.
合成实施例99.化合物D-15的合成Synthesis Example 99. Synthesis of Compound D-15
采用与合成实施例95相同的合成方法，不同在于，将2-氯-4，6-二苯基嘧啶用等当量的2-chloro-4，6-diphenyl-1，3，5-triazine代替，反应后得到黄色固体33.0g，收率78％。The same synthesis method as in Synthesis Example 95 was employed except that 2-chloro-4,6-diphenylpyrimidine was replaced with an equivalent amount of 2-chloro-4,6-diphenyl-1,3,5-triazine. After the reaction, 33.0 g of a yellow solid was obtained, yield 78%.
合成实施例100.化合物D-16的合成Synthesis Example 100. Synthesis of Compound D-16
Figure PCTCN2016093026-appb-000075
Figure PCTCN2016093026-appb-000075
干燥的1L三口烧瓶中加入中间体B-19-4(22.9g，50mmol，参见合成实施例53)并用200mL无水DMF溶解，室温，氮气保护，磁力搅拌下分批加入60％NaH(4g，0.1mol)，有大量气体产生，加完后继续室温搅拌1小时。然后在室温下，通过恒压滴液漏斗加入2-氯-4，6-二苯基嘧啶(16g，60mmol)的120mL无水DMF溶液，约1.5小时滴加完毕。加完继续室温搅拌3小时，然后慢慢滴加水淬灭反应，淬灭后加入300mL乙酸乙酯和200mL水搅拌30分钟，体系呈悬浊状态。抽滤，固体用二氯甲烷溶解，饱和食盐水洗，无水硫酸钠干燥，用5cm硅胶柱抽滤，减压旋干。柱色谱分离得 到化合物D-16，为黄色粉末状固体26.9g，收率78％。Intermediate B-19-4 (22.9 g, 50 mmol, see Synthesis Example 53) was added to a dry 1 L three-necked flask and dissolved in 200 mL anhydrous DMF. 0.1 mol), a large amount of gas was generated, and stirring was continued at room temperature for 1 hour after the addition. Then, a solution of 2-chloro-4,6-diphenylpyrimidine (16 g, 60 mmol) in 120 mL of anhydrous DMF was added at room temperature through a constant pressure dropping funnel, and the addition was completed over about 1.5 hours. After the addition was completed, stirring was continued at room temperature for 3 hours, and then the reaction was quenched by dropwise addition of water. After quenching, 300 mL of ethyl acetate and 200 mL of water were added and stirred for 30 minutes, and the system was suspended. After suction filtration, the solid was dissolved in dichloromethane, washed with saturated brine and dried over anhydrous sodium sulfate. Separated by column chromatography To compound D-16, 26.9 g of a yellow powdery solid, yield 78%.
合成实施例101.化合物D-17的合成Synthesis Example 101. Synthesis of Compound D-17
Figure PCTCN2016093026-appb-000076
Figure PCTCN2016093026-appb-000076
干燥的1L三口烧瓶中加入中间体M1(22.9g，50mmol)并用200mL无水DMF溶解，室温，氮气保护，磁力搅拌下分批加入60％NaH(4g，0.1mol)，有大量气体产生，加完后继续室温搅拌1小时。然后在室温下，通过恒压滴液漏斗加入2-氯-4-苯基嘧啶(23g，120mmol)的150mL无水DMF溶液，约1.5小时滴加完毕。加完继续室温搅拌3小时，然后慢慢滴加水淬灭反应，淬灭后加入300mL乙酸乙酯和200mL水搅拌30分钟，体系呈悬浊状态。抽滤，固体用二氯甲烷溶解，饱和食盐水洗，无水硫酸钠干燥，用5cm硅胶柱抽滤，减压旋干。柱色谱分离得到化合物D-17，为黄色粉末状固体29.4g，收率85％。Intermediate M1 (22.9 g, 50 mmol) was added to a dry 1 L three-necked flask and dissolved in 200 mL of anhydrous DMF. The mixture was stirred at room temperature under nitrogen. Under a magnetic stirring, 60% NaH (4 g, 0.1 mol) was added in portions, and a large amount of gas was produced. After completion, the mixture was stirred at room temperature for 1 hour. Then, a solution of 2-chloro-4-phenylpyrimidine (23 g, 120 mmol) in 150 mL of anhydrous DMF was added at room temperature through a constant pressure dropping funnel, and the addition was completed over about 1.5 hours. After the addition was completed, stirring was continued at room temperature for 3 hours, and then the reaction was quenched by dropwise addition of water. After quenching, 300 mL of ethyl acetate and 200 mL of water were added and stirred for 30 minutes, and the system was suspended. After suction filtration, the solid was dissolved in dichloromethane, washed with saturated brine and dried over anhydrous sodium sulfate. Column chromatography gave Compound D-17 as a yellow powdery solid (29.4 g, yield: 85%).
合成实施例102.化合物D-18的合成Synthesis Example 102. Synthesis of Compound D-18
采用与合成实施例101相同的合成方法，不同在于，将2-氯-4-苯基嘧啶置换为等当量的2-氯-4，6-二苯基嘧啶，反应完成后得到黄色固体33.3g，收率为79％。The same synthesis method as in Synthesis Example 101 was employed, except that 2-chloro-4-phenylpyrimidine was replaced with an equivalent amount of 2-chloro-4,6-diphenylpyrimidine, and after completion of the reaction, 33.3 g of a yellow solid was obtained. The yield was 79%.
合成实施例103.化合物D-19的合成Synthesis Example 103. Synthesis of Compound D-19
采用与合成实施例101相同的合成方法，不同在于，将2-氯-4-苯基嘧啶置换为等当量的2-氯-4-苯基喹唑啉，反应完成后得到黄色固体34.4g，收率为87％。The same synthesis method as in Synthesis Example 101 was employed, except that 2-chloro-4-phenylpyrimidine was replaced with an equivalent amount of 2-chloro-4-phenylquinazoline, and after completion of the reaction, 34.4 g of a yellow solid was obtained. The yield was 87%.
合成实施例104.化合物D-20的合成Synthesis Example 104. Synthesis of Compound D-20
采用与合成实施例101相同的合成方法，不同在于，将2-氯-4-苯基嘧啶置换为等当量的2-氯-喹喔啉，反应完成后得到黄色固体22.7g，收率为71％。The same synthesis method as in Synthesis Example 101 was employed, except that 2-chloro-4-phenylpyrimidine was replaced with an equivalent amount of 2-chloro-quinoxaline, and after completion of the reaction, 22.7 g of a yellow solid was obtained, yield 71. %.
合成实施例105.化合物D-21的合成Synthesis Example 105. Synthesis of Compound D-21
采用与合成实施例101相同的合成方法，不同在于，将2-氯-4-苯基嘧啶置换为2-氯-4-联苯基喹唑啉，反应完成后得到黄色固体35g，收率为74％。The same synthesis method as in Synthesis Example 101 was employed, except that 2-chloro-4-phenylpyrimidine was replaced with 2-chloro-4-biphenylquinazoline, and after completion of the reaction, 35 g of a yellow solid was obtained. 74%.
合成实施例106.化合物D-22的合成Synthesis Example 106. Synthesis of Compound D-22
采用与合成实施例101相同的合成方法，不同在于，将2-氯-4-苯基嘧啶置换为等当量的2-氯-4-联苯基嘧啶，反应完成后得到黄色固体34.1g，收率为81％。The same synthesis method as in Synthesis Example 101 was employed except that 2-chloro-4-phenylpyrimidine was replaced with an equivalent amount of 2-chloro-4-biphenylpyrimidine, and after completion of the reaction, 34.1 g of a yellow solid was obtained. The rate is 81%.
合成实施例107.化合物D-23的合成 Synthesis Example 107. Synthesis of Compound D-23
采用与合成实施例101相同的合成方法，不同在于，将2-氯-4-苯基嘧啶置换为等当量的2-氯-4，6-二苯基三嗪，反应完成后得到黄色固体33.8g，收率为80％。The same synthesis method as in Synthesis Example 101 was employed except that 2-chloro-4-phenylpyrimidine was replaced with an equivalent amount of 2-chloro-4,6-diphenyltriazine, and a yellow solid was obtained after completion of the reaction. g, the yield is 80%.
合成实施例108.化合物D-24的合成Synthesis Example 108. Synthesis of Compound D-24
采用与合成实施例88中制备化合物D-5相同的合成方法，不同在于，将5-bromo-2-phenylpyridine置换为等当量的5-溴-1，10-菲罗啉，反应完成后得到黄色固体4.95g，收率为67％。The same synthesis method as in the preparation of the compound D-5 in Synthesis Example 88 was employed, except that 5-bromo-2-phenylpyridine was replaced with an equivalent amount of 5-bromo-1,10-phenanthroline, and yellow was obtained after completion of the reaction. The solid was 4.95 g and the yield was 67%.
