CN116134983A

CN116134983A - Organic light emitting device

Info

Publication number: CN116134983A
Application number: CN202180051838.1A
Authority: CN
Inventors: 金旼俊; 李东勋; 徐尚德; 金永锡; 金东熙; 吴重锡; 金曙渊; 李多情
Original assignee: LG Chem Ltd
Current assignee: LG Chem Ltd
Priority date: 2020-08-24
Filing date: 2021-08-24
Publication date: 2023-05-16
Also published as: KR20220087587A; KR102671015B1

Abstract

The invention provides an organic light emitting device.

Description

Organic light emitting device

Technical Field

Cross reference to related applications

The present application claims priority based on korean patent application No. 10-2020-0106464 at month 8 and 24 at month 2021, korean patent application No. 10-2021-011912 at month 8, which are incorporated herein in their entirety by reference.

The present invention relates to an organic light emitting device.

Background

In general, the organic light emitting phenomenon refers to a phenomenon of converting electric energy into light energy using an organic substance. An organic light emitting device using an organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, and excellent brightness, driving voltage, and response speed characteristics, and thus a great deal of research is being conducted.

The organic light emitting device generally has a structure including an anode and a cathode and an organic layer between the anode and the cathode. In order to improve efficiency and stability of the organic light-emitting device, the organic layer is often formed of a multilayer structure formed of different materials, and may be formed of a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, or the like. In such a structure of an organic light emitting device, if a voltage is applied between both electrodes, holes are injected into the organic layer from the anode and electrons are injected into the organic layer from the cathode, and when the injected holes and electrons meet, excitons (exiton) are formed, and light is emitted when the excitons transition to the ground state again.

As for the organic matter used for the organic light emitting device as described above, development of new materials is continuously demanded.

Prior art literature

Patent literature

(patent document 0001) Korean patent laid-open No. 10-2000-0051826

Disclosure of Invention

Technical problem

The present invention relates to an organic light emitting device having improved driving voltage, efficiency and lifetime.

Solution to the problem

In order to solve the above problems, the present invention provides the following organic light emitting device:

an organic light emitting device, comprising:

an anode, a cathode, and a light-emitting layer between the anode and the cathode,

the light-emitting layer includes a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2:

[ chemical formula 1]

In the above-mentioned chemical formula 1,

Ar ₁ and Ar is a group ₂ Each independently is a substituted or unsubstituted C _6-60 An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S _2-60 A heteroaryl group, which is a group,

L ₁ and L ₂ Each independently is a single bond, or a substituted or unsubstituted C _6-60 An arylene group,

L ₃ is a single bond, or substituted or unsubstituted C _6-60 An arylene group,

R ₁ each independently hydrogen or deuterium; or two adjacent compounds are combined to form benzene ring, the rest is hydrogen or deuterium,

R ₂ each independently hydrogen or deuterium; or two adjacent compounds are combined to form benzene ring, the rest is hydrogen or deuterium,

[ chemical formula 2]

In the above-mentioned chemical formula 2,

a and B are each independently a benzene ring or naphthalene ring fused to an adjacent ring,

L' ₁ is a single bond, or substituted or unsubstituted C _6-60 An arylene group,

Ar' ₁ is substituted or unsubstituted C _6-60 An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S _2-60 A heteroaryl group, which is a group,

when A or B is a benzene ring, m is an integer of 1 to 4 independently of each other, when A or B is a naphthalene ring, m is an integer of 1 to 6 independently of each other,

one of R' is a substituent represented by the following chemical formula 3, the remainder being hydrogen or deuterium,

[ chemical formula 3]

In the above-mentioned chemical formula 3, a compound represented by formula 1,

L' ₂ 、L' ₃ and L' ₄ Each independently is a single bond, or a substituted or unsubstituted C _6-60 An arylene group,

Ar' ₂ is substituted or unsubstituted C _6-60 An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S _2-60 A heteroaryl group, which is a group,

Ar' ₃ is a substituent represented by the following chemical formula 4,

[ chemical formula 4]

In the above-mentioned chemical formula 4, a compound represented by formula 1,

c is a naphthalene ring fused to the adjacent ring,

x is O or S, and the X is O or S,

each R "is independently hydrogen or deuterium,

n1 is an integer of 1 to 4,

n2 is an integer from 1 to 6.

Effects of the invention

The organic light emitting device described above is excellent in driving voltage, efficiency and lifetime.

Drawings

Fig. 1 illustrates an example of an organic light-emitting device constituted by a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4.

Fig. 2 illustrates an example of an organic light-emitting device constituted by a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron suppression layer 7, a light-emitting layer 3, a hole blocking layer 8, an electron injection and transport layer 9, and a cathode 4.

Detailed Description

In the following, the invention will be described in more detail in order to aid understanding thereof.

In the present description of the invention,

represents a bond to other substituents.

In the present specification, the term "substituted or unsubstituted" means that it is selected from deuterium; a halogen group; a nitrile group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; alkylthio group [ ]

) The method comprises the steps of carrying out a first treatment on the surface of the Arylthio (/ ->

) The method comprises the steps of carrying out a first treatment on the surface of the Alkylsulfonyl (+)>

) The method comprises the steps of carrying out a first treatment on the surface of the Arylsulfonyl radical [ ]

) The method comprises the steps of carrying out a first treatment on the surface of the A silyl group; a boron base; an alkyl group; cycloalkyl; alkenyl groups; an aryl group; an aralkyl group; aralkenyl; alkylaryl groups; an alkylamino group; an aralkylamine group; heteroaryl amine groups; an arylamine group; aryl phosphino; or 1 or more substituents in the heterocyclic group containing N, O and 1 or more of S atoms, or substituted as exemplified above The substituent formed by connecting more than 2 substituents in the group is substituted or unsubstituted. For example, the "substituent in which 2 or more substituents are linked" may be a biphenyl group. That is, biphenyl may be aryl or may be interpreted as a substituent in which 2 phenyl groups are linked.

In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40. Specifically, the compound may have the following structure, but is not limited thereto.

In the present specification, in the ester group, oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, or an aryl group having 6 to 25 carbon atoms. Specifically, the compound may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25. Specifically, the compound may have the following structure, but is not limited thereto.

In the present specification, the silyl group specifically includes, but is not limited to, trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like.

In the present specification, the boron group specifically includes trimethylboron group, triethylboron group, t-butyldimethylboroyl group, triphenylboron group, phenylboron group, and the like, but is not limited thereto.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine, and iodine.

In the present specification, the alkyl group may be a straight chain or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the above alkyl group has 1 to 10 carbon atoms. According to another embodiment, the above alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, t-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, t-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like.

In the present specification, the alkenyl group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples thereof include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylene1-yl, 2-diphenylethylene1-yl, 2-phenyl-2- (naphthalen-1-yl) ethylene1-yl, 2-bis (diphenyl-1-yl) ethylene1-yl, stilbene, styryl and the like, but are not limited thereto.

In the present specification, cycloalkyl is not particularly limited, but is preferably cycloalkyl having 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, there are 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, but the present invention is not limited thereto.

In the present specification, the aryl group is not particularly limited, but is preferably an aryl group having 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group, such as phenyl, biphenyl, and terphenyl, but is not limited thereto. The polycyclic aryl group may be naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, and the like,

A group, a fluorenyl group, etc., but is not limited thereto.

In this specification, a fluorenyl group may be substituted, and 2 substituents may be combined with each other to form a spiro structure. In the case where the fluorenyl group is substituted, it may be that

Etc. However, the present invention is not limited thereto.

In this specification, the heterocyclic group is a heterocyclic group containing 1 or more of O, N, si and S as a hetero element, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60. Examples of the heterocyclic group include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, and the like,

Azolyl, (-) -and (II) radicals>

Diazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinesA group selected from the group consisting of acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolinyl, indolyl, carbazolyl, benzo- >

Oxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothiophenyl, benzofuranyl, phenanthroline (phenanthrinyl), iso>

Oxazolyl, thiadiazolyl, phenothiazinyl, dibenzofuranyl, and the like, but are not limited thereto.

In the present specification, the aryl groups in the aralkyl group, the aralkenyl group, the alkylaryl group, and the arylamine group are the same as those exemplified for the aryl groups described above. In the present specification, the alkyl group in the aralkyl group, alkylaryl group, and alkylamino group is the same as the above-mentioned alkyl group. In this specification, the heteroaryl group in the heteroaryl amine may be as described above with respect to the heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is the same as the above-described examples of alkenyl groups. In this specification, arylene is a 2-valent group, and the above description of aryl can be applied in addition to this. In this specification, the heteroarylene group is a 2-valent group, and the above description of the heterocyclic group can be applied thereto. In this specification, the hydrocarbon ring is not a 1-valent group, but a combination of 2 substituents, and the above description of the aryl group or cycloalkyl group can be applied. In this specification, a heterocyclic ring is not a 1-valent group but a combination of 2 substituents, and the above description of a heterocyclic group can be applied thereto.

The present invention will be described in detail with reference to the following configurations.

Anode and cathode

The anode and cathode used in the present invention refer to electrodes used in an organic light emitting device.

The anode material is usually used to smoothly inject holes into the organic layerIn this case, a substance having a large work function is preferable. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, and gold, and alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); znO of Al or SnO ₂ A combination of metals such as Sb and the like and oxides; poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene]Conductive polymers such as (PEDOT), polypyrrole and polyaniline, but not limited thereto.

As the cathode material, a material having a small work function is generally preferred in order to facilitate injection of electrons into the organic layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, and alloys thereof; liF/Al or LiO ₂ And/or Al, but is not limited thereto.

Light-emitting layer

An organic light emitting device according to the present invention includes a light emitting layer including a compound represented by the above chemical formula 1 (hereinafter referred to as a "first compound") and a compound represented by the above chemical formula 2 (hereinafter referred to as a "second compound") as host materials between an anode and a cathode. Specifically, the first compound functions as an N-type host material having a superior electron transport ability to that of the hole transport material, and the second compound functions as a P-type host material having a superior hole transport ability to that of the electron transport material, so that the ratio of holes to electrons in the light-emitting layer can be appropriately maintained. Accordingly, the excitons uniformly emit light in the entire light emitting layer, so that the light emitting efficiency and lifetime characteristics of the organic light emitting device can be simultaneously improved.

Next, the first compound and the second compound will be described in order.

(first Compound)

The first compound is represented by chemical formula 1. Specifically, the first compound is a compound obtained by reacting a carbazole-based core with a linking group L at the N atom ₃ And a compound having a triazinyl group attached thereto, wherein the compound is characterized in that no substituent other than hydrogen/deuterium is bonded to the carbazole-based core. In particularIn the first compound, since the electron transport ability is superior to that of a compound in which a substituent other than hydrogen and deuterium, for example, an aryl group or a heteroaryl group, is substituted on the carbazole-based core, electrons are efficiently transferred to the dopant substance, and the electron-hole recombination probability in the light-emitting layer can be improved.

In the above chemical formula 1 associated with the above first compound included in the organic light emitting device of the present invention, it may be that

R ₁ And R is ₂ Each independently is hydrogen or deuterium, or

R ₁ Adjacent ones of which combine with each other to form a benzene ring unsubstituted or substituted with deuterium, the remainder being each independently hydrogen or deuterium, R ₂ Each independently is hydrogen or deuterium, or

R ₁ Each independently is hydrogen or deuterium, R ₂ Two adjacent ones of which are bonded to each other to form a benzene ring unsubstituted or substituted with deuterium, the remainder each being independently hydrogen or deuterium, or

R ₁ Adjacent ones of which combine with each other to form a benzene ring unsubstituted or substituted with deuterium, the remainder being each independently hydrogen or deuterium, R ₂ Adjacent ones of which are bonded to each other to form a benzene ring unsubstituted or substituted with deuterium, and the remainder are each independently hydrogen or deuterium.

More specifically, the above-described first compound may be represented by any one of the following chemical formulas 1-1 to 1-10:

in the above 1-1 to 1-10,

L ₁ to L ₃ 、Ar ₁ And Ar is a group ₂ The same definition as in the above chemical formula 1.

In addition, L ₁ And L ₂ Each independently canWith single bond, or C unsubstituted or substituted by deuterium _6-20 Arylene groups.

Specifically, L ₁ And L ₂ Each independently may be a single bond, phenylene, or naphthylene.

More specifically, L ₁ And L ₂ Each independently may be a single bond, or any one selected from the following groups:

for example, it may be L ₁ And L ₂ Are all single bonds; or L ₁ And L ₂ One of which is a single bond and the other is any one selected from the following groups;

in addition, L ₃ May be a single bond, or C which is unsubstituted or substituted by deuterium _6-20 Arylene groups.

Specifically, L ₃ May be a single bond, phenylene, biphenyldiyl, or naphthylene.

For example, L ₃ Is a single bond, or is any one selected from the following groups:

In addition, ar ₁ And Ar is a group ₂ Each independently may be unsubstituted or deuterium substituted C _6-20 An aryl group; or is unsubstituted or selected from deuterium, C _1-10 Alkyl and C _6-20 C comprising 1 hetero atom in N, O and S substituted by more than 1 substituent in aryl _2-20 Heteroaryl groups.

Specifically, ar ₁ And Ar is a group ₂ Each independently is phenyl, biphenyl, naphthyl, phenanthryl, dibenzofuranyl, dibenzothienylCarbazolyl, benzonaphthofuranyl, or benzonaphthothienyl, where Ar ₁ And Ar is a group ₂ May be unsubstituted or selected from deuterium, C _1-10 Alkyl and C _6-20 More than 1 substituent in the aryl group is substituted.

More specifically, ar ₁ And Ar is a group ₂ Each independently may be phenyl, biphenyl, naphthyl, phenanthryl, dibenzofuranyl, dibenzothienyl, 9-phenylcarbazolyl, benzonaphthofuranyl, or benzonaphthothienyl.

More specifically, ar ₁ And Ar is a group ₂ Each independently may be any one selected from the following groups:

for example, it may be Ar ₁ And Ar is a group ₂ One of which is phenyl, naphthyl, dibenzofuranyl, or dibenzothienyl, and the other of which is phenyl, biphenyl, naphthyl, phenanthryl, dibenzofuranyl, dibenzothienyl, 9-phenylcarbazolyl, benzonaphthofuranyl, or benzonaphthothienyl.

At this time, ar ₁ And Ar is a group ₂ May be the same or different from each other.

