KR102716876B1 - Organic light emitting device - Google Patents

Abstract

The present specification relates to an organic light-emitting device including a first electrode; a second electrode provided opposite the first electrode; and at least one organic layer provided between the first electrode and the second electrode, wherein at least one of the organic layers includes a compound of chemical formula 1 and a compound of chemical formula 202, or a compound of chemical formula 1 and a compound of chemical formula 203.

Description

ORGANIC LIGHT EMITTING DEVICE

This specification relates to an organic light-emitting device.

This application claims the benefit of Korean Patent Application No. 10-2020-0170955 filed with the Korean Intellectual Property Office on December 9, 2020, the entire contents of which are incorporated herein by reference.

In this specification, an organic light-emitting device is a light-emitting device using an organic semiconductor material, and requires the exchange of holes and/or electrons between an electrode and the organic semiconductor material. Organic light-emitting devices can be largely divided into two types according to their operating principles. First, a light-emitting device is a type in which excitons are formed in an organic layer by photons that enter the device from an external light source, the excitons are separated into electrons and holes, and the electrons and holes are each transferred to different electrodes and used as a current source (voltage source). Second, a light-emitting device is a type in which holes and/or electrons are injected into an organic semiconductor material layer forming an interface with the electrodes by applying voltage or current to two or more electrodes, and is operated by the injected electrons and holes.

In general, the organic luminescence phenomenon refers to the phenomenon of converting electrical energy into light energy using organic materials. Organic light-emitting devices utilizing the organic luminescence phenomenon usually have a structure including an anode, a cathode, and an organic layer therebetween. Here, the organic layer is often composed of a multilayer structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device, and can be composed of, for example, a hole injection layer, a hole transport layer, a light-emitting layer, an electron suppression layer, an electron transport layer, and an electron injection layer. In the structure of such an organic light-emitting device, when a voltage is applied between the two 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 are formed, and when these excitons fall back to the ground state, light is emitted. Such organic light-emitting devices are known to have characteristics such as self-luminescence, high brightness, high efficiency, low operating voltage, wide viewing angle, and high contrast.

Materials used as organic layers in organic light-emitting devices can be classified into light-emitting materials and charge-transport materials, such as hole injection materials, hole transport materials, electron-blocking materials, electron transport materials, and electron injection materials, depending on their functions. Light-emitting materials include blue, green, and red light-emitting materials according to their emission colors, and yellow and orange light-emitting materials necessary for realizing better natural colors.

In addition, in order to increase color purity and luminescence efficiency through energy transfer, a host/dopant system can be used as a luminescent material. The principle is that a small amount of a dopant having a smaller energy band gap and superior luminescence efficiency than the host that mainly composes the luminescent layer is mixed into the luminescent layer, and excitons generated in the host are transported to the dopant to emit light with high efficiency. At this time, the wavelength of the host shifts to the wavelength of the dopant, so light of a desired wavelength can be obtained depending on the type of dopant used.

In order to fully demonstrate the excellent characteristics of the organic light-emitting device described above, the materials forming the organic layer within the device, such as hole injection materials, hole transport materials, luminescent materials, electron blocking materials, electron transport materials, and electron injection materials, must be supported by stable and efficient materials, and therefore, the development of new materials is continuously required.

International Patent Publication No. 2017-126443

An organic light-emitting device is described herein.

One embodiment of the present specification provides an organic light-emitting device including a first electrode; a second electrode provided opposite the first electrode; and at least one organic layer provided between the first electrode and the second electrode, wherein at least one of the organic layers includes a compound of the following chemical formula 1 and a compound of the following chemical formula 202, or a compound of the following chemical formula 1 and a compound of the following chemical formula 203.

[Chemical Formula 1]

[Chemical formula 202]

[Chemical formula 203]

In the above chemical formulas 1, 202 and 203,

Ar1 is a substituted or unsubstituted aryl group; a substituted or unsubstituted hydrocarbon ring group; or a substituted or unsubstituted heteroaryl group,

L is a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group,

R1 to R8 are the same as or different from each other, and are each independently hydrogen; deuterium; a nitrile group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group,

R9 is deuterium; a nitrile group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group,

Y1 to Y3 are the same or different from each other, and are each independently C or Si,

R11 to R14, Ar21 to Ar32, and Z1 to Z6 are the same as or different from each other, and each independently represents hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heterocyclic group; or a substituted or unsubstituted amine group, or are combined with adjacent substituents to form a substituted or unsubstituted ring,

a is an integer from 0 to 9, and when a is plural, R9 is the same or different, and at least one of the plural R9 is not deuterium,

r1 is an integer from 0 to 4,

r1', r2 and r3 are integers from 0 to 3, respectively.

When r1 and r1' are plural, R11 is equal to or different from each other,

When r2 is plural, R12 is equal to or different from each other,

When r3 is plural, R11 is equal to or different from each other,

r4 is an integer from 0 to 5,

When r4 is plural, R14 is equal to or different from each other,

p1 to p3 are 0 or 1, respectively,

When p1 to p3 are 0, Y1 to Y3 are direct bonds.

The organic light-emitting device of the present invention has high efficiency, low voltage, and long life characteristics, and when the compound of the present invention is included in the light-emitting layer of the organic light-emitting device, an organic light-emitting device having high color reproducibility can be manufactured.

Figures 1 and 2 illustrate examples of organic light-emitting devices according to the present invention.

The following describes this specification in more detail.

In this specification, when a part is said to "include" a certain component, this does not mean that other components are excluded, but rather that other components may be included, unless otherwise specifically stated.

In this specification, when it is said that a member is located "on" another member, this includes not only cases where a member is in contact with another member, but also cases where another member exists between the two members.

Examples of substituents in this specification are described below, but are not limited thereto.

The term "substitution" above means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position of the substitution is not limited as long as it is a position where the hydrogen atom is replaced, that is, a position where the substituent can be replaced, and when two or more are substituted, the two or more substituents may be the same or different from each other.

The term "substituted or unsubstituted" as used herein means substituted with one or more substituents selected from the group consisting of deuterium; a halogen group; a cyano group (-CN); a silyl group; a boron group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted amine group; a substituted or unsubstituted aryl group; and a substituted or unsubstituted heteroaryl group, or substituted with a substituent in which two or more substituents are linked among the above-mentioned substituents, or has no substituents. For example, "a substituent linked with two or more substituents" may be a biphenyl group. That is, the biphenyl group may be an aryl group, or may be interpreted as a substituent in which two phenyl groups are linked.

Examples of the above substituents are described below, but are not limited thereto.

In this specification, examples of halogen groups include fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

In the present specification, a silyl group can be represented by a chemical formula of -SiYaYbYc, wherein Ya, Yb and Yc can each be hydrogen; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group. Specific examples of the silyl group include, but are not limited to, a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, and a phenylsilyl group.

In the present specification, the boron group can be represented by the chemical formula of -BY4Y5, wherein Y4 and Y5 can each be hydrogen; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group. The boron group specifically includes, but is not limited to, a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, and a phenyl boron group.

In the present specification, the alkyl group may be linear or branched, and the carbon number is not particularly limited, but is preferably 1 to 60. According to one embodiment, the alkyl group has 1 to 30 carbon atoms. According to another embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. Specific examples of the alkyl group include, but are not limited to, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like.

