CN112375002B - 2,4, 7-trisubstituted fluorene compound and electronic device thereof - Google Patents

2,4, 7-trisubstituted fluorene compound and electronic device thereof Download PDF

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CN112375002B
CN112375002B CN202110059448.0A CN202110059448A CN112375002B CN 112375002 B CN112375002 B CN 112375002B CN 202110059448 A CN202110059448 A CN 202110059448A CN 112375002 B CN112375002 B CN 112375002B
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organic
trisubstituted
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CN112375002A (en
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朱向东
张业欣
陈华
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Weisipu New Material Suzhou Co ltd
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Suzhou Jiuxian New Material Co ltd
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Abstract

The invention provides a 2,4, 7-trisubstituted fluorene compound and an electronic device thereof. The 2,4, 7-trisubstituted fluorene compound has excellent film forming property and thermal stability by introducing a fluorene rigid structure, and can be used for preparing organic electroluminescent devices, organic field effect transistors and organic solar cells. In addition, the 2,4, 7-trisubstituted fluorene compound of the present invention can be used as a material constituting a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, a hole blocking layer or an electron transport layer, and can reduce driving voltage, improve efficiency, luminance, lifetime, and the like. The preparation method of the 2,4, 7-trisubstituted fluorene compound is simple, the raw materials are easy to obtain, and the industrial development requirement can be met.

Description

2,4, 7-trisubstituted fluorene compound and electronic device thereof
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and relates to a 2,4, 7-trisubstituted fluorene compound and an electronic device thereof. More particularly, the present invention relates to 2,4, 7-trisubstituted fluorene-based compounds suitable for electronic devices, particularly organic electroluminescent devices, organic field effect transistors and organic solar cells, and electronic devices comprising the same.
Background
The organic electroluminescent device has a series of advantages of self-luminescence, low-voltage driving, full curing, wide viewing angle, simple composition and process and the like, and compared with a liquid crystal display, the organic electroluminescent device does not need a backlight source. Therefore, the organic electroluminescent device has wide application prospect.
Organic electroluminescent devices generally comprise an anode, a metal cathode and an organic layer sandwiched therebetween. The organic layer mainly comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer. In addition, a host-guest structure is often used for the light-emitting layer. That is, the light emitting material is doped in the host material at a certain concentration to avoid concentration quenching and triplet-triplet annihilation, improving the light emitting efficiency. Therefore, the host material is generally required to have a higher triplet energy level and, at the same time, a higher stability.
At present, research on organic electroluminescent materials has been widely conducted in academia and industry, and a large number of organic electroluminescent materials with excellent performance have been developed. Third generation organic electroluminescent materials generally have a small singlet-triplet energy level difference (Δ)E ST) The triplet excitons can be converted into singlet excitons through reverse intersystem crossing (RISC) to emit light, and thus, the singlet excitons and the triplet excitons formed under electrical excitation can be simultaneously utilized, and the internal quantum efficiency of the device can reach 100%, so that the triplet excitons are regarded as one of organic light-emitting materials with wide application prospects in the future. However, the operational lifetime of devices, particularly blue devices, remains an open problem in this area. In view of the above, the future development direction of organic electroluminescent devices will be high efficiency, long lifetime, low cost white light devices and full color display devices, but the industrialization process of the technology still faces many key problems. Therefore, designing and searching a stable and efficient compound as a novel material of an organic electroluminescent device to overcome the defects of the organic electroluminescent device in the practical application process is a key point in the research work of the organic electroluminescent device material and the future research and development trend.
Disclosure of Invention
Problems to be solved by the invention
With the continuous development of the organic semiconductor industry, the requirements for the performance of semiconductor devices are continuously improved, higher efficiency, longer service life, lower working voltage and more saturated color purity are pursued, and higher requirements, such as higher electron/hole mobility, higher quantum efficiency and the like, are also put forward for corresponding organic semiconductor materials.
The invention aims to provide a 2,4, 7-trisubstituted fluorene compound which has high thermal stability, good transmission performance, adjustable triplet state energy level, simple preparation method, high fluorescence quantum yield and small difference between singlet state and triplet state energy levels, has the advantages of high luminous efficiency, long service life, low driving voltage and the like, and is an organic electroluminescent material with excellent performance.
Specifically, the invention provides a 2,4, 7-trisubstituted fluorene compound, which is represented by the following general formula (1):
Figure 94618DEST_PATH_IMAGE001
wherein the content of the first and second substances,
A1、A2and A3Each independently represents Ar or N (Ar)2；
Each Ar independently represents a hydrogen atom, a cyano group, optionally substituted by one or more R1Substituted C6-C35Aryl or optionally substituted by one or more R1Substituted 5-35 membered heteroaryl;
L1、L2and L3Each independently represents a single bond, carbonyl group, C6-C18Arylene or 5-18 membered heteroarylene;
m represents C (R)1)2Or
Figure 361651DEST_PATH_IMAGE002
；
The dotted line represents a bond;
y represents a single bond, C (R)1)2、NR1、O、S、S(=O)2、P(=O)R1、Si(R1)2Or Ge (R)1)2；
Each Z independently represents CR1Or N;
if present, each R1Each independently represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, N (= O)2、N(R2)2、OR2、SR2、C(=O)R2、P(=O)R2、Si(R2)3Or optionallyBy one or more R2Any one of the following substituted groups: c1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C6-C40Aryl and 5-40 membered heteroaryl; if present, each R2Each independently represents a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group or any one of the following groups optionally substituted: c1-C20Alkyl radical, C6-C30Aryl and 5-30 membered heteroaryl;
and, when M represents C (CH)3)2Z represents CH, L1、L2And L3Represents a single bond, A1、A2And A3Represents N (Ar)2When, A1、A2And A3At most one of N (Ph)2。
It is another object of the present invention to provide an electronic device (particularly, an organic light emitting device) using the 2,4, 7-trisubstituted fluorene compound, which has advantages of high efficiency, high durability, long lifetime, and the like.
Means for solving the problems
The fluorene compound is a special compound derived on the basis of a biphenyl structure, and has high thermal stability, chemical stability and carrier transport property. However, in the case of introducing no other group (substituent), the photoelectric characteristics of fluorene are relatively single, and the requirements of the organic light-emitting device on the material performance are often not satisfied, so that the modification or derivation of fluorene is a good choice.
Multi-site derived (multi-substituted) fluorene compounds have more "variability" than single-site derived (mono-substituted) fluorene compounds. The introduction of units (electron donating or electron withdrawing) with the same or different characteristics into the polysubstituted sites can realize richer photoelectric characteristics, for example, when all polysubstituted groups introduced on polysubstituted fluorene are electron donating units, the material often has better hole transport capability; when the polysubstitution groups are all electron-withdrawing units, the material often has better electron transport capacity; when the polysubstituent group contains electron-donating units and electron-withdrawing units, bipolar (bipolar) characteristics of the material, even Thermal Activation Delayed Fluorescence (TADF) characteristics, can be realized. In addition, the multi-site derived fluorene compound can also realize larger steric hindrance of molecules by introducing different rigid groups (such as rigid units including fused rings, bridged rings or spiro rings optionally containing heteroatoms) to adjacent or similar sites on a fluorene ring, so as to adjust the photoelectric properties of the molecules.
At present, the reports about multi-site derived fluorene compounds mainly focus on two-site derived fluorene compounds, such as 2,7, 2,4, etc. However, the fluorene compound derived from three sites is only rarely reported, the invention successfully realizes 2,4, 7-three site derivation of fluorene by ingenious synthesis route design, and the obtained tri-substituted fluorene compound can directionally adjust the physical and chemical properties of materials and has more suitable singlet state, triplet state and molecular orbital energy level. Therefore, the organic electroluminescent material is introduced into an electronic device with electroluminescent characteristics, so that the working life and the luminous efficiency of the device are improved, and the driving voltage of the device is reduced.
That is, the present invention is as defined in the above-mentioned embodiments.
ADVANTAGEOUS EFFECTS OF INVENTION
The 2,4, 7-trisubstituted fluorene compound has good film forming property and thermal stability. 2,4 and 7 sites belong to conjugated sites of fluorene, so that the transmission performance of the fluorene is better, the fluorene is more favorable for adjusting molecular singlet state/triplet state energy levels, and high fluorescence quantum efficiency is easier to obtain.
The 2,4, 7-tri-substituted fluorene compound has high electron injection and movement rate. Therefore, when the 2,4, 7-trisubstituted fluorene compound of the present invention is used to prepare an electron injection layer and/or an electron transport layer in an organic electroluminescent device, the electron transport efficiency from the electron transport layer to a light emitting layer can be improved, thereby improving the light emitting efficiency. Also, the driving voltage can be reduced, thereby enhancing the durability of the organic electroluminescent device.
The 2,4, 7-trisubstituted fluorene compound also has excellent hole blocking capability and excellent electron transport performance, and is stable in a thin film state. Therefore, when the 2,4, 7-trisubstituted fluorene compound is used for preparing a hole blocking layer in an organic electroluminescent device, the luminous efficiency of the device can be improved, the driving voltage can be reduced, the current resistance can be improved, and the maximum luminous brightness can be increased.
The 2,4, 7-trisubstituted fluorene compound can be used as a thermally activated delayed fluorescence guest material to be applied to a light emitting layer of an organic electroluminescent device, and the organic electroluminescent device with high light emitting efficiency, low driving voltage and long device life can be obtained by using the compound to manufacture the organic electroluminescent device.
The 2,4, 7-trisubstituted fluorene compound can be used as a material for forming a hole injection layer, a hole transport layer, a luminescent layer, an electron blocking layer, a hole blocking layer or an electron transport layer of an organic electroluminescent device. With the organic electroluminescent device of the present invention, excitons generated in the light emitting layer can be confined, further increasing the possibility of recombination of holes and electrons to achieve high light emitting efficiency. Further, the driving voltage is so low that high durability can be achieved.
In addition, the preparation method of the 2,4, 7-trisubstituted fluorene compound is simple, raw materials are easy to obtain, and the industrialized development requirements can be met.
Drawings
FIG. 1 is a thermogravimetric plot (TGA) of examples 1 and 2 (compounds 2-1 and 2-13) of the present invention.
FIG. 2 shows organic electroluminescence spectra of the organic electroluminescent devices 1 to 10 in examples 13 to 22 of the present invention.
FIG. 3 is a view showing the structures of organic electroluminescent devices of examples 13 to 25 and organic electroluminescent devices of comparative examples 1 to 9.
FIG. 4 is a current density-voltage curve (J-V) for example 1 (Compound 2-1), comparative examples HTL4 and HTL5, and a single hole device.
FIG. 5 is a current density-voltage curve (J-V) for example 6 (Compounds 1-5), comparative examples ETL2 and ETL3, and a single electron device.
Description of the reference numerals
1a substrate; 2 an anode; 3 a hole injection layer; 4 a hole transport layer; 5 an electron blocking layer; 6 a light emitting layer; 7 a hole blocking layer; 8 an electron transport layer; 9 an electron injection layer; 10 cathode.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
< fluorene-based Compound >
The fluorene-based compound of the present invention is a novel compound having a 2,4, 7-trisubstituted fluorene structure and is represented by the following general formula (1).
Figure 606556DEST_PATH_IMAGE001
In the above-mentioned general formula (1),
A1、A2and A3Each independently represents Ar or N (Ar)2；
Each Ar independently represents a hydrogen atom, a cyano group, optionally substituted by one or more R1Substituted C6-C35Aryl or optionally substituted by one or more R1Substituted 5-35 membered heteroaryl;
L1、L2and L3Each independently represents a single bond, carbonyl group, C6-C18Arylene or 5-18 membered heteroarylene;
m represents C (R)1)2Or
Figure 275435DEST_PATH_IMAGE003
；
The dotted line represents a bond;
y represents a single bond, C (R)1)2、NR1、O、S、S(=O)2、P(=O)R1、Si(R1)2Or Ge (R)1)2；
Each Z independently represents CR1Or N;
if present, each R1Each independently represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, N (= O)2、N(R2)2、OR2、SR2、C(=O)R2、P(=O)R2、Si(R2)3Or optionally substituted by one or more R2Any one of the following substituted groups: c1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C6-C40Aryl and 5-40 membered heteroaryl; if present, each R2Each independently represents a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group or any one of the following groups optionally substituted: c1-C20Alkyl radical, C6-C30Aryl and 5-30 membered heteroaryl;
and, when M represents C (CH)3)2Z represents CH, L1、L2And L3Represents a single bond, A1、A2And A3Represents N (Ar)2When, A1、A2And A3At most one of N (Ph)2。
Specifically, the 2,4, 7-trisubstituted fluorene compound of the present invention is represented by the following general formula (I) or (II).
Figure 596695DEST_PATH_IMAGE004
In the above general formulae (I) and (II), Ar, M and Z are as defined above;
and, in the general formula (II), when M represents C (CH)3)2When Z represents CH, at most one N (Ar)2Is N (Ph)2。
[ radical definitions ]
< A >
In the present invention, A (for example, A) in the above general formula (1)1、A2、A3) Is equal to L (e.g. L)1、L2、L3) Fragment-linked structural fragments, a plurality of a are the same as or different from each other. Specifically, each A (A)1、A2And A3) Each independently represents Ar or N (Ar)2. When A is Ar, it means that the Ar fragment is directly linked to the L fragment in the general formula (1); when A is N (Ar)2When used, it means that both Ar segments are simultaneously bonded to the L segment in the general formula (1) through a nitrogen atom.