Representative examples of the first compound represented by the above chemical formula 1 are as follows:

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on the other hand, the compound represented by the above chemical formula 1 can be produced by the following production method represented by the following reaction formula 1. The above-described production method may be more specifically described in the synthesis examples described below.

[ reaction type 1]

In the above reaction formula 1, R ₁ 、R ₃ 、Ar ₁ 、Ar ₂ 、L ₁ 、L ₂ And L ₃ X is as defined in the above chemical formula 1 ₁ Halogen, preferably Cl, br or I, more preferably Cl.

The above reaction formula 1 is an amine substitution reaction, preferably performed in the presence of a palladium catalyst and a base, and the reactive group used for the amine substitution reaction may be modified according to a technique known in the art. The above-described production method can be more specifically described in the production example described later.

In the present specification, on the other hand, equivalent (eq.) means molar equivalent.

As an example, in the above reaction formula 1, as the alkali component, it is possible to useSodium tert-butoxide (NaOtBu), potassium carbonate (potassium carbonate, K) ₂ CO ₃ ) Sodium bicarbonate (sodium bicarbonate, naHCO) ₃ ) Cesium carbonate (Cs) ₂ CO ₃ ) Sodium acetate (NaOAc), potassium acetate (potassium acetate, KOAc), sodium ethoxide (NaOEt), or triethylamine (Et) ₃ N), N-diisopropylethylamine (N, N-diisopropylethylamine, etN (iPr) ₂ ) Etc. Preferably, the alkali component may be sodium tert-butoxide (NaOtBu), potassium carbonate (K) ₂ CO ₃ ) Cesium carbonate (Cs) ₂ CO ₃ ) Potassium acetate (KOAc), or N, N-diisopropylethylamine (EtN (iPr) ₂ )。

In addition, in the above reaction scheme 1, as the above palladium catalyst, bis (tri (tert-butyl) phosphine) palladium (0) (bis (tris- (tert-butyl) phosphine) palladium (0), pd (P-tBu) ₃ ) ₂ ) Tetrakis (triphenylphosphine) palladium (0) (tetrakis (triphenylphosphine) paladium (0), tris (dibenzylideneacetone) dipalladium (0) (tris (dibenzylideneacetone) -dipalladium (0), pd) ₂ (dba) ₃ ) Bis (dibenzylideneacetone) palladium (0) (bis (dibenzylideneacetone) paladium (0)), pd (dba) ₂ )、Pd(PPh ₃ ) ₄ ) Or palladium (II) acetate, pd (OAc) ₂ ) Etc. Preferably, the palladium catalyst may be bis (tri (t-butyl) phosphine) palladium (0) (Pd (P-tBu) ₃ ) ₂ ) Tetrakis (triphenylphosphine) palladium (0) (Pd (PPh) ₃ ) ₄ ) Or bis (dibenzylideneacetone) palladium (0) (Pd (dba) ₂ ). In particular, in the above reaction scheme 1, bis (tri (t-butyl) phosphine) palladium (0) (Pd (P-tBu) ₃ ) ₂ ) Used as a catalyst.

(second Compound)

The second compound is represented by chemical formula 2. Specifically, the second compound is a compound in which a tertiary amine group is bonded to a carbazole-based core, and the tertiary amine group is bonded to a benzonaphthofuranyl group or a benzonaphthothiophenyl group, and the compound is characterized in that the carbazole-based polycyclic core is not bonded to a substituent other than tertiary amine and hydrogen/deuterium. In particular, the second compound can efficiently transfer holes to the dopant material as compared with a compound in which another aryl group or heteroaryl group such as a triazinyl group is substituted at the position where the tertiary amine group of the benzonaphthofuranyl group or the benzonaphthothiophenyl group is bonded, and therefore, the recombination probability of holes and electrons in the light-emitting layer can be improved together with the first compound having excellent electron transporting ability.

In the above chemical formula 2 related to the above second compound included in the organic light emitting device of the present invention, it may be that

[ chemical formula 3]

In the above-mentioned chemical formula 3, a compound represented by formula 1,

Ar' ₃ is a substituent represented by the following chemical formula 4,

[ chemical formula 4]

In the above-mentioned chemical formula 4, a compound represented by formula 1,

c is a naphthalene ring fused to the adjacent ring,

x is O or S, and the X is O or S,

each R "is independently hydrogen or deuterium,

n1 is an integer of 1 to 4,

n2 is an integer from 1 to 6.

More specifically, the above chemical formula 2 is represented by any one selected from the following chemical formulas 2-1 to 2-8:

In the above chemical formulas 2-1 to 2-8, L' ₁ 、Ar' ₁ And R' is as defined above, m1 is an integer from 1 to 4, and m2 is an integer from 1 to 6.

In addition, the above chemical formula 2 is represented by any one selected from the following chemical formulas 2-9 to 2-19:

in the above chemical formulas 2-9 to 2-19, L' ₁ 、Ar' ₁ And R' is as defined above.

In addition, L' ₁ Is a single bond or phenylene, more preferably L' ₁ Is a single bond.

Specifically, ar' ₁ Is phenyl, biphenyl, or naphthyl.

More specifically, ar' ₁ Any one selected from the following groups may be used, but is not limited thereto:

concrete embodimentsIn terms of L' ₂ Is a single bond, phenylene, or naphthylene.

For example, L' ₂ May be a single bond, or any one selected from the following groups:

specifically, L' ₃ Is a single bond, phenylene, biphenyldiyl, or naphthylene.

For example, L' ₃ Is a single bond, or is any one selected from the following groups:

specifically, L' ₄ Is a single bond or phenylene.

In addition, ar' ₂ Is phenyl, biphenyl, terphenyl, (naphthyl) phenyl, (phenanthryl) phenyl, naphthyl, phenanthryl, (phenyl) naphthyl, (phenyl) phenanthryl, dibenzofuranyl, or dibenzothienyl.

More specifically, ar' ₂ May be any one selected from the group consisting of,

On the other hand, the above chemical formula 4 is represented by any one selected from the following chemical formulas 4-1 to 4-6:

in the above chemical formulas 4-1 to 4-6, X, R ", n1 and n2 are the same as defined above.

In addition, the above chemical formula 4 is represented by any one selected from the following chemical formulas 4-7 to 4-12:

in the above chemical formulas 4-7 to 4-12, X is as defined above.

More specifically, ar' ₃ May be any one selected from the following groups.

Representative examples of the compounds represented by the above chemical formula 2 are shown below:

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on the other hand, in the compound represented by the above chemical formula 2, the compound in which the linking group between the carbazole mother nucleus polycyclic and the amine group is a single bond and the linking group between the amine group and the bonded benzonaphthofuranyl group or benzonaphthothiophenyl group is a single bond can be produced by the following production method represented by the following chemical formula 2. The above-described production method may be more specifically described in the synthesis examples described below.

[ reaction type 2]

In the above reaction scheme 2, A, B, m, L' ₁ 、L' ₃ 、Ar' ₁ 、Ar' ₂ And Ar' ₃ As defined in chemical formula 2 above,

X ₂ one of them is halogen and the others are hydrogen or deuterium. In particular, X ₂ Preferably Cl, br or I,

X ₃ halogen, in particular, X ₂ Are not mutually connected withAnd halogen. Preferably X ₃ Is Cl, br or I.

As an example, X ₂ One of them is Br or I, more preferably Br, X ₂ The balance of (a) is hydrogen or deuterium. As an example, X ₃ Is Cl or Br, more preferably Cl.

The above reaction formula 2 can be suitably used for the production of the amino group-related compound formula 3 of the compound formula 2, L' ₂ And L' ₄ A step of forming a compound having a single bond. As an example, in the manufacture of the above L' ₂ Compounds other than single bonds, i.e. L' ₂ Is substituted or unsubstituted C _6-60 In the case of the arylene compound, L 'may be introduced into the polycyclic carbazole-based mother nucleus by the Suzuki reaction or the like before the reaction with the amine compound in the above reaction formula 2' ₂ Corresponding substituted or unsubstituted C _6-60 Arylene, then undergoes an amine group introduction reaction as shown in equation 2 above. In addition, in the manufacture of the L' ₄ Compounds other than single bonds, i.e. L' ₄ Is substituted or unsubstituted C _6-60 In the case of the arylene compound, L 'may be introduced into the amine group bonded to the polycyclic amine group of the carbazole-based mother nucleus by the Suzuki reaction or the like after the reaction with the amine compound in the above reaction formula 2' ₄ Corresponding substituted or unsubstituted C _6-60 The arylene group is then subjected to a reaction for introducing a benzonaphthofuranyl group or a benzonaphthothiophenyl group as shown in the above reaction scheme 2.

The above reaction formula 2 is an amine substitution reaction, preferably performed in the presence of a palladium catalyst and a base, and the reactive group used for the amine substitution reaction may be modified according to a technique known in the art. The above-described production method can be more specifically described in the production example described later.

As an example, in the above reaction scheme 2, sodium t-butoxide (NaOtBu) and potassium carbonate (K) ₂ CO ₃ ) Sodium bicarbonate (NaHCO) ₃ ) Cesium carbonate (Cs) ₂ CO ₃ ) Sodium acetate (NaOAc), potassium acetate (KOAc), sodium ethoxide (NaOEt), or triethylamine (Et) ₃ N), N-diisopropylethylamine (EtN (iPr) ₂ ) Etc. Preferably, the alkali component may be t-butanolSodium (NaOtBu), potassium carbonate (K) ₂ CO ₃ ) Cesium carbonate (Cs) ₂ CO ₃ ) Potassium acetate (KOAc), or N, N-diisopropylethylamine (EtN (iPr) ₂ )。

In addition, in the above reaction formula 2, as the above palladium catalyst, bis (tri (t-butyl) phosphine) palladium (0) (Pd (P-tBu) ₃ ) ₂ ) Tetrakis (triphenylphosphine) palladium (0) (, tris (dibenzylideneacetone) dipalladium (0) (Pd) ₂ (dba) ₃ ) Bis (dibenzylideneacetone) palladium (0) (Pd (dba)) ₂ )、Pd(PPh ₃ ) ₄ ) Or palladium (II) acetate (Pd (OAc) ₂ ) Etc. Preferably, the palladium catalyst may be bis (tri (t-butyl) phosphine) palladium (0) (Pd (P-tBu) ₃ ) ₂ ) Tetrakis (triphenylphosphine) palladium (0) (Pd (PPh) ₃ ) ₄ ) Or bis (dibenzylideneacetone) palladium (0) (Pd (dba) ₂ ). In particular, in the above reaction scheme 2, bis (tri (t-butyl) phosphine) palladium (0) (Pd (P-tBu) ₃ ) ₂ ) Used as a catalyst.

In the above light emitting layer of the organic light emitting device of the present invention, the weight ratio of the compound represented by the above chemical formula 1 to the compound represented by the above chemical formula 2 is 1:99 to 99:1, 5:95 to 95:5, or 10:90 to 90:10, or 20:80 to 80:20, or 30:70 to 70:30, or 40:60 to 60:40, or 50:50.

In addition, the light-emitting layer further includes a dopant compound.

The light-emitting layer contains a compound of chemical formula 1 and a compound of chemical formula 2, and a dopant.

As an example, the light emitting layer includes the compound of chemical formula 1 and the compound of chemical formula 2 and the dopant in a content ratio of 100:1 to 1:1 on a weight basis.

In addition, the light emitting layer includes the compound of chemical formula 1 and the dopant in a content ratio of 100:1 to 2:1 by weight, and includes the total content of the compound of chemical formula 1 and the compound of chemical formula 2 and the dopant.

In addition, the light emitting layer includes the compound of chemical formula 1 and the dopant in a content ratio of 100:1 to 5:1 by weight, and includes the total content of the compound of chemical formula 1 and the compound of chemical formula 2 and the dopant.

The dopant material is not particularly limited as long as it is used in an organic light-emitting device. As an example, there are aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivative is an aromatic condensed ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene having an arylamino group,

And bisindenopyrene, etc., wherein the styrylamine compound is a compound in which at least 1 arylvinyl group is substituted on a substituted or unsubstituted arylamine, and is substituted or unsubstituted with 1 or 2 or more substituents selected from the group consisting of aryl, silyl, alkyl, cycloalkyl and arylamino groups. Specifically, there are styrylamine, styrylenediamine, styrylenetriamine, styrylenetetramine, and the like, but the present invention is not limited thereto. The metal complex includes, but is not limited to, iridium complex, platinum complex, and the like.

As an example, the dopant is a metal complex.

Specifically, the dopant is an iridium metal complex.

The organic layer includes a light-emitting layer, the light-emitting layer includes a dopant, and the dopant is selected from the following structural formulas.

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The above-described explicit structure is a dopant compound, and is not limited thereto.

Hole transport layer

The organic light emitting device according to the present invention may include a hole transport layer between the electron suppression layer and the anode.

The hole-transporting layer is a layer that receives holes from the hole-injecting layer and transports the holes to the light-emitting layer, and a hole-transporting substance that can receive holes from the anode or the hole-injecting layer and transfer the holes to the light-emitting layer is preferable, and a substance having a large mobility to the holes is preferable.

Specific examples of the hole transporting material include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers having both conjugated and unconjugated portions.

Hole injection layer

The organic light emitting device according to the present invention may further include a hole injection layer between the anode and the hole transport layer as needed.

The hole injection layer is a layer that injects holes from an electrode, and the following compounds are preferable as the hole injection substance: a compound which has a hole transporting ability, has an effect of injecting holes from the anode, has an excellent hole injecting effect for the light emitting layer or the light emitting material, prevents excitons generated in the light emitting layer from migrating to the electron injecting layer or the electron injecting material, and has an excellent thin film forming ability. In addition, it is preferable that the HOMO (highest occupied molecular orbital ) of the hole injecting substance is interposed between the work function of the anode substance and the HOMO of the surrounding organic layer.

Specific examples of the hole injection substance include, but are not limited to, metalloporphyrin (porphyrin), oligothiophenes, arylamine-based organic substances, hexanitrile hexaazabenzophenanthrene-based organic substances, quinacridone-based organic substances, perylene-based organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers.

Electron transport layer

The organic light emitting device according to the present invention may include an electron transport layer between the above-described light emitting layer and the cathode.