In the present specification, the amine group may be selected from the group consisting of -NH ₂ ; an alkylamine group; an N-alkylarylamine group; an arylamine group; an N-arylheteroarylamine group; an N-alkylheteroarylamine group and a heteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include a methylamine group; a dimethylamine group; an ethylamine group; a diethylamine group; a phenylamine group; a naphthylamine group; a biphenylamine group; anthracenylamine group; a 9-methylanthracenylamine group; a diphenylamine group; an N-phenylnaphthylamine group; a ditolylamine group; an N-phenyltolylamine group; a triphenylamine group; an N-phenylbiphenylamine group; an N-phenylnaphthylamine group; an N-biphenylnaphthylamine group; an N-naphthylfluorenylamine group; an N-phenylphenanthrenylamine group; an N-biphenylphenanthrenylamine group; Examples thereof include, but are not limited to, N-phenylfluorenylamine group; N-phenylterphenylamine group; N-phenanthrenylfluorenylamine group; N-biphenylfluorenylamine group.

In this specification, an N-alkylarylamine group means an amine group in which an alkyl group and an aryl group are substituted on N of the amine group.

In this specification, an N-arylheteroarylamine group means an amine group in which an aryl group and a heteroaryl group are substituted on N of the amine group.

In this specification, an N-alkylheteroarylamine group means an amine group in which an alkyl group and a heteroaryl group are substituted on N of the amine group.

In the present specification, the alkyl group among the alkylamine group, N-arylalkylamine group, alkylthioxy group, alkylsulfoxy group, and N-alkylheteroarylamine group is the same as the examples of the alkyl group described above. Specifically, the alkylthioxy group includes a methylthioxy group; an ethylthioxy group; a tert-butylthioxy group; a hexylthioxy group; an octylthioxy group, etc., and the alkylsulfoxy group includes, but is not limited to, a mesyl group; an ethylsulfoxy group; a propylsulfoxy group; a butylsulfoxy group.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group 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, examples thereof include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

In the present specification, the aryl group is not particularly limited, but preferably has 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 monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, or the like, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a triphenyl group, a chrysenyl group, a fluorenyl group, or the like, but is not limited thereto.

In the present specification, a heteroaryl group is a ring group containing at least one of N, O, P, S, Si, and Se as a heteroatom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. According to one embodiment, the number of carbon atoms of the heteroaryl group is 2 to 30. Examples of the heteroaryl group include, but are not limited to, a pyridine group, a pyrrole group, a pyrimidine group, a pyridazinyl group, a furan group, a thiophene group, an imidazole group, a pyrazole group, a dibenzofuran group, a dibenzothiophene group, a carbazole group, and the like.

In the present specification, a heterocyclic group is one that includes at least one atom other than carbon, i.e., a heteroatom, and specifically, the heteroatom includes at least one atom selected from the group consisting of O, N, Se, and S, and includes an aromatic heterocyclic group or an aliphatic heterocyclic group. The aromatic heterocyclic group can be represented by a heteroaryl group. An aliphatic heterocyclic group refers to a case where a heteroatom is included in an aliphatic hydrocarbon ring such as tetrahydrofuran or pyrrolidine, or a ring in which an aromatic and aliphatic ring are condensed, such as isoindoline, and a heteroatom is included. The heteroaryl group is also included in the scope of the heterocycle. The number of carbon atoms in the heterocyclic group is not particularly limited, but is preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and the heteroaryl group can be monocyclic or polycyclic.

In this specification, a ring refers to an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, or a heterocycle.

In this specification, a hydrocarbon ring is a general term for a ring composed of carbon and hydrogen. Types of hydrocarbon rings include, but are not limited to, an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, or a hydrocarbon ring in which an aliphatic and an aromatic are condensed with each other.

In this specification, the aromatic hydrocarbon ring has the same definition as the aryl group, except that it is not monovalent.

In the present specification, the aliphatic hydrocarbon ring includes a hydrocarbon ring having a single bond, a hydrocarbon ring including multiple bonds, or a ring in which rings including single bonds and multiple bonds are condensed. Therefore, among the aliphatic hydrocarbon rings, a ring formed by a single bond includes the cycloalkyl group. A hydrocarbon ring that includes a single bond and a double bond but is not an aromatic ring, such as cyclohexene, also belongs to the aliphatic hydrocarbon ring.

In the present specification, a heterocycle includes one or more non-carbon atoms, heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S. The heterocycle may be monocyclic or polycyclic, and may be an aromatic, aliphatic, or a condensed ring of aromatic and aliphatic groups, and the aromatic heterocycle may be selected from examples of heteroaryl groups among the heterocyclic groups, except that it is not monovalent.

In the present specification, an aliphatic heterocycle means an aliphatic ring containing at least one heteroatom. Examples of aliphatic heterocycles include, but are not limited to, oxirane, tetrahydrofuran, 1,4-dioxane, pyrrolidine, piperidine, morpholine, oxepane, azocaine, thiocane, tetrahydronaphthothiophene, tetrahydronaphthofuran, tetrahydrobenzothiophene, and tetrahydrobenzofuran.

In this specification, the aliphatic hydrocarbon ring group is defined as the aliphatic hydrocarbon ring group, except that it is monovalent.

In this specification, an arylene group is as defined for the above aryl group, except that it is divalent.

In this specification, a heteroarylene group is as defined for the heteroaryl group, except that it is divalent.

In this specification, the chemical formula 1 is any one of the following chemical formulas 1-1 to 1-3.

[Chemical Formula 1-1]

[Chemical Formula 1-2]

[Chemical Formula 1-3]

In the above chemical formulas 1-1 to 1-3, the definitions of R1 to R9, L, Ar1, and a are as defined in the above chemical formula 1.

In this specification, R1 to R8 are the same as or different from each other, and are each independently hydrogen or deuterium.

In this specification, R1 to R8 are hydrogen.

In this specification, R1 to R8 are deuterium.

In the present specification, at least one of R1 to R8 is hydrogen, and the rest are deuterium.

In the present specification, at least one of R1 to R8 is deuterium, and the others are hydrogen.

In the present specification, one of R1 to R8 is hydrogen and the others are deuterium.

In the present specification, one of R1 to R8 is deuterium and the others are hydrogen.

In the present specification, two of R1 to R8 are hydrogen and the rest are deuterium.

In the present specification, two of R1 to R8 are deuterium and the remainder are hydrogen.

In the present specification, three of R1 to R8 are hydrogen and the rest are deuterium.

In the present specification, three of R1 to R8 are deuterium and the remainder are hydrogen.

In the present specification, four of R1 to R8 are deuterium and the remainder are hydrogen.

In this specification, R1 to R4 are hydrogen, and R5 to R8 are deuterium.

In this specification, R1 to R4 are deuterium, and R5 to R8 are hydrogen.

In the present specification, R9 is deuterium, an aryl group substituted or unsubstituted with deuterium, or a heteroaryl group.

In the present specification, R9 is deuterium, an aryl group having 6 to 30 carbon atoms substituted or unsubstituted with deuterium, or a heteroaryl group having 3 to 30 carbon atoms.

In the present specification, R9 is a deuterium, an aryl group having 6 to 30 carbon atoms, which is unsubstituted or substituted with deuterium.

In the present specification, R9 is deuterium, a phenyl group, a phenyl group substituted with deuterium, a naphthyl group, a biphenyl group, or a dibenzofuran group.

In the present specification, R9 is an aryl group having 6 to 30 carbon atoms, which is unsubstituted or substituted with deuterium.

In the present specification, R9 is a phenyl group, a phenyl group substituted with deuterium, a naphthyl group, a biphenyl group, or a dibenzofuran group.

In the present specification, when a is plural, at least one of the plural R9 is an aryl group having 6 to 30 carbon atoms, unsubstituted or substituted with deuterium, or a heteroaryl group having 3 to 30 carbon atoms.

In the present specification, when a is 1, R9 is an aryl group having 6 to 30 carbon atoms, unsubstituted or substituted with deuterium, or a heteroaryl group having 3 to 30 carbon atoms.

In this specification, L is a direct bond or an unsubstituted arylene group.

In this specification, L is a direct bond or unsubstituted arylene group having 6 to 30 carbon atoms.