合成实施例109.化合物D-25的合成Synthesis Example 109. Synthesis of Compound D-25
Figure PCTCN2016093026-appb-000077
Figure PCTCN2016093026-appb-000077
在1L反应瓶中，将中间体M1(38.2g，0.1mol)、4-溴联苯(23.3g，0.1mol)、CuI(3.3g，17.1mmol)、K3PO4(21.8g，102.9mmol)、环己基二胺(2.3ml，34.3mmol)和甲苯(500ml)混合，在回流条件下搅拌反应1天，反应结束后，冷却至室温，用250ml乙酸乙酯萃取，有机层经无水硫酸镁后减压蒸馏除去溶剂，对得到的蒸馏剩余物进行柱分离(洗脱液：二氯甲烷/己烷)，得到化合物D-25-1(26.8g，收率50％)。Intermediate M1 (38.2 g, 0.1 mol), 4-bromobiphenyl (23.3 g, 0.1 mol), CuI (3.3 g, 17.1 mmol), K 3 PO 4 (21.8 g, 102.9 mmol) in a 1 L reaction flask , cyclohexyldiamine (2.3 ml, 34.3 mmol) and toluene (500 ml) were mixed, and the reaction was stirred under reflux for 1 day. After completion of the reaction, the mixture was cooled to room temperature and extracted with ethyl acetate (250 ml). After magnesium, the solvent was evaporated under reduced pressure, and the obtained distillation residue was subjected to column separation (eluent: dichloromethane/hexane) to afford Compound D-25-1 (26.8 g, yield 50%).
干燥的1L三口烧瓶中加入中间体D-25-1(26.8g，50mmol)并用200mL无水DMF溶解，室温，氮气保护，磁力搅拌下分批加入60％NaH(2g，50mmol)，有大量气体产生，加完后继续室温搅拌1小时。然后在室温下，通过恒压滴液漏斗加入2-氯-4，6-二苯基三嗪(16.1g，60mmol)的150mL无水DMF溶液，约1.5小时滴加完毕。加完继续室温搅拌3小时，然后慢慢滴加水淬灭反应，淬灭后加入300mL乙酸乙酯和200mL水搅拌30分钟，体系呈悬浊状态。抽滤，固体用二氯甲烷溶解，饱和食盐水洗，无水硫酸钠干燥，用5cm硅胶柱抽滤，减压旋干。柱色谱分离得到化合物D-25，为黄色粉末状固体34.5g，收率90％。Intermediate D-25-1 (26.8 g, 50 mmol) was added to a dry 1 L three-necked flask and dissolved in 200 mL of anhydrous DMF, and the mixture was stirred at room temperature under nitrogen, and 60% NaH (2 g, 50 mmol) was added in portions with magnetic stirring. After the addition, the mixture was stirred at room temperature for 1 hour. Then, a solution of 2-chloro-4,6-diphenyltriazine (16.1 g, 60 mmol) in 150 mL of anhydrous DMF was added at room temperature through a constant pressure dropping funnel, and the addition was completed over about 1.5 hours. After the addition was completed, stirring was continued at room temperature for 3 hours, and then the reaction was quenched by dropwise addition of water. After quenching, 300 mL of ethyl acetate and 200 mL of water were added and stirred for 30 minutes, and the system was suspended. After suction filtration, the solid was dissolved in dichloromethane, washed with saturated brine and dried over anhydrous sodium sulfate. Column chromatography gave Compound D-25 as a yellow powdery solid (34.5 g).
D-25的核磁波普数据：D-25 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.49(d，J＝65.0Hz，47H)，8.37(ddd，J＝5.3，3.9，2.7Hz，12H)，8.36(s，20H)，8.10(s，20H)，7.91(d，J＝5.0Hz，24H)，7.77(dd，J＝3.1，1.4Hz，4H)，7.75(s，10H)，7.76-7.39(m，75H)，7.16(s，7H)，7.11(s，10H). 1 H NMR (500 MHz, Chloroform) δ 8.49 (d, J = 65.0 Hz, 47H), 8.37 (ddd, J = 5.3, 3.9, 2.7 Hz, 12H), 8.36 (s, 20H), 8.10 (s, 20H) ), 7.91 (d, J = 5.0 Hz, 24H), 7.77 (dd, J = 3.1, 1.4 Hz, 4H), 7.75 (s, 10H), 7.76-7.39 (m, 75H), 7.16 (s, 7H) , 7.11 (s, 10H).
合成实施例110.化合物D-26的合成 Synthesis Example 110. Synthesis of Compound D-26
采用与合成实施例109相同的合成方法，不同在于，在第一步反应中将4-溴联苯置换为等当量的溴苯，在第二步反应中将2-氯-4，6-二苯基三嗪置换为等当量的2-氯-4，6-二联苯基三嗪，反应完成后得到黄色固体35.8g，收率为85％。The same synthesis method as in Synthesis Example 109 was employed, except that 4-bromobiphenyl was replaced with an equivalent amount of bromobenzene in the first step reaction, and 2-chloro-4,6-di was used in the second step. The phenyltriazine was replaced by an equivalent amount of 2-chloro-4,6-diphenyltriazine, and after completion of the reaction, 35.8 g of a yellow solid was obtained in a yield of 85%.
合成实施例111.化合物D-27的合成Synthesis Example 111. Synthesis of Compound D-27
采用与合成实施例109相同的合成方法，不同在于，在第一步反应中将4-溴联苯置换为等当量的溴苯，将中间体M1置换为等当量的中间体B-27-1，反应完成后得到化合物D-27为黄色固体。The same synthesis method as in Synthesis Example 109 was employed, except that 4-bromobiphenyl was replaced with an equivalent amount of bromobenzene in the first step, and intermediate M1 was replaced with an equivalent amount of intermediate B-27-1. After completion of the reaction, Compound D-27 was obtained as a yellow solid.
D-27的核磁波普数据：D-27 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.42(s，16H)，8.36(s，15H)，8.24(s，5H)，8.10(d，J＝2.5Hz，21H)，7.89(d，J＝2.9Hz，4H)，7.81(d，J＝60.0Hz，23H)，7.72(s，2H)，7.67(d，J＝45.0Hz，16H)，7.58(s，11H)，7.47(t，J＝22.5Hz，59H)，7.39(s，1H). 1 H NMR (500MHz, Chloroform) δ8.42 (s, 16H), 8.36 (s, 15H), 8.24 (s, 5H), 8.10 (d, J = 2.5Hz, 21H), 7.89 (d, J = 2.9 Hz, 4H), 7.81 (d, J = 60.0 Hz, 23H), 7.72 (s, 2H), 7.67 (d, J = 45.0 Hz, 16H), 7.58 (s, 11H), 7.47 (t, J = 22.5) Hz, 59H), 7.39 (s, 1H).
合成实施例112.化合物B-28的合成Synthesis Example 112. Synthesis of Compound B-28
采用与合成实施例109相同的合成方法，不同在于，在第一步反应中将中间体M1置换为等当量的中间体M4，反应完成后得到化合物D-28为黄色固体。The same synthesis method as in Synthesis Example 109 was employed, except that the intermediate M1 was replaced with an equivalent of the intermediate M4 in the first step, and the compound D-28 was obtained as a yellow solid.
合成实施例113化合物D-29的合成Synthesis of Synthesis Example 113 Compound D-29
采用与合成实施例109相同的合成方法，不同在于，在第一步反应中将4-溴联苯置换为等当量的溴苯，将中间体M1置换为等当量的中间体M5；在第二步反应中将2-氯-4，6-二苯基三嗪置换为等当量的2-氯-4，6-二联苯基三嗪，反应完成后得到化合物D-29为黄色固体。The same synthesis method as in Synthesis Example 109 was employed, except that 4-bromobiphenyl was replaced with an equivalent amount of bromobenzene in the first step reaction, and intermediate M1 was replaced with an equivalent amount of intermediate M5; In the step reaction, 2-chloro-4,6-diphenyltriazine was replaced with an equivalent amount of 2-chloro-4,6-diphenyltriazine. After completion of the reaction, compound D-29 was obtained as a yellow solid.
合成实施例114.化合物D-30的合成Synthesis Example 114. Synthesis of Compound D-30
Figure PCTCN2016093026-appb-000078
Figure PCTCN2016093026-appb-000078
在1L反应瓶中，将中间体M1(38.2g，0.1mol)、溴苯(15.7g，0.1mol)、CuI(3.3g，17.1mmol)、Cs2CO3(21.8g，102.9mmol)、环己基二胺(2.3ml，34.3mmol)和甲苯(500ml)混合，在回流条件下搅拌反应1天，反应结束后，冷却至室温，用250ml乙酸乙酯萃取，有机层经无水硫酸镁后减压蒸馏除去溶剂，对得到的蒸馏剩余物进行柱分离(洗 脱液∶二氯甲烷/己烷)，得到化合物D-30-1(20.2g，收率44％)。Intermediate M1 (38.2 g, 0.1 mol), bromobenzene (15.7 g, 0.1 mol), CuI (3.3 g, 17.1 mmol), Cs 2 CO 3 (21.8 g, 102.9 mmol), ring in a 1 L reaction flask Hexyldiamine (2.3 ml, 34.3 mmol) and toluene (500 ml) were mixed, and the reaction was stirred under reflux for 1 day. After completion of the reaction, the mixture was cooled to room temperature and extracted with ethyl acetate (250 ml). The solvent was removed by pressure distillation, and the obtained distillation residue was subjected to column chromatography (eluent: methylene chloride/hexane) to afford Compound D-30-1 (20.2 g, yield 44%).