< Ar >
When there are a plurality of Ar's in the general formula, they may be the same as or different from each other. Specifically, each Ar in the above general formulae (I) and (II) independently represents a hydrogen atom, a cyano group, optionally substituted with one or more R1Substituted C6-C35Aryl or optionally substituted by one or more R1Substituted 5-35 membered heteroaryl.
In the present invention, the term "aryl" refers to a monovalent group derived from an aromatic hydrocarbon, which may be linked to another structural fragment; accordingly, "C6-C35Aryl "refers to an aryl group having from 6 to 35 ring-forming carbon atoms in the structure; for example, phenyl, naphthyl, anthracenyl, fluorenyl, and the like.
In the present invention, the term "heteroaryl" refers to a monovalent group derived from a heteroarene, which may be linked to another fragment; accordingly, "5-35 membered heteroaryl" refers to heteroaryl groups containing 5 to 35 ring-forming atoms (including carbon and heteroatoms) in the structure; for example, pyridyl, pyrimidinyl, pyrazinyl, triazinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, and the like. In the 5-35 membered heteroaryl group, the heteroatom is selected from N, O, S, P, As and/or Si, preferably N, O and/or S; the number of heteroatoms may be from 1 to 10, preferably from 1 to 5.
Aryl or heteroaryl groups in the present invention also encompass systems which do not contain only aryl or heteroaryl groups, but also include those in which a plurality of aryl or heteroaryl groups may also be interrupted by non-aromatic units (preferably less than 10% of non-hydrogen atoms), which may be, for example, carbon atoms, nitrogen atoms, oxygen atoms or carbonyl groups. For example, monovalent fragments derived from 9, 9' -spirobifluorene, 9-diarylfluorene, triarylamines, diarylethers, etc., are also considered aryl or heteroaryl groups in the sense of the present invention, as are systems in which two or more aryl groups are interrupted by linear or cyclic alkylene or silylene groups. Furthermore, monovalent moieties in which two or more aryl or heteroaryl groups are linked to one another, such as biphenyl, terphenyl or quaterphenyl, are likewise to be regarded as aryl or heteroaryl in the sense of the present invention.
C represented by Ar6-C35Aryl or 5-35 membered heteroaryl may be exemplified by: phenyl, naphthyl, anthracenyl, benzanthracenyl, phenanthrenyl, benzophenanthrenyl, pyrenyl, perylenyl, fluoranthenyl, benzofluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, idophenyl, terphenyl, quaterphenyl, pentabiphenyl, terphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthrenyl, hydropyranyl, cis-or trans-indenofluorenyl, cis-or trans-monobenzindenofluorenyl, cis-or trans-dibenzoindenofluorenyl, trimeric indenyl, isotridecyl, spirotrimeric indenyl, spiroisotridecyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, benzothienyl, isobenzothienyl, dibenzothienyl, indolyl, isoindolyl, carbazolyl, indolocarbazolyl, indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolyl, benzo-6, 7-quinolyl, benzo-7, 8-quinolyl, indazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxaloimidazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthroixazolyl, benzothiazolyl, pyridazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinylExamples of the "phenanthrenyl" group include a quinoxalinyl group, a 1, 5-diazanthryl group, a 2, 7-diazpyrenyl group, a 2, 3-diazpyrenyl group, a 1, 6-diazpyrenyl group, a 1, 8-diazpyrenyl group, a 4,5,9, 10-tetraazaperylenyl group, a pyrazinyl group, a phenazinyl group, a phenoxazinyl group, a phenothiazinyl group, a fluoryl group, a naphthyridinyl group, an azacarbazolyl group, a benzocarbazinyl group, a phenanthrolinyl group, a benzotriazolyl group, a purinyl group, a pteridinyl group, an indolizinyl group, and a benzothiadiazolyl.
Preferably, in the present invention, each Ar independently represents a hydrogen atom, a cyano group or any one of the following groups:
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Figure 514579DEST_PATH_IMAGE029
Figure 542578DEST_PATH_IMAGE030
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Figure 241730DEST_PATH_IMAGE032
Figure 141553DEST_PATH_IMAGE033
Figure 520712DEST_PATH_IMAGE034
Figure 556801DEST_PATH_IMAGE035
Figure 182955DEST_PATH_IMAGE036
；
wherein the dotted line represents a bond to the L fragment or nitrogen atom.
More preferably, in the present invention, each Ar independently represents a hydrogen atom, a cyano group, or any one of the following groups:
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Figure 204372DEST_PATH_IMAGE039
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Figure 672580DEST_PATH_IMAGE041
Figure 580493DEST_PATH_IMAGE042
Figure 669803DEST_PATH_IMAGE043
Figure 637759DEST_PATH_IMAGE044
Figure 733891DEST_PATH_IMAGE045
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Figure 373000DEST_PATH_IMAGE047
Figure 89021DEST_PATH_IMAGE048
Figure 406869DEST_PATH_IMAGE049
Figure 922164DEST_PATH_IMAGE050
Figure 704176DEST_PATH_IMAGE051
Figure 13934DEST_PATH_IMAGE052
；
wherein the dotted line represents a bond to the L fragment or nitrogen atom.
Further preferably, in the present invention, each Ar independently represents a hydrogen atom, a cyano group, or any one of the following groups:
Figure 632129DEST_PATH_IMAGE053
Figure 685535DEST_PATH_IMAGE054
Figure 853211DEST_PATH_IMAGE055
Figure 333871DEST_PATH_IMAGE056
Figure 937897DEST_PATH_IMAGE057
Figure 529415DEST_PATH_IMAGE058
Figure 489281DEST_PATH_IMAGE059
Figure 468738DEST_PATH_IMAGE060
Figure 248475DEST_PATH_IMAGE061
Figure 456734DEST_PATH_IMAGE062
Figure 271106DEST_PATH_IMAGE063
Figure 890306DEST_PATH_IMAGE064
Figure 157340DEST_PATH_IMAGE065
Figure 356240DEST_PATH_IMAGE066
Figure 602282DEST_PATH_IMAGE067
Figure 595646DEST_PATH_IMAGE068
；
wherein the dotted line represents a bond to the L fragment or nitrogen atom.
< L >
In the present invention, L (e.g., L) in the above general formula (1)1、L2、L3) Is simultaneously with the mother nucleus and A (e.g. A)1、A2、A3) Fragment-linked structural fragments, a plurality of L's being the same or different from each other. Specifically, each L (L)1、L2And L3) Each independently represents a single bond, carbonyl group, C6-C18Arylene or 5-18 membered heteroarylene.
In the present invention, the term "arylene" refers to a divalent group derived from an aromatic hydrocarbon, which may link two additional structural segments; accordingly, "C6-C18Arylene "refers to an arylene group having from 6 to 18 ring-forming carbon atoms in the structure; for example, phenylene, naphthylene, anthracenylene, fluorenylene, and the like.
In the present invention, the term "heteroarylene" refers to a divalent group derived from a heteroarene, to which two additional segments may be attached; correspondingly, "5-18 membered heteroarylene" refers to a heteroarylene group containing from 5 to 18 ring-forming atoms (including carbon and heteroatoms) in the structure; for example, pyridinylene, dibenzofuranylene, dibenzothiophenylene, carbazolyl, etc. 5-18 membered heteroarylene, the heteroatom selected from N, O, S, P, As and/or Si, preferably N, O and/or S; the number of heteroatoms may be from 1 to 10, preferably from 1 to 5.
Arylene or heteroarylene groups in the present invention also encompass systems which do not contain only arylene or heteroarylene groups, but also include those in which a plurality of arylene or heteroarylene groups may also be interrupted by non-aromatic units (preferably less than 10% of non-hydrogen atoms), which may be, for example, carbon atoms, nitrogen atoms, oxygen atoms or carbonyl groups. For example, as with systems in which two or more arylene groups are interrupted by linear or cyclic alkylene or silylene groups, divalent moieties derived from 9, 9' -spirobifluorene, 9-diarylfluorene, triarylamine, diarylether, and the like are also considered arylene or heteroarylene groups in the sense of the present invention. Furthermore, divalent fragments in which two or more arylene or heteroarylene groups are linked to one another, such as biphenylene, terphenylene or quaterphenylene groups, are likewise considered arylene or heteroarylene in the sense of the present invention.
C represented by L6-C18Arylene or 5-18 membered heteroarylene can be exemplified by: phenylene, naphthylene, anthrylene, benzanthrylene, phenanthrylene, benzophenanthrylene, pyrenylene, peryleneene, fluoranthenylene, benzofluoranthenylene, tetracenylene, pentacenylene, biphenylene, benzilidene, terphenylene, tetracenylene, pentabiphenylene, terphenylene, fluorenylene, spirobifluorenylene, dihydrophenanthrylene, dihydropyrenylene, tetrahydropyrenylene, cis-or trans-indenofluorenyl, cis-or trans-monobenzindenofluorenyl, cis-or trans-dibenzoindenofluorenyl, trimerization indenyl, isotridecylindenyl, spirotrimerization indenyl, spiroisotridecylindenyl, benzofuranylene, isobenzofuranylene, dibenzofuranylene, benzothienylene, phenyleneIsobenzothienyl, dibenzothienyl, indolyl, isoindolinyl, carbazolyl, indolylenocarbazolyl, indenocarbazolyl, pyridinylene, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolyl, benzo-6, 7-quinolyl, benzo-7, 8-quinolyl, indazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridinylimidazolyl, pyrazinoimidazolyl, quinoxalinyl, benzoxazolyl, naphthoxazolyl, anthraxazolyl, phenanthreneoxazolyl, benzothiazolyl, pyridazinyl, pyrimidyl, benzimidinyl, quinoxalinyl, 1, 5-diazahrenyl, 2, 7-diazapyryl, 2, 3-diazpyrenylene, 1, 6-diazpyrenylene, 1, 8-diazpyrenylene, 4,5,9, 10-tetraazaperylenyl, pyrazinylene, phenazinylene, phenoxazylene, phenothiazinylene, erythroylene, naphthyrylene, azacarbazolyl, benzocarbazinyl, phenanthrolinylene, benzotriazolene, purinylene, pteridinylene, indolizinylene, benzothiadiazolylene, and the like.
Preferably, in the present invention, each L (L)1、L2And L3) Each independently represents a single bond, carbonyl group, C6-C12Arylene or 5-to 12-membered heteroarylene, preferably a single bond, carbonyl group, phenylene (e.g., 1, 2-phenylene, 1, 3-phenylene, 1, 4-phenylene, etc.), biphenylene (e.g., 2 ' -biphenylene, 3 ' -biphenylene, 4' -biphenylene), naphthylene (e.g., 1, 4-naphthylene, 1, 5-naphthylene, 1, 8-naphthylene, etc.), anthracenylene (e.g., 9, 10-anthracenylene), fluorenylene (e.g., 1,4 fluorenylene, 1, 5-fluorenylene, 1, 8-fluorenylene, etc.), dibenzofuranylene (e.g., 1,4 dibenzofuranyl, 1, 5-dibenzofuranyl, 1, 8-dibenzofuranyl, etc.), dibenzothiophenylene (e.g., 1, 4-dibenzothiophenyl group, 1, 5-dibenzothiophenyl group, 1, 8-dibenzothiophenyl group, etc.) or a carbazolyl group (e.g., 1, 4-carbazolyl group, 1, 5-carbazolyl group, 1, 8-carbazolyl group, etc.), more preferably a single bond, 1, 4-phenylene group, 1, 4-naphthylene group, 9, 10-naphthylene groupAnthracenyl, 1, 4-fluorenylidene, 1, 4-dibenzothiophenylidene or 1, 4-carbazolyl, further preferably a single bond, i.e. the A-segment is directly attached to the parent nucleus, for example of the formula (I) or of the formula (II).
< M >
In the present invention, M in the general formulae (1), (I) and (II) is a structural fragment at the 9-position of the fluorene ring, specifically C (R)1)2Or
Figure 146713DEST_PATH_IMAGE069
Wherein the dotted lines represent bonds to the carbon atoms at positions 1a and 8a, respectively, of the fluorene ring.
< Y >
Y represents a single bond, C (R)1)2、NR1、O、S、S(=O)2、P(=O)R1、Si(R1)2Or Ge (R)1)2Specific examples are C (CH)3)2(at this time R1Is CH3）、O、S、S(=O)2PH (= O) (in this case R)1H), etc. Preferably, in the present invention, Y represents a single bond, C (CH)3)2、NCH3O, S or S (= O)2Preferably a single bond, C (CH)3)2、NCH3O or S, more preferably a single bond, C (CH)3)2Or O, more preferably a single bond or O.
< Z >
In the present invention, each Z in the above general formulae (1), (I) and (II) and the structural formula representing M independently represents CR1Or N, e.g. N, C-H, C-F, C-Cl, C-Br, C-I, C-CN, C-NO2C-Ph, C-Ph-Ph, etc. When Z is CR1And R is1When hydrogen is present, the ring atoms in the corresponding ring system are sp2Hybridized carbon atoms and unsubstituted; when Z is CR1And R is1When not hydrogen atoms, the ring atoms of the corresponding ring system remain sp2Hybridized carbon atoms, but substituted by corresponding substituents; when Z is N, the ring atoms in the corresponding ring system are sp2Hybridized with nitrogen atoms.Preferably, in the present invention, Z represents CR1Preferably CH.