The electron transporting layer is a layer that receives electrons from the cathode or an electron injecting layer formed on the cathode and transports the electrons to the light emitting layer, and suppresses the transfer of holes from the light emitting layer, and an electron transporting substance that can well receive electrons from the cathode and transfer them to the light emitting layer is preferable, and a substance having a large mobility for electrons is preferable.

As a specific example of the electron transporting substance, there is an Al complex of 8-hydroxyquinoline containing Alq ₃ But not limited to, complexes of (c) and (d), organic radical compounds, hydroxyflavone-metal complexes, and the like. The electron transport layer may be used with any desired cathode material as used in the art. In particular, examples of suitable cathode materials are the usual materials having a low work function accompanied by an aluminum layer or a silver layer. In particular cesium, barium, calcium, ytterbium and samarium, in each case accompanied by an aluminum layer or a silver layer.

Electron injection layer

The organic light emitting device according to the present invention may further include an electron injection layer between the electron transport layer and the cathode as needed.

The electron injection layer is a layer that injects electrons from an electrode, and preferably the following compound is used: a compound which has an ability to transport electrons, an effect of injecting electrons from a cathode, an excellent electron injection effect for a light-emitting layer or a light-emitting material, prevents excitons generated in the light-emitting layer from migrating to a hole injection layer, and has excellent thin film forming ability.

Specific examples of the substance that can be used in the electron injection layer include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, and the like,

Azole,/->

The diazoles, triazoles, imidazoles, perylenetetracarboxylic acids, fluorenylenemethanes, anthrones, and the like, and their derivatives, metal complexes, and nitrogen-containing five-membered ring derivatives, and the like, but are not limited thereto.

Examples of the metal complex include, but are not limited to, lithium 8-hydroxyquinoline, zinc bis (8-hydroxyquinoline), copper bis (8-hydroxyquinoline), manganese bis (8-hydroxyquinoline), aluminum tris (2-methyl-8-hydroxyquinoline), gallium tris (8-hydroxyquinoline), beryllium bis (10-hydroxybenzo [ h ] quinoline), zinc bis (10-hydroxybenzo [ h ] quinoline), gallium chloride bis (2-methyl-8-quinoline) (o-cresol) gallium, aluminum bis (2-methyl-8-quinoline) (1-naphthol), gallium bis (2-methyl-8-quinoline) (2-naphthol).

Organic light emitting device

A structure of an organic light emitting device according to the present invention is illustrated in fig. 1. Fig. 1 illustrates an example of an organic light-emitting device constituted by a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4. Fig. 2 illustrates an example of an organic light-emitting device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron suppression layer 7, a light-emitting layer 3, a hole blocking layer 8, an electron injection and transport layer 9, and a cathode 4.

The organic light emitting device according to the present invention can be manufactured by sequentially laminating the above-described constitution. This can be manufactured as follows: PVD (physical Vapor Deposition: physical vapor deposition) methods such as sputtering (sputtering) or electron beam evaporation (e-beam evaporation) are used to deposit a metal or a metal oxide having conductivity or an alloy thereof on a substrate to form an anode, then the above layers are formed on the anode, and then a substance that can be used as a cathode is deposited thereon.

In addition to this method, an organic light-emitting device can be manufactured by sequentially depositing a cathode material to an anode material on a substrate in reverse order of the above-described constitution (WO 2003/012890). The light-emitting layer may be formed of the host and the dopant not only by vacuum vapor deposition but also by solution coating. Here, the solution coating method refers to spin coating, dip coating, blade coating, inkjet printing, screen printing, spray coating, roll coating, and the like, but is not limited thereto.

On the other hand, the organic light emitting device according to the present invention may be a bottom emission (bottom emission) device, a top emission (top emission) device, or a bi-directional light emitting device, and in particular, may be a bottom emission device requiring relatively high light emitting efficiency.

The production of the compound represented by the above chemical formula 1 and the organic light emitting device including the same is specifically illustrated in the following examples. However, the following examples are given by way of illustration of the present invention, and the scope of the present invention is not limited thereto.

Examples (example)

(production of first Compound)

PREPARATION EXAMPLE 1-1 Synthesis of Compound 1-1

9H-carbazole (9H-carbazole) (10 g,59.8 mmol), compound substance (sub) 1 (25.6 g,62.8 mmol), potassium phosphate (Potassium Phosphate) (K) ₃ PO ₄ 38.1g,179.4 mmol) was added to 200mL of xylene (xylene), stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (Pd (t-Bu) ₃ P) ₂ 0.6g,1.2 mmol). After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 17.7g of compound 1-1 was obtained. (yield 55%, MS: [ M+H) ] ⁺ ＝539)。

PREPARATION EXAMPLE 1-2 Synthesis of Compounds 1-2

9H-carbazole (10 g,59.8 mmol), compound 2 (25.6 g,62.8 mmol), potassium phosphate (38.1 g,179.4 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.2 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 19g of compound 1-2 was obtained. (yield 59%, MS: [ M+H)] ⁺ ＝539)。

PREPARATION EXAMPLE 1-3 Synthesis of Compounds 1-3

9H-carbazole (10 g,59.8 mmol), compound 3 (27.2 g,62.8 mmol), potassium phosphate (38.1 g,179.4 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.2 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 18.5g of compounds 1 to 3 was obtained. (yield 55%, MS: [ M+H) ] ⁺ ＝564)。

PREPARATION EXAMPLES 1-4 Synthesis of Compounds 1-4

9H-carbazole (10 g,59.8 mmol), compound 4 (30.4 g,62.8 mmol), potassium phosphate (38.1 g,179.4 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.2 mmol) was charged. After 3 hours, the reaction was completed and cooled toThe solvent was removed under reduced pressure at room temperature. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 20.9g of compounds 1 to 4 was obtained. (yield 57%, MS: [ M+H)] ⁺ ＝615)。

PREPARATION EXAMPLES 1-5 Synthesis of Compounds 1-5

9H-carbazole (10 g,59.8 mmol), compound 5 (29.5 g,62.8 mmol), sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.2 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 23.3g of compounds 1 to 5 was obtained. (yield 65%, MS: [ M+H ] ] ⁺ ＝601)。

Preparation examples 1-6 Synthesis of Compounds 1-6

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9H-carbazole (10 g,59.8 mmol), compound 6 (29.5 g,62.8 mmol), sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.2 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 20.5g of compounds 1 to 6 were obtained. (Yield 57%, MS: [ M+H ]] ⁺ ＝601)。

PREPARATION EXAMPLES 1-7 Synthesis of Compounds 1-7

9H-carbazole (10 g,59.8 mmol), compound 7 (27.2 g,62.8 mmol), sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.2 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 19.2g of compounds 1 to 7 were obtained. (yield 57%, MS: [ M+H) ] ⁺ ＝565)。

Preparation examples 1-8 Synthesis of Compounds 1-8

9H-carbazole (10 g,59.8 mmol), compound 8 (32.7 g,62.8 mmol), sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.2 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 26.4g of compounds 1 to 8 were obtained. (yield 68%, MS: [ M+H)] ⁺ ＝651)。

Preparation examples 1-9 Synthesis of Compounds 1-9

9H-carbazole (10 g,59.8 mmol), compound 9 (30.4 g,62.8 mmol), sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.2 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 24.6g of compounds 1 to 9 were obtained. (yield 67%, MS: [ M+H) ] ⁺ ＝615)。

PREPARATION EXAMPLES 1-10 Synthesis of Compounds 1-10

9H-carbazole (10 g,59.8 mmol), compound 10 (30.4 g,62.8 mmol), sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.2 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 23.5g of compounds 1 to 10 were obtained. (yield 64%, MS: [ M+H)] ⁺ ＝615)。

PREPARATION EXAMPLES 1-11 Synthesis of Compounds 1-11

9H-carbazole (10 g,59.8 mmol), compound 11 (27.2 g,62.8 mmol), sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-tert-butylphosphine) palladium is added0) (0.6 g,1.2 mmol). After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 17.5g of compounds 1 to 11 was obtained. (yield 52%, MS: [ M+H) ] ⁺ ＝565)。

PREPARATION EXAMPLES 1-12 Synthesis of Compounds 1-12

9H-carbazole (10 g,59.8 mmol), compound 12 (27.9 g,62.8 mmol), sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.2 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 18.2g of compounds 1 to 12 were obtained. (yield 53%, MS: [ M+H)] ⁺ ＝575)。

PREPARATION EXAMPLES 1-13 Synthesis of Compounds 1-13

9H-carbazole (10 g,59.8 mmol), compound 13 (29.5 g,62.8 mmol), sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.2 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. Concentrating the compound Purification by silica gel column chromatography gave 19.4g of compounds 1-13. (yield 54%, MS: [ M+H)] ⁺ ＝601)。

PREPARATION EXAMPLES 1-14 Synthesis of Compounds 1-14

9H-carbazole (10 g,59.8 mmol), compound 14 (35.1 g,62.8 mmol), sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.2 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 28.4g of compounds 1 to 14 was obtained. (yield 69%, MS: [ M+H)] ⁺ ＝690)。

PREPARATION EXAMPLES 1-15 Synthesis of Compounds 1-15

9H-carbazole (10 g,59.8 mmol), compound 15 (31 g,62.8 mmol), sodium t-butoxide (7.5 g,77.7 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.2 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 26.1g of compounds 1 to 15 was obtained. (yield 70%, MS: [ M+H) ] ⁺ ＝625)。

PREPARATION EXAMPLES 1-16 Synthesis of Compounds 1-16

9H-carbazole (10 g,59.8 mmol), compound 16 (31.4 g,62.8 mmol), sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.2 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 22.2g of compounds 1 to 16 were obtained. (yield 59%, MS: [ M+H)] ⁺ ＝631)。

Preparation examples 1 to 17 Synthesis of Compounds 1 to 17

9H-carbazole (10 g,59.8 mmol), compound 17 (26.4 g,62.8 mmol), sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.2 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 18.1g of compounds 1 to 17 was obtained. (yield 55%, MS: [ M+H) ] ⁺ ＝551)。

PREPARATION EXAMPLES 1-18 Synthesis of Compounds 1-18

9H-carbazole (10 g,59.8 mmol), compound substance 18 (32 g,62.8 mmol), sodium tert-butoxide (7.5 g,77.7 mmol) were added under nitrogen atmosphere200mL of xylene was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.2 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 24.5g of compounds 1 to 18 were obtained. (yield 64%, MS: [ M+H)] ⁺ ＝641)。

PREPARATION EXAMPLES 1-19 Synthesis of Compounds 1-19

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9H-carbazole (10 g,59.8 mmol), compound 19 (31.1 g,62.8 mmol), sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.2 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 25.1g of compounds 1 to 19 were obtained. (yield 67%, MS: [ M+H) ] ⁺ ＝627)。

PREPARATION EXAMPLES 1-20 Synthesis of Compounds 1-20

9H-carbazole (10 g,59.8 mmol), compound (20) (33 g,62.8 mmol), sodium t-butoxide (7.5 g,77.7 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.2 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, and after washing with water 2 times, the organic layer was separated, and then washed with waterThe filtrate was filtered after anhydrous magnesium sulfate treatment, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 20g of compounds 1 to 20 were obtained. (yield 51%, MS: [ M+H ]] ⁺ ＝657)。

Preparation examples 1-21 Synthesis of Compounds 1-21

7H-benzo [ c ] under nitrogen atmosphere]Carbazole (7H-benzol [ c ]]carbazole) (10 g,46 mmol), compound 21 (18.1 g,48.3 mmol), potassium phosphate (29.3 g,138.1 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 14.3g of compounds 1 to 21 were obtained. (yield 56%, MS: [ M+H) ] ⁺ ＝555)。

PREPARATION EXAMPLES 1-22 Synthesis of Compounds 1-22

7H-benzo [ c ] under nitrogen atmosphere]Carbazole (10 g,46 mmol), compound 7 (21 g,48.3 mmol), sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 14.7g of compounds 1 to 22 was obtained. (yield 52%, MS: [ M+H)] ⁺ ＝615)。

PREPARATION EXAMPLES 1-23 Synthesis of Compounds 1-23

7H-benzo [ c ] under nitrogen atmosphere]Carbazole (10 g,46 mmol), compound (22) (26.9 g,48.3 mmol), sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 22g of compounds 1 to 23 were obtained. (yield 65%, MS: [ M+H ] ] ⁺ ＝737)。

PREPARATION EXAMPLES 1-24 Synthesis of Compounds 1-24

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7H-benzo [ c ] under nitrogen atmosphere]Carbazole (10 g,46 mmol), compound 23 (16.6 g,48.3 mmol), sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 12.1g of compounds 1 to 24 were obtained. (yield 50%, MS: [ M+H)] ⁺ ＝525)。

PREPARATION EXAMPLES 1-25 Synthesis of Compounds 1-25

7H-benzo [ c ] under nitrogen atmosphere]Carbazole (10 g,46 mmol), compound 24 (16.6 g,48.3 mmol), sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 12.5g of compounds 1 to 25 were obtained. (yield 52%, MS: [ M+H) ] ⁺ ＝525)。

PREPARATION EXAMPLES 1-26 Synthesis of Compounds 1-26

7H-benzo [ c ] under nitrogen atmosphere]Carbazole (10 g,46 mmol), compound (25.1 g,48.3 mmol), sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 20.3g of compounds 1 to 26 were obtained. (yield 63%, MS: [ M+H)] ⁺ ＝701)。

Preparation examples 1 to 27 Synthesis of Compounds 1 to 27

7H-benzo [ c ] under nitrogen atmosphere]Carbazole (10 g,46 mmol), compound 26 (25.4 g,48.3 mmol), sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 2 hours, the reactionAnd finally, cooling to normal temperature, and decompressing to remove the solvent. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 18.2g of compounds 1 to 27 were obtained. (yield 56%, MS: [ M+H) ] ⁺ ＝707)。

PREPARATION EXAMPLES 1-28 Synthesis of Compounds 1-28

Under nitrogen atmosphere, 5H-benzo [ b ]]Carbazole (5H-benzob)]carbazole) (10 g,46 mmol), compound 27 (17.8 g,48.3 mmol), potassium phosphate (29.3 g,138.1 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 16.9g of compounds 1 to 28 were obtained. (yield 67%, MS: [ M+H)] ⁺ ＝549)。