在1L反应瓶中，将中间体D-30-1(23g，50mmol)、1-(4-溴苯基)-2-苯基-1H-苯并咪唑(20.9g，60mmol)、CuI(1.7g，8.5mmol)、Cs2CO3(21.8g，102.9mmol)、环己基二胺(1.2ml，17mmol)和甲苯(300ml)混合，在回流条件下搅拌反应1天，反应结束后，冷却至室温，用150ml乙酸乙酯萃取，有机层经无水硫酸镁后减压蒸馏除去溶剂，对得到的蒸馏剩余物进行柱分离(洗脱液：二氯甲烷/己烷)，得到化合物D-30(30.9g，收率85％)。In a 1 L reaction flask, intermediate D-30-1 (23 g, 50 mmol), 1-(4-bromophenyl)-2-phenyl-1H-benzimidazole (20.9 g, 60 mmol), Cu. g, 8.5 mmol), Cs 2 CO 3 (21.8 g, 102.9 mmol), cyclohexyldiamine (1.2 ml, 17 mmol) and toluene (300 ml) were mixed, and the reaction was stirred under reflux for 1 day. After completion of the reaction, the mixture was cooled. After extracting with 150 ml of ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, and then evaporated to remove the solvent, and the residue obtained was subjected to column separation (eluent: dichloromethane/hexane) to give compound D-30. (30.9 g, yield 85%).
合成实施例115.化合物D-31的合成Synthesis Example 115. Synthesis of Compound D-31
采用与合成实施例109相同的合成方法，不同在于，在第一步反应中将4-溴联苯置换为等当量的溴苯，在第二步反应中将2-氯-4，6-二苯基三嗪置换为等当量的2-溴-二苯并[f，h]喹喔啉，反应完成后得到化合物D-31为黄色固体。The same synthesis method as in Synthesis Example 109 was employed, except that 4-bromobiphenyl was replaced with an equivalent amount of bromobenzene in the first step reaction, and 2-chloro-4,6-di was used in the second step. The phenyltriazine was replaced by an equivalent amount of 2-bromo-dibenzo[f,h]quinoxaline. After completion of the reaction, compound D-31 was obtained as a yellow solid.
合成实施例116.化合物D-32的合成Synthesis Example 116. Synthesis of Compound D-32
Figure PCTCN2016093026-appb-000079
Figure PCTCN2016093026-appb-000079
合成中间体D-32-1：在250ml三口瓶中，将中间体化合物M1(19.1g，50mmol)、3-溴联苯(11.7.9g，50mmol)、CuI(1.8g，10mmol)，反式-二氨基环己烷(5.4ml，50mmol)和碳酸铯(16g，50mmol)形成的混合物加热回流3小时。然后将反应混合物冷却至室温，过滤，用二氯甲烷洗涤滤饼，得到的有机相用去离子水充分洗涤，然后用无水硫酸钠干燥。将干燥后的有机相进行减压除去溶剂，得到的残余物进行柱分离，得到白色化合物D-32-1(16.3g，产率61％)。Synthesis of intermediate D-32-1: Intermediate compound M1 (19.1 g, 50 mmol), 3-bromobiphenyl (11.7.9 g, 50 mmol), CuI (1.8 g, 10 mmol) in a 250 ml three-necked flask, trans A mixture of diaminocyclohexane (5.4 ml, 50 mmol) and cesium carbonate (16 g, 50 mmol) was heated to reflux for 3 h. The reaction mixture was then cooled to room temperature, filtered, and the filter cake was washed with dichloromethane, and the organic phase was washed thoroughly with water and then dried over anhydrous sodium sulfate. The organic phase after drying was evaporated under reduced pressure, and the residue obtained was purified, mjjjjjjj
合成化合物D-32：在250ml三口瓶中，将中间体化合物D-32-1(26.7g，50mmol)、2-(4-溴苯基)-4，6-二苯基-1，3，5-三嗪(21.3g，55mmol)、CuI(1.8g，10mmol)，反式-二氨基环己烷(5.4ml，50mmol)和碳酸铯(16g，50mmol)形成的混合物加热回流3小时。然后将反应混合物冷却至室温，过滤，用二氯甲烷洗涤滤饼，得到的有机相用去离子水充分洗涤，然后用无水硫酸钠干燥。将干燥后的有机相进行减压除去溶剂，得到的残余物进行柱分离，得到淡黄色化合物D-32(35.8g，产率85％)。Synthesis of Compound D-32: Intermediate compound D-32-1 (26.7 g, 50 mmol), 2-(4-bromophenyl)-4,6-diphenyl-1,3, in a 250 ml three-necked flask. A mixture of 5-triazine (21.3 g, 55 mmol), CuI (1.8 g, 10 mmol), s-di-diamino-hexanes (5.4 ml, 50 mmol) and cesium carbonate (16 g, 50 mmol) was refluxed for 3 hours. The reaction mixture was then cooled to room temperature, filtered, and the filter cake was washed with dichloromethane, and the organic phase was washed thoroughly with water and then dried over anhydrous sodium sulfate. The organic phase after drying was evaporated under reduced pressure, and the residue obtained was purified, mjjjjjjj
D-32的核磁波普数据： D-32 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.53(s，3H)，8.40(s，4H)，8.34(s，4H)，8.19(s，1H)，8.08(s，4H)，7.89(d，J＝5.0Hz，5H)，7.68(d，J＝49.9Hz，4H)，7.60(dd，J＝5.8，2.8Hz，1H)，7.58(s，1H)，7.52-7.43(m，13H)，7.39(s，1H)，7.14(s，1H)，7.09(s，2H). 1 H NMR (500MHz, Chloroform) δ8.53 (s, 3H), 8.40 (s, 4H), 8.34 (s, 4H), 8.19 (s, 1H), 8.08 (s, 4H), 7.89 (d, J =5.0 Hz, 5H), 7.68 (d, J = 49.9 Hz, 4H), 7.60 (dd, J = 5.8, 2.8 Hz, 1H), 7.58 (s, 1H), 7.52-7.43 (m, 13H), 7.39 (s, 1H), 7.14 (s, 1H), 7.09 (s, 2H).
合成实施例117.化合物D-33的合成Synthesis Example 117. Synthesis of Compound D-33
Figure PCTCN2016093026-appb-000080
Figure PCTCN2016093026-appb-000080
采用与合成实施例116相同的合成方法，不同在于，第一步将3-溴联苯用等当量的2-溴-二苯并呋喃代替，第二步反应中将2-(4-溴苯基)-4，6-二苯基-1，3，5-三嗪用等当量的2-(3-溴苯基)-4-苯基喹唑啉代替反应后得到黄色固体32.3g，两步总收率为47％。The same synthesis method as in Synthesis Example 116 was employed except that 3-bromobiphenyl was replaced with an equivalent amount of 2-bromo-dibenzofuran in the first step, and 2-(4-bromobenzene) was used in the second step. 4,6-diphenyl-1,3,5-triazine was replaced with an equivalent of 2-(3-bromophenyl)-4-phenylquinazoline to give a yellow solid, 32.3 g, The total yield of the step was 47%.
D-33的核磁波普数据：D-33 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.55(s，20H)，8.45(d，J＝7.2Hz，3H)，8.42(s，39H)，8.47-8.14(m，73H)，8.12(d，J＝15.0Hz，41H)，8.08-7.86(m，35H)，7.82(t，J＝2.7Hz，7H)，7.80(d，J＝3.6Hz，24H)，7.81-7.58(m，71H)，7.52(dd，J＝18.2，8.2Hz，44H)，7.39(s，10H)，7.31(s，5H)，7.16(s，11H)，7.11(s，16H). 1 H NMR (500MHz, Chloroform) δ8.55 (s, 20H), 8.45 (d, J = 7.2Hz, 3H), 8.42 (s, 39H), 8.47-8.14 (m, 73H), 8.12 (d, J =15.0 Hz, 41H), 8.08-7.86 (m, 35H), 7.82 (t, J = 2.7 Hz, 7H), 7.80 (d, J = 3.6 Hz, 24H), 7.81 - 7.58 (m, 71H), 7.52 (dd, J = 18.2, 8.2 Hz, 44H), 7.39 (s, 10H), 7.31 (s, 5H), 7.16 (s, 11H), 7.11 (s, 16H).
合成实施例118.化合物D-34的合成Synthesis Example 118. Synthesis of Compound D-34
Figure PCTCN2016093026-appb-000081
Figure PCTCN2016093026-appb-000081
采用与合成实施例116相同的合成方法，不同在于，第一步将3-溴联苯用等当量的2-溴萘并呋喃代替，第二步反应中将2-(4-溴苯基)-4，6-二苯基-1，3，5-三嗪用等当量的2-(4-溴苯基)-4，6-二苯基嘧啶代替反应后得到黄色固体34.3g，两步总收率为53％。The same synthesis method as in Synthesis Example 116 was employed except that 3-bromobiphenyl was replaced with an equivalent of 2-bromonaphthofuran in the first step, and 2-(4-bromophenyl) was used in the second step. -4,6-Diphenyl-1,3,5-triazine was replaced with an equivalent of 2-(4-bromophenyl)-4,6-diphenylpyrimidine to give a yellow solid 34.3 g, two steps The total yield was 53%.