< R1And R2 >
As optionally substituted substituents, fragments of Ar, Z and/or M may each have one or more R1. When there are multiple R in the structure1When they are the same or different from each other. Specifically, each R1Each independently represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, N (= O)2、N(R2)、OR2、SR2、C(=O)R2、P(=O)R2、Si(R2)3Or any of the following groups optionally substituted with one or more deuterium atoms: c1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C6-C40Aryl and 5-40 membered heteroaryl.
In the present invention, the term "alkyl" refers to a monovalent group derived from an alkane, which may be linked to another structural fragment; accordingly, "C1-C20Alkyl "refers to an alkyl group having 1 to 20 carbon atoms in the structure. From R1Is represented by C1-C20Alkyl groups may be exemplified by: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, 3-methylheptyl, n-nonyl, n-decyl, hexadecyl, octadecyl, eicosyl, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl and the like. C1-C20The alkyl group may be linear, branched or cyclic.
In the present invention, the term "alkenyl" refers to a monovalent group derived from an alkene, which may be attached to another structural fragment; accordingly, "C2-C20Alkenyl "means a structure containing 2 to 20 carbon atomsAlkenyl groups of (a). From R1Is represented by C2-C20Alkenyl groups may be exemplified by: vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, 2-ethylhexenyl, allyl, cyclohexenyl and the like. C2-C20The alkenyl group may be linear, branched or cyclic.
In the present invention, the term "alkynyl" refers to a monovalent group derived from an alkyne, which may be linked to another structural fragment; accordingly, "C2-C20Alkynyl "refers to alkynyl groups having 2 to 20 carbon atoms in the structure. From R1Is represented by C2-C20Alkynyl groups may illustrate: ethynyl, isopropynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl and the like. C2-C20The alkynyl group may be linear, branched or cyclic.
From R1Is represented by C6-C40Aryl and 5-40 membered heteroaryl groups may be exemplified by: phenyl, naphthyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazolyl, benzofurocarbazolyl, benzofluorenocarbazolyl, benzanthracenyl, benzophenanthryl, fluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothienyl, carbazolyl, phenylthiospirodiclofen, phenylthiopenyl, phenylthio,NPhenylcarbazolyl, indolocarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenylboranyl, triphenylphosphinyl, diphenylphosphinyloxy, triphenylsilyl, tetraphenylsilyl, 9, 10-dihydroacridinyl, phenoxazinyl, phenothiazinyl and the like, preferably phenyl, naphthyl, dibenzofuranyl (e.g. fully deuterated and/or phenyl-substituted dibenzofuranyl), benzofurocarbazolyl, indolocarbazolyl (e.g. phenyl-substituted indolocarbazolyl), indenocarbazolyl (e.g. dimethyl-substituted indenocarbazolyl), 9, 10-dihydroacridinyl (e.g. dimethyl-substituted 9, 10-dihydroacridinyl) and phenoxazinyl. From R1Is represented by C6-C40Aryl or C5-C40Heteroaryl groups may be substituted by one or more R2Substituted, e.g. when R1In the case of a 9, 10-dihydroacridinyl radical, the hydrogen atom in position 9 thereof may be represented by at least one R which is methyl2Substituted, as well as when R1In the case of indolocarbazolyl, the nitrogen atom in the indole ring may be bonded to R which is represented by phenyl2。
Preferably, if present, each R is1Each independently represents a hydrogen atom, a deuterium atom or optionally substituted by one or more R2Any one of the following substituted groups: methyl, ethyl, propyl, butyl, phenyl, naphthyl, dibenzofuranyl (e.g., fully deuterated and/or phenyl-substituted dibenzofuranyl), benzofurocarbazolyl, indolocarbazolyl (e.g., phenyl-substituted indolocarbazolyl), indenocarbazolyl (e.g., dimethyl-substituted indenocarbazolyl), 9, 10-dihydroacridinyl (e.g., dimethyl-substituted 9, 10-dihydroacridinyl), and phenoxazinyl.
Each R1All of which may have one or more R2. When there are multiple R in the structure2When they are the same or different from each other. Specifically, each R2Each independently represents a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group or any of the following groups optionally substituted with one or more deuterium atoms: c1-C20Alkyl radical, C6-C30Aryl and 5-30 membered heteroaryl, preferably deuterium atom, C1-C20Alkyl (e.g. methyl) and C6-C30Aryl (e.g., phenyl).
From R2Is represented by C1-C20Alkyl groups can be exemplified by the groups described above for R1Is represented by C1-C20Alkyl groups are the same.
From R2Is represented by C6-C30Aryl radicals may be illustrated by the above-mentioned radicals R1Is represented by C6-C40Aryl is the same group.
From R2The 5-30 membered heteroaryl group represented may be exemplified by R15-to 40-membered heteroaryl groups represented by the formula are the same.
From R2Is represented by C1-C20Alkyl radical, C6-C30The aryl group or 5-to 30-membered heteroaryl group may be unsubstituted or may have a substituent. The substituents may be exemplified by: a deuterium atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; cyano, and the like.
Preferably, in the present invention, each R is2Each independently represents a deuterium atom, C1-C20Alkyl or C6-C30Aryl preferably each independently represents a deuterium atom, methyl or phenyl.
In some embodiments of the present invention, the fluorene compound of the present invention is selected from any one of the following compounds:
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。
< production method >
The 2,4, 7-trisubstituted fluorene compound of the present invention can be produced, for example, by any one of the following methods:
the method comprises the following steps: starting with the 4-substituted starting material, the 2-and 7-derived sites are subsequently introduced simultaneously.
Figure 101078DEST_PATH_IMAGE167
The second method comprises the following steps: starting with a 2,4 disubstituted starting material, a 7-position derivatization site is subsequently introduced.
Figure 960450DEST_PATH_IMAGE168
The third method comprises the following steps: starting with a 4,7 disubstituted starting material, a 2-position derivatization site is subsequently introduced.
Figure 569285DEST_PATH_IMAGE169
The purification of the resulting compound can be carried out by the following method: for example, purification by column chromatography, adsorption purification using silica gel, activated carbon, activated clay, or the like, recrystallization or crystallization using a solvent, sublimation purification, or the like. The resulting compound can be identified by mass spectrometry, elemental analysis, or the like.
< electronic device >
The 2,4, 7-trisubstituted fluorene compound can be used for producing organic luminescent materials, and further can be used for producing corresponding electronic devices in a layered configuration mode. In particular, the 2,4, 7-trisubstituted fluorene compound of the present invention may be used in organic electroluminescent devices, organic solar cells, organic diodes (especially organic field effect transistors), and the like. Particularly in the case of organic electroluminescent devices or solar cells, the assembly may have, but is not limited to, a plug structure (the device has one or more p-doped hole transport layers and/or one or more n-doped electron transport layers) or an inverted structure (the upper electrode and the hole transport layer are located on the same side, while the substrate is on the opposite side, as seen from the light-emitting layer). The injection layer, the transport layer, the light-emitting layer, the barrier layer, and the like may be formed by forming a layer structure between electrodes, the layer structure including the 2,4, 7-trisubstituted fluorene compound of the present invention or the layer structure including the 2,4, 7-trisubstituted fluorene compound of the present invention. However, the use scenario of the 2,4, 7-trisubstituted fluorene compound of the present invention is not limited to the above exemplary embodiments.
< organic electroluminescent device >
The organic electroluminescent device of the present invention comprises: the organic light-emitting device includes a first electrode, a second electrode provided so as to face the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the at least one organic layer includes the 2,4, 7-trisubstituted fluorene compound of the present invention.
Fig. 3 is a view showing the configuration of an organic electroluminescent device of the present invention. As shown in fig. 3, in the organic electroluminescent device of the present invention, for example, an anode 2, a hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a light emitting layer 6, a hole blocking layer 7, an electron transport layer 8, an electron injection layer 9, and a cathode 10 are sequentially disposed on a substrate 1.
The organic electroluminescent device of the present invention is not limited to such a structure, and for example, some organic layers may be omitted in the multi-layer structure. For example, a configuration may be adopted in which the hole injection layer 3 between the anode 2 and the hole transport layer 4, the hole blocking layer 7 between the light-emitting layer 6 and the electron transport layer 8, and the electron injection layer 9 between the electron transport layer 8 and the cathode 10 are omitted, and finally the anode 2, the hole transport layer 4, the electron blocking layer 5, the light-emitting layer 6, the electron transport layer 8, and the cathode 10 are provided in this order on the substrate 1.
The organic electroluminescent device of the present invention may be manufactured by materials and methods well known in the art, except that the organic layer includes the 2,4, 7-trisubstituted fluorene compound represented by the above general formula (1), (I) or (II). In addition, in the case where the organic electroluminescent device includes a plurality of organic layers, the organic layers may be formed of the same substance or different substances.
For example, the organic electroluminescent device of the present invention can be manufactured by sequentially laminating a first electrode, an organic layer, and a second electrode on a substrate. At this time, the following can be made: an anode is formed by depositing metal, a metal oxide having conductivity, or an alloy thereof on a substrate by a PVD (physical vapor deposition) method such as a sputtering method or an electron beam evaporation method, an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed on the anode, and a substance which can be used as a cathode is deposited on the organic layer. However, the production method is not limited thereto.
In one example, the first electrode is an anode and the second electrode is a cathode, or the first electrode is a cathode and the second electrode is an anode.
The anode of the organic electroluminescent device of the present invention may be made of a known electrode material. For example, an electrode material having a large work function, such as a metal of vanadium, chromium, copper, zinc, gold, or an alloy thereof; gold such as zinc oxide, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), etcA metal oxide; such as ZnO, Al or SnO2A combination of a metal such as Sb and an oxide; poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene]And conductive polymers such as PEDOT, polypyrrole, and polyaniline. Among these, ITO is preferable.
As the hole injection layer of the organic electroluminescent device of the present invention, a known material having a hole injection property can be used. Examples thereof include: porphyrin compounds represented by copper phthalocyanine, naphthalenediamine compounds, star-shaped triphenylamine compounds, triphenylamine trimers such as arylamine compounds having a structure in which 3 or more triphenylamine structures are connected by a single bond or a divalent group containing no hetero atom in the molecule, tetramers, receptor-type heterocyclic compounds such as hexacyanoazatriphenylene, and coating-type polymer materials. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.
The hole transport layer of the organic electroluminescent element of the present invention preferably contains the 2,4, 7-trisubstituted fluorene compound of the present invention. In addition, other known materials having a hole-transporting property can be used. Examples thereof include: a compound containing a m-carbazolylphenyl group; such asN,N' -Diphenyl-N,N' -di (m-tolyl) benzidine (TPD),N,N' -Diphenyl-N,N' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB),N,N,N′,NBenzidine derivatives such as' -tetrakisbiphenylylbenzidine; 1, 1-bis [ (di-4-tolylamino) phenyl]Cyclohexane (TAPC); various triphenylamine trimers and tetramers; 9,9 ', 9 ' ' -triphenyl-9H,9′H,9′′H-3,3 ', 6', 3 "-tricarbazole (Tris-PCz), and the like. These may be used as a single layer formed by separately forming a film or by mixing them with other materials to form a film, or may be used as a laminated structure of layers formed by separately forming a film, a laminated structure of layers formed by mixing films, or a laminated structure of layers formed by separately forming a film and layers formed by mixing films. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.
In addition, in the hole injection layer or the hole transport layer, a material obtained by further P-doping tribromoaniline antimony hexachloride, an axial olefin derivative, or the like to a material generally used in the layer, a polymer compound having a structure of a benzidine derivative such as TPD in a partial structure thereof, or the like may be used.
The electron blocking layer of the organic electroluminescent device preferably contains the 2,4, 7-trisubstituted fluorene compound of the present invention. In addition, other known compounds having an electron blocking effect may be used. For example, there may be mentioned: 4,4', 4' ' -tris (A-bis (R)) (N-carbazolyl) triphenylamine (TCTA), 9-bis [4- (carbazol-9-yl) phenyl]Carbazole derivatives such as fluorene, 1, 3-bis (carbazol-9-yl) benzene (mCP), and 2, 2-bis (4-carbazol-9-ylphenyl) adamantane (Ad-Cz); 9- [4- (carbazol-9-yl) phenyl]-9- [4- (triphenylsilyl) phenyl]-9H-compounds having triphenylsilyl and triarylamine structures represented by fluorene; and compounds having an electron-blocking effect, such as monoamine compounds having a high electron-blocking property and various triphenylamine dimers. These may be used as a single layer formed by film formation alone or by mixing with other materials to form a film, or may be used as a laminated structure of layers formed by film formation alone, a laminated structure of layers formed by mixing into a film, or a laminated structure of layers formed by film formation alone and layers formed by mixing into a film. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.
The light-emitting layer of the organic electroluminescent element of the present invention preferably contains the 2,4, 7-trisubstituted fluorene compound of the present invention. In addition to this, Alq can also be used3Various metal complexes such as metal complexes of a first hydroxyquinoline derivative, compounds having a pyrimidine ring structure, anthracene derivatives, bisstyrylbenzene derivatives, pyrene derivatives, oxazole derivatives, polyparaphenylene vinylene derivatives, and the like.
The light emitting layer may be composed of a host material and a dopant material. The host material preferably contains the 2,4, 7-trisubstituted fluorene compound of the present invention. In addition to this, use can also be made ofmCBP, mCP, thiazole derivatives, benzimidazole derivatives,Polydialkylfluorene derivatives, heterocyclic compounds having a partial structure in which an indole ring is a condensed ring, and the like.