Preparation examples 1 to 29 Synthesis of Compounds 1 to 29

Under nitrogen atmosphere, 5H-benzo [ b ]]Carbazole (10 g,46 mmol), compound 28 (20.3 g,48.3 mmol), sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. Subjecting the concentrated compound to a silica gel column Chromatography gave 19.3g of compounds 1-29. (yield 70%, MS: [ M+H)] ⁺ ＝601)。

PREPARATION EXAMPLES 1-30 Synthesis of Compounds 1-30

Under nitrogen atmosphere, 5H-benzo [ b ]]Carbazole (10 g,46 mmol), compound 29 (21.7 g,48.3 mmol), sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 17.7g of compounds 1 to 30 were obtained. (yield 61%, MS: [ M+H)] ⁺ ＝631)。

PREPARATION EXAMPLES 1-31 Synthesis of Compounds 1-31

Under nitrogen atmosphere, 5H-benzo [ b ]]Carbazole (10 g,46 mmol), compound (30) (24.6 g,48.3 mmol), sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 20g of compounds 1 to 31 were obtained. (yield 63%, MS: [ M+H) ] ⁺ ＝690)。

PREPARATION EXAMPLES 1-32 Synthesis of Compounds 1-32

Under nitrogen atmosphere, 5H-benzo [ b ]]Carbazole (10 g,46 mmol), compound (31) (25.1 g,48.3 mmol), sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 21.3g of compounds 1 to 32 was obtained. (yield 66%, MS: [ M+H)] ⁺ ＝701)。

PREPARATION EXAMPLES 1-33 Synthesis of Compounds 1-33

Under nitrogen atmosphere, 5H-benzo [ b ]]Carbazole (10 g,46 mmol), compound (32) (19 g,48.3 mmol), sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 14g of compounds 1 to 33 were obtained. (yield 53%, MS: [ M+H) ] ⁺ ＝575)。

PREPARATION EXAMPLES 1-34 Synthesis of Compounds 1-34

Under nitrogen atmosphere, 5H-benzo [ b ]]Carbazole (10 g,46 mmol), compound 33 (22.7 g,48.3 mmol), sodium tert-butoxide (5.7)g,59.8 mmol) was added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 15.3g of compounds 1 to 34 were obtained. (yield 51%, MS: [ M+H ]] ⁺ ＝651)。

PREPARATION EXAMPLES 1-35 Synthesis of Compounds 1-35

Under nitrogen atmosphere, 5H-benzo [ b ]]Carbazole (10 g,46 mmol), compound 17 (20.3 g,48.3 mmol), sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 18.2g of compounds 1 to 35 were obtained. (yield 66%, MS: [ M+H) ] ⁺ ＝601)。

PREPARATION EXAMPLES 1-36 Synthesis of Compounds 1-36

Under nitrogen atmosphere, 11H-benzo [ a ]]Carbazole (11H-benzoa)]carbazole) (10 g,46 mmol), compound 34 (22.7 g,48.3 mmol), sodium t-butoxide (5.7 g,59.8 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound is again completelyAfter being dissolved in chloroform and washed with water for 2 times, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 15g of compounds 1 to 36 were obtained. (yield 50%, MS: [ M+H)] ⁺ ＝651)。

PREPARATION EXAMPLES 1-37 Synthesis of Compounds 1-37

Under nitrogen atmosphere, 11H-benzo [ a ]]Carbazole (10 g,46 mmol), compound (35) (21.7 g,48.3 mmol), sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 20.3g of compounds 1 to 37 were obtained. (yield 70%, MS: [ M+H) ] ⁺ ＝631)。

PREPARATION EXAMPLES 1-38 Synthesis of Compounds 1-38

Under nitrogen atmosphere, 11H-benzo [ a ]]Carbazole (10 g,46 mmol), compound (36) (27.1 g,48.3 mmol), sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 20.4g of compounds 1 to 38 were obtained. (yield 60%, MS: [ M+H)] ⁺ ＝741)。

PREPARATION EXAMPLES 1-39 Synthesis of Compounds 1-39

Under nitrogen atmosphere, 11H-benzo [ a ]]Carbazole (10 g,46 mmol), compound 37 (25.4 g,48.3 mmol), sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 17.9g of compounds 1 to 39 was obtained. (yield 55%, MS: [ M+H) ] ⁺ ＝707)。

PREPARATION EXAMPLES 1-40 Synthesis of Compounds 1-40

Under nitrogen atmosphere, 11H-benzo [ a ]]Carbazole (10 g,46 mmol), compound 38 (24.6 g,48.3 mmol), sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 15.9g of compounds 1 to 40 were obtained. (yield 50%, MS: [ M+H)] ⁺ ＝691)。

PREPARATION EXAMPLES 1-41 Synthesis of Compounds 1-41

7H-dibenzo [ b, g ] under nitrogen atmosphere]Carbazole (7H-dibenzo [ b, g)]carbazole) (10 g,37.4 mmol), compound 39 (14.7 g,39.3 mmol), potassium phosphate (23.8 g,112.2 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 11.5g of compounds 1 to 41 were obtained. (yield 51%, MS: [ M+H ] ] ⁺ ＝605)。

PREPARATION EXAMPLES 1-42 Synthesis of Compounds 1-42

7H-dibenzo [ b, g ] under nitrogen atmosphere]Carbazole (10 g,37.4 mmol), compound (40) (19 g,39.3 mmol), sodium tert-butoxide (4.7 g,48.6 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 13.9g of compounds 1 to 42 were obtained. (yield 52%, MS: [ M+H)] ⁺ ＝715)。

PREPARATION EXAMPLES 1-43 Synthesis of Compounds 1-43

Under nitrogen atmosphere, 6H-dibenzo [ b, H]Carbazole (6H-dibenzo [ b, H ]]carbazole) (10 g,37.4 mmol), compound 41 (14.1 g,39.3 mmol), potassium phosphate (23.8 g,112.2 mmol) were added to 200mLIn xylene, stirring and refluxing. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 13.6g of compounds 1 to 43 was obtained. (yield 62%, MS: [ M+H) ] ⁺ ＝589)。

PREPARATION EXAMPLES 1-44 Synthesis of Compounds 1-44

Under nitrogen atmosphere, 6H-dibenzo [ b, H]Carbazole (10 g,37.4 mmol), compound 42 (19.6 g,39.3 mmol), sodium tert-butoxide (4.7 g,48.6 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 19.1g of compounds 1 to 44 were obtained. (yield 70%, MS: [ M+H)] ⁺ ＝731)。

PREPARATION EXAMPLES 1-45 Synthesis of Compounds 1-45

Under nitrogen atmosphere, 13H-dibenzo [ a, H]Carbazole (13H-dibenzo [ a, H ]]carbazole) (10 g,37.4 mmol), compound 43 (16 g,39.3 mmol), potassium phosphate (23.8 g,112.2 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved again in chloroform After washing with water 2 times, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 14.1g of compounds 1 to 45 was obtained. (yield 59%, MS: [ M+H)] ⁺ ＝639)。

PREPARATION EXAMPLES 1-46 Synthesis of Compounds 1-46

Under nitrogen atmosphere, 13H-dibenzo [ a, H]Carbazole (10 g,37.4 mmol), compound 44 (17.7 g,39.3 mmol), sodium tert-butoxide (4.7 g,48.6 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 13.7g of compounds 1 to 46 was obtained. (yield 54%, MS: [ M+H)] ⁺ ＝681)。

PREPARATION EXAMPLES 1-47 Synthesis of Compounds 1-47

7H-dibenzo [ c, g ] under nitrogen atmosphere]Carbazole (7H-dibenzo [ c, g)]carbazole) (10 g,37.4 mmol), compound 45 (14.1 g,39.3 mmol), potassium phosphate (23.8 g,112.2 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 12.1g of compounds 1 to 47 was obtained. (yield 55%, MS: [M+H] ⁺ ＝589)。

(production of the second Compound)

Synthesis example 1 Synthesis of Compound AA

1-bromo-3-chloro-2-fluorobenzene (1-bromo3-chloroo-2-fluorobenzene) (15 g,71.6 mmol) and (1-hydroxynaphthalen-2-yl) boric acid ((1-hydroxynaphthalen-2-yl) carboxylic acid) (14.8 g,78.8 mmol) were added to 300mL of Tetrahydrofuran (THF) under nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (K) ₂ CO ₃ 29.7g,214.9 mmol) of bis (tri-t-butylphosphine) palladium (0) (Pd (t-Bu) ₃ P) ₂ 0.4g,0.7 mmol). After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 14.2g of compound aa_p1 was produced. (yield 73%, MS: [ M+H)] ⁺ ＝273)。

Compound AA_P1 (15 g,55 mmol) and potassium carbonate (22.8 g,165 mmol) were added to 300mL of Dimethylformamide (DMF) under nitrogen, stirred and refluxed. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 10.3g of compound AA was produced. (yield 74%, MS: [ M+H ] ] ⁺ ＝253)。

Synthesis example 2 Synthesis of Compound AB

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Compound AB was produced by the same method as in synthesis example 1 using 1-bromo-4-chloro-2-fluorobenzene (1-bromo4-chloro-2-fluorobenzene) instead of 1-bromo-3-chloro-2-fluorobenzene.

Synthesis example 3 Synthesis of Compound AC

Compound AC was produced by the same method as in synthesis example 1 using 2-bromo-4-chloro-1-fluorobenzene (2-bromo4-chloro-1-fluorobenzene) instead of 1-bromo-3-chloro-2-fluorobenzene.

Synthesis example 4 Synthesis of Compound AD

Compound AD was produced by the same method as in synthesis example 1 using 2-bromo-1-chloro-3-fluorobenzene (2-bromoo-1-chloroo-3-fluorobenzene) instead of 1-bromo-3-chloro-2-fluorobenzene.

Synthesis example 5 Synthesis of Compound AE

Compound AE was produced by the same method as in synthesis example 1 using 1-bromo-2-fluorobenzene (1-bromoo-2-fluorobenzene) instead of 1-bromo-3-chloro-2-fluorobenzene and (3-chloro-1-hydroxynaphthalen-2-yl) boric acid ((3-chloro-1-hydroxynaphthalen-2-yl) instead of (1-hydroxynaphthalen-2-yl) boric acid.

Synthesis example 6 Synthesis of Compound AF

Compound AF was produced by the same method as in synthesis example 1 using 1-bromo-2-fluorobenzene instead of 1-bromo-3-chloro-2-fluorobenzene and (4-chloro-1-hydroxynaphthalen-2-yl) boric acid instead of (1-hydroxynaphthalen-2-yl) boric acid.

Synthesis example 7 Synthesis of Compound BA

Compound BA was produced by the same method as in synthesis example 1 using (2-hydroxynaphthalen-1-yl) boronic acid ((2-hydroxynaphthalen-1-yl) boronic acid) instead of (1-hydroxynaphthalen-2-yl) boronic acid.

Synthesis example 8 Synthesis of Compound BB

Compound BB was produced by the same method as in synthesis example 1 using 1-bromo-4-chloro-2-fluorobenzene instead of 1-bromo-3-chloro-2-fluorobenzene and (2-hydroxynaphthalen-1-yl) boric acid instead of (1-hydroxynaphthalen-2-yl) boric acid.

Synthesis example 9 Synthesis of Compound BC

Compound BC was produced by the same method as in synthesis example 1, using 2-bromo-4-chloro-1-fluorobenzene instead of 1-bromo-3-chloro-2-fluorobenzene and (2-hydroxynaphthalen-1-yl) boric acid instead of (1-hydroxynaphthalen-2-yl) boric acid.

Synthesis example 10 Synthesis of Compound BD

Compound BD was produced by the same procedure as in synthesis example 1 using 1-bromo-2-fluorobenzene instead of 1-bromo-3-chloro-2-fluorobenzene and (3-chloro-2-hydroxynaphthalen-1-yl) boric acid instead of (1-hydroxynaphthalen-2-yl) boric acid.

Synthesis example 11 Synthesis of Compound BE

Compound BE was produced by the same method as in synthesis example 1 using 1-bromo-2-fluorobenzene instead of 1-bromo-3-chloro-2-fluorobenzene and (4-chloro-2-hydroxynaphthalen-1-yl) boric acid instead of (1-hydroxynaphthalen-2-yl) boric acid.

Synthesis example 12 Synthesis of Compound CA

Compound CA was produced by the same method as in synthesis example 1 using (3-hydroxynaphthalen-2-yl) boronic acid ((3-hydroxynaphthalen-2-yl) boronic acid) instead of (1-hydroxynaphthalen-2-yl) boronic acid.

Synthesis example 13 Synthesis of Compound CB

Compound CB was produced by the same method as in synthesis example 1, using 1-bromo-4-chloro-2-fluorobenzene instead of 1-bromo-3-chloro-2-fluorobenzene and (3-hydroxynaphthalen-2-yl) boric acid instead of (1-hydroxynaphthalen-2-yl) boric acid.

Synthesis example 14 Synthesis of Compound CC

Compound CC was produced by the same method as in synthesis example 1 using 2-bromo-4-chloro-1-fluorobenzene instead of 1-bromo-3-chloro-2-fluorobenzene and (3-hydroxynaphthalen-2-yl) boric acid instead of (1-hydroxynaphthalen-2-yl) boric acid.

Synthesis example 15 Synthesis of Compound CD

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Compound CD was produced by the same method as in synthesis example 1, using 2-bromo-1-chloro-3-fluorobenzene instead of 1-bromo-3-chloro-2-fluorobenzene and (3-hydroxynaphthalen-2-yl) boric acid instead of (1-hydroxynaphthalen-2-yl) boric acid.

Synthesis example 16 Synthesis of Compound CE

Compound CE was produced by the same method as in synthesis example 1 using 1-bromo-2-fluorobenzene instead of 1-bromo-3-chloro-2-fluorobenzene and (4-chloro-3-hydroxynaphthalen-2-yl) boric acid instead of (1-hydroxynaphthalen-2-yl) boric acid.

Synthesis example 17 Synthesis of Compound CF

Compound CF was produced by the same method as in synthesis example 1 using 1-bromo-2-fluorobenzene instead of 1-bromo-3-chloro-2-fluorobenzene and (1-chloro-3-hydroxynaphthalen-2-yl) boric acid instead of (1-hydroxynaphthalen-2-yl) boric acid.