合成实施例119.化合物D-35的合成Synthesis Example 119. Synthesis of Compound D-35
Figure PCTCN2016093026-appb-000082
Figure PCTCN2016093026-appb-000082
采用与合成实施例116相同的合成方法，不同在于，第一步将3-溴联苯用等当量的3-溴-N-苯基咔唑代替，第二步反应中将2-(4-溴苯基)-4，6-二苯基-1，3，5-三嗪用等当量的2-(4-溴苯基)-4-苯基喹唑啉代替反应后得到黄色固体35g，两步总收率为49％。 The same synthesis method as in Synthesis Example 116 was employed except that 3-bromobiphenyl was replaced with an equivalent amount of 3-bromo-N-phenylcarbazole in the first step, and 2-(4- in the second step. Bromophenyl)-4,6-diphenyl-1,3,5-triazine was replaced with an equivalent of 2-(4-bromophenyl)-4-phenylquinazoline to give a yellow solid, 35 g. The total yield in two steps was 49%.
合成实施例119.化合物D-36的合成Synthesis Example 119. Synthesis of Compound D-36
Figure PCTCN2016093026-appb-000083
Figure PCTCN2016093026-appb-000083
采用与合成实施例84中合成化合物D-1相同的合成方法，不同在于，将2-氯吡啶用等当量的2-(3-溴苯基)-4-苯基喹唑啉代替，反应后得到黄色固体34.9g，收率为74％。The same synthesis method as in the synthesis of the compound D-1 in Synthesis Example 84 was employed, except that 2-chloropyridine was replaced with an equivalent of 2-(3-bromophenyl)-4-phenylquinazoline, after the reaction. 34.9 g of a yellow solid was obtained in a yield of 74%.
合成实施例120.化合物D-37的合成Synthesis Example 120. Synthesis of Compound D-37
Figure PCTCN2016093026-appb-000084
Figure PCTCN2016093026-appb-000084
N2保护下，三口瓶中加入碘苯22g(0.11mol)，中间体M10(46.1g，0.1mol)，氯化亚铜2g(20mmol)，水合1，10-菲啰啉4g(20mmol)，氢氧化钾16.8g(0.3mol)，二甲苯300ml。反应体系保持回流反应20h，反应完全，蒸馏水洗涤反应体系，然后用100ml乙酸乙酯萃取三次，合并得到的有机层，用MgSO4干燥有机层，并用旋转蒸发器除去溶剂，对除去溶剂的剩余物进行柱分离，得到中间体化合物为白色固体(52.3g，86％)。Under N 2 protection, 22 g (0.11 mol) of iodobenzene, intermediate M10 (46.1 g, 0.1 mol), 2 g (20 mmol) of cuprous chloride, and 4 g (20 mmol) of 1,10-phenanthroline were added to the three-necked flask. Potassium hydroxide 16.8 g (0.3 mol), xylene 300 ml. The reaction system was kept under reflux for 20 hours, and the reaction was completed. The reaction mixture was washed with distilled water, and then extracted three times with 100 ml of ethyl acetate. The organic layer obtained was combined, dried over MgSO 4 and solvent was evaporated to remove solvent. Column separation gave the intermediate compound as a white solid (52.3 g, 86%).
氮气保护下，向装有机械搅拌，低温温度计，恒压漏斗的1L三口瓶中加入上述中间体化合物31克(50mmol)，THF500ml，液氮降温至-80℃以下，向其中滴加入2.4M的正丁基锂23ml(55mmol)，控温不超过-80℃，滴加完毕后保温-80℃以下15mn，开始向其中滴加硼酸三异丙酯14.2g(75mmol)，滴加完毕后控温-80℃之下反应1h，升温至室温，并在室温下继续反应5h，将反应液倒入100ml浓盐酸和1L水配制的稀酸中，搅拌，分出上层有机相，水相用600ml二氯甲烷提取一次，合并有机相，减压浓缩干得到淡黄色油状物。柱色谱分离得到白色固体26克，收率90％。Under a nitrogen atmosphere, 31 g (50 mmol) of the above intermediate compound, 500 ml of THF were added to a 1 L three-necked flask equipped with a mechanical stirring, a low temperature thermometer, and a constant pressure funnel. The liquid nitrogen was cooled to below -80 ° C, and 2.4 M was added dropwise thereto. 23 ml (55 mmol) of n-butyllithium, the temperature control does not exceed -80 ° C, after the completion of the dropwise addition, the temperature is -80 ° C below 15 mn, and the dropwise addition of 14.2 g (75 mmol) of triisopropyl borate is added thereto, and the temperature is controlled after the addition. The reaction was carried out at -80 ° C for 1 h, the temperature was raised to room temperature, and the reaction was continued at room temperature for 5 h. The reaction solution was poured into a dilute acid of 100 ml of concentrated hydrochloric acid and 1 L of water, and stirred, and the upper organic phase was separated, and the aqueous phase was 600 ml. The methyl chloride was extracted once. Column chromatography gave 26 g of a white solid in a yield of 90%.
在氮气保护下，将中间体硼酸(5.78g，10mmol)、2-chloro-4-phenyl quinazoline(2.4g， 10mmol)、Pd(PPh3)4(0.58g，0.5mmol)、Na2CO3(5.3g，50mmol)、60mL甲苯和20mLEtOH混合，向该混合物中加入蒸馏水20mL，然后在110℃下搅拌反应2小时。反应完成后，用蒸馏水洗涤反应体系，然后用100ml乙酸乙酯萃取三次，合并得到的有机层，用MgSO4干燥有机层，并旋蒸除去溶剂，最后对除去溶剂的剩余物进行柱分离，得到黄色固体化合物D-37(6.2g，84％)。Intermediate boronic acid (5.78 g, 10 mmol), 2-chloro-4-phenyl quinazoline (2.4 g, 10 mmol), Pd(PPh 3 ) 4 (0.58 g, 0.5 mmol), Na 2 CO 3 (under Na2CO3) 5.3 g, 50 mmol), 60 mL of toluene and 20 mLEtOH were mixed, and 20 mL of distilled water was added to the mixture, followed by stirring at 110 ° C for 2 hours. After completion of the reaction, the reaction system was washed with distilled water, and then extracted three times with 100 ml of ethyl acetate. The obtained organic layer was combined, dried over MgSO 4 and evaporated to remove solvent. Yellow solid compound D-37 (6.2 g, 84%).
D-37的核磁波普数据：D-37 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.49(d，J＝65.0Hz，6H)，8.40(s，1H)，8.19-7.89(m，7H)，7.89-7.73(m，7H)，7.63(d，J＝15.0Hz，11H)，7.60-7.45(m，19H)，7.33(s，2H)，7.16(s，2H)，7.11(s，3H). 1 H NMR (500MHz, Chloroform) δ8.49 (d, J = 65.0Hz, 6H), 8.40 (s, 1H), 8.19-7.89 (m, 7H), 7.89-7.73 (m, 7H), 7.63 (d , J = 15.0 Hz, 11H), 7.60-7.45 (m, 19H), 7.33 (s, 2H), 7.16 (s, 2H), 7.11 (s, 3H).
合成实施例121.化合物D-38的合成Synthesis Example 121. Synthesis of Compound D-38
采用与合成实施例120中合成化合物D-37相同的合成方法，不同在于，将2-chloro-4-phenyl quinazoline用等当量的2-(4-bromophenyl)-5-phenyl-1，3，4-oxadiazole代替，反应后得到化合物D-38为黄色固体6.11g，收率为81％。The same synthesis method as in the synthesis of compound D-37 in Synthesis Example 120 was employed, except that 2-chloro-4-phenyl quinazoline was used in an equivalent amount of 2-(4-bromophenyl)-5-phenyl-1,3,4. Instead of -oxadiazole, the compound D-38 was obtained as a yellow solid, 6.11 g, yield 81%.
合成实施例122.化合物D-39的合成Synthesis Example 122. Synthesis of Compound D-39
采用与合成实施例120中合成化合物D-37相同的合成方法，不同在于第一步反应中将中间体M10置换为当量的中间体M9；在第三步反应中将2-chloro-4-phenyl quinazoline用等当量的2-(3-bromophenyl)-4，6-diphenyl-1，3，5-triazine代替，反应后得到化合物D-39为黄色固体7.58g，收率为90％。The same synthesis method as in the synthesis of the compound D-37 in Synthesis Example 120 was employed, except that the intermediate M10 was replaced with the equivalent of the intermediate M9 in the first step; in the third step, 2-chloro-4-phenyl was used. The quinazoline was replaced with an equivalent amount of 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine. After the reaction, compound D-39 was obtained as a yellow solid, 7.58 g, yield: 90%.
D-39的核磁波普数据：D-39 nuclear magnetic pop data:
1H NMR(500MHz，Chloroform)δ8.54(s，6H)，8.52-8.33(m，24H)，8.09(s，5H)，7.69(s，3H)，7.63-7.55(m，23H)，7.50(d，J＝10.0Hz，34H)，7.32(s，4H)，7.24(d，J＝85.0Hz，10H)，7.36-6.89(m，19H). 1 H NMR (500MHz, Chloroform) δ8.54 (s, 6H), 8.52-8.33 (m, 24H), 8.09 (s, 5H), 7.69 (s, 3H), 7.63-7.55 (m, 23H), 7.50 (d, J = 10.0 Hz, 34H), 7.32 (s, 4H), 7.24 (d, J = 85.0 Hz, 10H), 7.36-6.89 (m, 19H).