As the doping material, the 2,4, 7-trisubstituted fluorene derivative of the present invention is preferably contained. In addition to these, aromatic amine derivatives, styryl amine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like can be used. Examples thereof include pyrene derivatives, anthracene derivatives, quinacridones, coumarins, rubrenes, perylenes and their derivatives, benzopyran derivatives, rhodamine derivatives, aminostyryl derivatives, spirobifluorene derivatives, and the like. These may be used as a single layer formed by film formation alone or by mixing with other materials to form a film, or may be used as a laminated structure of layers formed by film formation alone, a laminated structure of layers formed by mixing into a film, or a laminated structure of layers formed by film formation alone and layers formed by mixing into a film. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.
The hole blocking layer of the organic electroluminescent device of the present invention preferably contains the 2,4, 7-trisubstituted fluorene compound of the present invention. In addition, the hole-blocking layer may be formed using another compound having a hole-blocking property. For example, 2,4, 6-tris (3-phenyl) -1,3, 5-triazine (T2T), 1,3, 5-tris (1-phenyl-1) can be usedHA metal complex of a phenanthroline derivative such as benzimidazol-2-yl) benzene (TPBi) or Bathocuproine (BCP), a quinolyl derivative such as aluminum (III) bis (2-methyl-8-quinolinolato) -4-phenylphenolate (BAlq), or a compound having a hole-blocking effect such as various rare earth complexes, oxazole derivatives, triazole derivatives, or triazine derivatives. These may be used as a single layer formed by separately forming a film or by mixing them with other materials to form a film, or may be used as a laminated structure of layers formed by separately forming a film, a laminated structure of layers formed by mixing films, or a laminated structure of layers formed by separately forming a film and layers formed by mixing films. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.
The above-described material having a hole-blocking property can also be used for formation of an electron transport layer described below. That is, by using the known material having a hole-blocking property, a layer which serves as both a hole-blocking layer and an electron-transporting layer can be formed.
The electron transport layer of the organic electroluminescent device of the present invention preferably contains the 2,4, 7-trisubstituted fluorene compound of the present invention. In addition, the compound may be formed using other compounds having an electron-transporting property. For example, Alq can be used3Metal complexes of quinolinol derivatives including BAlq; various metal complexes; a triazole derivative; a triazine derivative; an oxadiazole derivative; a pyridine derivative; bis (10-hydroxybenzo [2 ]H]Quinoline) beryllium (Be (bq)2) (ii) a Such as 2- [4- (9, 10-dinaphthalen-2-anthracen-2-yl) phenyl]-1-phenyl-1HBenzimidazole derivatives such as benzimidazole (ZADN); a thiadiazole derivative; an anthracene derivative; a carbodiimide derivative; quinoxaline derivatives; pyridoindole derivatives; phenanthroline derivatives; silole derivatives and the like. These may be used as a single layer formed by separately forming a film or by mixing them with other materials to form a film, or may be used as a laminated structure of layers formed by separately forming a film, a laminated structure of layers formed by mixing films, or a laminated structure of layers formed by separately forming a film and layers formed by mixing films. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.
As the electron injection layer of the organic electroluminescent device of the present invention, a material known per se can be used. For example, alkali metal salts such as lithium fluoride and cesium fluoride; alkaline earth metal salts such as magnesium fluoride; metal complexes of quinolinol derivatives such as lithium quinolinol; and metal oxides such as alumina.
In the electron injection layer or the electron transport layer, a material obtained by further N-doping a metal such as cesium, a triarylphosphine oxide derivative, or the like can be used as a material generally used for the layer.
As the cathode of the organic electroluminescent device of the present invention, an electrode material having a low work function such as aluminum, magnesium, or an alloy having a low work function such as magnesium-silver alloy, magnesium-indium alloy, aluminum-magnesium alloy is preferably used as the electrode material.
As the substrate of the present invention, a substrate in a conventional organic light emitting device, such as glass or plastic, can be used. In the present invention, a glass substrate is selected.
The production of the compound represented by the above general formula (1), (I) or (II) and the organic electroluminescent device comprising the same will be specifically described in the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.
Example 1: synthesis of Compound 2-1
(Synthesis of Compound M1)
The synthetic route for compound M1 is shown below:
Figure 555827DEST_PATH_IMAGE170
in a 100 mL two-necked flask, 1.6 g (6.2 mmol) of 4-bromo-fluorenone was dissolved in 50 mL of dichloromethane, and the mixture was stirred in an ice bath. 0.67 mL (12.8 mmol) of liquid bromine was added dropwise from a constant pressure dropping funnel. After the addition, the system was gradually warmed to room temperature and reacted for 6 hours. After the reaction is completed, the reaction solution is poured into saturated sodium bisulfite solution, dichloromethane is used for extraction for 3 times, and after an organic phase is dried by anhydrous sodium sulfate, the solvent is removed by rotary drying to obtain a crude product. Crude product petroleum ether: dichloromethane = 5: the eluent of 1 (volume ratio) was separated and purified on a silica gel column to obtain 2.3g M1 with a yield of 90%. Ms (ei): m/z 417.05 [ M+]. Calculated value of elemental analysis C13H5Br3O (%): c37.45, H1.21, N3.84; measured value: c37.41, H1.20, N3.80.
(Synthesis of Compound M2)
The synthetic route for compound M2 is shown below:
Figure 566508DEST_PATH_IMAGE171
sequentially adding the components into a 250 mL two-neck flask8.3 g (20.0 mmol) of M1, 11.0 g (65.0 mmol) of diphenylamine, 9.0 g (87.0 mmol) of sodium tert-butoxide, 0.1 g (0.3 mmol) of tri-tert-butylphosphine tetrafluoroborate and 0.27g (0.3 mmol) of tris (dibenzylideneacetone) dipalladium were added, and after degassing the reaction system, under a nitrogen atmosphere, 150 mL of toluene was added, and the mixture was stirred and heated to reflux for 12 hours. After the reaction is completed, cooling the system to room temperature, carrying out vacuum filtration, washing filter residue with a large amount of dichloromethane, concentrating the filtrate to obtain a crude product, and adding petroleum ether: dichloromethane = 3: 2 (volume ratio) on silica gel column to obtain 11.6 g of yellow solid with 85% yield. Ms (ei): m/z 681.43 [ M+]. Calculated value of elemental analysis C49H35N3O (%): c86.32, H5.17, N6.16; measured value: c86.25, H5.12, N6.15.
(Synthesis of Compound 2-1)
The synthetic route of compound 2-1 is shown below:
Figure 534464DEST_PATH_IMAGE172
to a dry, clean, 250 mL three-necked flask, 2.0g (8.9 mmol) of 2-bromobiphenyl and 150 mL of anhydrous tetrahydrofuran are added under nitrogen and dissolved with stirring at room temperature. The system was cooled to-78 ℃ and 3.9 mL (2.5M, 9.8 mmol) of n-butyllithium were added dropwise at this temperature and stirring continued at this temperature for 1.5 h. 5.5 g (8.1 mmol) of M2 were then added in one portion, the cold bath was removed after addition, the reaction warmed to room temperature by itself and stirring was continued overnight. And after the reaction is finished, washing with water, drying and spin-drying to obtain a white solid.
The white solid was transferred to a 250 mL single-neck flask equipped with a reflux condenser, 100 mL glacial acetic acid was added and heated to reflux, 3 mL concentrated HCl was added dropwise, and the reaction was continued under reflux overnight. After the reaction, the heating was turned off, the reaction mixture was cooled to room temperature, poured into ice water, and filtered to obtain a white solid. The crude product was further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 5: 1 (vol.)) to give 5.6 g of white crystals in yield85%。MS (EI)：m/z 817.78 [M+]. Calculated value of elemental analysis C61H43N3(%): c89.56, H5.30, N5.14; measured value: c89.50, H5.25, N5.14.
The thermogravimetric analysis of compound 2-1 was performed using SDT-2960 type thermogravimetric analysis, and the results are shown in FIG. 1.
Example 2: synthesis of Compounds 2-13
(Synthesis of Compound M3)
The synthetic route for compound M3 is shown below:
Figure 692913DEST_PATH_IMAGE173
to a clean 250 mL three-necked flask were added 4.1 g (10 mmol) of M1, 4.2 g (40 mmol) of anhydrous sodium carbonate, 9.7 g (35 mmol) of 2-boronic acid 4, 6-diphenyl-1, 3, 5-triazine, 115.4 mg (0.1 mmol) of tetrakis (triphenylphosphine) palladium, and 100 mL of a mixed solvent (toluene: water: ethanol = 5: 1: 1 (volume ratio)) in this order under a nitrogen atmosphere, and the system was heated to reflux and reacted overnight under reflux. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200 mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 4: 1 (vol.)) to give 7.4 g of a yellow solid in 85% yield. Ms (ei): m/z 873.59 [ M+]. Calculated value of elemental analysis C58H35N9O (%): c79.71, H4.04, N14.42; measured value: c79.60, H4.01, N14.40.
(Synthesis of Compounds 2 to 13)
The synthetic routes for compounds 2-13 are shown below:
Figure 404517DEST_PATH_IMAGE174
to a dry, clean, 250 mL three-necked flask, 2.0g (8.9 mmol) of 2-bromobiphenyl and 150 mL of anhydrous tetrahydrofuran are added under nitrogen and dissolved with stirring at room temperature. The system was cooled to-78 ℃ and 3.9 mL (2.5M, 9.8 mmol) of n-butyllithium were added dropwise at this temperature and stirring continued at this temperature for 1.5 h. 7.1 g (8.1 mmol) of M3 were then added in one portion, the cold bath was removed after addition, the reaction warmed to room temperature by itself and stirring was continued overnight. And after the reaction is finished, washing with water, drying and spin-drying to obtain a white solid.
The white solid was transferred to a 250 mL single-neck flask equipped with a reflux condenser, 100 mL glacial acetic acid was added and heated to reflux, 3 mL concentrated HCl was added dropwise, and the reaction was continued under reflux overnight. After the reaction, the heating was turned off, the reaction mixture was cooled to room temperature, poured into ice water, and filtered to obtain a white solid. The crude product was further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 5: 1 (vol.)) to give 7.5 g of white crystals with a yield of 84%. MS (EI) M/z 1009.20 [ M ]+]. Calculated value of elemental analysis C70H43N9(%): c83.23, H4.29, N12.48; measured value: c83.20, H4.29, N12.45.
The thermogravimetric curves of compounds 2 to 13 were measured by the SDT-2960 type thermogravimetric analysis, and the results are shown in FIG. 1.
Example 3: synthesis of Compounds 1-23
(Synthesis of Compound M4)
The synthetic route for compound M4 is shown below:
Figure 269705DEST_PATH_IMAGE175
to a clean 250 mL three-necked flask were added 2.6 g (10 mmol) of methyl o-iodobenzoate, 4.2 g (40 mmol) of anhydrous sodium carbonate, 1.9 g (10 mmol) of 2, 4-dichlorophenylboronic acid, 115.4 mg (0.1 mmol) of tetrakis (triphenylphosphine) palladium, and 100 mL of a mixed solvent (toluene: water: ethanol = 5: 1: 1 (volume ratio)) in this order under a nitrogen atmosphere, and the system was heated to reflux and reacted overnight under reflux. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured outInto about 200 mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 2: 3 (vol.)) to obtain 2.6 g of a white liquid with a yield of 95%. Ms (ei): m/z 281.19 [ M+]. Calculated value of elemental analysis C14H10Cl9O2(%): c59.81, H3.59; measured value: c59.75, H3.55.
(Synthesis of Compound M5)
The synthetic route for compound M5 is shown below:
Figure 720147DEST_PATH_IMAGE176
to a dry, clean 25 mL single-neck flask, 2.6 g (9.5 mmol) of M4 and 10 mL of concentrated sulfuric acid were added under nitrogen and slowly heated to 60 ℃ for 3 hours. The system was cooled to room temperature, poured into ice water and filtered to give a yellow solid. The crude product was further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 5: 2 (vol.)) to yield 1.8g of a yellow solid in 76% yield. MS (EI) M/z 249.20 [ M +]. Calculated value of elemental analysis C13H6Cl2O (%): c62.69, H2.43; measured value: c62.60, H2.40.
(Synthesis of Compound M6)
The synthetic route for compound M6 is shown below:
Figure 303575DEST_PATH_IMAGE177
to a clean 250 mL three-necked flask were added 2.0g (8 mmol) of M5, 4.2 g (40 mmol) of anhydrous sodium carbonate, 2.4 g (20 mmol) of phenylboronic acid, 115.4 mg (0.1 mmol) of tetrakis (triphenylphosphine) palladium, and 100 mL of a mixed solvent (toluene: water: ethanol = 5: 1: 1 (volume ratio)) in this order under a nitrogen atmosphere, and the system was heated to reflux and reacted overnight under reflux. After the reaction is finished, stopping heating, and enabling the reaction system to automatically reactAnd cooling to room temperature. The reaction solution was poured into about 200 mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 5: 2 (vol.)) to give 2.5 g of a yellow solid with a yield of 95%. Ms (ei): m/z 332.19 [ M+]. Calculated value of elemental analysis C25H16O (%): c90.33, H4.85; measured value: c90.30, H4.80.