Synthesis example 18 Synthesis of Compound DA

1-bromo-3-chlorobenzene (1-bromoo-3-chlorobenzene) (15 g,78.3 mmol) and (1- (methylthio) naphthalen-2-yl) boronic acid ((1- (methylthio) naphthalen-2-yl) acrylic acid) (18.8 g,86.2 mmol) were added to 300mL of THF under nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (K) ₂ CO ₃ 32.5g,235 mmol) of bis (tri-t-butylphosphine) palladium (0) (Pd (t-Bu) was dissolved in 97mL of water and then poured into the vessel after stirring the vessel sufficiently ₃ P) ₂ 0.4g,0.8 mmol). After reacting for 12 hours, cooling to normal temperature, and mixing the organic layer with waterAfter the separation of the layers, the organic layer was distilled. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 16.2g of compound da_p1 was produced. (yield 73%, MS: [ M+H)] ⁺ ＝285)

Compound da_p1 (15 g,52.7 mmol) and hydrogen peroxide (3.6 g,105.3 mmol) were added to 200mL of acetic acid (AcOH) under nitrogen atmosphere, stirred and refluxed. After 3 hours, the reaction was poured into water, the crystals were allowed to fall, and filtration was performed. The filtered solid was dissolved in chloroform, and after washing with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added, and after stirring, filtration was performed, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 10.4g of compound DA_P2 was produced. (yield 66%, MS: [ M+H) ] ⁺ ＝301)

Under nitrogen, the compound DA_P2 (15 g,49.9 mmol) was added to 200mL of H ₂ SO ₄ In (3) stirring. After 2 hours, at the end of the reaction, the reaction was poured into water, the crystals were allowed to fall, and filtration was performed. The filtered solid was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 9.2g of compound DA was produced. (yield 69%, MS: [ M+H)] ⁺ ＝269)

Synthesis example 19 Synthesis of Compound DB

Compound DB was produced by the same method as in synthesis example 18 using 1-bromo-4-chlorobenzene (1-bromoo-4-chlorobenzene) instead of 1-bromo-3-chlorobenzene.

Synthesis example 20 Synthesis of Compound DC

Compound DC was produced by the same method as in synthesis example 18.

Synthesis example 21 Synthesis of Compound DD

Compound DD was produced by the same method as in synthesis example 18 using 1-bromo-2-chlorobenzene (1-bromoo-2-chlorobenzene) instead of 1-bromo-3-chlorobenzene.

Synthesis example 22 Synthesis of Compound DE

Compound DE was produced by the same method as in synthesis example 18 using bromobenzene (bromobenzene) instead of 1-bromo-3-chlorobenzene, using (3-chloro-1- (methylthio) naphthalen-2-yl) boronic acid ((3-chloro-1- (methylthio) naphthalen-2-yl) boronic acid) instead of (1- (methylthio) naphthalen-2-yl) boronic acid.

Synthesis example 23 Synthesis of Compound DF

Compound DF was produced by the same method as in synthesis example 18 using bromobenzene instead of 1-bromo-3-chlorobenzene and (4-chloro-1- (methylthio) naphthalen-2-yl) boronic acid ((4-chloro-1- (methylthioo) naphthalen-2-yl) boronic acid) instead of (1- (methylthio) naphthalen-2-yl) boronic acid.

Synthesis example 24 Synthesis of Compound EA

Compound EA was produced by the same method as in synthesis example 18 using (2- (methylthio) naphthalen-1-yl) boronic acid ((2- (methylthio) naphthalen-1-yl) boronic acid) instead of (1- (methylthio) naphthalen-2-yl) boronic acid.

Synthesis example 25 Synthesis of Compound EB

Compound EB was produced by the same method as in synthesis example 18 using 1-bromo-4-chlorobenzene instead of 1-bromo-3-chlorobenzene and 2- (methylthio) naphthalen-1-yl) boronic acid instead of (1- (methylthio) naphthalen-2-yl) boronic acid.

Synthesis example 26 Synthesis of Compound EC

Compound EC was produced by the same method as in synthesis example 18 using 2- (methylthio) naphthalen-1-yl) boronic acid instead of (1- (methylthio) naphthalen-2-yl) boronic acid.

Synthesis example 27 Synthesis of Compound ED

Compound ED was produced by the same method as in synthesis example 18 using bromobenzene instead of 1-bromo-3-chlorobenzene and (3-chloro-2- (methylthio) naphthalen-1-yl) boronic acid ((3-chloro-2- (methylthioo) naphthalen-1-yl) boronic acid) instead of (1- (methylthio) naphthalen-2-yl) boronic acid.

Synthesis example 28 Synthesis of Compound EF

Compound EE was produced by the same method as in synthesis example 18 using bromobenzene instead of 1-bromo-3-chlorobenzene and (4-chloro-2- (methylthio) naphthalen-1-yl) boronic acid ((4-chloro-2- (methylthioo) naphthalen-1-yl) boronic acid) instead of (1- (methylthio) naphthalen-2-yl) boronic acid.

Synthesis example 29 Synthesis of Compound FA

Compound FA was produced by the same method as in synthesis example 18 using (3- (methylthio) naphthalen-2-yl) boronic acid ((3- (methylthio) naphthalen-2-yl) boronic acid) instead of (methylthio) naphthalen-2-yl) boronic acid.

Synthesis example 30 Synthesis of Compound FB

Compound FB was produced by the same method as in synthesis example 18 using 1-bromo-4-chlorobenzene instead of 1-bromo-3-chlorobenzene and (3- (methylthio) naphthalen-2-yl) boric acid instead of (1- (methylthio) naphthalen-2-yl) boric acid.

Synthesis example 31 Synthesis of Compound FC

Compound FC was produced by the same method as in synthesis example 18 using (3- (methylthio) naphthalen-2-yl) boric acid instead of (methylthio) naphthalen-2-yl) boric acid.

Synthesis example 32 Synthesis of Compound FD

Compound FD was produced by the same method as in synthesis example 18 using 1-bromo-2-chlorobenzene instead of 1-bromo-3-chlorobenzene and (3- (methylthio) naphthalen-2-yl) boric acid instead of (1- (methylthio) naphthalen-2-yl) boric acid.

Synthesis example 33 Synthesis of Compound FE

Compound FE was produced by the same method as in synthesis example 18 using bromobenzene instead of 1-bromo-3-chlorobenzene and (4-chloro-3- (methylthio) naphthalen-2-yl) boronic acid ((4-chloro-3- (methylthioo) naphthalen-2-yl) boronic acid) instead of (1- (methylthio) naphthalen-2-yl) boronic acid.

Synthesis example 34 Synthesis of Compound FF

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Compound FF was produced by the same method as in synthesis example 18 using bromobenzene instead of 1-bromo-3-chlorobenzene and (1-chloro-3- (methylthio) naphthalen-2-yl) boronic acid ((1-chloro-3- (methylthioo) naphthalen-2-yl) boronic acid) instead of (1- (methylthio) naphthalen-2-yl) boronic acid.

PREPARATION EXAMPLE 2-1 Synthesis of Compound 2-1

Compound 1 (10 g,31 mmol), compound amine (amine) 1 (8.8 g,32.6 mmol), sodium tert-butoxide (NaOtBu, 3.9g,40.3 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (Pd (t-Bu) ₃ P) ₂ 0.3g,0.6 mmol). After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 9g of compound substance 1-1 was obtained. (yield 57%, MS: [ M+H) ] ⁺ ＝511)。

Compound 1-1 (10 g,19.6 mmol), compound AC (5.2 g,20.6 mmol), sodium tert-butoxide (2.4 g,25.5 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 2 hours, cooling to normal temperature after the reaction is finished, and decompressing to remove the solventAnd (3) an agent. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.8g of compound 2-1 was obtained. (yield 55%, MS: [ M+H)] ⁺ ＝727)。

PREPARATION EXAMPLE 2-2 Synthesis of Compound 2-2

Compound 1 (10 g,31 mmol), compound amine 2 (7.1 g,32.6 mmol), sodium t-butoxide (3.9 g,40.3 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 9.4g of compound matters 1-2 was obtained. (yield 66%, MS: [ M+H) ] ⁺ ＝461)。

Compound 1-2 (10 g,166.1 mmol), compound AD (44.1 g,174.4 mmol), sodium tert-butoxide (20.8 g,216 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (1.7 g,3.3 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 67.4g of compound 2-2 was obtained. (yield 60%, MS: [ M+H)] ⁺ ＝677)。

PREPARATION EXAMPLE 2-3 Synthesis of Compound 2-3

Compound 1 (10 g,31 mmol), compound amine 3 (8.8 g,32.6 mmol), sodium t-butoxide (3.9 g,40.3 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 11.1g of compound matters 1-3 was obtained. (yield 70%, MS: [ M+H) ] ⁺ ＝511)。

Compound 1-3 (10 g,19.6 mmol), compound AE (5.2 g,20.6 mmol), sodium tert-butoxide (2.4 g,25.5 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.4g of compound 2-3 was obtained. (yield 52%, MS: [ M+H)] ⁺ ＝727)。

PREPARATION EXAMPLE 2-4 Synthesis of Compounds 2-4

Compound 1 (10 g,31 mmol), compound amine 4 (8 g,32.6 mmol), sodium tert-butoxide (3.9 g,40.3 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. Will be concentrated The condensed compound was purified by silica gel column chromatography to obtain 10.4g of compound matters 1 to 4. (yield 69%, MS: [ M+H)] ⁺ ＝487)。

Compound 1-4 (10 g,20.5 mmol), compound BB (5.5 g,21.6 mmol), sodium tert-butoxide (2.6 g,26.7 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.1g of compound 2-4 was obtained. (yield 56%, MS: [ M+H)] ⁺ ＝703)。

PREPARATION EXAMPLE 2-5 Synthesis of Compounds 2-5

Compound 1 (10 g,31 mmol), compound amine 5 (8 g,32.6 mmol), sodium tert-butoxide (3.9 g,40.3 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.5g of compound matters 1 to 5 were obtained. (yield 56%, MS: [ M+H) ] ⁺ ＝487)。

Compound 1-5 (10 g,20.5 mmol), compound BC (5.5 g,21.6 mmol), sodium tert-butoxide (2.6 g,26.7 mmol) are added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroformAfter washing with water 2 times, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.2g of compound 2-5 was obtained. (yield 57%, MS: [ M+H)] ⁺ ＝703)。

PREPARATION EXAMPLES 2-6 Synthesis of Compounds 2-6

Compound 1 (10 g,31 mmol), compound amine 6 (6.5 g,32.6 mmol), sodium t-butoxide (3.9 g,40.3 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.2g of compound matters 1 to 6 were obtained. (yield 60%, MS: [ M+H) ] ⁺ ＝441)。

Compound 1-6 (10 g,22.7 mmol), compound BC (6 g,23.8 mmol), sodium t-butoxide (2.8 g,29.5 mmol) are added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 9.7g of compound 2-6 was obtained. (yield 65%, MS: [ M+H ]] ⁺ ＝657)。

PREPARATION EXAMPLES 2-7 Synthesis of Compounds 2-7

Compound 1 (15 g,46.6 mmol) and 2 (10.1 g,48.9 mmol) are added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (K) ₂ CO ₃ 19.3g,139.7 mmol) of bis (tri-t-butylphosphine) palladium (0) (Pd (t-Bu) ₃ P) ₂ 0.2g,0.5 mmol). After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 14.8g of compound substance 1-7-1 was produced. (yield 79%, MS: [ M+H) ] ⁺ ＝404)。

Compound 1 (10 g,31 mmol), compound amine 7 (6.5 g,32.6 mmol), sodium t-butoxide (NaOtBu, 3.9g,40.3 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (Pd (t-Bu) ₃ P) ₂ 0.3g,0.6 mmol). After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.2g of compound matters 1-7-2 was obtained. (yield 60%, MS: [ M+H)] ⁺ ＝441)。

Compound 1-7-2 (10 g,18.6 mmol), compound CB (4.9 g,19.6 mmol), sodium tert-butoxide (2.3 g,24.2 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 9.3g of compound 2-7 was obtained. (yield 66%, MS: [ M+H) ] ⁺ ＝753)。

PREPARATION EXAMPLES 2-8 Synthesis of Compounds 2-8

Compound 1 (10 g,31 mmol), compound amine 7 (5.5 g,32.6 mmol), sodium t-butoxide (3.9 g,40.3 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 2.5g of compound matters 1 to 8 were obtained. (yield 58%, MS: [ M+H)] ⁺ ＝141)。

Compound 1-8 (10 g,24.4 mmol), compound CC (6.5 g,25.6 mmol), sodium tert-butoxide (3 g,31.7 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.8g of compound 2-8 was obtained. (yield 51%, MS: [ M+H ] ] ⁺ ＝627)

PREPARATION EXAMPLES 2-9 Synthesis of Compounds 2-9

Compound 1 (10 g,31 mmol), compound amine 8 (5.5 g,32.6 mmol), sodium t-butoxide (3.9 g,40.3 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was charged. After 3 hours, the reaction junctionThe bundle was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.9g of compound substance 1-9-1 was obtained. (yield 62%, MS: [ M+H)] ⁺ ＝411)。

Compound 1-9-1 (10 g,24.4 mmol), compound 3 (4.9 g,25.6 mmol), sodium t-butoxide (3 g,31.7 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.9g of compound matters 1-9-2 was obtained. (yield 62%, MS: [ M+H) ] ⁺ ＝521)。

1,4-Di of Compound Material 1-9-2 (15 g,28.8 mmol) and bis (pinacolato) diboron (bis (pinacolato) Diboron) (8 g,31.7 mmol) in 300mL under a nitrogen atmosphere

The alkane (1, 4-dioxane) was stirred while refluxing. Then, potassium acetate (KOAc, 4.2g,43.2 mmol) was added thereto, and after stirring thoroughly, bis (dibenzylideneacetone) palladium (0) (Pd (dba) ₂ 0.5g,0.9 mmol) and tricyclohexylphosphine (PCy ₃ 0.5g,1.7 mmol). The reaction mixture was cooled to room temperature after 7 hours of reaction, and the organic layer was separated from the water by chloroform and distilled. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 12.7g of compound matters 1-9-3 were produced. (yield 72%, MS: [ M+H)] ⁺ ＝613)。

Compounds 1-9-3 (15 g,24.5 mmol) and under nitrogen atmosphereCompound CD (6.5 g,25.7 mmol) is added to 300mL of THF, stirred and refluxed. Then, potassium carbonate (K) ₂ CO ₃ 10.2g,73.5 mmol) of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was dissolved in 30mL of water and the mixture was stirred well. After 11 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 12.2g of compounds 2 to 9 was produced. (yield 71%, MS: [ M+H) ] ⁺ ＝703)。