In this specification, L is a direct bond or unsubstituted arylene group having 6 to 20 carbon atoms.

In this specification, L is a direct bond or unsubstituted arylene group having 6 to 15 carbon atoms.

In this specification, L is a direct bond, a phenylene group, a divalent biphenyl group, or a divalent naphthyl group.

In this specification, L is a direct bond.

In this specification, L is a phenylene group.

In this specification, L is a divalent biphenyl group.

In this specification, L is a divalent naphthyl group.

In one embodiment of the present specification, more than 40% of the substitutable positions of L are substituted with deuterium.

In another embodiment, more than 50% of the substitutable positions of L are substituted with deuterium.

In another embodiment, more than 60% of the substitutable positions of L are substituted with deuterium.

In another embodiment, more than 70% of the substitutable positions of L are substituted with deuterium.

In another embodiment, more than 80% of the substitutable positions of L are substituted with deuterium.

In another embodiment, more than 90% of the substitutable positions of L are substituted with deuterium.

In the present specification, Ar1 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted hydrocarbon ring group having 6 to 30 carbon atoms; or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

In the present specification, Ar1 is an aryl group having 6 to 30 carbon atoms which is unsubstituted or substituted with deuterium, an aryl group having 6 to 30 carbon atoms which is unsubstituted or substituted with an aryl group, or a heteroaryl group having 6 to 30 carbon atoms which is unsubstituted or substituted with an aryl group.

In the present specification, Ar1 is a substituted phenyl group; a substituted naphthyl group; a terphenyl group; a substituted biphenyl group; a phenanthrene group; a triphenylene group; a dibenzofuran group; a dibenzothiophene group; a substituted carbazole group; a benzonaphthofuran group; or a 2,3-dihydroindene group.

In the present specification, Ar1 is a phenyl group substituted with deuterium, an aryl group or a heteroaryl group; a naphthyl group substituted with deuterium or an aryl group; a terphenyl group; a biphenyl group substituted with deuterium; a phenanthrene group; a triphenylene group; a dibenzofuran group; a dibenzothiophene group; a carbazole group substituted with an aryl group; a benzonaphthofuran group; or a 2,3-dihydroindene group.

In the present specification, Ar1 is a phenyl group substituted with deuterium, a phenyl group, a naphthyl group or a dibenzofuran group; a naphthyl group substituted with deuterium, a phenyl group or a naphthyl group; a terphenyl group; a biphenyl group substituted with deuterium; a phenanthrene group; a triphenylene group; a dibenzofuran group; a dibenzothiophene group; a carbazole group substituted with a phenyl group; a benzonaphthofuran group; or a 2,3-dihydroindene group.

In one embodiment of the present specification, 40% or more of the substitutable positions of Ar1 are substituted with deuterium.

In another embodiment, more than 50% of the substitutable positions of Ar1 are substituted with deuterium.

In another embodiment, more than 60% of the substitutable positions of Ar1 are substituted with deuterium.

In another embodiment, more than 70% of the substitutable positions of Ar1 are substituted with deuterium.

In another embodiment, more than 80% of the substitutable positions of Ar1 are substituted with deuterium.

In another embodiment, more than 90% of the substitutable positions of Ar1 are substituted with deuterium.

In another embodiment, the substitutable positions of Ar1 are 100% substituted with deuterium.

In another embodiment, more than 50% of the substitutable positions of R9 are substituted with deuterium.

In another embodiment, more than 60% of the substitutable positions of R9 are substituted with deuterium.

In another embodiment, more than 70% of the substitutable positions of R9 are substituted with deuterium.

In another embodiment, more than 80% of the substitutable positions of R9 are substituted with deuterium.

In another embodiment, more than 90% of the substitutable positions of R9 are substituted with deuterium.

In another embodiment, the substitutable positions of R9 are 100% substituted with deuterium.

In one embodiment of the present specification, 20% or more of the substitutable positions of the compound represented by the chemical formula 1 are substituted with deuterium.

In another embodiment, 30% or more of the substitutable positions of the compound represented by the chemical formula 1 are substituted with deuterium.

In another embodiment, more than 40% of the substitutable positions of the compound represented by the chemical formula 1 are substituted with deuterium.

In another embodiment, more than 50% of the substitutable positions of the compound represented by the chemical formula 1 are substituted with deuterium.

In another embodiment, more than 60% of the substitutable positions of the compound represented by the chemical formula 1 are substituted with deuterium.

In another embodiment, more than 70% of the substitutable positions of the compound represented by the chemical formula 1 are substituted with deuterium.

In another embodiment, more than 80% of the substitutable positions of the compound represented by the chemical formula 1 are substituted with deuterium.

In another embodiment, more than 90% of the substitutable positions of the compound represented by the chemical formula 1 are substituted with deuterium.

In another embodiment, the substitutable positions of the compound represented by the chemical formula 1 are 100% substituted with deuterium.

In this specification, the chemical formula 202 is any one of the following chemical formulas 2-1 to 2-3.

[Chemical Formula 2-1]

[Chemical Formula 2-2]

[Chemical Formula 2-3]

In the chemical formulas 2-1 to 2-3 above, Y1, R11 to R14, r1 to r4, Z1 and Z2 are as defined in the chemical formula 202 above,

R15 to R17 are the same as or different from each other and are each hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

r5 and r7 are integers from 0 to 4, respectively.

When r5 is plural, R15 is equal to or different from each other,

When r7 is plural, R17 is equal to or different from each other,

r6 is an integer from 0 to 8, and when r6 is plural, R16 is equal to or different from each other.

In this specification, the chemical formula 203 is any one of the following chemical formulas 2-4 to 2-12.

[Chemical Formula 2-4]

[Chemical Formula 2-5]

[Chemical Formula 2-6]

[Chemical Formula 2-7]

[Chemical Formula 2-8]

[Chemical Formula 2-9]

[Chemical Formula 2-10]

[Chemical Formula 2-11]

[Chemical Formula 2-12]

In the chemical formulas 2-4 to 2-12 above, R11 to R13, r2, r3, Y2, Y3, and Z3 to Z6 are as defined in the chemical formula 203 above,

R15 to R20 are the same as or different from each other and are each hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group,

r1 is an integer from 0 to 3,

When r1 is plural, R11 is equal to or different from each other,

r5, r7, r8, and r10 are integers from 0 to 4, respectively,

When r5 is plural, R15 is equal to or different from each other,

When r7 is plural, R17 is equal to or different from each other,

When r8 is plural, R18 is equal to or different from each other,

When r10 is plural, R20 is equal to or different from each other,

r6 and r9 are integers from 0 to 8, respectively.

When r6 is plural, R16 is equal to or different from each other,

When r9 is plural, R19 is equal to or different from each other.

In this specification, the chemical formula 202 is the following chemical formula 2-13.

[Chemical Formula 2-13]

In the chemical formula 2-13 above, R11 to R14 and r1 to r4 are as defined in the chemical formula 202 above,

Y4 is O or S,

R21 is hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

r11 is an integer from 0 to 4,

When r11 is plural, R21 is equal to or different from each other.

In this specification, Y1 is C.

In this specification, Y2 is C.

In this specification, Y3 is C.

In this specification, Y1 is Si.

In this specification, Y2 is Si.

In this specification, Y3 is Si.

In the present specification, R11 and R12 are the same as or different from each other, and each independently represents hydrogen; a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; a silyl group substituted or unsubstituted with an alkyl group; an amine group substituted or unsubstituted with an aryl group; or a substituted or unsubstituted heterocyclic group having 3 to 30 carbon atoms.

In the present specification, R11 and R12 are the same as or different from each other, and each independently represent hydrogen; an alkyl group having 1 to 10 carbon atoms substituted or unsubstituted with an alkyl group or an aryl group; a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; a silyl group substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms; an amine group substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms; or a heterocyclic group having 3 to 30 carbon atoms substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms.