本发明中具体合成实施例中化合物的分析检测数据列在下表1中。The analytical test data of the compounds in the specific synthetic examples of the present invention are listed in Table 1 below.
表1：Table 1:
Figure PCTCN2016093026-appb-000085
Figure PCTCN2016093026-appb-000085
Figure PCTCN2016093026-appb-000086
Figure PCTCN2016093026-appb-000086
Figure PCTCN2016093026-appb-000087
Figure PCTCN2016093026-appb-000087
Figure PCTCN2016093026-appb-000088
Figure PCTCN2016093026-appb-000088
Figure PCTCN2016093026-appb-000089
Figure PCTCN2016093026-appb-000089
Figure PCTCN2016093026-appb-000090
Figure PCTCN2016093026-appb-000090
器件实施例Device embodiment
应用以下器件结构进行OLED器件评测：ITO/HIL/HTL/EML/ETL/LiF/Al(上述缩写分别对应ITO阳极/空穴注入层/空穴传输层/发光层/电子传输层/电子注入层/LiF和Al的负极，以下上述缩写的意义相同)，下图示出了器件中各功能层所使用材料的结构式(所有材料均购自百灵威试剂，纯度＞99.9％)：OLED device evaluation was performed using the following device structure: ITO/HIL/HTL/EML/ETL/LiF/Al (the above abbreviations correspond to ITO anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer, respectively) /LiF and Al negative, the following abbreviations have the same meaning), the following figure shows the structural formula of the materials used in each functional layer of the device (all materials are purchased from the Belling reagent, purity >99.9%):
Figure PCTCN2016093026-appb-000091
Figure PCTCN2016093026-appb-000091
器件实施例1.本发明的化合物作为空穴注入材料Device Example 1. Compound of the present invention as a hole injecting material
将涂布了ITO(150nm)透明导电层的玻璃板在商用清洗剂中超声处理，在去离子水中冲洗，在丙酮∶乙醇混合溶剂(体积比1∶1)中超声除油，在洁净环境下烘烤至完全除去水份，用紫外光和臭氧清洗，并用Satella(ULVAC)的低能阳离子束轰击表面；The glass plate coated with the ITO (150 nm) transparent conductive layer was sonicated in a commercial cleaning agent, rinsed in deionized water, and ultrasonically degreased in an acetone:ethanol mixed solvent (1:1 by volume) in a clean environment. Bake to complete removal of water, wash with UV light and ozone, and bombard the surface with a low energy cation beam from Satella (ULVAC);
把上述带有阳极的玻璃基片置于真空腔内，抽真空至1×10-5～9×10-3pa，在上述阳极层膜上真空蒸镀化合物C-1，形成厚度为60nm的空穴注入层；在空穴注入层之上真空蒸镀化合物NPB，形成厚度为20nm的空穴传输层，蒸镀速率为0.1nm/s；The above-mentioned glass substrate with an anode was placed in a vacuum chamber, and evacuated to 1 × 10 -5 to 9 × 10 -3 Pa, and the compound C-1 was vacuum-deposited on the above anode layer film to form a thickness of 60 nm. a hole injection layer; a vacuum evaporation of the compound NPB over the hole injection layer to form a hole transport layer having a thickness of 20 nm, the evaporation rate is 0.1 nm / s;
在上述空穴传输层上形成电致发光层，具体操作为：将作为发光层主体的CBP[4，4′-N，N′-二咔唑-联苯]放置在真空气相沉积设备的小室中，将作为掺杂剂的 (piq)2Ir(acac)[二-(1-苯基异喹啉基)乙酰丙酮铱(III)]放置在真空气相沉积设备的另一室中，以不同的速率同时蒸发两种材料，(piq)2Ir(acac)的浓度为4％，蒸镀总膜厚为30nm；Forming an electroluminescent layer on the above hole transport layer, specifically: placing CBP [4, 4'-N, N'-dicarbazole-biphenyl] as a main body of the light-emitting layer in a chamber of a vacuum vapor deposition apparatus (piq) 2 Ir(acac)[di-(1-phenylisoquinolinyl)acetylacetonate ruthenium (III)] is placed in another chamber of the vacuum vapor deposition apparatus to be different The rate of evaporation of the two materials simultaneously, (piq) 2 Ir (acac) concentration of 4%, the total thickness of the deposited film is 30nm;
在发光层之上真空蒸镀Bphen形成厚膜为20nm的电子传输层，其蒸镀速率为0.1nm/s；The Bphen was vacuum-deposited on the light-emitting layer to form an electron transport layer having a thick film of 20 nm, and the evaporation rate was 0.1 nm/s;
在电子传输层上真空蒸镀0.5nm的LiF作为电子注入层和厚度为150nm的Al层作为器件的阴极。0.5 nm of LiF was vacuum-deposited on the electron transport layer as an electron injection layer and an Al layer having a thickness of 150 nm as a cathode of the device.
器件实施例2.本发明化合物作为空穴注入材料Device Example 2. The compound of the present invention is used as a hole injecting material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为化合物C-3。An organic electroluminescent device was obtained in the same manner as in Example 1 except that the compound C-1 was replaced with the compound C-3.
器件实施例3.本发明化合物作为空穴注入材料Device Example 3. The compound of the present invention is used as a hole injecting material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为化合物C-4。An organic electroluminescent device was obtained in the same manner as in Example 1 except that the compound C-1 was replaced with the compound C-4.
器件实施例4.本发明化合物作为空穴注入材料Device Example 4. Compound of the present invention as a hole injecting material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为化合物C-11。An organic electroluminescent device was obtained in the same manner as in Example 1 except that the compound C-1 was replaced with the compound C-11.
器件实施例5.本发明化合物作为空穴注入材料Device Example 5. The compound of the present invention is used as a hole injecting material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为化合物C-12。An organic electroluminescent device was obtained in the same manner as in Example 1 except that the compound C-1 was replaced with the compound C-12.
器件实施例6.本发明化合物作为空穴注入材料Device Example 6. The compound of the present invention is used as a hole injecting material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为化合物C-13。An organic electroluminescent device was obtained in the same manner as in Example 1 except that the compound C-1 was replaced with the compound C-13.
器件实施例7.本发明化合物作为空穴注入材料Device Example 7. Compound of the present invention as a hole injecting material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为化合物C-15。An organic electroluminescent device was obtained in the same manner as in Example 1 except that the compound C-1 was replaced with the compound C-15.
器件实施例8.本发明化合物作为空穴传输材料Device Example 8. The compound of the present invention is used as a hole transporting material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将NPB替换为化合物B-1。An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and NPB was replaced with Compound B-1.
器件实施例9.本发明化合物作为空穴传输材料Device Example 9. The compound of the present invention is used as a hole transporting material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将NPB替换为化合物B-3。 An organic electroluminescent device was obtained in the same manner as in Example 1 except that Compound C-1 was replaced with 2-TNATA and NPB was replaced with Compound B-3.
器件实施例10.本发明化合物作为空穴传输材料Device Example 10. The compound of the present invention as a hole transporting material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将NPB替换为化合物B-4。An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and NPB was replaced with Compound B-4.
器件实施例11.本发明化合物作为空穴传输材料Device Example 11. Compound of the invention as a hole transport material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将NPB替换为化合物B-6。An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and NPB was replaced with Compound B-6.
器件实施例12.本发明化合物作为空穴传输材料Device Example 12. Compound of the invention as a hole transport material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将NPB替换为化合物B-9。An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and NPB was replaced with Compound B-9.
器件实施例13.本发明化合物作为空穴传输材料Device Example 13. Compound of the Invention as a Hole Transport Material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将NPB替换为化合物B-10。An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and NPB was replaced with Compound B-10.
器件实施例14.本发明化合物作为空穴传输材料Device Example 14. The compound of the present invention as a hole transporting material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将NPB替换为化合物B-12。An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and NPB was replaced with Compound B-12.
器件实施例15.本发明化合物作为空穴传输材料Device Example 15. Compound of the Invention as a Hole Transport Material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将NPB替换为化合物B-13。An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and NPB was replaced with Compound B-13.
器件实施例16.本发明化合物作为空穴传输材料Device Example 16. Compound of the invention as a hole transport material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将NPB替换为化合物B-17。An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and NPB was replaced with Compound B-17.
器件实施例17.本发明化合物作为空穴传输材料Device Example 17. Compound of the Invention as a Hole Transport Material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将NPB替换为化合物B-18。An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and NPB was replaced with Compound B-18.
器件实施例18.本发明化合物作为空穴传输材料Device Example 18. A compound of the invention as a hole transport material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将NPB替换为化合物B-21。An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and NPB was replaced with Compound B-21.
器件实施例19.本发明化合物作为空穴传输材料Device Example 19. Compound of the Invention as a Hole Transport Material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将NPB替换为化合物B-30。 An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and NPB was replaced with Compound B-30.
器件实施例20.本发明化合物作为红色磷光主体材料Device Example 20. The compound of the present invention is used as a red phosphorescent host material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将CBP替换为化合物A-1。An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and CBP was replaced with Compound A-1.
器件实施例21.本发明化合物作为红色磷光主体材料Device Example 21. The compound of the present invention is used as a red phosphorescent host material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将CBP替换为化合物A-4。An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and CBP was replaced with Compound A-4.