(Synthesis of Compound M7)
The synthetic route for compound M7 is shown below:
Figure 553291DEST_PATH_IMAGE178
in a 100 mL three-neck flask with a reflux condenser tube and a dropping funnel, 0.5 g (3.0 mmol) of iodine simple substance and 50 mL of glacial acetic acid are added under the protection of nitrogen, stirred and dissolved, about 1.9 g (15.0 mmol) of hypophosphorous acid is added, and the temperature is raised to 120 ℃ to react until the system color is faded. 2.5 g (7.6 mmol) of M6 were then added in one portion and after further heating under reflux for 4 h, cooled to room temperature, poured into water to precipitate a large amount of white solid, filtered, washed with water and dried to give 2.2g of white crystalline solid in 92% yield. Ms (ei): m/z 318.48 [ M+]. Calculated value of elemental analysis C25H18(%): c94.30, H5.70; measured value: c94.25 and H5.70.
(Synthesis of Compound M8)
The synthetic route for compound M8 is shown below:
Figure 600881DEST_PATH_IMAGE179
2.2g (7.0 mmol) of the M7 solid are transferred into a 100 mL three-necked flask equipped with a dropping funnel, 30 mL of tetrahydrofuran are added under nitrogen, dissolved with stirring and cooled in an ice-water bath. 2.0g (20.8 mmol) of sodium tert-butoxide was added while cooling on ice, and after stirring for 10 min while maintaining this temperature, 3.0 g (21.0 mmol) of methyl iodide was added. The system is continuously stirred for 30 minThe ice bath was removed and the system allowed to warm to room temperature on its own and the reaction was continued at room temperature overnight. After the reaction, insoluble matter was removed by suction filtration, and the filtrate was concentrated and purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 10: 1 (volume ratio)) to obtain 2.3g of a white solid with a yield of 95%. Ms (ei): m/z 346.48 [ M+]. Calculated value of elemental analysis C27H22(%): c93.60, H6.40; measured value: c93.55, H6.36.
(Synthesis of Compound M9)
The synthetic route for compound M9 is shown below:
Figure 910640DEST_PATH_IMAGE180
in a 100 mL two-necked flask, 2.3g (6.6 mmol) of M8 in 50 mL of dichloromethane was stirred in an ice bath. 0.44 mL (8.5 mmol) of liquid bromine was added dropwise from a constant pressure dropping funnel. After the addition, the system was gradually warmed to room temperature and reacted for 6 hours. After the reaction is completed, the reaction solution is poured into saturated sodium bisulfite solution, dichloromethane is used for extraction for 3 times, and after an organic phase is dried by anhydrous sodium sulfate, the solvent is removed by rotary drying to obtain a crude product. Crude product petroleum ether: dichloromethane = 10: 1 (volume ratio) on silica gel column to obtain 2.7g of white solid with 96% yield. Ms (ei): m/z 425.05 [ M+]. Calculated value of elemental analysis C27H21Br (%): c76.24, H4.98; measured value: c76.20, H4.95.
(Synthesis of Compounds 1 to 23)
The synthetic routes for compounds 1-23 are shown below:
Figure 794413DEST_PATH_IMAGE181
to a clean 250 mL three-necked flask, 2.8 g (6.6 mmol) of M9, 4.2 g (40 mmol) of anhydrous sodium carbonate, 2.4 g (8.0 mmol) of (10-phenylanthracen-9-yl) boronic acid, 115.4 mg (0.1 mmol) of tetrakis (triphenylphosphine) palladium, and 100 mL of a mixed solvent were added in this order under nitrogen(toluene: water: ethanol = 5: 1: 1 (volume ratio)), the system was warmed to reflux and reacted overnight under reflux. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200 mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 5: 2 (vol.)) to give 3.4 g of a green solid in 85% yield. Ms (ei): m/z 598.19 [ M+]. Calculated value of elemental analysis C47H34(%): c94.28, H5.72; measured value: c95.20, H5.70.
Example 4: synthesis of Compounds 1-47
(Synthesis of Compounds 1 to 47)
The synthetic routes for compounds 1-47 are shown below:
Figure 847820DEST_PATH_IMAGE182
to a clean 250 mL three-necked flask were added 2.8 g (6.6 mmol) of M9, 4.2 g (40 mmol) of anhydrous sodium carbonate, 3.1 g (8.0 mmol) of 4,4,5, 5-tetramethyl-2- (10- (phenyl-d 5) anthracen-9-yl) -1,3, 2-dioxaborane, 115.4 mg (0.1 mmol) of tetrakis (triphenylphosphine) palladium, and 100 mL of a mixed solvent (toluene: water: ethanol = 5: 1: 1 (volume ratio)) in this order under nitrogen, the system was warmed to reflux and reacted overnight under reflux. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200 mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 5: 2 (vol.)) to give 3.4 g of a green solid in 85% yield. Ms (ei): m/z 603.19 [ M+]. Calculated value of elemental analysis C47H29D5(%): c93.49, H6.51; measured value: c93.40, H6.50.
Example 5: synthesis of Compounds 1-46
(Synthesis of Compound M10)
The synthetic route for compound M10 is shown below:
Figure 687600DEST_PATH_IMAGE183
to a clean 250 mL three-necked flask were added 2.0g (8 mmol) of M5, 4.2 g (40 mmol) of anhydrous sodium carbonate, 2.5 g (20 mmol) of deuterated phenylboronic acid, 115.4 mg (0.1 mmol) of tetrakis (triphenylphosphine) palladium, and 100 mL of a mixed solvent (toluene: water: ethanol = 5: 1: 1 (volume ratio)) in this order under a nitrogen atmosphere, and the system was heated to reflux and reacted overnight under reflux. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200 mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 5: 2 (vol.)) to give 2.6 g of a yellow solid with a yield of 95%. Ms (ei): m/z 342.19 [ M+]. Calculated value of elemental analysis C25H6D10O (%): c87.68, H7.65; measured value: c87.60, H7.60.
(Synthesis of Compound M11)
The synthetic route for compound M11 is shown below:
Figure 230577DEST_PATH_IMAGE184
in a 100 mL three-neck flask with a reflux condenser tube and a dropping funnel, 0.5 g (3.0 mmol) of iodine simple substance and 50 mL of glacial acetic acid are added under the protection of nitrogen, stirred and dissolved, about 1.9 g (15.0 mmol) of hypophosphorous acid is added, and the temperature is raised to 120 ℃ to react until the system color is faded. 2.6 g (7.6 mmol) of M10 was added in one portion, and after further heating and refluxing for 4 h, it was cooled to room temperature, poured into water to precipitate a large amount of white solid, filtered, washed with water and dried to give 2.3g of white solid in 92% yield. Ms (ei): m/z 328.48 [ M+]. Calculated value of elemental analysis C25H8D10 (%)：C 91.41，H 8.59(ii) a Measured value: c91.35, H8.55.
(Synthesis of Compound M12)
The synthetic route for compound M12 is shown below:
Figure 523018DEST_PATH_IMAGE185
2.3g (7.0 mmol) of the M11 solid are transferred into a 100 mL three-necked flask equipped with a dropping funnel, 30 mL of tetrahydrofuran are added under nitrogen, dissolved with stirring and cooled in an ice-water bath. 2.0g (20.8 mmol) of sodium tert-butoxide was added while cooling on ice, and after stirring for 10 min while maintaining this temperature, 3.0 g (21.0 mmol) of methyl iodide was added. The system was stirred for 30 min and then the ice bath was removed, the system allowed to warm to room temperature and the reaction continued overnight at room temperature. After the reaction, insoluble matter was removed by suction filtration, and the filtrate was concentrated and purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 10: 1 (volume ratio)) to obtain 2.4 g of a white solid with a yield of 95%. Ms (ei): m/z 356.48 [ M+]. Calculated value of elemental analysis C27H12D10(%): c90.96, H9.04; measured value: c90.80, H9.01.
(Synthesis of Compound M13)
The synthetic route for compound M13 is shown below:
Figure 380116DEST_PATH_IMAGE186
in a 100 mL two-necked flask, 2.4 g (6.6 mmol) of M12 in 50 mL of dichloromethane was stirred in an ice bath. 0.44 mL (8.5 mmol) of liquid bromine was added dropwise from a constant pressure dropping funnel. After the addition, the system was gradually warmed to room temperature and reacted for 6 hours. After the reaction is completed, the reaction solution is poured into saturated sodium bisulfite solution, dichloromethane is used for extraction for 3 times, and after an organic phase is dried by anhydrous sodium sulfate, the solvent is removed by rotary drying to obtain a crude product. Crude product petroleum ether: dichloromethane = 10: 1 (volume ratio) on silica gel column to obtain 2.9 g of white solid with 96% yield. Ms (ei):m/z 435.05 [M+]. Calculated value of elemental analysis C27H11D10Br (%): c74.48, H7.17; measured value: c74.47, H7.17.
(Synthesis of Compounds 1 to 46)
The synthetic routes for compounds 1-46 are shown below:
Figure 385987DEST_PATH_IMAGE187
to a clean 250 mL three-necked flask were added 2.9 g (6.6 mmol) of M13, 4.2 g (40 mmol) of anhydrous sodium carbonate, 2.4 g (8.0 mmol) of (10-phenylanthracen-9-yl) boronic acid, 115.4 mg (0.1 mmol) of tetrakis (triphenylphosphine) palladium, and 100 mL of a mixed solvent (toluene: water: ethanol = 5: 1: 1 (volume ratio)) in this order under a nitrogen atmosphere, and the system was heated to reflux and reacted overnight under reflux. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200 mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 5: 2 (vol.)) to give 3.5 g of a green solid with a yield of 85%. Ms (ei): m/z 608.19 [ M+]. Calculated value of elemental analysis C47H24D10(%): c92.72, H7.28; measured value: c92.70, H7.25.
Example 6: synthesis of Compounds 1-5
(Synthesis of Compound M14)
The synthetic route for compound M14 is shown below:
Figure 37548DEST_PATH_IMAGE188
a250 mL two-necked flask was charged with 8.3 g (20.0 mmol) of M1, 16.5 g (65.0 mmol) of pinacol diboron, 8.5 g (87.0 mmol) of potassium acetate, and 0.22 g (0.3 mmol) of DPPF palladium dichloride in this order, the reaction system was degassed, 150 mL of dioxane was added under nitrogen protection, and the mixture was stirredThe reaction was heated to reflux for 12 hours. After the reaction is completed, cooling the system to room temperature, carrying out vacuum filtration, washing filter residue with a large amount of dichloromethane, concentrating the filtrate to obtain a crude product, and adding petroleum ether: dichloromethane = 2: 3 vol% of eluent was applied to a silica gel column for separation and purification to obtain 8.4 g of yellow solid with a yield of 75%. Ms (ei): m/z 558.43 [ M+]. Calculated value of elemental analysis C31H41B3O7(%): c66.72, H7.41; measured value: c66.70, H7.40.
(Synthesis of Compound M15)
The synthetic route for compound M15 is shown below:
Figure 82864DEST_PATH_IMAGE189
to a clean 250 mL three-necked flask, 5.6 g (10 mmol) of M14, 4.2 g (40 mmol) of anhydrous sodium carbonate, 8.5 g (33 mmol) of 3-bromo-1, 10-phenanthroline, 115.4 mg (0.1 mmol) of tetrakis (triphenylphosphine) palladium, and 100 mL of a mixed solvent (toluene: water: ethanol = 5: 1: 1 (volume ratio)) were sequentially added under nitrogen, and the system was heated to reflux and reacted overnight under reflux. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200 mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 1: 3 (vol.)) to give 2.5 g of an orange-yellow solid with a yield of 34%. Ms (ei): m/z 714.59 [ M+]. Calculated value of elemental analysis C49H26N6O (%): c82.34, H3.67, N11.76; measured value: c82.20, H3.65, N11.70.
(Synthesis of Compound M16)
The synthetic route for compound M16 is shown below:
Figure 540390DEST_PATH_IMAGE190
in a 100 mL three-neck flask with a reflux condenser tube and a dropping funnel, 0.5 g (3.0 mmol) of iodine simple substance and 50 mL of glacial acetic acid are added under the protection of nitrogen, stirred and dissolved, about 1.9 g (15.0 mmol) of hypophosphorous acid is added, and the temperature is raised to 120 ℃ to react until the system color is faded. Then, 5.4 g (7.6 mmol) of M15 was added in one portion, and after further heating and refluxing for 4 hours, it was cooled to room temperature, poured into water to precipitate a large amount of white solid, filtered, washed with water and dried to obtain 4.8g of white solid with a yield of 92%. Ms (ei): m/z 700.48 [ M+]. Calculated value of elemental analysis C49H28N6(%): c83.98, H4.03, N11.99; measured value: c83.90, H4.01, N11.90.
(Synthesis of Compounds 1 to 5)
The synthetic routes for compounds 1-5 are shown below:
Figure 89183DEST_PATH_IMAGE191
4.9 g (7.0 mmol) of the M16 solid are transferred into a 100 mL three-necked flask equipped with a dropping funnel, 30 mL of tetrahydrofuran are added under nitrogen, dissolved with stirring and cooled in an ice-water bath. 2.0g (20.8 mmol) of sodium tert-butoxide was added while cooling on ice, and after stirring for 10 min while maintaining this temperature, 3.0 g (21.0 mmol) of methyl iodide was added. The system was stirred for 30 min and then the ice bath was removed, the system allowed to warm to room temperature and the reaction continued overnight at room temperature. After the reaction, insoluble matter was removed by suction filtration, and the filtrate was concentrated and purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 5: 1 (volume ratio)) to obtain 4.8g of a white solid with a yield of 95%. Ms (ei): m/z 728.48 [ M+]. Calculated value of elemental analysis C51H32N6(%): c84.04, H4.43, N11.53; measured value: c84.00, H4.40, N11.50.