In the present specification, R11 and R12 are the same as or different from each other, and each independently represent hydrogen; a methyl group; a methyl group substituted with a methyl group or a phenyl group; a terbutyl group; a silyl group substituted with a methyl group; a phenyl group; a hexahydrocarbazole group; or an amine group substituted with a phenyl group.

In the present specification, R13 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; or an amine group substituted or unsubstituted with an aryl group.

In the present specification, R13 is an alkyl group having 1 to 10 carbon atoms, unsubstituted or substituted with an aryl group having 6 to 30 carbon atoms; or an amine group substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms.

In the present specification, R13 is a methyl group substituted or unsubstituted with a phenyl group; or an amine group substituted with a phenyl group or a terbutylphenyl group.

In the present specification, Z1 to Z6 are the same as or different from each other, and each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

In the present specification, Z1 to Z6 are the same as or different from each other, and each independently represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In the present specification, Z1 to Z6 are the same as or different from each other, and each independently represents a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

In the present specification, Z1 to Z6 are the same as or different from each other, and each independently represents a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

In the present specification, Z1 to Z6 are the same as or different from each other, and are each independently a methyl group, an ethyl group, a propyl group, a butyl group, a terbutyl group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracene group, or a phenanthrene group.

In the present specification, Z1 to Z6 are the same as or different from each other, and are each independently a methyl group, an ethyl group, a phenyl group, or a naphthyl group.

In the present specification, Z1 to Z6 are the same as or different from each other, and each independently represents a methyl group or a phenyl group.

In the present specification, Z1 and Z2 are combined with each other to form a ring.

In the present specification, Z3 and Z4 are combined with each other to form a ring.

In the present specification, Z5 and Z6 are combined with each other to form a ring.

In the present specification, Z1 and Z2 are combined with each other to form a hydrocarbon ring having 6 to 30 carbon atoms or a heterocycle having 6 to 30 carbon atoms.

In the present specification, Z3 and Z4 are combined with each other to form a hydrocarbon ring having 6 to 30 carbon atoms or a heterocycle having 6 to 30 carbon atoms.

In the present specification, Z5 and Z6 are combined with each other to form a hydrocarbon ring having 6 to 30 carbon atoms or a heterocycle having 6 to 30 carbon atoms.

In the present specification, Z1 and Z2 are combined with each other to form a hydrocarbon ring having 6 to 30 carbon atoms or a heterocycle having 6 to 20 carbon atoms.

In the present specification, Z3 and Z4 are combined with each other to form a hydrocarbon ring having 6 to 30 carbon atoms or a heterocycle having 6 to 20 carbon atoms.

In the present specification, Z5 and Z6 are combined with each other to form a hydrocarbon ring having 6 to 30 carbon atoms or a heterocycle having 6 to 20 carbon atoms.

In the present specification, Z1 and Z2 are combined with each other to form a fluorene ring, a xanthene ring, or a dibenzosilole ring.

In the present specification, Z3 and Z4 are combined with each other to form a fluorene ring, a xanthene ring, or a dibenzosilole ring.

In the present specification, Z5 and Z6 are combined with each other to form a fluorene ring, a xanthene ring, or a dibenzosilole ring.

In the present specification, Z1 to Z6 are the same as or different from each other, and are each independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, or are combined with each other to form a hydrocarbon ring having 6 to 30 carbon atoms or a heterocycle having 6 to 30 carbon atoms.

In the present specification, Z1 to Z6 are the same as or different from each other, and are each independently a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, or are combined with each other to form a fluorene ring, a xanthene ring, or a dibenzosilole ring.

In the present specification, Ar21 to Ar32 are bonded to adjacent substituents to form a ring.

In claim 1, the chemical formula 1 is any one selected from the following compounds.

In this specification, the chemical formula 2 is one selected from the following compounds.

The substituents of the compounds of the above chemical formulae 1, 202 and 203 can be combined by a method known in the art, and the type, position or number of the substituents can be changed according to a technique known in the art.

The conjugation length and energy band gap of the above heterocyclic compound are closely related. Specifically, the longer the conjugation length of the compound, the smaller the energy band gap.

In the present invention, compounds having various energy band gaps can be synthesized by introducing various substituents into the core structure as described above. In addition, in the present invention, HOMO and LUMO energy levels of the compound can also be controlled by introducing various substituents into the core structure having the structure described above.

In addition, by introducing various substituents into the core structure having the structure as described above, it is possible to synthesize a compound having the unique characteristics of the introduced substituent. For example, by introducing a substituent mainly used in hole injection layer materials, hole transport materials, light-emitting layer materials, and electron transport layer materials used in the manufacture of organic light-emitting devices into the core structure, it is possible to synthesize a material satisfying the conditions required for each organic layer.

In addition, the organic light-emitting device according to the present invention is an organic light-emitting device including a first electrode; a second electrode provided opposite the first electrode; and one or more organic layers provided between the first electrode and the second electrode, characterized in that one or more of the organic layers includes the compound described above.

The organic light-emitting device of the present invention can be manufactured using a conventional method and material for manufacturing an organic light-emitting device, except that one or more organic layers are formed using the above-described compound.

The above heterocyclic compound can be formed into an organic layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light-emitting device. Here, the solution coating method refers to spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited thereto.

The organic layer of the organic light-emitting device of the present invention may be formed as a single-layer structure, but may be formed as a multilayer structure in which two or more organic layers are laminated. For example, the organic light-emitting device of the present invention may have a structure including, as organic layers, a hole injection layer, a hole transport layer, a layer that simultaneously injects holes and transports holes, a light-emitting layer, an electron transport layer, an electron injection layer, etc. However, the structure of the organic light-emitting device is not limited thereto, and may include a smaller number of organic layers or a larger number of organic layers.

In the organic light-emitting device of the present invention, the organic layer may include a light-emitting layer, and the light-emitting layer may include a compound of chemical formula 1 and a compound of chemical formula 202.

In the organic light-emitting device of the present invention, the organic layer may include a light-emitting layer, and the light-emitting layer may include a compound of the chemical formula 1 and a compound of the chemical formula 203.

In the organic light-emitting device of the present invention, the light-emitting layer contains the compound of the chemical formula 202 and the compound of the chemical formula 1 as a dopant and a host of the light-emitting layer, respectively.

In the organic light-emitting device of the present invention, the light-emitting layer contains the compound of the chemical formula 203 and the compound of the chemical formula 1 as a dopant and a host of the light-emitting layer, respectively.

In the organic light-emitting device of the present invention, the light-emitting layer contains the host and the dopant in a mass ratio of 99:1 to 50:50, respectively.

In the organic light-emitting device of the present invention, the light-emitting layer contains the host and the dopant in a mass ratio of 99:1 to 80:20, respectively.

In the organic light-emitting device of the present invention, the light-emitting layer contains the host and the dopant in a mass ratio of 99:1 to 90:10, respectively.

In the organic light-emitting device of the present invention, the organic layer may include at least one layer among an electron transport layer, an electron injection layer, and a layer that simultaneously injects electrons and transports electrons, and at least one layer among the layers may include the compound of the chemical formula 1 and the compound of the chemical formula 202.

In the organic light-emitting device of the present invention, the organic layer includes an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer includes a compound of the chemical formula 1 and a compound of the chemical formula 202.

In the organic light-emitting device of the present invention, the organic layer includes an electron transport layer, and the electron transport layer includes a compound of chemical formula 1 and a compound of chemical formula 202.

In the organic light-emitting device of the present invention, the organic layer may include at least one layer selected from a hole injection layer, a hole transport layer, and a layer that simultaneously injects holes and transports holes, and at least one layer among the layers includes the compound of the chemical formula 1 and the compound of the chemical formula 202.