器件实施例22.本发明化合物作为红色磷光主体材料Device Example 22. The compound of the invention as a red phosphorescent host material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将CBP替换为化合物A-6。An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and CBP was replaced with Compound A-6.
器件实施例23.本发明化合物作为红色磷光主体材料Device Example 23. The compound of the present invention as a red phosphorescent host material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将CBP替换为化合物A-9。An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and CBP was replaced with Compound A-9.
器件实施例24.本发明化合物作为红色磷光主体材料Device Example 24. The compound of the present invention as a red phosphorescent host material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将CBP替换为化合物A-14。An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and CBP was replaced with Compound A-14.
器件实施例25.本发明化合物作为红色磷光主体材料Device Example 25. The compound of the present invention as a red phosphorescent host material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将CBP替换为化合物A-21。An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and CBP was replaced with Compound A-21.
器件实施例26.本发明化合物作为红色磷光主体材料Device Example 26. The compound of the present invention as a red phosphorescent host material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将CBP替换为化合物D-4。An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and CBP was replaced with Compound D-4.
器件实施例27.本发明化合物作为红色磷光主体材料Device Example 27. The compound of the invention as a red phosphorescent host material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将CBP替换为化合物D-6。An organic electroluminescent device was obtained in the same manner as in Example 1 except that the compound C-1 was replaced with 2-TNATA and the CBP was replaced with the compound D-6.
器件实施例28.本发明化合物作为红色磷光主体材料Device Example 28. The compound of the present invention as a red phosphorescent host material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将CBP替换为化合物D-10。An organic electroluminescent device was obtained in the same manner as in Example 1 except that the compound C-1 was replaced with 2-TNATA and the CBP was replaced with the compound D-10.
器件实施例29.本发明化合物作为红色磷光主体材料Device Example 29. The compound of the present invention as a red phosphorescent host material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将CBP替换为化合物D-25。 An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and CBP was replaced with Compound D-25.
器件实施例30.本发明化合物作为红色磷光主体材料Device Example 30. The compound of the present invention as a red phosphorescent host material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将CBP替换为化合物D-27。An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and CBP was replaced with Compound D-27.
器件实施例31.本发明化合物作为红色磷光主体材料Device Example 31. A compound of the invention as a red phosphorescent host material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将CBP替换为化合物D-33。An organic electroluminescent device was obtained in the same manner as in Example 1 except that Compound C-1 was replaced with 2-TNATA and CBP was replaced with Compound D-33.
器件实施例32.本发明化合物作为红色磷光主体材料Device Example 32. A compound of the invention as a red phosphorescent host material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将CBP替换为化合物D-37。An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, and CBP was replaced with Compound D-37.
器件实施例33.本发明化合物分别用作空穴注入材料、空穴传输材料和红色磷光主体材料Device Example 33. The compound of the present invention was used as a hole injecting material, a hole transporting material, and a red phosphorescent host material, respectively.
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为C-10，将NPB替换为化合物B-8，将CBP替换为化合物D-25。An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with C-10, NPB was replaced with Compound B-8, and CBP was replaced with Compound D-25.
器件实施例34.本发明化合物分别用作空穴注入材料、空穴传输材料和红色磷光主体材料Device Example 34. The compound of the present invention was used as a hole injecting material, a hole transporting material, and a red phosphorescent host material, respectively.
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为C-13，将NPB替换为化合物B-6，将CBP替换为化合物D-37。An organic electroluminescent device was obtained in the same manner as in Example 1 except that the compound C-1 was replaced with C-13, the NPB was replaced with the compound B-6, and the CBP was replaced with the compound D-37.
器件实施例35.本发明化合物分别用作空穴注入材料、空穴传输材料和红色磷光主体材料Device Example 35. The compound of the present invention is used as a hole injecting material, a hole transporting material, and a red phosphorescent host material, respectively.
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为C-3，将NPB替换为化合物B-30，将CBP替换为化合物D-4。An organic electroluminescent device was obtained in the same manner as in Example 1, except that Compound C-1 was replaced with C-3, NPB was replaced with Compound B-30, and CBP was replaced with Compound D-4.
器件实施例36.本发明化合物作为绿色磷光主体材料Device Example 36. The compound of the present invention is used as a green phosphorescent host material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将CBP替换为化合物D-32，将(piq)2Ir(acac)替换为Ir(ppy)3，掺杂浓度改变为10％。An organic electroluminescent device was prepared in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, CBP was replaced with Compound D-32, and (piq) 2 Ir(acac) was replaced with Ir(ppy) 3 , the doping concentration was changed to 10%.
器件实施例37.本发明化合物作为绿色磷光主体材料Device Example 37. The compound of the present invention is used as a green phosphorescent host material
采用与实施例26相同的方法制备得到有机电致发光器件，不同在于，将化合物D-32替换为D-39。An organic electroluminescent device was obtained in the same manner as in Example 26 except that the compound D-32 was replaced with D-39.
器件实施例38.本发明化合物分别用作空穴注入材料、空穴传输材料和绿色磷光主体材料。 Device Example 38. The compounds of the present invention were used as a hole injecting material, a hole transporting material, and a green phosphorescent host material, respectively.
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为C-3，将NPB替换为化合物B-8，将CBP替换为化合物D-32，将(piq)2Ir(acac)替换为Ir(ppy)3，掺杂浓度改变为10％。An organic electroluminescent device was prepared in the same manner as in Example 1, except that Compound C-1 was replaced with C-3, NPB was replaced with Compound B-8, and CBP was replaced with Compound D-32. Piq) 2 Ir(acac) was replaced by Ir(ppy) 3 and the doping concentration was changed to 10%.
器件实施例39.本发明化合物分别用作空穴注入材料、空穴传输材料和绿色磷光主体材料。Device Example 39. The compounds of the present invention were used as a hole injecting material, a hole transporting material, and a green phosphorescent host material, respectively.
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为C-11，将NPB替换为化合物B-30，将CBP替换为化合物D-39，将(piq)2Ir(acac)替换为Ir(ppy)3，掺杂浓度改变为10％。An organic electroluminescent device was prepared in the same manner as in Example 1, except that Compound C-1 was replaced with C-11, NPB was replaced with Compound B-30, and CBP was replaced with Compound D-39. Piq) 2 Ir(acac) was replaced by Ir(ppy) 3 and the doping concentration was changed to 10%.
对比实施例1.2-TNATA作为空穴注入材料，NPB作为空穴传输材料，CBP作为红色磷光主体材料Comparative Example 1.2 - TNATA as a hole injecting material, NPB as a hole transporting material, and CBP as a red phosphorescent host material
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA。An organic electroluminescent device was obtained in the same manner as in Example 1 except that the compound C-1 was replaced with 2-TNATA.
对比实施例2.2-TNATA作为空穴注入材料，NPB作为空穴传输材料，CBP作为绿色磷光主体材料，Comparative Example 2.2-TNATA as a hole injecting material, NPB as a hole transporting material, and CBP as a green phosphorescent host material,
采用与实施例1相同的方法制备得到有机电致发光器件，不同在于，将化合物C-1替换为2-TNATA，将(piq)2Ir(acac)替换为Ir(ppy)3，掺杂浓度改变为10％。An organic electroluminescent device was prepared in the same manner as in Example 1, except that Compound C-1 was replaced with 2-TNATA, (piq) 2 Ir(acac) was replaced with Ir(ppy) 3 , and doping concentration was used. Change to 10%.
测试实施例1Test Example 1
红光器件在亮度1000cd/m2下，使用Keithley 2602数字源表亮度计(北京师范大学光电仪器厂)测定器件实施例1-25以及对比例1中制备得到的有机电致发光器件的驱动电压和电流效率，结果见表1。The red light device was used to measure the driving voltages of the organic electroluminescent devices prepared in the device examples 1-25 and the comparative example 1 using a Keithley 2602 digital source meter luminance meter (Beijing Normal University Optoelectronic Instrument Factory) at a luminance of 1000 cd/m 2 . And current efficiency, the results are shown in Table 1.
测试实施例2Test Example 2
绿光器件在亮度2000cd/m2下，使用Keithley 2602数字源表亮度计(北京师范大学光电仪器厂)测定器件实施例26-27以及对比例2中制备得到的有机电致发光器件的驱动电压和电流效率，结果见表1。The driving voltage of the organic electroluminescent device prepared in the device examples 26-27 and the comparative example 2 was measured using a Keithley 2602 digital source meter luminance meter (Beijing Normal University Optoelectronic Instrument Factory) at a luminance of 2000 cd/m 2 . And current efficiency, the results are shown in Table 1.
表2：Table 2:
Figure PCTCN2016093026-appb-000092
Figure PCTCN2016093026-appb-000092
Figure PCTCN2016093026-appb-000093
Figure PCTCN2016093026-appb-000093
Figure PCTCN2016093026-appb-000094
Figure PCTCN2016093026-appb-000094
由表1中器件实施例1-7与对比实施例1，在有机电致发光器件结构中其他材料相同的情况下，本发明C系列化合物代替对比器件实施例1中2-TNATA作为空穴注入材料。C系列化合物优选的芳胺类取代基提升母核的HOMO能级，提高单载流子性能；其器件性能获得了更低的驱动电压以及较高的电流效率，并提高了发光器件的发光效率，显示出本发明材料具有更加高效的空穴注入性。From the device examples 1-7 in Table 1 and the comparative example 1, in the case where the other materials in the organic electroluminescent device structure are the same, the C series compound of the present invention replaces the 2-TNATA in the comparative device example 1 as a hole injection. material. The preferred arylamine substituents of the C series compounds enhance the HOMO energy level of the mother nucleus and improve the single carrier performance; the device performance achieves lower driving voltage and higher current efficiency, and improves the luminous efficiency of the light emitting device. It shows that the material of the present invention has more efficient hole injectability.