PREPARATION EXAMPLE 2-10 Synthesis of Compounds 2-10

Compound 1-8 (10 g,24.4 mmol), compound 4 (4.9 g,25.6 mmol), sodium tert-butoxide (3 g,31.7 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.2g of compound substance 1-8-1 was obtained. (yield 57%, MS: [ M+H)] ⁺ ＝521)。

1, 4-Di of Compound material 1-8-1 (15 g,28.8 mmol) and bis (pinacolato) diboron (8 g,31.7 mmol) in 300mL under nitrogen

The alkane was refluxed while stirring. Then, potassium acetate (KOAc, 4.2g,43.2 mmol) was added thereto, and after stirring thoroughly, bis (dibenzylideneacetone) palladium (0) (Pd (dba) ₂ 0.5g,0.9 mmol) and tricyclohexylphosphine (PCy) ₃ 0.5g,1.7 mmol). Reaction 5After cooling to room temperature for an hour, the organic layer was separated from the water by chloroform and distilled. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 11.8g of compound matters 1-8-2 was produced. (yield 67%, MS: [ M+H) ] ⁺ ＝613)。

Compound 1-8-2 (15 g,24.5 mmol) and compound CA (6.5 g,25.7 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (K) ₂ CO ₃ 10.2g,73.5 mmol) of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was dissolved in 30mL of water and the mixture was stirred well. After 11 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 11.9g of compounds 2 to 10 was produced. (yield 69%, MS: [ M+H)] ⁺ ＝703)。

PREPARATION EXAMPLE 2-11 Synthesis of Compounds 2-11

Compound 5 (10 g,26.9 mmol), compound amine 9 (6.9 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.8g of compound substance 5-1 was obtained. (yield 61%, MS: [ M+H) ] ⁺ ＝537)。

Under nitrogen atmosphere, the compound is preparedMass 5-1 (10 g,18.6 mmol), compound AA (4.9 g,19.6 mmol), sodium tert-butoxide (2.3 g,24.2 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 9g of compounds 2 to 11 were obtained. (yield 64%, MS: [ M+H)] ⁺ ＝753)。

PREPARATION EXAMPLE 2-12 Synthesis of Compounds 2-12

Compound 5 (10 g,26.9 mmol), compound amine 10 (6.2 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.9g of compound substance 5-2 was obtained. (yield 65%, MS: [ M+H ] ] ⁺ ＝511)。

Compound 5-2 (10 g,19.6 mmol), compound BB (5.2 g,20.6 mmol), sodium tert-butoxide (2.4 g,25.5 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.4g of compound 2-12 was obtained. (yield 52%，MS:[M+H] ⁺ ＝727)。

PREPARATION EXAMPLE 2-13 Synthesis of Compounds 2-13

Compound 5 (10 g,26.9 mmol), compound amine 11 (5.5 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.5g of compound substance 5-3 was obtained. (yield 65%, MS: [ M+H ] ] ⁺ ＝485)。

Compound 5-3 (10 g,20.6 mmol), compound CE (5.5 g,21.7 mmol), sodium tert-butoxide (2.6 g,26.8 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.5g of compound 2-13 was obtained. (yield 52%, MS: [ M+H)] ⁺ ＝701)。

PREPARATION EXAMPLE 2-14 Synthesis of Compounds 2-14

Compound 6 (10 g,31 mmol), compound amine 12 (7.1 g,32.6 mmol), sodium t-butoxide (3.9 g,40.3 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-tertiary)Butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.4g of compound substance 6-1 was obtained. (yield 52%, MS: [ M+H) ] ⁺ ＝461)。

Compound 6-1 (10 g,21.7 mmol), compound AC (5.8 g,22.8 mmol), sodium tert-butoxide (2.7 g,28.2 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 10g of compounds 2 to 14 were obtained. (yield 68%, MS: [ M+H)] ⁺ ＝677)。

PREPARATION EXAMPLES 2-15 Synthesis of Compounds 2-15

Compound 6 (10 g,31 mmol), compound amine 13 (9.6 g,32.6 mmol), sodium t-butoxide (3.9 g,40.3 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 10.5g of compound substance 6-2 was obtained. (yield 63%, MS: [ M+H) ] ⁺ ＝537)。

Compound 6-2 (10 g,18.6 mmol), compound BA (4.9 g,19.6 mmol) were reacted under nitrogen) Sodium tert-butoxide (2.3 g,24.2 mmol) was added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.1g of compound 2-15 was obtained. (yield 51%, MS: [ M+H ]] ⁺ ＝753)。

PREPARATION EXAMPLE 2-16 Synthesis of Compounds 2-16

Compound 6 (10 g,31 mmol), compound amine 10 (7.1 g,32.6 mmol), sodium t-butoxide (3.9 g,40.3 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 9g of compound substance 6-3 was obtained. (yield 63%, MS: [ M+H) ] ⁺ ＝461)。

Compound 6-3 (10 g,21.7 mmol), compound CA (5.8 g,22.8 mmol), sodium tert-butoxide (2.7 g,28.2 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 9g of compounds 2 to 16 were obtained. (yield 61%, MS: [ M+H)] ⁺ ＝677)。

PREPARATION EXAMPLE 2-17 Synthesis of Compounds 2-17

Compound 7 (10 g,26.9 mmol), compound amine 14 (6.2 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.2g of compound substance 7-1 was obtained. (yield 58%, MS: [ M+H) ] ⁺ ＝461)。

Compound 7-1 (10 g,19.6 mmol), compound AC (5.2 g,20.6 mmol), sodium tert-butoxide (2.4 g,25.5 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.1g of compound 2-17 was obtained. (yield 50%, MS: [ M+H)] ⁺ ＝727)。

PREPARATION EXAMPLES 2-18 Synthesis of Compounds 2-18

Compound 8 (10 g,21.1 mmol), compound amine 10 (4.9 g,22.1 mmol), sodium tert-butoxide (2.6 g,27.4 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After the lapse of 2 hours, the reaction time was set,after the reaction, the mixture was cooled to room temperature and the solvent was removed by reducing the pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.9g of compound substance 8-1 was obtained. (yield 61%, MS: [ M+H) ] ⁺ ＝613)。

Compound 8-1 (10 g,16.3 mmol), compound CE (4.3 g,17.1 mmol), sodium tert-butoxide (2 g,21.2 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7g of compounds 2 to 18 were obtained. (yield 52%, MS: [ M+H)] ⁺ ＝829)。

PREPARATION EXAMPLE 2-19 Synthesis of Compounds 2-19

Compound 9 (10 g,31 mmol), compound amine 15 (9.6 g,32.6 mmol), sodium t-butoxide (3.9 g,40.3 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 10.7g of compound substance 9-1 was obtained. (yield 64%, MS: [ M+H) ] ⁺ ＝537)。

Compound 9-1 (10 g,18.6 mmol), compound BB (4.9 g,19.6 mmol), sodium tert-butoxide (2.3 g,24.2 mmol) were added to 200mL of xylene under nitrogenStirring and refluxing. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.4g of compound 2-19 was obtained. (yield 60%, MS: [ M+H)] ⁺ ＝753)。

PREPARATION EXAMPLE 2-20 Synthesis of Compounds 2-20

Compound 9 (10 g,31 mmol), compound amine 4 (8 g,32.6 mmol), sodium tert-butoxide (3.9 g,40.3 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.6g of compound substance 9-2 was obtained. (yield 57%, MS: [ M+H) ] ⁺ ＝487)。

Compound 9-2 (10 g,20.5 mmol), compound CA (5.5 g,21.6 mmol), sodium tert-butoxide (2.6 g,26.7 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.2g of compound 2-20 was obtained. (yield 57%, MS: [ M+H)] ⁺ ＝703)。

PREPARATION EXAMPLE 2-21 Synthesis of Compounds 2-21

Compound 9 (10 g,31 mmol), compound amine 16 (7.1 g,32.6 mmol), sodium t-butoxide (3.9 g,40.3 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.6g of compound substance 9-3 was obtained. (yield 53%, MS: [ M+H) ] ⁺ ＝461)。

Compound 9-3 (10 g,21.7 mmol), compound CF (5.8 g,22.8 mmol), sodium tert-butoxide (2.7 g,28.2 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.9g of compound 2-21 was obtained. (yield 54%, MS: [ M+H)] ⁺ ＝677)。

PREPARATION EXAMPLE 2-22 Synthesis of Compounds 2-22

Compound 10 (10 g,26.9 mmol), compound amine 16 (7.6 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization.Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 10.5g of compound substance 10-1 was obtained. (yield 70%, MS: [ M+H) ] ⁺ ＝561)。

Compound 10-1 (10 g,17.8 mmol), compound AB (4.7 g,18.7 mmol), sodium tert-butoxide (2.2 g,23.2 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 9.6g of compound 2-22 was obtained. (yield 69%, MS: [ M+H)] ⁺ ＝777)。

PREPARATION EXAMPLE 2-23 Synthesis of Compounds 2-23

Compound 11 (10 g,26.9 mmol), compound amine 17 (5.2 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.1g of compound substance 11-1 was obtained. (yield 56%, MS: [ M+H) ] ⁺ ＝475)。

Compound 11-1 (10 g,21.1 mmol), compound CB (5.6 g,22.1 mmol), sodium tert-butoxide (2.6 g,27.4 mmol) are added to 200mL of xylene under nitrogen, stirred and refluxed. Then, put into double (triple)T-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8g of compound 2-23 was obtained. (yield 55%, MS: [ M+H)] ⁺ ＝691)。

PREPARATION EXAMPLE 2-24 Synthesis of Compounds 2-24

Compound 12 (10 g,26.9 mmol), compound amine 8 (4.8 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.4g of compound substance 12-1 was obtained. (yield 68%, MS: [ M+H) ] ⁺ ＝461)。

Compound 12-1 (10 g,21.7 mmol), compound CC (5.8 g,22.8 mmol), sodium tert-butoxide (2.7 g,28.2 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.7g of compound 2-24 was obtained. (yield 59%, MS: [ M+H)] ⁺ ＝677)。

PREPARATION EXAMPLE 2-25 Synthesis of Compounds 2-25

Compound 13 (10 g,26.9 mmol), compound amine 18 (6.9 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.5g of compound substance 13-1 was obtained. (yield 59%, MS: [ M+H) ] ⁺ ＝537)。

Compound 13-1 (10 g,18.6 mmol), compound AD (4.9 g,19.6 mmol), sodium tert-butoxide (2.3 g,24.2 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.3g of compound 2-25 was obtained. (yield 59%, MS: [ M+H)] ⁺ ＝753)。

PREPARATION EXAMPLES 2-26 Synthesis of Compounds 2-26

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Compound 13 (10 g,26.9 mmol), compound amine 4 (6.9 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound is completely dissolved againAfter washing with chloroform and water 2 times, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.6g of compound substance 13-2 was obtained. (yield 53%, MS: [ M+H) ] ⁺ ＝537)。

Compound 13-2 (10 g,18.6 mmol), compound BB (4.9 g,19.6 mmol), sodium tert-butoxide (2.3 g,24.2 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.3g of compound 2-26 was obtained. (yield 59%, MS: [ M+H)] ⁺ ＝753)。

PREPARATION EXAMPLES 2-27 Synthesis of Compounds 2-27

Compound 14 (10 g,26.9 mmol), compound amine 19 (6.9 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.4g of compound substance 14-1 was obtained. (yield 58%, MS: [ M+H) ] ⁺ ＝537)。

Compound 14-1 (10 g,18.7 mmol), compound AC (5 g,19.6 mmol), sodium t-butoxide (2.3 g,24.3 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. Warp yarnAfter 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 9.7g of compound 2-27 was obtained. (yield 69%, MS: [ M+H)] ⁺ ＝751)。

PREPARATION EXAMPLES 2-28 Synthesis of Compounds 2-28

Compound 15 (10 g,26.9 mmol), compound amine 14 (6.2 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.5g of compound substance 15-1 was obtained. (yield 55%, MS: [ M+H) ] ⁺ ＝511)

Compound 15-1 (10 g,19.6 mmol), compound CF (5.2 g,20.6 mmol), sodium tert-butoxide (2.4 g,25.5 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 9.4g of compounds 2 to 28 was obtained. (yield 66%, MS: [ M+H)] ⁺ ＝727)。

PREPARATION EXAMPLES 2-29 Synthesis of Compounds 2-29

Compound 16 (10 g,26.9 mmol), compound amine 7 (4.8 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.9g of compound substance 16-1 was obtained. (yield 64%, MS: [ M+H) ] ⁺ ＝461)

Compound 16-1 (10 g,21.7 mmol), compound CD (5.8 g,22.8 mmol), sodium tert-butoxide (2.7 g,28.2 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.1g of compounds 2 to 29 was obtained. (yield 55%, MS: [ M+H)] ⁺ ＝677)。

PREPARATION EXAMPLE 2-30 Synthesis of Compounds 2-30

Compound 17 (10 g,26.9 mmol), compound amine 20 (6.2 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and separatedThe organic layer was treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.4g of compound 17-1 was obtained. (yield 61%, MS: [ M+H) ] ⁺ ＝511)。

Compound 17-1 (10 g,19.6 mmol), compound CA (5.2 g,20.6 mmol), sodium tert-butoxide (2.4 g,25.5 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.7g of compound 2-30 was obtained. (yield 61%, MS: [ M+H)] ⁺ ＝727)。

PREPARATION EXAMPLE 2-31 Synthesis of Compounds 2-31

Compound 18 (10 g,26.9 mmol), compound amine 21 (2.6 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 5.7g of compound substance 18-1 was obtained. (yield 55%, MS: [ M+H) ] ⁺ ＝385)。

Compound 18-1 (10 g,26 mmol), compound CB (6.9 g,27.3 mmol), sodium tert-butoxide (3.2 g,33.8 mmol) are added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 3 hours, the reaction was completed and cooled to normal temperatureThe solvent was removed by warm and reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 10.5g of compound 2-31 was obtained. (yield 67%, MS: [ M+H)] ⁺ ＝601)。