In the organic light-emitting device of the present invention, the organic layer may include at least one layer among an electron transport layer, an electron injection layer, and a layer that simultaneously injects electrons and transports electrons, and at least one layer among the layers may include the compound of the chemical formula 1 and the compound of the chemical formula 203.

In the organic light-emitting device of the present invention, the organic layer includes an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer includes a compound of the chemical formula 1 and a compound of the chemical formula 203.

In the organic light-emitting device of the present invention, the organic layer includes an electron transport layer, and the electron transport layer includes a compound of chemical formula 1 and a compound of chemical formula 203.

In the organic light-emitting device of the present invention, the organic layer may include at least one layer selected from a hole injection layer, a hole transport layer, and a layer that simultaneously injects holes and transports holes, and at least one layer among the layers includes the compound of the chemical formula 1 and the compound of the chemical formula 203.

In one embodiment of the present specification, the first electrode is an anode and the second electrode is a cathode.

In another embodiment, the first electrode is a cathode and the second electrode is an anode.

(1) Anode/hole transport layer/light emitting layer/cathode

(2) Anode/hole injection layer/hole transport layer/light emitting layer/cathode

(3) Anode/hole injection layer/hole buffer layer/hole transport layer/light emitting layer/cathode

(4) Anode/hole transport layer/light emitting layer/electron transport layer/cathode

(5) Anode/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode

(6) Anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/cathode

(7) Anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode

(8) Anode/hole injection layer/hole buffer layer/hole transport layer/light emitting layer/electron transport layer/cathode

(9) Anode/hole injection layer/hole buffer layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode

(10) Anode/hole transport layer/electron suppression layer/light emitting layer/electron transport layer/cathode

(11) Anode/hole transport layer/electron suppression layer/light emitting layer/electron transport layer/electron injection layer/cathode

(12) Anode/hole injection layer/hole transport layer/electron suppression layer/light emitting layer/electron transport layer/cathode

(13) Anode/hole injection layer/hole transport layer/electron suppression layer/light emitting layer/electron transport layer/electron injection layer/cathode

(14) Anode/hole transport layer/light emitting layer/hole suppression layer/electron transport layer/cathode

(15) Anode/hole transport layer/light emitting layer/hole suppression layer/electron transport layer/electron injection layer/cathode

(16) Anode/hole injection layer/hole transport layer/light emitting layer/hole suppression layer/electron transport layer/cathode

(17) Anode/hole injection layer/hole transport layer/light emitting layer/hole suppression layer/electron transport layer/electron injection layer/cathode

(18) Anode/hole injection layer/hole transport layer/electron suppression layer/light emitting layer/hole blocking layer/electron injection and transport layer/cathode

The structure of the organic light-emitting device of the present invention may have a structure as shown in Fig. 1, but is not limited thereto.

The structure of the organic light-emitting device of the present invention may have a structure as shown in Fig. 2, but is not limited thereto.

Figure 1 illustrates the structure of an organic light-emitting device in which an anode (2), a light-emitting layer (3), and a cathode (4) are sequentially laminated on a substrate (1). In this structure, the compound represented by the chemical formula 1 may be included in the light-emitting layer (3).

FIG. 2 illustrates the structure of an organic light-emitting device in which an anode (2), a hole injection layer (5), a hole transport layer (6), a light-emitting layer (7), an electron transport layer (8), an electron injection layer (9), and a cathode (4) are sequentially laminated on a substrate (1). In this structure, the compound represented by the chemical formula 1 may be included in the light-emitting layer (7).

For example, the organic light-emitting device according to the present invention can be manufactured by forming an anode by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, and then forming an organic layer including at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, a layer that simultaneously transports and injects holes, an emission layer, an electron transport layer, an electron injection layer, and a layer that simultaneously transports and injects electrons, and then depositing a material that can be used as a cathode thereon. In addition to this method, the organic light-emitting device can also be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate.

The above organic layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, but is not limited thereto and may have a single layer structure. In addition, the organic layer may be manufactured with a smaller number of layers by using various polymer materials and a solvent process other than a deposition method, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer.

The above anode is an electrode that injects holes, and as the anode material, a material having a high work function is preferably used so that holes can be smoothly injected into the organic layer. Specific examples of the anode material that can be used in the present invention include, but are not limited to, metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline.

The above cathode is an electrode that injects electrons, and it is preferable that the cathode material be a material having a low work function so that electrons can be easily injected into the organic layer. Specific examples of the cathode material include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayered materials such as LiF/Al or LiO ₂ /Al.

The above hole injection layer is a layer that facilitates the injection of holes from the anode to the light-emitting layer, and the hole injection material is a material that can well inject holes from the anode at a low voltage. It is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include, but are not limited to, metal porphyrine, oligothiophene, arylamine-based organic compounds, hexanitrilehexaazatriphenylene-based organic compounds, quinacridone-based organic compounds, perylene-based organic compounds, anthraquinone, and conductive polymers of polyaniline and polythiophene-based compounds. The thickness of the hole injection layer may be 1 to 150 nm. When the thickness of the above hole injection layer is 1 nm or more, there is an advantage of being able to prevent the hole injection characteristics from being deteriorated, and when it is 150 nm or less, there is an advantage of being able to prevent the driving voltage from being increased to improve the movement of holes due to the thickness of the hole injection layer being too thick.

The above-mentioned hole transport layer can play a role in facilitating the transport of holes. As a hole transport material, a material that can transport holes from the anode or the hole injection layer and transfer them to the light-emitting layer is suitable, and a material with high mobility for holes is suitable. Specific examples include, but are not limited to, arylamine-based organic substances, conductive polymers, and block copolymers having both conjugated and non-conjugated portions.

An additional hole buffer layer may be provided between the hole injection layer and the hole transport layer, and includes a hole injection or transport material known in the art.

An electron blocking layer may be provided between the hole transport layer and the light emitting layer. The electron blocking layer may be made of the aforementioned spiro compound or a material known in the art.

The above-described light-emitting layer can emit red, green or blue light, and can be made of a phosphorescent material or a fluorescent material. The above-described light-emitting material is a material that can emit light in the visible light range by transporting holes and electrons from the hole transport layer and the electron transport layer respectively and combining them, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include, but are not limited to, 8-hydroxy-quinoline aluminum complex (Alq ₃ ); carbazole series compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compounds; benzoxazole, benzthiazole and benzimidazole series compounds; poly(p-phenylenevinylene) (PPV) series polymers; spiro compounds; polyfluorene, rubrene, etc.

The host material of the light-emitting layer includes a condensed aromatic ring derivative or a heterocyclic compound. Specifically, the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and the heterocyclic compound includes, but is not limited to, carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, etc.

When the emitting layer emits red light, the emitting dopant may include, but is not limited to, a phosphorescent material such as PIQIr(acac)(bis(1-phenylisoquinoline)acetylacetonateiridium), PQIr(acac)(bis(1-phenylquinoline)acetylacetonate iridium), PQIr(tris(1-phenylquinoline)iridium), PtOEP(octaethylporphyrin platinum), or a fluorescent material such as Alq ₃ (tris(8-hydroxyquinolino)aluminum). When the emitting layer emits green light, the emitting dopant may include, but is not limited to, a phosphorescent material such as Ir(ppy) ₃ (fac tris(2-phenylpyridine)iridium), or a fluorescent material such as Alq3(tris(8-hydroxyquinolino)aluminum). When the emitting layer emits blue light, a phosphorescent material such as (4,6-F2ppy) ₂ Irpic, or a fluorescent material such as spiro-DPVBi, spiro-6P, distilbenzene (DSB), distriarylene (DSA), PFO polymers, or PPV polymers can be used as the emitting dopant, but is not limited thereto.