Example 7: synthesis of Compounds 1-50
(Synthesis of Compound M17)
The synthetic route for compound M17 is shown below:
Figure 990274DEST_PATH_IMAGE192
to a clean 250 mL three-necked flask were added 2.6 g (10 mmol) of methyl o-iodobenzoate, 4.2 g (40 mmol) of anhydrous sodium carbonate, 2.2g (10 mmol) of 4-bromo-2-fluorobenzeneboronic acid, 115.4 mg (0.1 mmol) of tetrakis (triphenylphosphine) palladium, and 100 mL of a mixed solvent (toluene: water: ethanol = 5: 1: 1 (volume ratio)) in this order under a nitrogen atmosphere, and the system was heated to reflux and reacted overnight under reflux. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200 mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 2: 3 (vol.)) to obtain 2.5 g of a white liquid with a yield of 80%. Ms (ei): m/z 309.19 [ M+]. Calculated value of elemental analysis C14H10BrFO2(%): c54.40, H3.26; measured value: c54.30, H3.22.
(Synthesis of Compound M18)
The synthetic route for compound M18 is shown below:
Figure 257308DEST_PATH_IMAGE193
to a dry, clean 25 mL single-neck flask, 2.5 g (8.0 mmol) of M17 and 30 mL of concentrated sulfuric acid were added under nitrogen and slowly heated to 60 ℃ for 3 hours. The system was cooled to room temperature, poured into ice water and filtered to give a yellow solid. The crude product was further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 5: 2 (vol.)) to give 1.6 g of a yellow solid in 70% yield. MS (EI) M/z 277.20 [ M +]. Calculated value of elemental analysis C13H6BrFO (%): c56.35, H2.18; measured value: c56.30, H2.15.
(Synthesis of Compound M19)
The synthetic route for compound M19 is shown below:
Figure 456208DEST_PATH_IMAGE194
in a 100 mL three-neck flask with a reflux condenser tube and a dropping funnel, 0.5 g (3.0 mmol) of iodine simple substance and 50 mL of glacial acetic acid are added under the protection of nitrogen, stirred and dissolved, about 1.9 g (15.0 mmol) of hypophosphorous acid is added, and the temperature is raised to 120 ℃ to react until the system color is faded. 2.1 g (7.6 mmol) of M18 were then added in one portion and the mixture was heated under reflux for 4 h, cooled to room temperature, poured into water to precipitate a large amount of white solid, filtered, washed with water and dried to give 1.8g of white crystalline solid in 92% yield. Ms (ei): m/z 263.48 [ M+]. Calculated value of elemental analysis C13H8BrF (%): c59.35, H3.06; measured value: c59.30, H3.00.
(Synthesis of Compound M20)
The synthetic route of compound M20 is shown below:
Figure 921824DEST_PATH_IMAGE195
1.8g (7.0 mmol) of the above M19 was transferred into a 100 mL three-necked flask equipped with a dropping funnel, 30 mL of tetrahydrofuran was added under nitrogen, dissolved with stirring, and cooled with an ice-water bath. 2.0g (20.8 mmol) of sodium tert-butoxide was added while cooling on ice, and after stirring for 10 min while maintaining this temperature, 3.0 g (21.0 mmol) of methyl iodide was added. The system was stirred for 30 min and then the ice bath was removed, the system allowed to warm to room temperature and the reaction continued overnight at room temperature. After the reaction, insoluble matter was removed by suction filtration, and the filtrate was concentrated and purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 10: 1 (volume ratio)) to obtain 1.9 g of a white solid with a yield of 95%. Ms (ei): m/z 290.48 [ M+]. Calculated value of elemental analysis C15H12BrF (%): c61.88, H4.15; measured value: c61.80, H4.12.
(Synthesis of Compound M21)
The synthetic route of compound M21 is shown below:
Figure 180767DEST_PATH_IMAGE196
in a 250 mL two-necked flask, 5.8 g (20.0 mmol) of M20, 5.3 g (22.0 mmol) of pinacol diboron, 4.7 g (43.5 mmol) of potassium acetate, and 0.22 g (0.3 mmol) of DPPF palladium dichloride were sequentially charged, and after degassing the reaction system, 150 mL of dioxane was added under nitrogen protection, and the mixture was stirred and heated to reflux for 12 hours. After the reaction is completed, cooling the system to room temperature, carrying out vacuum filtration, washing filter residue with a large amount of dichloromethane, concentrating the filtrate to obtain a crude product, and adding petroleum ether: dichloromethane = 3: 2 (volume ratio) of eluent on silica gel column to obtain 5.8 g of white solid with 85% yield. Ms (ei): m/z 338.43 [ M+]. Calculated value of elemental analysis C21H24BFO2(%): c74.57, H7.15; measured value: c74.50, H7.10.
(Synthesis of Compound M22)
The synthetic route for compound M22 is shown below:
Figure 935097DEST_PATH_IMAGE197
to a clean 250 mL three-necked flask were added 3.4 g (10 mmol) of M21, 4.2 g (40 mmol) of anhydrous sodium carbonate, 3.5 g (13 mmol) of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine, 115.4 mg (0.1 mmol) of tetrakis (triphenylphosphine) palladium, and 100 mL of a mixed solvent (toluene: water: ethanol = 5: 1: 1 (volume ratio)) in this order under a nitrogen atmosphere, and the system was heated to reflux and reacted overnight under reflux. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200 mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 6: 1 (vol.)) to obtain 3.5 g of a white solid with a yield of 80%. Ms (ei): m/z 443.59 [ M+]. Calculated value of elemental analysis C30H22FN3(%): c81.24, H5.00, N9.47; measured value: c80.20, H5.00, N9.46.
(Synthesis of Compound M23)
The synthetic route for compound M23 is shown below:
Figure 983693DEST_PATH_IMAGE198
in a 100 mL two-necked flask, 2.4 g (6.6 mmol) of M22 in 50 mL of dichloromethane was stirred in an ice bath. 0.44 mL (8.5 mmol) of liquid bromine was added dropwise from a constant pressure dropping funnel. After the addition, the system was gradually warmed to room temperature and reacted for 6 hours. After the reaction is completed, the reaction solution is poured into saturated sodium bisulfite solution, dichloromethane is used for extraction for 3 times, and after an organic phase is dried by anhydrous sodium sulfate, the solvent is removed by rotary drying to obtain a crude product. Crude product petroleum ether: dichloromethane = 6: 1 (volume ratio) on silica gel column to obtain 2.8 g of white solid with 90% yield. Ms (ei): m/z 522.05 [ M+]. Calculated value of elemental analysis C30H21BrFN3(%): c68.97, H4.05, N8.04; measured value: c68.90, H4.02, N8.00.
(Synthesis of Compound M24)
The synthetic route for compound M24 is shown below:
Figure 507078DEST_PATH_IMAGE199
to a clean 250 mL three-necked flask, 4.2 g (8 mmol) of M23, 4.2 g (40 mmol) of anhydrous sodium carbonate, 2.4 g (20 mmol) of phenylboronic acid, 115.4 mg (0.1 mmol) of tetrakis (triphenylphosphine) palladium, and 100 mL of a mixed solvent (toluene: water: ethanol = 5: 1: 1 (volume ratio)) were sequentially added under nitrogen, and the system was heated to reflux and reacted overnight under reflux. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200 mL of water and extracted with dichloromethane. The organic phase is dried over anhydrous sodium sulfate, concentrated under reduced pressure and purified by column chromatographyAfter step purification (350 mesh silica gel, eluent petroleum ether: dichloromethane = 5: 1 (volume ratio)) 3.9 g of white solid was obtained, yield 95%. Ms (ei): m/z 519.19 [ M+]. Calculated value of elemental analysis C36H26FN3(%): c83.21, H5.04, N8.09; measured value: c83.10, H5.00, N8.05.
(Synthesis of Compounds 1 to 50)
The synthetic routes for compounds 1-50 are shown below:
Figure 936922DEST_PATH_IMAGE200
to a dry, clean 250 mL three-necked flask were added, in order, 6.2 g (12 mmol) of Compound M24, 4.3 g (15 mmol) of 5, 7-dihydro-7, 7-dimethyl-indeno [2,1-B]Carbazole and 16.3 g (50 mmol) of cesium carbonate. The system was back and forth replaced with nitrogen three times to remove air therefrom. Adding 150 mL ofN-methyl pyrrolidone, gradually warmed to 180%oC, and reacting at the temperature overnight. After the reaction is cooled, inorganic salt is removed by suction filtration, and the residue is obtained after the filtrate is distilled under reduced pressure. The crude product was further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 4: 1 (vol.)) to give 7.5 g of a green solid with a yield of 80%. Ms (ei): m/z 783.03 [ M+]. Calculated value of elemental analysis C57H42N4(%): c87.44, H5.41, N7.16; measured value: c87.40, H5.40, N7.12.
Example 8: synthesis of Compounds 1-66
(Synthesis of Compound M25)
The synthetic route for compound M25 is shown below:
Figure 975286DEST_PATH_IMAGE201
to a clean 250 mL three-necked flask, under nitrogen, were added 3.4 g (10 mmol) of M22, 4.2 g (40 mmol) of anhydrous sodium carbonate, 3.1 g (13 mmol) of 2-chloro-4-phenylquinazoline, and 115.4 mg (0.1 mmol)Tetrakis (triphenylphosphine) palladium and 100 mL of a mixed solvent (toluene: water: ethanol = 5: 1: 1 (volume ratio)), the system was warmed to reflux and reacted overnight in a refluxed state. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200 mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 6: 1 (vol.)) to obtain 3.3 g of a white solid with a yield of 80%. Ms (ei): m/z 416.59 [ M+]. Calculated value of elemental analysis C29H21FN2(%): c83.63, H5.08, N6.73; measured value: c83.60, H5.00, N6.70.
(Synthesis of Compound M26)
The synthetic route for compound M26 is shown below:
Figure 515988DEST_PATH_IMAGE202
in a 100 mL two-necked flask, 2.7g (6.6 mmol) of M25 in 50 mL of dichloromethane was stirred in an ice bath. 0.44 mL (8.5 mmol) of liquid bromine was added dropwise from a constant pressure dropping funnel. After the addition, the system was gradually warmed to room temperature and reacted for 6 hours. After the reaction is completed, the reaction solution is poured into saturated sodium bisulfite solution, dichloromethane is used for extraction for 3 times, and after an organic phase is dried by anhydrous sodium sulfate, the solvent is removed by rotary drying to obtain a crude product. Crude product petroleum ether: dichloromethane = 6: 1 (volume ratio) on silica gel column to obtain 2.9 g of white solid with 90% yield. Ms (ei): m/z 494.05 [ M+]. Calculated value of elemental analysis C29H20BrFN2(%): c70.31, H4.07, N5.65; measured value: c70.25, H4.02, N5.62.
(Synthesis of Compound M27)
The synthetic route for compound M27 is shown below:
Figure 159459DEST_PATH_IMAGE203
to a clean 250 mL three-necked flask, 4.0 g (8 mmol) of M26, 4.2 g (40 mmol) of anhydrous sodium carbonate, 2.4 g (20 mmol) of phenylboronic acid, 115.4 mg (0.1 mmol) of tetrakis (triphenylphosphine) palladium, and 100 mL of a mixed solvent (toluene: water: ethanol = 5: 1: 1 (volume ratio)) were sequentially added under nitrogen, and the system was heated to reflux and reacted overnight under reflux. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200 mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 5: 1 (vol.)) to obtain 3.7 g of a white solid with a yield of 95%. Ms (ei): m/z 492.19 [ M+]. Calculated value of elemental analysis C35H25FN2(%): c85.34, H5.12, N5.69; measured value: c85.30, H5.10, N5.65.
(Synthesis of Compounds 1-66)
The synthetic routes for compounds 1-66 are shown below:
Figure 307675DEST_PATH_IMAGE204
to a dry, clean 250 mL three-necked flask were added 5.9 g (12 mmol) of Compound M27, followed by 4.3 g (15 mmol) of 5, 7-dihydro-7, 7-dimethyl-indeno [2,1-B]Carbazole and 16.3 g (50 mmol) of cesium carbonate. The system was back and forth replaced with nitrogen three times to remove air therefrom. Adding 150 mL ofN-methyl pyrrolidone, gradually warmed to 180%oC, and reacting at the temperature overnight. After the reaction is cooled, inorganic salt is removed by suction filtration, and the residue is obtained after the filtrate is distilled under reduced pressure. The crude product was further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 3: 1 (vol.)) to give 7.5 g of an orange solid with a yield of 80%. Ms (ei): m/z 755.03 [ M+]. Calculated value of elemental analysis C56H41N3(%): c88.97, H5.47, N5.56; measured value: c88.90, H5.40, N5.52.
Example 9: synthesis of Compound 6-1
(Synthesis of Compound 6-1)
The synthetic route of compound 6-1 is shown below:
Figure 36597DEST_PATH_IMAGE205
6.8 g (10 mmol) of M2, 3.7 g (40 mmol) of phenol and 32 mL of methanesulfonic acid were added in this order to a clean 250 mL three-necked flask under nitrogen, and the temperature of the system was raised to 140%oC and reacting under the condition overnight. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200 mL of water, and the crude product was obtained by suction filtration and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 1: 1 (volume ratio)) to obtain 6.5 g of a white solid with a yield of 78%. Ms (ei): m/z 833.59 [ M+]. Calculated value of elemental analysis C61H43N3O (%): c87.85, H5.20, N5.04; measured value: c87.60, H5.15, N4.99.