器件实施例8-19与对比实施例1，在有机电致发光器件结构中其他材料相同的情况下，本发明B系列化合物代替对比器件实施例1中NPB作为空穴传输材料。B系列化合物优选咔唑基、二苯并呋喃基、二苯并噻吩基等取代基，使母核HOMO能级稍有提升，使其与主体能级更匹配，相对更高的三线态能级使得可以同时起到激子阻挡层的作用，提高了单载流子的注入传输性能，并具有较强的空穴传输能力，获得了更高的电流效率和较低的驱动电压在同样的器件结构下，提高了发光器件的发光效率。Device Examples 8-19 and Comparative Example 1, in the case where the other materials in the structure of the organic electroluminescent device were the same, the B series compound of the present invention replaced the NPB in Comparative Device Example 1 as a hole transporting material. The B series compounds are preferably a substituent such as a carbazolyl group, a dibenzofuranyl group or a dibenzothiophenyl group, which slightly raises the HOMO level of the mother core to match the host level, and a relatively higher triplet level. It can simultaneously act as an exciton blocking layer, improve the injection transport performance of single carriers, and has strong hole transport capability, achieving higher current efficiency and lower driving voltage in the same device. Under the structure, the luminous efficiency of the light emitting device is improved.
器件实施例20-32与对比器件实施例1，在有机电致发光器件结构中其他材料相同的情况下，本发明A、D系列化合物代替对比器件实施例1中CBP作为红光主体材料。A系列化合物的中性芳基对母核影响少，其单载流子性能良好；其器件具有更低的电压和更高的电流效率。D系列化合物优选吡啶基、苯基吡啶基、喹啉基等具有拉电子性能取代基，其双载流子性能良好、复合区域宽，进一步降低了器件的工作电压和更高的电流效率显示了本发明中材料的优异的载流子传输平衡性以及能级匹配性。Device Examples 20-32 and Comparative Device Example 1, in the case where the other materials in the organic electroluminescent device structure were the same, the A and D series compounds of the present invention replaced the CBP in the comparative device Example 1 as a red light host material. The neutral aryl groups of the A series compounds have less influence on the mother nucleus and have good single carrier performance; their devices have lower voltage and higher current efficiency. The D series compounds preferably have a substituent of a pull-electron property such as a pyridyl group, a phenylpyridyl group or a quinolyl group, and have good double carrier performance and a wide composite region, further reducing the operating voltage of the device and higher current efficiency. Excellent carrier transport balance and energy level matching of the materials of the present invention.
器件实施例36/37与对比器件实施例2，在有机电致发光器件结构中其他材料相同的情况下，本发明D-32、D-39化合物代替对比器件实施例2中CBP作为绿光主体材料，电流效率从30cd/A提升到了40cd/A，具有十分显著的提升效果，同时工作电压也得到了大幅度的降低。器件实施例33-35与对比器件实施例1，在有机电致发光器件结构和其他材料相同的情况下，分别同时选择本发明的不同类型材料C-10、C-13、C-3代替2-TNATA；B-8、B-6、B-30代替NPB以及用D-25、D-37、D-4代替CBP， 在红光器件中明显降低了有机电致发光器件的工作电压和提高了电流效率；在绿光器件38、39中，也起到了降低电压和提高效率的效果，显示了本发明化合物的优异性。Device Example 36/37 and Comparative Device Example 2, in the case where the other materials in the structure of the organic electroluminescent device are the same, the D-32, D-39 compound of the present invention replaces the CBP in the second embodiment of the comparative device as the green light body. The material, the current efficiency is increased from 30cd/A to 40cd/A, which has a very significant improvement effect, and the operating voltage is also greatly reduced. Device Examples 33-35 and Comparative Device Example 1, in the case where the organic electroluminescent device structure and other materials are the same, the different types of materials C-10, C-13, C-3 of the present invention are simultaneously selected instead of 2 -TNATA; B-8, B-6, B-30 instead of NPB and D-25, D-37, D-4 instead of CBP, In the red light device, the operating voltage of the organic electroluminescent device is significantly reduced and the current efficiency is improved; in the green light device 38, 39, the voltage reduction and the efficiency are also improved, showing the superiority of the compound of the present invention. .
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。 The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solutions of the present invention within the scope of the technical idea of the present invention. These simple variants All fall within the scope of protection of the present invention.

Claims (17)

  1. 一种化合物，具备苯并环辛四烯并二吲哚结构，结构由如下通式(I)表示，a compound having a benzocyclooctadecenedioxan structure, the structure being represented by the following formula (I),
    Figure PCTCN2016093026-appb-100001
    Figure PCTCN2016093026-appb-100001
    其中，环A为
    Figure PCTCN2016093026-appb-100002
    虚线为拼接位置；    Where ring A is
    Figure PCTCN2016093026-appb-100002
    The dotted line is the stitching position;
    Ar为氢、C6～C30的芳基氨基或杂芳基氨基、取代或未取代的C6～C30的芳基、取代或未取代的C2～C30的杂芳基，；两个Ar可以相同也可以不同，Ar is hydrogen, a C 6 -C 30 arylamino or heteroarylamino group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted C 2 -C 30 heteroaryl group; Ar can be the same or different.
    R1至R12各自独立地为氢、卤素、C6～C30的芳基氨基或杂芳基氨基、取代或未取代的C1～C30烷基、取代或未取代的C2～C30烯基、取代或未取代的C2～C30炔基、取代或未取代的C3～C30环烷基、取代或未取代的C2～C30杂环烷基、取代或未取代的C6～C30芳基、取代或未取代的C2～C30杂芳基；或者，R1～R4和/或R5～R8可以分别形成环。R 1 to R 12 are each independently hydrogen, halogen, C 6 -C 30 arylamino or heteroarylamino, substituted or unsubstituted C 1 -C 30 alkyl, substituted or unsubstituted C 2 -C 30 alkenyl, substituted or unsubstituted C 2 -C 30 alkynyl, substituted or unsubstituted C 3 -C 30 cycloalkyl, substituted or unsubstituted C 2 -C 30 heterocycloalkyl, substituted or unsubstituted a C 6 -C 30 aryl group, a substituted or unsubstituted C 2 -C 30 heteroaryl group; or, R 1 to R 4 and/or R 5 to R 8 may each form a ring.
  2. 根据权利要求1所述的化合物，其特征在于，R1至R12各自独立地为氢、取代或未取代的C6～C30芳基、取代或未取代的C2～C30杂芳基、C6～C30的芳基氨基或杂芳基氨基。The compound according to claim 1, wherein each of R 1 to R 12 is independently hydrogen, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted C 2 -C 30 heteroaryl group. An arylamino or heteroarylamino group of C 6 to C 30 .
  3. 根据权利要求1所述的化合物，其特征在于，Ar、R1至R12各自独立地为选自由苯基、联苯基、三联苯基、萘基、蒽基、菲基、茚基、芴基及其衍生物、荧蒽基、三亚苯基、芘基、苝基、
    Figure PCTCN2016093026-appb-100003
    基和并四苯基、呋喃基、噻吩基、吡咯基、苯并呋喃基、苯并噻吩基、异苯并呋喃基、吲哚基、二苯并呋喃基、二苯并噻吩基、咔唑基及其衍生物、苯并间二氧杂环戊烯基、吡啶基、苯基吡啶基、喹啉基、取代喹啉基、喹唑啉基、取代喹唑啉基、喹喔啉基、取代喹喔啉基、嘧啶基、取代嘧啶基、邻菲啰啉基、三嗪基、取代三嗪基、苯并咪唑基、噁唑基、二苯氨基、苯基萘基氨基、4-三苯氨基、3-三苯氨基、4-[N-苯基-N-(二苯并呋喃-3-基)]苯基氨基、4-[N-苯基-N-(二苯并噻吩-3-基)]苯基氨基所组成的的组中的至少一种基团或多种基团通过单键或稠合连接的组合，R1～R4和/或R5～R8可以分别形成环。    The compound according to claim 1, wherein each of Ar, R 1 to R 12 is independently selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, anthracenyl, anthracenyl And its derivatives, fluoranthene, triphenylene, fluorenyl, fluorenyl,
    Figure PCTCN2016093026-appb-100003
    And tetraphenyl, furyl, thienyl, pyrrolyl, benzofuranyl, benzothienyl, isobenzofuranyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazole And derivatives thereof, benzodioxolyl, pyridyl, phenylpyridyl, quinolyl, substituted quinolinyl, quinazolinyl, substituted quinazolinyl, quinoxalinyl, Substituted quinoxalinyl, pyrimidinyl, substituted pyrimidinyl, phenanthroline, triazinyl, substituted triazinyl, benzimidazolyl, oxazolyl, diphenylamino, phenylnaphthylamino, 4-tri Phenylamino, 3-triphenylamino, 4-[N-phenyl-N-(dibenzofuran-3-yl)]phenylamino, 4-[N-phenyl-N-(dibenzothiophene- At least one group or groups of groups consisting of 3-yl)]phenylamino groups may be bonded by a single bond or a fused bond, and R 1 to R 4 and/or R 5 to R 8 may be respectively Form a ring.