A hole-suppressing layer may be provided between the electron transport layer and the light-emitting layer, and a material known in the art may be used.

The above electron transport layer can play a role in facilitating electron transport. As the electron transport material, a material that can well inject electrons from the cathode and transfer them to the light-emitting layer, and a material with high electron mobility is suitable. Specific examples include, but are not limited to, Al complexes of 8-hydroxyquinoline; complexes containing Alq ₃ ; organic radical compounds; and hydroxyflavone-metal complexes. The thickness of the electron transport layer can be 1 to 50 nm. When the thickness of the electron transport layer is 1 nm or more, there is an advantage in that the electron transport characteristics can be prevented from being deteriorated, and when it is 50 nm or less, there is an advantage in that the driving voltage can be prevented from being increased to improve the movement of electrons due to the thickness of the electron transport layer being too thick.

The above electron injection layer can play a role in facilitating electron injection. As the electron injection material, a compound having the ability to transport electrons, an excellent electron injection effect from the cathode, an excellent electron injection effect for the light-emitting layer or the light-emitting material, preventing movement of excitons generated in the light-emitting layer to the hole injection layer, and excellent thin film forming ability is preferable. Specific examples thereof include, but are not limited to, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, and their derivatives, metal complex compounds, and nitrogen-containing 5-membered ring derivatives.

As the above metal complex compounds, 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h]quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)(o-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, Bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc., but are not limited thereto.

The above hole blocking layer is a layer that blocks holes from reaching the cathode, and can generally be formed under the same conditions as the electron injection layer. Specifically, examples thereof include, but are not limited to, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, and aluminum complexes.

The organic light-emitting device according to the present invention may be a front-emitting type, a back-emitting type, or a double-sided emitting type depending on the material used.

The organic light-emitting device of the present invention can be manufactured using a conventional method and material for manufacturing an organic light-emitting device, except that one or more organic layers are formed using the above-described compound.

The method for producing the compound of the above chemical formula 1 and the production of an organic light-emitting device using the same are specifically described in the following examples. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

In the following reaction formula, the type and number of substituents can be selected appropriately by those skilled in the art from known starting materials to synthesize various types of intermediates. The reaction type and reaction conditions known in the art can be used.

By appropriately combining the manufacturing formulas and the intermediates described in the examples of this specification based on common technical knowledge, all of the compounds of the chemical formula 1 described in this specification can be manufactured.

<Synthetic example>

1. Synthesis of intermediate A

Synthesis Example 1-1. Synthesis of Intermediate A-1

9-Bromoanthracene (50 g, 194 mmol) and (2-(naphthalen-1-yl)phenyl)boronic acid (48 g, 194 mmol) were dissolved in THF (1000 ml), and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.39 mmol) and 200 ml of 2 M K ₂ CO ₃ aqueous solution were added, and the mixture was stirred under reflux for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. Recrystallization from ethyl acetate gave intermediate A-1 (57 g, yield 77%).

Synthesis Example 1-2. Synthesis of Intermediate A

Intermediate A-1 (57 g, 150 mmol) was dissolved in 700 ml of DMF, and then N-bromosuccinimide (26.7 g, 150 mmol) dissolved in 100 ml of DMF was slowly added dropwise. After stirring at room temperature for 2 hours, 1500 ml of water was added dropwise. When a solid was formed, it was filtered, dissolved in chloroform, and extracted several times with distilled water. Intermediate A was obtained by recrystallization from ethyl acetate. (52 g, yield 76%)

2. Synthesis of intermediate B

Synthesis Example 2-1. Synthesis of Intermediate B-1

Intermediate B-1 was obtained through the same synthesis as in step 1-1 except that dibenzo[b,d]furan-2-ylboronic acid was used instead of (2-(naphthalen-1-yl)phenyl)boronic acid.

Synthesis Example 2-2. Synthesis of Intermediate B

Intermediate B was obtained through the same synthesis as in Synthesis Example 1-2, except that Intermediate B-1 was used instead of Intermediate A-1.

3. Synthesis of compound 1

Synthesis Example 3-1. Synthesis of Intermediate 1-a

1-Bromo-4-chloro-3-fluoro-2-iodobenzene (100 g, 298 mmol) and (3-hydroxynaphthalen-2-yl)boronic acid (56 g, 298 mmol) were dissolved in THF (1500 ml), and Pd(PPh ₃ ) ₄ (6.9 g, 6.0 mmol) and 300 ml of 2 M Na2CO3 aqueous solution were added, and the mixture was refluxed and stirred for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure, and the residue was purified using column chromatography to obtain compound 1-a (75 g, yield 71%).

Synthesis Example 3-2. Synthesis of Intermediate 1-b

Intermediate 1-a (75 g, 213 mmol) was dissolved in DMF (1000 ml), K ₂ CO ₃ (88 g, 640 mmol) was added, and the mixture was refluxed for 2 hours. After cooling the reaction solution, it was poured into 3 L of distilled water to generate a solid. The solid was filtered, dissolved in chloroform, extracted several times with water, and the organic layer was dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure, and the residue was purified using column chromatography to obtain intermediate 1-b (54 g, 76%).

Synthesis Example 3-3. Synthesis of Intermediate 1-c

Intermediate 1-b (54 g, 163 mmol) and phenylboronic acid (20 g, 163 mmol) were dissolved in THF (800 ml), and Pd(PPh ₃ ) ₄ (3.8 g, 3.3 mmol) and 200 ml of 2 M K ₂ CO ₃ aqueous solution were added, and the mixture was stirred under reflux for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure, and the residue was purified using column chromatography to obtain intermediate 1-c (39 g, yield 73%).

Synthesis Example 3-4. Synthesis of Intermediate 1-d

Intermediate 1-c (39 g, 119 mmol) and bis(pinacolato)diboron (36 g, 142 mmol), KOAc (23 g, 237 mmol) were added to a flask with 300 ml of dioxane and dispersed. Pd(dba) ₂ (1.36 g, 2.4 mmol), PCy3 (1.33 g, 4.7 mmol) were added, and the mixture was stirred under reflux for 24 hours. After completion of the reaction, dioxane was removed by distillation under reduced pressure. After dissolving in chloroform, the mixture was extracted three times with distilled water, and the organic layer was distilled under reduced pressure to remove chloroform. Intermediate 1-d was obtained by purification using column chromatography. (35 g, yield 70%)

Synthesis Example 3-5. Synthesis of Compound 1

Intermediate 1-d (20 g, 48 mmol) and intermediate A (21.9 g, 48 mmol) were dissolved in THF (250 ml), and bis(tri-tert-butylphosphine)palladium(0) (0.05 g, 0.09 mmol) and 50 ml of 2M _{K2CO3 aqueous} solution were added, and the mixture was stirred under reflux for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. Compound 1 (16 g, yield 50%) was obtained by recrystallization from EA. [M+H ⁺ ]= 672.25

4. Synthesis of compound 2

Synthesis Example 4-1. Synthesis of Intermediate 2-a

Intermediate 2-a was obtained by the same synthesis procedure as in Synthetic Example 3-1, except that 5-bromo-1-chloro-3-fluoro-2-iodobenzene was used instead of 1-bromo-4-chloro-3-fluoro-2-iodobenzene.

Synthesis Example 4-2. Synthesis of Intermediate 2-b

Intermediate 2-b was obtained by the same synthesis as in Synthesis Example 3-2, except that Intermediate 2-a was used instead of Intermediate 1-a.

Synthesis Example 4-3. Synthesis of Intermediate 2-c

Intermediate 2-c was obtained by the same synthesis as in Synthesis Example 3-3, except that Intermediate 2-b was used instead of Intermediate 1-b.