PREPARATION EXAMPLE 2-32 Synthesis of Compounds 2-32

Compound 19 (10 g,26.9 mmol), compound amine 21 (2.6 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 5.9g of compound substance 19-1 was obtained. (yield 57%, MS: [ M+H) ] ⁺ ＝385)。

Compound 19-1 (10 g,26 mmol), compound AA (6.9 g,27.3 mmol), sodium tert-butoxide (3.2 g,33.8 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.7g of compound 2-32 was obtained. (yield 56%, MS: [ M+H)] ⁺ ＝601)。

PREPARATION EXAMPLE 2-33 Synthesis of Compounds 2-33

Compound 20 (10 g,26.9 mmol), compound amine 7 (4.8 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.2g of compound substance 20-1 was obtained. (yield 66%, MS: [ M+H) ] ⁺ ＝461)。

Compound 20-1 (10 g,21.7 mmol), compound CB (5.8 g,22.8 mmol), sodium tert-butoxide (2.7 g,28.2 mmol) are added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.5g of compound 2-33 was obtained. (yield 51%, MS: [ M+H ]] ⁺ ＝677)。

PREPARATION EXAMPLE 2-34 Synthesis of Compounds 2-34

Compound 21 (10 g,26.9 mmol), compound amine 22 (4 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and the organic layer was separated and treated with anhydrous magnesium sulfate After filtration, the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7g of compound substance 21-1 was obtained. (yield 60%, MS: [ M+H)] ⁺ ＝435)。

Compound 21 (10 g,23 mmol), compound BB (6.1 g,24.2 mmol), sodium tert-butoxide (2.9 g,29.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 9.1g of compounds 2 to 34 was obtained. (yield 61%, MS: [ M+H)] ⁺ ＝651)。

PREPARATION EXAMPLES 2-35 Synthesis of Compounds 2-35

Compound 22 (10 g,26.9 mmol), compound amine 7 (4.8 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 6.3g of compound substance 22-1 was obtained. (yield 51%, MS: [ M+H ] ] ⁺ ＝461)。

Compound 22 (10 g,21.7 mmol), compound AF (5.8 g,22.8 mmol), sodium tert-butoxide (2.7 g,28.2 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the process is carried out,the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.8g of compound 2-35 was obtained. (yield 53%, MS: [ M+H)] ⁺ ＝677)。

PREPARATION EXAMPLES 2-36 Synthesis of Compounds 2-36

Compound 1-8 (10 g,24.4 mmol), compound DC (6.9 g,25.6 mmol), sodium tert-butoxide (3 g,31.7 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 9.1g of compound 2-36 was obtained. (yield 58%, MS: [ M+H) ] ⁺ ＝643)。

PREPARATION EXAMPLE 2-37 Synthesis of Compounds 2-37

Compound 1 (10 g,31 mmol), compound amine 23 (6.5 g,32.6 mmol), sodium t-butoxide (3.9 g,40.3 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.9g of compound matters 1 to 9 were obtained. (yield 58%, MS: [ M+H)] ⁺ ＝441)。

Compound 1-9 (10 g,22.7 mmol), compound DD (6.4 g,23.8 mmol), sodium tert-butoxide (2.8 g,29.5 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 9.8g of compound 2-37 was obtained. (yield 64%, MS: [ M+H) ] ⁺ ＝673)。

PREPARATION EXAMPLES 2-38 Synthesis of Compounds 2-38

Compound 1 (10 g,31 mmol), compound amine 24 (9.6 g,32.6 mmol), sodium t-butoxide (3.9 g,40.3 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 9.8g of compound matters 1 to 10 were obtained. (yield 59%, MS: [ M+H)] ⁺ ＝537)。

Compound 1-10 (10 g,18.6 mmol), compound EC (5.3 g,19.6 mmol), sodium tert-butoxide (2.3 g,24.2 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. Concentrating the mixture The resultant was purified by silica gel column chromatography to obtain 8.6g of Compound 2-38. (yield 60%, MS: [ M+H)] ⁺ ＝769)。

PREPARATION EXAMPLES 2-39 Synthesis of Compounds 2-39

Compound 1 (10 g,31 mmol), compound amine 25 (9.6 g,32.6 mmol), sodium t-butoxide (3.9 g,40.3 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 11.6g of compound matters 1 to 11 were obtained. (yield 70%, MS: [ M+H)] ⁺ ＝537)。

Compound 1-11 (10 g,18.6 mmol), compound FD (5.3 g,19.6 mmol), sodium tert-butoxide (2.3 g,24.2 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.6g of compound 2-39 was obtained. (yield 60%, MS: [ M+H) ] ⁺ ＝769)。

PREPARATION EXAMPLE 2-40 Synthesis of Compounds 2-40

Under nitrogen atmosphere, compound 6 (10 g,31 mmol), compound amine 20 (7.1 g,32.6 mmol), sodium t-butoxide (3.9g,40.3 mmol) was added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.6g of compound substance 6-4 was obtained. (yield 53%, MS: [ M+H)] ⁺ ＝461)。

Compound 6-4 (10 g,21.7 mmol), compound EA (6.1 g,22.8 mmol), sodium tert-butoxide (2.7 g,28.2 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8g of compound 2-40 was obtained. (yield 53%, MS: [ M+H) ] ⁺ ＝693)。

PREPARATION EXAMPLE 2-41 Synthesis of Compounds 2-41

Compound 6 (10 g,31 mmol), compound amine 26 (8 g,32.6 mmol), sodium tert-butoxide (3.9 g,40.3 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.8g of compound substance 6-5 was obtained. (yield 52%, MS: [ M+H)] ⁺ ＝487)。

Compound 6-5 (10 g,20.5 mmol), compound EC (5.8 g,21.6 mmol), sodium tert-butoxide (2.6 g,26.7 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 10.2g of compound 2-41 was obtained. (yield 69%, MS: [ M+H) ] ⁺ ＝719)。

PREPARATION EXAMPLE 2-42 Synthesis of Compounds 2-42

Compound 6 (10 g,31 mmol), compound amine 27 (6 g,32.6 mmol), sodium t-butoxide (3.9 g,40.3 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.8g of compound substance 6-6 was obtained. (yield 67%, MS: [ M+H)] ⁺ ＝425)。

Compound 6-6 (10 g,23.6 mmol), compound FA (6.6 g,24.7 mmol), sodium tert-butoxide (2.9 g,30.6 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.2 g, compound 2-42. (yield 66%, MS: [ M+H)] ⁺ ＝657)。

PREPARATION EXAMPLES 2-43 Synthesis of Compounds 2-43

Compound 6 (10 g,31 mmol), compound amine 28 (8.8 g,32.6 mmol), sodium t-butoxide (3.9 g,40.3 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 10.4g of compound matters 6-7 was obtained. (yield 66%, MS: [ M+H)] ⁺ ＝511)。

Compound 6-7 (10 g,19.6 mmol), compound FB (5.5 g,20.6 mmol), sodium tert-butoxide (2.4 g,25.5 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.9g of compound 2-43 was obtained. (yield 61%, MS: [ M+H) ] ⁺ ＝743)。

PREPARATION EXAMPLE 2-44 Synthesis of Compounds 2-44

Under nitrogen, compound 23 (10 g,25.1 mmol), compound amine 20 (5.8 g,26.4 mmol), sodium tert-butoxide (3.1 g,32.6 mmol) were added to 200mL of xylene, stirred andand (5) refluxing. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 9.2g of compound substance 23-1 was obtained. (yield 68%, MS: [ M+H)] ⁺ ＝537)。

Compound 23-1 (10 g,18.6 mmol), compound FB (5.3 g,19.6 mmol), sodium tert-butoxide (2.3 g,24.2 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8g of compound 2-44 was obtained. (yield 56%, MS: [ M+H) ] ⁺ ＝769)。

PREPARATION EXAMPLES 2-45 Synthesis of Compounds 2-45

Compound 9 (10 g,31 mmol), compound amine 29 (9.6 g,32.6 mmol), sodium t-butoxide (3.9 g,40.3 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 10.5g of compound substance 9-4 was obtained. (yield 63%, MS: [ M+H)] ⁺ ＝537)。

Compound 9-4 (10 g,18.6 under nitrogenmmol), compound EA (5.3 g,19.6 mmol), sodium t-butoxide (2.3 g,24.2 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.2g of compound 2-45 was obtained. (yield 57%, MS: [ M+H) ] ⁺ ＝769)。

PREPARATION EXAMPLES 2-46 Synthesis of Compounds 2-46

Compound 10-1 (10 g,17.8 mmol), compound FB (5 g,18.7 mmol), sodium tert-butoxide (2.2 g,23.2 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.6g of compound 2-46 was obtained. (yield 61%, MS: [ M+H)] ⁺ ＝793)。

PREPARATION EXAMPLES 2-47 Synthesis of Compounds 2-47

Compound 24 (10 g,26.9 mmol), compound amine 22 (4 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, it is converted intoThe compound was completely dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7g of compound 24-1 was obtained. (yield 60%, MS: [ M+H) ] ⁺ ＝435)。

Compound 24-1 (10 g,23 mmol), compound FA (6.5 g,24.2 mmol), sodium tert-butoxide (2.9 g,29.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.1g of compound 2-47 was obtained. (yield 53%, MS: [ M+H)] ⁺ ＝667)。

PREPARATION EXAMPLES 2-48 Synthesis of Compounds 2-48

Compound 25 (10 g,22.3 mmol), compound amine 4 (5.7 g,23.4 mmol), sodium tert-butoxide (2.8 g,29 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 9.3g of compound substance 25-1 was obtained. (yield 68%, MS: [ M+H) ] ⁺ ＝613)。

Compound 25-1 (10 g,16.3 mmol), compound EA (4.6 g,17.1 mmol), sodium tert-butoxide (2 g,21.2 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2g,0.3 mmol). After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.5g of compound 2-48 was obtained. (yield 62%, MS: [ M+H) ^]+ ＝845)。

PREPARATION EXAMPLES 2-49 Synthesis of Compounds 2-49

Compound 26 (10 g,26.9 mmol), compound amine 30 (5.2 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8g of compound substance 26-1 was obtained. (yield 63%, MS: [ M+H) ] ⁺ ＝475)。

Compound 26-1 (10 g,21.1 mmol), compound FB (5.9 g,22.1 mmol), sodium tert-butoxide (2.6 g,27.4 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 10.1g of compound 2-49 was obtained. (yield 63%, MS: [ M+H)] ⁺ ＝761)。

PREPARATION EXAMPLE 2-50 Synthesis of Compounds 2-50

Compound 15 (10 g,26.9 mmol), compound amine 31 (6.2 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.1g of compound substance 15-2 was obtained. (yield 59%, MS: [ M+H) ] ⁺ ＝511)。

Compound 15-2 (10 g,19.6 mmol), compound FC (5.5 g,20.6 mmol), sodium tert-butoxide (2.4 g,25.5 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.3g of compound 2-50 was obtained. (yield 50%, MS: [ M+H)] ⁺ ＝743)。

PREPARATION EXAMPLES 2-51 Synthesis of Compounds 2-51

Compound 16 (10 g,26.9 mmol), compound amine 21 (2.6 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved again in chloroform, and water was usedAfter washing 2 times, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6g of compound substance 16-2. (yield 58%, MS: [ M+H) ] ⁺ ＝385)。

Compound 16-2 (10 g,26 mmol), compound FC (7.3 g,27.3 mmol), sodium tert-butoxide (3.2 g,33.8 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 9.3g of compound 2-51 was obtained. (yield 58%, MS: [ M+H)] ⁺ ＝617)。

PREPARATION EXAMPLE 2-52 Synthesis of Compounds 2-52

Compound 16 (10 g,26.9 mmol), compound amine 21 (2.6 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6g of compound substance 16-2. (yield 58%, MS: [ M+H) ] ⁺ ＝385)。

Compound 17-2 (10 g,18.6 mmol), compound DE (5.3 g,19.6 mmol), sodium tert-butoxide (2.3 g,24.2 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 3 hours, the reactionAnd finally, cooling to normal temperature, and decompressing to remove the solvent. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 10g of compound 2-52 was obtained. (yield 70%, MS: [ M+H)] ⁺ ＝766)。

PREPARATION EXAMPLE 2-53 Synthesis of Compounds 2-53

Compound 18 (10 g,26.9 mmol), compound amine 32 (8.3 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 10.7g of compound substance 18-2 was obtained. (yield 68%, MS: [ M+H) ] ⁺ ＝587)。

Compound 18-2 (10 g,17 mmol), compound EB (4.8 g,17.9 mmol), sodium tert-butoxide (2.1 g,22.2 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.5g of compound 2-53 was obtained. (yield 61%, MS: [ M+H)] ⁺ ＝819)。

PREPARATION EXAMPLE 2-54 Synthesis of Compounds 2-54

Compound 19 (10 g,26.9 mmol), compound amine 33 (6.9 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 9.2g of compound substance 19-2 was obtained. (yield 64%, MS: [ M+H) ] ⁺ ＝537)。

Compound 19-2 (10 g,18.6 mmol), compound DD (5.3 g,19.6 mmol), sodium tert-butoxide (2.3 g,24.2 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 9.9g of compound 2-54 was obtained. (yield 69%, MS: [ M+H)] ⁺ ＝769)。

PREPARATION EXAMPLE 2-55 Synthesis of Compounds 2-55

Compound 27 (10 g,26.9 mmol), compound amine 34 (5.5 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved again in chloroform, and after washing with water 2 times, the organic layer was separated,the mixture was treated with anhydrous magnesium sulfate, then, the filtrate was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.3g of compound substance 27-1 was obtained. (yield 64%, MS: [ M+H) ] ⁺ ＝485)。

PREPARATION EXAMPLE 2-56 Synthesis of Compounds 2-56

Compound 20 (10 g,26.9 mmol), compound amine 35 (6.9 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.8g of compound substance 20-2 was obtained. (yield 61%, MS: [ M+H) ] ⁺ ＝537)。

Compound 20-2 (10 g,18.6 mmol), compound DC (5.3 g,19.6 mmol), sodium tert-butoxide (2.3 g,24.2 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 3 hours, the reaction is finished, cooled to normal temperature,the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8g of compounds 2-56 was obtained. (yield 56%, MS: [ M+H)] ⁺ ＝769)。

PREPARATION EXAMPLE 2-57 Synthesis of Compounds 2-57

Compound 21 (10 g,26.9 mmol), compound amine 36 (5.5 g,28.2 mmol), sodium tert-butoxide (3.4 g,34.9 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.7g of compound substance 21-2 was obtained. (yield 59%, MS: [ M+H) ] ⁺ ＝485)。

Compound 21-2 (10 g,20.6 mmol), compound EE (5.8 g,21.7 mmol), sodium tert-butoxide (2.6 g,26.8 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was charged. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed by depressurization. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 10.3g of compound 2-57 was obtained. (yield 70%, MS: [ M+H)] ⁺ ＝717)。

Example 1

ITO (indium tin oxide) is added to the mixture to form a mixture of 1000 angstroms

angstrom), and the glass substrate coated with the film in thickness was put into distilled water in which a detergent was dissolved, and washed with ultrasonic waves. In this case, a product of fei he er (Fischer co.) was used as the detergent, and distilled water was filtered twice using a Filter (Filter) manufactured by millbore co. After washing the ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After the distilled water washing is completed, ultrasonic washing is performed by using solvents of isopropanol, acetone and methanol, and the obtained product is dried and then conveyed to a plasma cleaning machine. After the substrate was cleaned with oxygen plasma for 5 minutes, the substrate was transferred to a vacuum vapor deposition machine.