Example 10: synthesis of Compounds 6-11
(Synthesis of Compounds 6 to 11)
The synthetic route for compounds 6-11 is shown below:
Figure 177728DEST_PATH_IMAGE206
7.8 g (9 mmol) of M3, 3.7 g (36 mmol) of phenol and 25 mL of methanesulfonic acid were added in this order to a clean 250 mL three-necked flask under nitrogen, and the temperature of the system was raised to 140oC and reacting under the condition overnight. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200 mL of water, and the crude product was obtained by suction filtration and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 2: 1 (vol.)) to obtain 6.9 g of a green solid with a yield of 75%. Ms (ei): m/z 1025.59 [ M+]. Calculated value of elemental analysis C70H43N9O (%): c81.93, H4.22, N12.28; measured value: c81.80, H4.15, N12.25.
Example 11: synthesis of Compounds 1-39
(Synthesis of Compound M28)
The synthetic route for compound M28 is shown below:
Figure 675705DEST_PATH_IMAGE207
to a dry, clean 25 mL single-neck flask were added 2.0g (8.5 mmol) of 2-bromo-5-chlorobenzoic acid, 0.27g (8.5 mmol) of methanol and 1.3 mL of concentrated sulfuric acid and slowly heated to 65 ℃ for 3 hours. The system was cooled to room temperature, poured into ice water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 3: 2 (vol.)) to give 2.0g of a colorless liquid with a yield of 94%. Ms (ei): m/z 247.90 [ M+]. Calculated value of elemental analysis C8H6BrClO2(%): c38.51, H2.42; measured value: c38.50, H2.40.
(Synthesis of Compound M29)
The synthetic route for compound M29 is shown below:
Figure 181773DEST_PATH_IMAGE208
to a clean 100 mL three-necked flask, 2.5 g (12.2 mmol) of M28, 3.2 g (30.0 mmol) of anhydrous sodium carbonate, 1.7 g (11.0 mmol) of 2-chlorobenzeneboronic acid, 58.0 mg (0.05 mmol) of tetrakis (triphenylphosphine) palladium and 45mL of a mixed solvent (1, 4-dioxane: water = 10: 1 (volume ratio)) were sequentially added under nitrogen, and the system was heated to reflux and reacted overnight under reflux. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200 mL of water and extracted with dichloromethane. The organic phase is dried over anhydrous sodium sulfate, concentrated under reduced pressure and further purified by column chromatography(350 mesh silica gel, eluent petroleum ether: dichloromethane = 3: 2 (vol.)) gave 3.2 g of a colorless liquid in a yield of 93%. Ms (ei): m/z 281.03 [ M+]. Calculated value of elemental analysis C14H10Cl2O2(%): c59.81, H3.59; measured value: c59.75, H3.55.
(Synthesis of Compound M30)
The synthetic route for compound M30 is shown below:
Figure 709575DEST_PATH_IMAGE209
to a dry, clean 25 mL single neck flask were added 2.0g (7.1 mmol) of M29 and 10 mL concentrated sulfuric acid and slowly heated to 65 deg.C for 3 hours. The system was cooled to room temperature, poured into ice water and filtered to give a yellow solid. The crude product was further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 5: 2 (vol.)) to give 1.3 g of a yellow solid in 73% yield. Ms (ei): m/z 249.28 [ M+]. Calculated value of elemental analysis C13H6Cl2O (%): c62.69, H2.43; measured value: c62.65, H2.40.
(Synthesis of Compound M31)
The synthetic route for compound M31 is shown below:
Figure 592081DEST_PATH_IMAGE210
to a clean 100 mL three-necked flask were added 3.0 g (12.0 mmol) of M30, 3.8 g (36.1 mmol) of anhydrous sodium carbonate, 3.2 g (26.5 mmol) of phenylboronic acid, 115.4 mg (0.1 mmol) of tetrakis (triphenylphosphine) palladium, and 45mL of a mixed solvent (toluene: water: ethanol = 30: 8: 7 (volume ratio)) in this order under a nitrogen atmosphere, and the system was heated to reflux and reacted overnight under reflux. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200 mL of water and extracted with dichloromethane. The organic phase is dried over anhydrous sodium sulfate, concentrated under reduced pressure, andfurther purification by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 5: 2 (vol.)) gave 3.3 g of yellow solid in 83% yield. Ms (ei): m/z 332.20 [ M+]. Calculated value of elemental analysis C25H16O (%): c90.33, H4.85; measured value: c90.30, H4.80.
(Synthesis of Compound M32)
The synthetic route for compound M32 is shown below:
Figure 944565DEST_PATH_IMAGE211
under the protection of nitrogen, 1.0 g (6.0 mmol) of iodine simple substance and 50 mL of glacial acetic acid are added into a 100 mL three-necked bottle provided with a reflux condenser tube and a dropping funnel, stirred and dissolved, about 3.8 g (30.0 mmol) of hypophosphorous acid is added, and the temperature is raised to 100 ℃ to react until the system color is faded. Then 5.0 g (15.2 mmol) of M31 was added in one portion, the temperature was raised to 120 ℃ for reaction, heating and refluxing were continued for 4 h, then cooling to room temperature, pouring into water to precipitate a large amount of white solid, filtering, washing with water, and drying to obtain 4.4 g of white crystalline solid with a yield of 92%. Ms (ei): m/z 318.24 [ M+]. Calculated value of elemental analysis C25H18(%): c94.30, H5.70; measured value: c94.20, H5.65.
(Synthesis of Compound M33)
The synthetic route for compound M33 is shown below:
Figure 949430DEST_PATH_IMAGE212
3.0 g (9.4 mmol) of M32 were transferred to a 100 mL three-necked flask, 40 mL of tetrahydrofuran were added under nitrogen, dissolved with stirring, and cooled with an ice-water bath. While cooling on ice, 2.7g (28.3 mmol) of sodium tert-butoxide was added, and after stirring at this temperature for a further 15 min, 4.0 g (28.3 mmol) of methyl iodide were added. After stirring the system for 30 min, the ice bath was removed and the system was allowed to warm to room temperature and allowed to react at room temperature overnight. After the reaction, insoluble matter was removed by suction filtrationAfter the filtrate was concentrated, the filtrate was purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 10: 1 (volume ratio)) to obtain 3.0 g of a white solid with a yield of 92%. Ms (ei): m/z 346.27 [ M+]. Calculated value of elemental analysis C27H22(%): c93.60, H6.40; measured value: c93.50, H6.35.
(Synthesis of Compound M34)
The synthetic route for compound M34 is shown below:
Figure 387364DEST_PATH_IMAGE213
a100 mL two-necked flask was charged with 2.2g (6.3 mmol) of M33 and 50 mL of methylene chloride, and the mixture was stirred in an ice bath with exclusion of light. 0.42 mL (8.2 mmol) of liquid bromine was added dropwise from a constant pressure dropping funnel. After the addition, the system was gradually warmed to room temperature and reacted for 6 hours. After the reaction is completed, the reaction solution is poured into saturated sodium bisulfite solution, dichloromethane is used for extraction for 3 times, and after an organic phase is dried by anhydrous sodium sulfate, the solvent is removed by spin drying to obtain a crude product. Crude product petroleum ether: dichloromethane = 10: 1 (volume ratio) on silica gel column to obtain 2.7g of white solid with 96% yield. Ms (ei): m/z 425.32 [ M+]. Calculated value of elemental analysis C27H21Br (%): c76.24, H4.98; measured value: c76.20, H4.95.
(Synthesis of Compound M35)
The synthetic route for compound M35 is shown below:
Figure 621031DEST_PATH_IMAGE214
into a 250 mL two-necked flask were charged 4.0 g (9.4 mmol) of M34, 5 g (10.8 mmol) of pinacol diboron, 2.8 g (28.2 mmol) of potassium acetate, and 80.0 mg (0.1 mmol) of Pd (dppf) Cl in this order2After the reaction system was degassed, 150 mL of dioxane was added under nitrogen protection, and the mixture was stirred and heated to reflux for 12 hours. After the reaction is completed, the system is cooledCooling to room temperature, carrying out suction filtration under reduced pressure, washing filter residues with a large amount of dichloromethane, concentrating the filtrate to obtain a crude product, and reacting the crude product with petroleum ether: dichloromethane = 3: 2 (volume ratio) of eluent on silica gel column to obtain 3.5 g of white solid with 79% of yield. Ms (ei): m/z 472.40 [ M+]. Calculated value of elemental analysis C33H33BO2(%): c83.90, H7.04; measured value: c83.80, H7.00.
(Synthesis of Compounds 1-39)
The synthetic routes for compounds 1-39 are shown below:
Figure 93600DEST_PATH_IMAGE215
to a clean 100 mL three-necked flask, 2.8 g (5.9 mmol) of M35, 1.7 g (16.0 mmol) of anhydrous sodium carbonate, 1.8g (5.3 mmol) of 9- (deuterated phenyl-d 5) -10-bromoanthracene, 68.5 mg (0.06 mmol) of tetrakis (triphenylphosphine) palladium, and 45mL of a mixed solvent (toluene: water: ethanol = 30: 8: 7 (volume ratio)) were sequentially added under nitrogen, and the system was heated to reflux and reacted overnight under reflux. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200 mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 5: 2 (vol.)) to give 3.0 g of a green solid in 84% yield. Ms (ei): m/z 603.75 [ M+]. Calculated value of elemental analysis C47H29D5(%): c93.49, H6.51; measured value: c93.40, H6.45.
Example 12: synthesis of Compounds 1-132
(Synthesis of Compound M36)
The synthetic route for compound M36 is shown below:
Figure 941471DEST_PATH_IMAGE216
5.0 g (19.5 mmol) of 9-bromoanthracene, 1.7 g (12.3 mmol) of anhydrous potassium carbonate, and 4.3 g (20.4 mmol) of dibenzo [ b, d ] in that order were placed in a clean 250 mL three-necked flask under nitrogen]Furan-4-ylboronic acid, 112.4 mg (0.1 mmol) of tetrakis (triphenylphosphine) palladium, and 90 mL of a mixed solvent (toluene: water: ethanol = 30: 8: 7 (volume ratio)), the system was warmed to reflux, and reacted under reflux overnight. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200 mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 4: 1 (vol.)) to give 6.0 g of a yellow solid with a yield of 90%. Ms (ei): m/z 344.64 [ M+]. Calculated value of elemental analysis C26H16O (%): c90.67, H4.68; measured value: c90.65, H4.60.
(Synthesis of Compound M37)
The synthetic route for compound M37 is shown below:
Figure 929018DEST_PATH_IMAGE217
to a clean 250 mL single neck flask were added 2.5 g (5.9 mmol) of M36 and 80 mL of dichloromethane, stirred in ice bath away from light, and 1.86 g (10.45 mmol) of NBS (added in three portions, 0.5 eq for the first, 0.5 eq for the second, and 0.2 eq for the third) was added, after completion of the reaction, the reaction was poured into about 100 mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 5: 1 (vol.)) to give 3.4 g of a yellow solid in 92% yield. Ms (ei): m/z 423.45 [ M+]. Calculated value of elemental analysis C26H15BrO (%): c73.77, H3.57; measured value: c73.65, H3.50.
(Synthesis of Compound M38)
The synthetic route for compound M38 is shown below:
Figure 153326DEST_PATH_IMAGE218
into a 250 mL two-necked flask were charged 8.0 g (18.8 mmol) of M9, 5.0 g (10.8 mmol) of pinacol diboron, 5.5 g (56.4 mmol) of potassium acetate, and 0.16g (0.2 mmol) of Pd (dppf) Cl2After the reaction system was degassed, 150 mL of dioxane was added under nitrogen protection, and the mixture was stirred and heated to reflux for 12 hours. After the reaction is completed, cooling the system to room temperature, carrying out vacuum filtration, washing filter residue with a large amount of dichloromethane, concentrating the filtrate to obtain a crude product, and adding petroleum ether: dichloromethane = 3: 2 (volume ratio) of eluent on silica gel column to obtain 7g of white solid with 79% of yield. Ms (ei): m/z 472.24 [ M+]. Calculated value of elemental analysis C33H33BO2(%): c83.90, H7.04; measured value: c83.85, H6.95.
(Synthesis of Compounds 1-132)
The synthetic routes for compounds 1-132 are shown below:
Figure 480402DEST_PATH_IMAGE219
to a clean 100 mL three-necked flask were added 2.5 g (5.9 mmol) of M38, 1.7 g (12.4 mmol) of anhydrous potassium carbonate, 2.5 g (5.3 mmol) of M37, 68.3 mg (0.06 mmol) of tetrakis (triphenylphosphine) palladium, and 45mL of a mixed solvent (toluene: water: ethanol = 30: 8: 7 (volume ratio)) in this order under a nitrogen atmosphere, and the system was warmed to reflux and reacted overnight under reflux. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200 mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane = 3: 2 (vol.)) to give 3.5 g of a green solid with a yield of 86%. Ms (ei): m/z 688.67 [ M+]. Calculated value of elemental analysis C53H36O (%)：C 92.41, H5.27; measured value: c92.40, H5.20.
Example 13: preparation of the organic electroluminescent device 1 (organic EL device 1).
A hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a light emitting layer 6, a hole blocking layer 7, an electron transport layer 8, an electron injection layer 9 and a cathode 10 were sequentially formed on a transparent anode 2 previously formed on a glass substrate 1 to prepare an organic electroluminescent device as shown in fig. 3.
Specifically, a glass substrate on which an ITO film having a film thickness of 100 nm was formed was subjected to ultrasonic treatment in a Decon 90 alkaline cleaning solution, rinsed in deionized water, washed three times in acetone and ethanol, respectively, baked in a clean environment to completely remove moisture, washed with ultraviolet light and ozone, and bombarded on the surface with a low-energy cation beam. Placing the glass substrate with ITO electrode into a vacuum chamber, and vacuumizing to 4 × 10-4-2×10-5Pa. Then, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene (HIL 2) was deposited on the ITO electrode-equipped glass substrate at a deposition rate of 0.2 nm/sec to form a layer having a thickness of 10 nm as a hole injection layer. On the hole injection layer, HTL1 was deposited at a deposition rate of 2.0 nm/s to form a layer having a thickness of 30 nm as a hole transport layer. On the hole transport layer, double source co-evaporation was performed at a deposition rate of 2.0 nm/s for the compounds 1 to 23 as host materials and 0.16 nm/s for the BD1 as dopant material to form a layer with a thickness of 20 nm as a light emitting layer, and the doping weight ratio of the BD1 was 8 wt%. 50wt% ETL1/50wt% Liq was vapor-deposited on the light-emitting layer at a vapor deposition rate of 2.0 nm/s to form a layer having a film thickness of 40 nm as an electron-transporting layer. 8-hydroxyquinoline-lithium (Liq) was vapor-deposited on the electron transport layer at a vapor deposition rate of 0.2 nm/s to form a layer having a thickness of 2 nm as an electron injection layer. Finally, aluminum was deposited at a deposition rate of 3.0 nm/s or more to form a cathode having a film thickness of 100 nm.
Examples 14 to 25: and (3) preparing the organic EL devices 2-13.
Organic EL devices 2 to 13 were produced under the same conditions as the organic EL device 1 except that the compounds in tables 1 and 2 below were used instead of the compound in each layer of example 13.
Comparative examples 1 to 9: preparation of organic EL devices comparative examples 1 to 9.
Organic EL device comparative examples 1 to 9 were produced under the same conditions as the organic EL device 1 except that the compounds in tables 1 and 2 below were used instead of the compound in each layer of example 13.
TABLE 1
Figure 76337DEST_PATH_IMAGE220
TABLE 2
Figure 488864DEST_PATH_IMAGE221
The examples and comparative examples relate to the following structures of compounds:
Figure 313601DEST_PATH_IMAGE222
Figure 495183DEST_PATH_IMAGE223
Figure 950436DEST_PATH_IMAGE224
Figure 663308DEST_PATH_IMAGE225
Figure 229418DEST_PATH_IMAGE226
Figure 265507DEST_PATH_IMAGE227
Figure 953978DEST_PATH_IMAGE228
Figure 341097DEST_PATH_IMAGE229
Figure 445319DEST_PATH_IMAGE230
Figure 913078DEST_PATH_IMAGE231
Figure 710133DEST_PATH_IMAGE232
Figure 381286DEST_PATH_IMAGE233
Figure 554778DEST_PATH_IMAGE234
Figure 565459DEST_PATH_IMAGE235
Figure 346465DEST_PATH_IMAGE236
Figure 442597DEST_PATH_IMAGE237
the light emission characteristics of the organic EL devices 1 to 13 produced in examples 13 to 25 and the organic EL devices produced in comparative examples 1 to 9 were measured when a dc voltage was applied in the atmosphere at normal temperature. The measurement results are shown in tables 3 to 7.
The current-luminance-voltage characteristics of the device were obtained from a Keithley source measuring system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with calibrated silicon photodiodes, the electroluminescence spectra were measured with a Photo research PR655 spectrometer, the external quantum efficiency of the device was determined by the literatureAdv. Mater., 2003, 15, 1043, 1048.
The lifetime of the device was measured as: the device lifetime with BD1, GD1, and RG1 as dopants is 1000 cd/m2For initial luminance, attenuation to 900 cd/m2(corresponding to 90%, where the initial brightness is taken as 100%: 90% decay). All devices were encapsulated in a nitrogen atmosphere.
TABLE 3
Figure 950938DEST_PATH_IMAGE238
As can be seen from Table 3, the 2,4, 7-trisubstituted fluorene compounds of the present invention obtained excellent performance data. Compared with the main body material commonly used in the prior art, the 2,4, 7-trisubstituted fluorene compound can effectively reduce the working voltage, improve the efficiency and prolong the service life of devices. Compared with BH2 in comparative example 2 of the organic EL device, compounds 1 to 46 in the organic EL device 3 introduce a deuterated benzene group at the 4-position, and reduce vibration relaxation and energy loss by means of an atomic emphasis effect, so that the efficiency and the service life of the device are finally and remarkably improved.
TABLE 4
Figure 81706DEST_PATH_IMAGE239
As can be seen from Table 4, the 2,4, 7-trisubstituted fluorene compounds of the present invention obtained excellent performance data. Compared with the electron transport materials commonly used in the prior art, the 2,4, 7-trisubstituted fluorene compound can effectively reduce the working voltage, improve the efficiency and prolong the service life of devices. Compared with ETL2 in comparative example 4 of the organic EL device, a third phenanthroline unit is introduced into the 4-position of compounds 1-5 in the organic EL device 4, and can better form a coordination bond with Liq, so that in the device, the whole electron transport layer is more stable, the transport efficiency is more excellent, and finally the service life and efficiency of the device are remarkably improved. In addition, as can be seen from the J-V curve of the single-electron device in fig. 5, the electron transport performance of the 2,4, 7-trisubstituted fluorene compound is more excellent than that of the mono-substituted and di-substituted fluorene compounds, and the advantages of the 2,4, 7-trisubstituted fluorene compound in molecular design are reflected.
TABLE 5
Figure 220563DEST_PATH_IMAGE240
As can be seen from Table 5, the 2,4, 7-trisubstituted fluorene compounds of the present invention obtained excellent performance data. Compared with the hole transport material commonly used in the prior art, the 2,4, 7-trisubstituted fluorene compound can effectively reduce the working voltage, improve the efficiency and prolong the service life of devices. Compared with the HTL4 in comparative example 4 of the organic EL device, the compound 2-1 in the organic EL device 6 introduces a third diphenylamino group at the 7-position, which properly increases the HOMO level of the whole molecule, and significantly increases the hole transport property, thereby improving the efficiency and lifetime of the device. However, it was found after the test that the device voltages of comparative examples 5 and 6 of the organic EL device are relatively high because once the 2,4, 7-trisubstituted-9, 9-dimethyl fluorene compound of the present invention substitutes two or three diphenylamino groups at three sites of 2,4,7, the HOMO energy level rises to above-5.4 eV, and the HOMO (-6.0 eV) energy level difference from the host material (BH 1) of blue light is too large, which causes the device operating voltage to rise, thereby affecting the overall performance. In addition, as can be seen from the J-V curve of the single-hole device in fig. 4, the 2,4, 7-trisubstituted fluorene compound has more excellent hole transport performance than the monosubstituted and disubstituted fluorene compounds, and shows the advantages of the 2,4, 7-trisubstituted fluorene compound in molecular design.
TABLE 6
Figure 115575DEST_PATH_IMAGE241
As can be seen from Table 6, the 2,4, 7-trisubstituted fluorene compounds of the present invention obtained excellent performance data. Compared with the common main material in the prior art, the 2,4, 7-trisubstituted fluorene compound can effectively reduce the working voltage, improve the efficiency and prolong the service life of devices, no matter the compound is used as the main material independently or together with other materials.
TABLE 7
Figure 365291DEST_PATH_IMAGE242
As can be seen from Table 7, the 2,4, 7-trisubstituted fluorene compounds of the present invention obtained excellent performance data. Compared with the main body material commonly used in the prior art, the 2,4, 7-trisubstituted fluorene compound can effectively reduce the working voltage, improve the efficiency and prolong the service life of devices.
Industrial applicability
The 2,4, 7-trisubstituted fluorene compound of the present invention has excellent luminous efficiency and life characteristics, and low driving voltage. Therefore, an organic electroluminescent device having an excellent lifetime can be prepared from the compound.

Claims (6)

1. A2, 4, 7-tri-substituted fluorene compound is selected from the following compounds:
Figure FDA0002984117950000011
Figure FDA0002984117950000021
Figure FDA0002984117950000031
Figure FDA0002984117950000041
Figure FDA0002984117950000051
Figure FDA0002984117950000061
Figure FDA0002984117950000071
Figure FDA0002984117950000081
Figure FDA0002984117950000091
Figure FDA0002984117950000101
Figure FDA0002984117950000111
Figure FDA0002984117950000121
Figure FDA0002984117950000131
Figure FDA0002984117950000141
Figure FDA0002984117950000151
Figure FDA0002984117950000161
Figure FDA0002984117950000171
Figure FDA0002984117950000181
Figure FDA0002984117950000191
Figure FDA0002984117950000201
Figure FDA0002984117950000211
Figure FDA0002984117950000221
Figure FDA0002984117950000231
Figure FDA0002984117950000241
Figure FDA0002984117950000251
Figure FDA0002984117950000261
2. an electronic device comprising the 2,4, 7-trisubstituted fluorene-based compound according to claim 1.
3. The electronic device according to claim 2, wherein the electronic device is an organic electroluminescent device, an organic field effect transistor or an organic solar cell, wherein
The organic electroluminescent device includes: a first electrode, a second electrode provided so as to face the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the at least one organic layer contains the 2,4, 7-trisubstituted fluorene compound according to claim 1.
4. The electronic device of claim 3, wherein the at least one organic layer is a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, a hole blocking layer, or an electron transport layer.
5. Use of the 2,4, 7-trisubstituted fluorene compound according to claim 1 as a hole injection material, a hole transport material, a light emitting material, an electron blocking material, a hole blocking material or an electron transport material in an electronic device.
6. Use according to claim 5, wherein the electronic device is an organic electroluminescent device, an organic field effect transistor or an organic solar cell, wherein
The organic electroluminescent device includes: a first electrode, a second electrode provided so as to face the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, the at least one organic layer containing the 2,4, 7-trisubstituted fluorene compound according to claim 1;
the at least one organic layer is a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, a hole blocking layer, or an electron transport layer.
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Families Citing this family (10)

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CN113087675A (en) * 2021-03-29 2021-07-09 武汉华星光电半导体显示技术有限公司 Organic compound, manufacturing method thereof and display panel
CN113501810B (en) * 2021-06-09 2022-05-20 浙江华显光电科技有限公司 Organic compound and organic photoelectric element containing same
CN113416537A (en) * 2021-06-09 2021-09-21 上海大学 Host-guest composition and organic electroluminescent element comprising same
CN113621386B (en) * 2021-09-06 2023-05-26 国信宝威(北京)科技有限公司 Discotic liquid crystal compound and application thereof
CN113845431B (en) * 2021-10-20 2024-03-29 上海钥熠电子科技有限公司 Spirofluorene derivative amine compound and organic electroluminescent device comprising the same
WO2023072976A1 (en) * 2021-10-29 2023-05-04 Merck Patent Gmbh Compounds for electronic devices
CN113845467A (en) * 2021-11-10 2021-12-28 西安瑞联新材料股份有限公司 Compound with phenanthrocarbazole as core and application thereof
CN116143737A (en) * 2021-11-16 2023-05-23 烟台显华科技集团股份有限公司 Compound with anthracene-linked asymmetric dibenzoheterocycle and application thereof
CN114430010A (en) * 2022-01-13 2022-05-03 吉林奥来德光电材料股份有限公司 Organic electroluminescent composition and organic electroluminescent device
CN115124433A (en) * 2022-07-12 2022-09-30 北京八亿时空液晶科技股份有限公司 Spirobifluorene derivative and application thereof

Family Cites Families (9)

* Cited by examiner, † Cited by third party
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JP3848224B2 (en) * 2002-08-27 2006-11-22 キヤノン株式会社 Spiro compound and organic light emitting device using the same
CN101440082A (en) * 2008-12-12 2009-05-27 南京邮电大学 Spirofluorene xanthene material, and preparation and use thereof
KR101716069B1 (en) * 2012-11-12 2017-03-13 메르크 파텐트 게엠베하 Materials for electronic devices
CN105829279B (en) * 2013-12-26 2018-06-08 罗门哈斯电子材料韩国有限公司 Organic electroluminescent compounds and the Organnic electroluminescent device for including it
CN104193738B (en) * 2014-08-21 2016-05-18 上海道亦化工科技有限公司 A kind of electric transmission compound based on benzimidazole
KR101910498B1 (en) * 2016-06-08 2018-10-22 (주)씨엠디엘 The novel organic electroluminescent compounds and organic electroluminescent device including the same
CN106632219B (en) * 2016-12-30 2019-06-11 上海升翕光电科技有限公司 Spirofluorene derivative and preparation method thereof and organic luminescent device
KR20200127628A (en) * 2019-05-03 2020-11-11 덕산네오룩스 주식회사 An organic electronic element comprising compound for organic electronic element and an electronic device thereof
CN111440135B (en) * 2020-04-16 2023-06-23 烟台显华化工科技有限公司 Compound, light extraction material and organic electroluminescent device

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