Synthesis Example 4-4. Synthesis of Intermediate 2-d

Intermediate 2-d was obtained by the same synthesis as in Synthesis Example 3-4, except that intermediate 2-c was used instead of intermediate 1-c.

Synthesis Example 4-5. Synthesis of Compound 2

Compound 2 was obtained by the same synthesis as in Synthesis Example 3-5, except that Intermediate 2-d was used instead of Intermediate 1-d and 9-bromo-10-phenylanthracene was used instead of Intermediate A. [M+H ⁺ ]= 547.2

5. Synthesis of compound 3

Synthesis Example 5-1. Synthesis of Intermediate 3-a

Intermediate 3-a was obtained by the same synthesis procedure as in Synthetic Example 3-1, except that 5-bromo-1-chloro-3-fluoro-2-iodobenzene was used instead of 1-bromo-4-chloro-3-fluoro-2-iodobenzene, and (1-hydroxynaphthalen-2-yl)boronic acid was used instead of (3-hydroxynaphthalen-2-yl)boronic acid.

Synthesis Example 5-2. Synthesis of Intermediate 3-b

Intermediate 3-b was obtained by the same synthesis as in Synthesis Example 3-2, except that Intermediate 3-a was used instead of Intermediate 1-a.

Synthesis Example 5-3. Synthesis of Intermediate 3-c

Intermediate 3-c was obtained by the same synthesis as in Synthesis Example 3-3, except that intermediate 3-b was used instead of intermediate 1-b.

Synthesis Example 5-4. Synthesis of Intermediate 3-d

Intermediate 3-d was obtained by the same synthesis as in Synthesis Example 3-4, except that intermediate 3-c was used instead of intermediate 1-c.

Synthesis Example 5-5. Synthesis of Compound 3

Compound 3 was obtained by the same synthesis as in Synthesis Example 3-5, except that intermediate 3-d was used instead of intermediate 1-d and 9-bromo-10-(naphthalen-2-yl)anthracene was used instead of intermediate A. [M+H ⁺ ]= 597.2

6. Synthesis of compound 4

Synthesis Example 6-1. Synthesis of Intermediate 4-a

Intermediate 4-a was obtained by the same synthesis procedure as in Synthetic Example 3-1, except that 6-bromo-1-iodonaphthalen-2-ol was used instead of 1-bromo-4-chloro-3-fluoro-2-iodobenzene, and (5-chloro-2-fluorophenyl)boronic acid was used instead of (3-hydroxynaphthalen-2-yl)boronic acid.

Synthesis Example 6-2. Synthesis of Intermediate 4-b

Intermediate 4-b was obtained by the same synthesis as in Synthesis Example 3-2, except that intermediate 4-a was used instead of intermediate 1-a.

Synthesis Example 6-3. Synthesis of Intermediate 4-c

Intermediate 4-c was obtained by the same synthesis as in Synthesis Example 3-3, except that intermediate 4-b was used instead of intermediate 1-b.

Synthesis Example 6-4. Synthesis of Intermediate 4-d

Intermediate 4-d was obtained by the same synthesis as in Synthesis Example 3-4, except that intermediate 4-c was used instead of intermediate 1-c.

Synthesis Example 6-5. Synthesis of Compound 4

Compound 4 was obtained by the same synthesis as in Synthesis Example 3-5, except that Intermediate 4-d was used instead of Intermediate 1-d and Intermediate B was used instead of Intermediate A. [M+H ⁺ ]= 637.2

7. Synthesis of compound 5

Synthesis Example 7-1. Synthesis of Intermediate 5-a

Intermediate 5-a was obtained by the same synthesis procedure as in Synthetic Example 3-1, except that 5-bromo-1-chloro-3-fluoro-2-iodobenzene was used instead of 1-bromo-4-chloro-3-fluoro-2-iodobenzene, and (2-hydroxynaphthalen-1-yl)boronic acid was used instead of (3-hydroxynaphthalen-2-yl)boronic acid.

Synthesis Example 7-2. Synthesis of Intermediate 5-b

Intermediate 5-b was obtained by the same synthesis as in Synthesis Example 3-2, except that intermediate 5-a was used instead of intermediate 1-a.

Synthesis Example 7-3. Synthesis of Intermediate 5-c

Intermediate 5-c was obtained by the same synthesis as in Synthesis Example 3-3, except that intermediate 5-b was used instead of intermediate 1-b.

Synthesis Example 7-4. Synthesis of Intermediate 5-d

Intermediate 5-d was obtained by the same synthesis as in Synthesis Example 3-4, except that intermediate 5-c was used instead of intermediate 1-c.

Synthesis Example 7-5. Synthesis of Compound 5

Compound 5 was obtained by the same synthesis as in Synthetic Example 3-5, except that intermediate 5-d was used instead of intermediate 1-d and 9-{[1,1'-biphenyl]-3-yl}-10-bromoanthracene was used instead of intermediate A. [M+H ⁺ ]= 623.2

8. Synthesis of compound 6

Synthesis Example 8-1. Synthesis of Intermediate 6-a

2-Bromo-4-chloro-1-fluorobenzene (100 g, 477 mmol) and (3-hydroxynaphthalen-2-yl)boronic acid (90 g, 477 mmol) were dissolved in THF (1600 ml), Pd(PPh ₃ ) ₄ (11.0 g, 9.5 mmol) and 400 ml of 2 M K ₂ CO ₃ aqueous solution were added, and the mixture was refluxed and stirred for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure, and the residue was purified using column chromatography to obtain compound 6-a (95 g, yield 73%).

Synthesis Example 8-2. Synthesis of Intermediate 6-b

Intermediate 6-a (95 g, 348 mmol) was dissolved in 1000 ml of DMF, and then N-bromosuccinimide (62 g, 348 mmol) dissolved in 200 ml of DMF was slowly added dropwise. After stirring at room temperature for 2 hours, DMF was removed by distillation under reduced pressure. Dissolved in chloroform, extracted several times with distilled water, and then distilled under reduced pressure to remove the solvent. Compound 6-b was obtained by purification using column chromatography. (55 g, yield 45%)

Synthesis Example 8-3. Synthesis of Intermediate 6-c

Intermediate 6-b (55 g, 156 mmol) was dissolved in DMF (800 ml), and K ₂ CO ₃ (65 g, 470 mmol) was added and stirred under reflux for 2 hours. After cooling the reaction solution, it was poured into 2 L of distilled water to generate a solid. The solid was filtered, dissolved in chloroform, extracted several times with water, and the organic layer was dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure, and the residue was purified using column chromatography to obtain intermediate 6-c (35 g, 67%).

Synthesis Example 8-4. Synthesis of Intermediate 6-d

Intermediate 6-c (35 g, 106 mmol) and naphthal-1-ylboronic acid (18 g, 106 mmol) were dissolved in THF (500 ml), and Pd(PPh ₃ ) ₄ (2.4 g, 2.1 mmol) and 100 ml of 2 M K ₂ CO ₃ aqueous solution were added, and the mixture was stirred under reflux for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure, and the residue was purified using column chromatography to obtain intermediate 6-d (27 g, yield 68%).