On the ITO transparent electrode thus prepared, as a hole injection layer, the following compound HI-1 was used

A hole injection layer was formed by thermal vacuum evaporation, and the following compound a-1 was p-doped (p-doping) at a concentration of 1.5%. Vacuum vapor deposition of the following compound HT-1 on the hole injection layer to form a film thickness

Is provided. Next, on the hole transport layer, the film thickness is +.>

The electron-inhibiting layer was formed by vacuum evaporation of the following compound EB-1. Next, on the vapor-deposited film of the above compound EB-1, the following compound 1-1, compound 2-1 as a main body and the following compound Dp-7 as a dopant were subjected to vacuum vapor deposition at a weight ratio of 49:49:2 to form->

A red light emitting layer of thickness. On the above-mentioned light-emitting layer, the film thickness is +.>

The hole blocking layer was formed by vacuum evaporation of the following compound HB-1. Next, on the hole blocking layer, the following compound ET-1 and the following compound LiQ were vacuum evaporated at a weight ratio of 2:1, thereby giving ∈1>

Form an electron injection and transport layer. On the electron injection and transport layer, lithium fluoride (LiF) is sequentially added +. >

Is made of aluminum +.>

And vapor deposition is performed to form a cathode.

In the above process, the vapor deposition rate of the organic matter is maintained

To->

Lithium fluoride maintenance of cathode>

Is kept at>

Is to maintain a vacuum degree of 2X 10 during vapor deposition ^-7 Up to 5X 10 ^-6 The support is thus fabricated into an organic light emitting device.

Examples 2 to 195

An organic light-emitting device was manufactured in the same manner as in example 1 above, except that in the organic light-emitting device of example 1, instead of the compound 1-1 as the first host and the compound 2-1 as the second host, the compound of chemical formula 1 as the first host and the compound of chemical formula 2 as the second host were used by co-evaporation at a weight ratio of 1:1 as described in table 1 below.

When a current was applied to the organic light emitting devices manufactured in examples 1 to 195 described above, voltage and efficiency (15 mA/cm ² Benchmark), the results are shown in table 1 below. Lifetime T95 refers to the time (hr) required for the luminance to decrease from the initial luminance (6000 nit) to 95%.

TABLE 1

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Comparative examples 1 to 60

An organic light-emitting device was manufactured in the same manner as in example 1 above, except that the organic light-emitting device of example 1 was used as a first host by co-evaporation of the compounds B-1 to B-6 instead of the compound of chemical formula 1 and as a second host by weight ratio of 1:1, as described in table 2 below. Compounds B-1, B-2, B-3, B-4, B-5 and B-6 used in Table 2 below are shown below.

When a current was applied to the organic light emitting devices manufactured in comparative examples 1 to 60, voltage and efficiency (15 mA/cm were measured ² Benchmark), the results are shown in table 2 below. Lifetime T95 refers to the time (hr) required for the luminance to decrease from the initial luminance (6000 nit) to 95%.

TABLE 2

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Comparative examples 61 to 140

An organic light-emitting device was manufactured in the same manner as in example 1 above, except that the organic light-emitting device of example 1 was used as a second host by co-evaporation with the compound of chemical formula 1 as a first host in a weight ratio of 1:1, using the compounds C-1 to C-8 instead of the compound of chemical formula 2, as described in table 3 below. Compounds C-1, C-2, C-3, C-4, C-5, C-6, C-7, C-8 used in Table 3 below are shown below.

When a current was applied to the organic light emitting devices manufactured in the above comparative examples 61 to 140, the voltage and the efficiency (15 mA/cm ² Benchmark), the results are shown in table 3 below. Lifetime T95 refers to the time (hr) required for the luminance to decrease from the initial luminance (6000 nit) to 95%.

TABLE 3

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Comparative examples 141 to 150

An organic light-emitting device was manufactured in the same manner as in example 1 above, except that the compound of chemical formula 1 was used as a host and the compound of chemical formula 2 was not used as a second host in the organic light-emitting device of example 1 as described in table 4 below.

When a current was applied to the organic light emitting devices manufactured in the above comparative examples 141 to 150, the voltage and the efficiency (15 mA/cm ² Benchmark), the results are shown in table 4 below. Lifetime T95 refers to the time (hr) required for the luminance to decrease from the initial luminance (6000 nit) to 95%.

TABLE 4

Comparative examples 151 to 160

An organic light-emitting device was manufactured in the same manner as in example 1 above, except that the compound of chemical formula 2 was used as a host and the compound of chemical formula 1 was not used as a first host in the organic light-emitting device of example 1 as described in table 5 below.

When a current was applied to the organic light emitting devices manufactured in the above comparative examples 151 to 160, voltage and efficiency (15 mA/cm were measured ² Benchmark), the results are shown in table 5 below. Lifetime T95 refers to the time (hr) required for the luminance to decrease from the initial luminance (6000 nit) to 95%.

TABLE 5

The results of tables 1 to 5 described above were obtained when current was applied to the organic light emitting devices fabricated according to examples 1 to 195 and comparative examples 1 to 160. The red organic light-emitting device of example 1 described above uses a conventionally widely used material, and has a structure in which compound EB-1 is used as an electron-inhibiting layer and Dp-7 is used as a red dopant. Specifically, examples 1 to 195 were subjected to co-evaporation of the compound of chemical formula 1 and the compound of chemical formula 2 to be used as a host of a red light emitting layer to manufacture an organic light emitting device. Comparative examples 1 to 60 organic light emitting devices were manufactured by co-evaporation of compounds B-1 to B-6 instead of the compound of chemical formula 1 and the compound of chemical formula 2. In addition, comparative examples 61 to 140 were organic light emitting devices manufactured by co-evaporation of compounds C-1 to C-8 instead of the compound of chemical formula 2 and the compound of chemical formula 1. Comparative examples 141 to 150 used no compound of chemical formula 2 but only the compound of chemical formula 1 to manufacture an organic light emitting device. Further, comparative examples 151 to 160 manufactured organic light emitting devices using not the compound of chemical formula 1 but only the compound of chemical formula 2.

As shown in table 1 above, it can be seen that: according to the present invention, the organic light emitting devices of examples 1 to 195, in which the compound of chemical formula 1 and the compound of chemical formula 2 were co-evaporated to serve as a red light emitting layer, have reduced driving voltage, increased efficiency and lifetime, as compared with the comparative example. Further, as shown in table 2, the organic light emitting devices of comparative examples 1 to 60, in which the compound of chemical formula 1 was replaced with the compounds B-1 to B-6 and co-evaporated with the compound of chemical formula 2 to be used as red light emitting layers, showed substantially the results of an increase in driving voltage, a decrease in efficiency and a decrease in lifetime, as compared with the organic light emitting devices of examples 1 to 195 according to the present invention. Further, as shown in the above table 3, the organic light emitting devices of comparative examples 61 to 140, in which the compound of chemical formula 2 was replaced with the compounds C-1 to C-8 and co-evaporated with the compound of chemical formula 1 to be used as red light emitting layers, exhibited the results of increased driving voltage, reduced efficiency and reduced lifetime, as compared with the organic light emitting devices of examples 1 to 195 according to the present invention. Further, as shown in tables 4 and 5, it is known that the organic light emitting devices of comparative examples 141 to 150 using only the compound of chemical formula 1 as a main body and the organic light emitting devices of comparative examples 151 to 160 using only the compound of chemical formula 2 as a main body have an increased driving voltage, reduced efficiency and lifetime, as compared with the organic light emitting devices of examples 1 to 195 according to the present invention.

From these results, it is found that the reason why the driving voltage is improved and the efficiency and lifetime are improved is that the combination of the compound of chemical formula 1 as the first host and the compound of chemical formula 2 as the second host of the present invention forms well energy transfer to the red dopant in the red light emitting layer. This finally confirmed that the combination of the compounds according to the embodiments of the present invention, i.e., the combination of the compound of chemical formula 1 and the compound of chemical formula 2, combines electrons and holes to form excitons through a more stable balance in the light emitting layer, compared to the combination with the compound of the comparative example, thereby greatly improving efficiency and lifetime. From the above, it was confirmed that when the compound of chemical formula 1 and the compound of chemical formula 2 of the present invention are combined and co-vapor deposited to be used as a host of a red light emitting layer, the driving voltage, light emitting efficiency and lifetime characteristics of the organic light emitting device can be improved.

[ description of the symbols ]

1: substrate 2: anode

3: light emitting layer 4: cathode electrode

5: hole injection layer 6: hole transport layer

7: electron suppression layer 8: hole blocking layer

9: electron injection and transport layers.

Claims

1. An organic light emitting device, comprising:

An anode, a cathode, and a light emitting layer between the anode and the cathode,

the light emitting layer includes a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2:

chemical formula 1

In the chemical formula 1 described above, a compound having the formula,

R ₁ each independently hydrogen or deuterium; or two adjacent R ₁ To form a benzene ring, the balance being hydrogen or deuterium,

R ₂ each independently hydrogen or deuterium; or two adjacent R ₂ To form a benzene ring, the balance being hydrogen or deuterium,

chemical formula 2

In the chemical formula 2 described above, the chemical formula,

chemical formula 3

In the chemical formula 3 described above, the chemical formula,

Ar' ₂ is substituted or unsubstituted C _6-60 An aryl group; or substituted or unsubstituted containing any one or more selected from N, O and SC _2-60 A heteroaryl group, which is a group,

Ar' ₃ is a substituent represented by the following chemical formula 4,

chemical formula 4

In the chemical formula 4 described above, the chemical formula,

c is a naphthalene ring fused to the adjacent ring,

x is O or S, and the X is O or S,

each R "is independently hydrogen or deuterium,

n1 is an integer of 1 to 4,

n2 is an integer from 1 to 6.

2. The organic light-emitting device according to claim 1, wherein the first compound is represented by any one of the following chemical formulas 1-1 to 1-10:

in the 1-1 to 1-10,

L ₁ to L ₃ 、Ar ₁ And Ar is a group ₂ As defined in claim 1.

3. The organic light-emitting device of claim 1, wherein L ₁ And L ₂ Each independently is a single bond, phenylene, or naphthylene.

4. The organic light-emitting device of claim 1, wherein L ₃ Is a single bond, phenylene, biphenyldiyl or naphthylene.

5. The organic light-emitting device of claim 1, wherein Ar ₁ And Ar is a group ₂ Each independently is phenyl, biphenyl, naphthyl, phenanthryl, dibenzofuranyl, dibenzothiazylA phenoyl, carbazolyl, benzonaphthofuranyl or benzonaphthothienyl group,

wherein Ar is ₁ And Ar is a group ₂ Unsubstituted; or is selected from deuterium, C _1-10 Alkyl and C _6-20 More than 1 substituent in the aryl group is substituted.

6. The organic light-emitting device of claim 1, wherein Ar ₁ And Ar is a group ₂ Each independently is any one selected from the following groups:

7. the organic light-emitting device according to claim 1, wherein the first compound is any one selected from the group consisting of:

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8. the organic light-emitting device according to claim 1, wherein the chemical formula 2 is represented by any one selected from the following chemical formulas 2-1 to 2-8:

in the chemical formulas 2-1 to 2-8,

L' ₁ 、Ar' ₁ and R' is as defined in claim 1,

m1 is an integer of 1 to 4,

m2 is an integer from 1 to 6.

9. The organic light-emitting device according to claim 1, wherein the chemical formula 2 is represented by any one selected from the following chemical formulas 2-9 to 2-19:

in the chemical formulas 2-9 to 2-19,

L' ₁ 、Ar' ₁ and R' is as defined in claim 1.

10. The organic light-emitting device of claim 1, wherein L' ₁ Is a single bond or phenylene.

11. The organic light-emitting device of claim 1, wherein Ar' ₁ Is phenyl, biphenyl, or naphthyl.

12. The organic light-emitting device of claim 1, wherein L' ₂ Is a single bond, phenylene, or naphthylene.

13. The organic light-emitting device of claim 1, wherein L' ₃ Is a single bond, phenylene, biphenyldiyl, or naphthylene.

14. The organic light-emitting device of claim 1, wherein L' ₄ Is a single bond or phenylene.

15. The organic light-emitting device of claim 1, wherein Ar' ₂ Is phenyl, biphenyl, terphenyl, (naphthyl) phenyl, (phenanthryl) phenyl, naphthyl,Phenanthryl, (phenyl) naphthyl, (phenyl) phenanthryl, dibenzofuranyl, or dibenzothienyl.

16. The organic light-emitting device of claim 1, wherein Ar' ₂ Is any one selected from the following groups:

17. the organic light-emitting device according to claim 1, wherein the chemical formula 4 is represented by any one selected from the following chemical formulas 4-1 to 4-6:

in the chemical formulas 4-1 to 4-6,

x, R ", n1 and n2 are as defined in claim 1.

18. The organic light-emitting device according to claim 1, wherein the chemical formula 4 is represented by any one selected from the following chemical formulas 4-7 to 4-12:

In the chemical formulas 4-7 to 4-12,

x is as defined in claim 1.

19. The organic light-emitting device of claim 1, wherein Ar' ₃ Is any one selected from the following groups:

20. the organic light-emitting device according to claim 1, wherein the compound represented by the chemical formula 2 is any one selected from the group consisting of:

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