  4. 如权利要求1所述的化合物，结构由如下通式(II)表示， The compound according to claim 1, wherein the structure is represented by the following formula (II):
    Figure PCTCN2016093026-appb-100004
    Figure PCTCN2016093026-appb-100004
    其中，Ar1、Ar2相同或不同，分别独立地为C1-C10烷基、取代或未取代的C6-C30芳基、取代或未取代的C2-C30杂芳基；Wherein, Ar 1 and Ar 2 are the same or different and are each independently a C 1 -C 10 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted C 2 -C 30 heteroaryl group;
    其中，R1至R12相同或不同，各自独立地为氢、卤素、取代或未取代的C1-C30烷基、取代或未取代的C2-C30烯基、取代或未取代的C2-C30炔基、取代或未取代的C3-C30环烷基、取代或未取代的C2-C30杂环烷基、取代或未取代的C6-C30芳基、取代或未取代的C2-C30杂芳基；或者，R1～R4相同或不同，相邻的基团可以相互成环；R5～R8相同或不同，相邻的基团可以相互成环；R9～R12相同或不同，相邻的基团可以相互成环。Wherein R 1 to R 12 are the same or different and are each independently hydrogen, halogen, substituted or unsubstituted C 1 -C 30 alkyl, substituted or unsubstituted C 2 -C 30 alkenyl, substituted or unsubstituted C 2 -C 30 alkynyl, substituted or unsubstituted C 3 -C 30 cycloalkyl, substituted or unsubstituted C 2 -C 30 heterocycloalkyl, substituted or unsubstituted C 6 -C 30 aryl, a substituted or unsubstituted C 2 -C 30 heteroaryl group; or, R 1 to R 4 are the same or different, adjacent groups may form a ring with each other; R 5 to R 8 may be the same or different, and adjacent groups may be R to each other; R 9 to R 12 are the same or different, and adjacent groups may form a ring with each other.
  5. 如权利要求1所述的化合物，结构由如下通式(III)表示，The compound according to claim 1, wherein the structure is represented by the following formula (III).
    Figure PCTCN2016093026-appb-100005
    Figure PCTCN2016093026-appb-100005
    其中，Ar3、Ar4相同或不同，分别独立地为C1-C10烷基、取代或未取代的C6-C30芳基、取代或未取代的C2-C30杂芳基；Wherein, Ar 3 and Ar 4 are the same or different and are each independently a C 1 -C 10 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted C 2 -C 30 heteroaryl group;
    其中，R13至R24相同或不同，各自独立地为氢、卤素、取代或未取代的C1-C30烷基、取代或未取代的C2-C30烯基、取代或未取代的C2-C30炔基、取代或未取代的C3-C30环烷基、取代或未取代的C2-C30杂环烷基、取代或未取代的C6-C30芳基、取代或未取代的C2-C30杂芳基；或者，R13～R16相同或不同，相邻的基团可以相互成环；R17～R20相同或不同，相邻的基团可以相互成环；R21～R24相同或不同，相邻的基团可以相互成环。Wherein R 13 to R 24 are the same or different and each independently is hydrogen, halogen, substituted or unsubstituted C 1 -C 30 alkyl, substituted or unsubstituted C 2 -C 30 alkenyl, substituted or unsubstituted C 2 -C 30 alkynyl, substituted or unsubstituted C 3 -C 30 cycloalkyl, substituted or unsubstituted C 2 -C 30 heterocycloalkyl, substituted or unsubstituted C 6 -C 30 aryl, a substituted or unsubstituted C 2 -C 30 heteroaryl group; or, R 13 to R 16 are the same or different, and adjacent groups may form a ring with each other; R 17 to R 20 may be the same or different, and adjacent groups may be each other to form a ring; R 21 ~ R 24 are the same or different, and adjacent groups may form a ring with each other.
  6. 根据权利要求1所述的化合物，其特征在于，Ar、R1～R12为氢、或选自由苯基、甲苯基、联苯基、萘基、菲基、三亚苯基、荧蒽基、屈基、芴基、茚并芴基组成的组中的的基团。The compound according to claim 1, wherein Ar, R 1 to R 12 are hydrogen or are selected from the group consisting of phenyl, tolyl, biphenyl, naphthyl, phenanthryl, triphenylene, fluoranthene, a group in the group consisting of thiol, fluorenyl, and indenyl.
  7. 根据权利要求5的化合物，其为选自下述A-1～A-24化合物中的化合物， A compound according to claim 5 which is a compound selected from the group consisting of the following A-1 to A-24 compounds,
    Figure PCTCN2016093026-appb-100006
    Figure PCTCN2016093026-appb-100006
  8. 根据权利要求1所述的化合物，其特征在于，Ar、R1～R12为氢、或选自由咔唑基、二苯并呋喃基、二苯并噻吩基、吲哚并咔唑基、苯并呋喃并咔唑基、苯并噻吩并咔唑基组成的组中的基团。The compound according to claim 1, wherein Ar, R 1 to R 12 are hydrogen or are selected from the group consisting of carbazolyl, dibenzofuranyl, dibenzothiophenyl, indolocarbazole, and benzene. And a group in the group consisting of furocarbazolyl and benzothienooxazolyl.
  9. 根据权利要求8所述的化合物，其为选自下述B-1～B-30化合物中的化合物，The compound according to claim 8, which is a compound selected from the group consisting of the following B-1 to B-30 compounds,
    Figure PCTCN2016093026-appb-100007
    Figure PCTCN2016093026-appb-100007
    Figure PCTCN2016093026-appb-100008
    Figure PCTCN2016093026-appb-100008
  10. 根据权利要求1所述的化合物，其特征在于，Ar、R1～R12为氢、或C6～C30的芳基氨基或杂芳基氨基。The compound according to claim 1, wherein Ar, R 1 to R 12 are hydrogen or a C 6 to C 30 arylamino group or a heteroarylamino group.
  11. 根据权利要求10所述的化合物，为下述C-1～C-15化合物中的化合物，The compound according to claim 10, which is a compound of the following C-1 to C-15 compounds,
    Figure PCTCN2016093026-appb-100009
    Figure PCTCN2016093026-appb-100009
    Figure PCTCN2016093026-appb-100010
    Figure PCTCN2016093026-appb-100010
  12. 根据权利要求1所述的化合物，其特征在于，Ar、R1～R12为氢、或选自由吡啶基、苯基吡啶基、喹啉基、取代喹啉基、喹唑啉基、取代喹唑啉基、喹喔啉基、取代喹喔啉基、嘧啶基、取代嘧啶基、邻菲啰啉基、三嗪基、取代三嗪基、苯并咪唑基、噁唑基组成的组中的基团。The compound according to claim 1, wherein Ar, R 1 to R 12 are hydrogen or are selected from pyridyl, phenylpyridyl, quinolyl, substituted quinolinyl, quinazolinyl, substituted quinolin In the group consisting of oxazoline, quinoxalinyl, substituted quinoxalinyl, pyrimidinyl, substituted pyrimidinyl, phenanthroline, triazinyl, substituted triazinyl, benzimidazolyl, oxazolyl Group.
  13. 根据权利要求12所述的化合物，其为下述D-1～D-39化合物中的化合物，The compound according to claim 12 which is a compound of the following D-1 to D-39 compounds,
    Figure PCTCN2016093026-appb-100011
    Figure PCTCN2016093026-appb-100011
    Figure PCTCN2016093026-appb-100012
    Figure PCTCN2016093026-appb-100012
    Figure PCTCN2016093026-appb-100013
    Figure PCTCN2016093026-appb-100013
  14. 一种有机电致发光器件，该器件包括第一电极、第二电极和插入所述第一电极和第二电极之间的一层或多成有机层，其特征在于，所述有机层包含权利要求1～13中任一项所述的化合物。An organic electroluminescent device comprising a first electrode, a second electrode, and one or more organic layers interposed between the first electrode and the second electrode, wherein the organic layer comprises a right The compound according to any one of claims 1 to 13.
  15. 根据权利要求14所述的有机电致发光器件，所述有机层包含空穴注入层，所述空穴注入层包含权利要求1～13中任一项所述的化合物。The organic electroluminescent device according to claim 14, wherein the organic layer comprises a hole injecting layer, and the hole injecting layer comprises the compound according to any one of claims 1 to 13.
  16. 根据权利要求14所述的有机电致发光器件，所述有机层包含空穴传输层，所述空穴传输层包含权利要求1～13中任一项所述的化合物。The organic electroluminescent device according to claim 14, wherein the organic layer comprises a hole transporting layer, and the hole transporting layer comprises the compound according to any one of claims 1 to 13.
  17. 根据权利要求14所述的有机电致发光器件，所述有机层包含发光层，所述发光层包含权利要求1～13中任一项所述的化合物。 The organic electroluminescent device according to claim 14, wherein the organic layer comprises a light-emitting layer comprising the compound according to any one of claims 1 to 13.
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