Synthesis Example 8-5. Synthesis of Intermediate 6-e

Intermediate 6-d (27 g, 71 mmol), bis(pinacolato)diboron (22 g, 86 mmol), KOAc (14 g, 143 mmol) were added to a flask with 200 ml of dioxane and dispersed. Pd(dba) ₂ (0.82 g, 1.4 mmol), PCy3 (0.8 g, 2.9 mmol) were added, and the mixture was stirred under reflux for 24 hours. After completion of the reaction, dioxane was removed by distillation under reduced pressure. After dissolving in chloroform, the mixture was extracted three times with distilled water, and the organic layer was distilled under reduced pressure to remove chloroform. Intermediate 6-e was obtained by purification using column chromatography. (23 g, yield 69%)

Synthesis Example 8-6. Synthesis of compound 6

Intermediate 6-e (20 g, 43 mmol) and 9-bromo-10-phenylanthracene (14.2 g, 43 mmol) were dissolved in THF (210 ml), and bis(tri-tert-butylphosphine)palladium(0) (0.04 g, 0.09 mmol) and 50 ml of 2M _{K2CO3 aqueous} solution were added, and the mixture was stirred under reflux for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. Compound 6 (13 g, yield 51%) was obtained by recrystallization from EA. [M+H ⁺ ]= 597.2

9. Synthesis of compound 7

Synthesis Example 9-1. Synthesis of Intermediate 7-a

2-Bromonaphthalen-1-ol (100 g, 448 mmol) and (5-chloro-2-fluorophenyl)boronic acid (78 g, 448 mmol) were dissolved in THF (1500 ml), and Pd(PPh ₃ ) ₄ (10.4 g, 9.0 mmol) and 400 ml of 2 M K ₂ CO ₃ aqueous solution were added, and the mixture was refluxed and stirred for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure, and the residue was purified using column chromatography to obtain compound 7-a (106 g, yield 86%).

Synthesis Example 9-2. Synthesis of Intermediate 7-b

Intermediate 7-a (106 g, 389 mmol) was dissolved in DMF (2000 ml), and K ₂ CO ₃ (161 g, 1166 mmol) was added and stirred under reflux for 2 hours. After cooling the reaction solution, it was poured into 5 L of distilled water to generate a solid. The solid was filtered, dissolved in chloroform, extracted several times with water, and the organic layer was dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure, and the residue was purified using column chromatography to obtain intermediate 7-b (75 g, 76%).

Synthesis Example 9-3. Synthesis of Intermediate 7-c

Intermediate 7-b (75 g, 297 mmol) was dissolved in 1000 ml of DMF, and then N-bromosuccinimide (53 g, 297 mmol) dissolved in 100 ml of DMF was slowly added dropwise. After stirring at room temperature for 2 hours, DMF was removed by distillation under reduced pressure. Dissolved in chloroform, extracted several times with distilled water, and then distilled under reduced pressure to remove the solvent. Compound 7-c was obtained by purification using column chromatography. (71 g, yield 72%)

Synthesis Example 9-4. Synthesis of Intermediate 7-d

Intermediate 7-c (71 g, 214 mmol) and phenylboronic acid (26 g, 214 mmol) were dissolved in THF (1000 ml), and Pd(PPh ₃ ) ₄ (4.9 g, 4.3 mmol) and 250 ml of 2 M K ₂ CO ₃ aqueous solution were added, and the mixture was stirred under reflux for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure, and the residue was purified using column chromatography to obtain intermediate 7-d (52 g, yield 74%).

Synthesis Example 9-5. Synthesis of Intermediate 7-e

Intermediate 7-d (52 g, 158 mmol), bis(pinacolato)diboron (48 g, 190 mmol), KOAc (31 g, 316 mmol) were added to a flask with 400 ml of dioxane and dispersed. Pd(dba) ₂ (1.82 g, 3.2 mmol), PCy3 (1.77 g, 6.3 mmol) were added, and the mixture was stirred under reflux for 24 hours. After completion of the reaction, dioxane was removed by distillation under reduced pressure. After dissolving in chloroform, the mixture was extracted three times with distilled water, and the organic layer was distilled under reduced pressure to remove chloroform. Intermediate 7-e was obtained by purification using column chromatography. (41 g, yield 62%)

Synthesis Example 9-6. Synthesis of Compound 7

Intermediate 7-e (20 g, 48 mmol) and 9-bromo-10-(naphthalen-1-yl)anthracene (18 g, 48 mmol) were dissolved in THF (250 ml), and bis(tri-tert-butylphosphine)palladium(0) (0.05 g, 0.1 mmol) and 50 ml of 2M _{K2CO3 aqueous} solution were added, and the mixture was stirred under reflux for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. Compound 7 (15 g, yield 53%) was obtained by recrystallization from EA. [M+H ⁺ ]= 597.2

10. Synthesis of compound 8

Synthesis Example 10-1. Synthesis of Intermediate 8-a

3-Bromonaphthalene-2,7-diol (100 g, 418 mmol) and (2-chloro-6-fluorophenyl)boronic acid (73 g, 418 mmol) were dissolved in THF (1400 ml), and Pd(PPh ₃ ) ₄ (9.7 g, 8.4 mmol) and 400 ml of 2 M K ₂ CO ₃ aqueous solution were added, and the mixture was stirred under reflux for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure, and the residue was purified using column chromatography to obtain compound 8-a (92 g, yield 76%).

Synthesis Example 10-2. Synthesis of Intermediate 8-b

Intermediate 8-a (92 g, 319 mmol) was dissolved in DMF (1500 ml), and K ₂ CO ₃ (132 g, 956 mmol) was added, and the mixture was stirred under reflux for 2 hours. After cooling the reaction solution, it was poured into 3 L of distilled water to generate a solid. The solid was filtered, dissolved in chloroform, extracted several times with water, and the organic layer was dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure, and the residue was purified using column chromatography to obtain intermediate 8-b (54 g, 63%).

Synthesis Example 10-3. Synthesis of Intermediate 8-c

Intermediate 8-b was dissolved in acetonitrile (1000 ml), and then K ₂ CO ₃ (83 g, 603 mmol) and nonafluorobutane-1-sulfonyl fluoride (91 g, 301 mmol) dissolved in 200 ml of distilled water were added. After stirring at room temperature for 3 hours, acetonitrile was removed by distillation under reduced pressure, and the solution was dissolved in chloroform and extracted several times with water. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure to remove the organic solvent, and purified using column chromatography to obtain compound 8-c (81 g, yield 73%).

Synthesis Example 10-4. Synthesis of Intermediate 8-d

Intermediate 8-c (81 g, 147 mmol) and phenylboronic acid (18 g, 147 mmol) were dissolved in THF (500 ml), and Pd(PPh ₃ ) ₄ (3.4 g, 2.9 mmol) and 150 ml of 2 M K ₂ CO ₃ aqueous solution were added, and the mixture was stirred under reflux for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure, and the residue was purified using column chromatography to obtain intermediate 8-d (37 g, yield 76%).

Synthesis Example 10-5. Synthesis of Intermediate 8-e

Intermediate 8-d (37 g, 113 mmol), bis(pinacolato)diboron (34 g, 135 mmol), KOAc (22 g, 225 mmol) were added to a flask with 300 ml of dioxane and dispersed. Pd(dba) ₂ (1.29 g, 2.3 mmol), PCy3 (1.26 g, 4.5 mmol) were added, and the mixture was stirred under reflux for 24 hours. After completion of the reaction, dioxane was removed by distillation under reduced pressure. After dissolving in chloroform, the mixture was extracted three times with distilled water, and the organic layer was distilled under reduced pressure to remove chloroform. Intermediate 8-e was obtained by purification using column chromatography. (35 g, yield 74%)

Synthesis Example 10-6. Synthesis of Compound 8

Intermediate 8-e (20 g, 48 mmol) and 9-bromo-10-(naphthalen-2-yl)anthracene (18 g, 48 mmol) were dissolved in THF (250 ml), and bis(tri-tert-butylphosphine)palladium(0) (0.05 g, 0.1 mmol) and 50 ml of 2 M K ₂ CO ₃ aqueous solution were added, and the mixture was stirred under reflux for 24 h. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The mixture was recrystallized from EA to obtain compound 8 (16 g, yield 56%). [M+H ⁺ ]= 597.2

11. Synthesis of compound 9

Synthesis Example 11-1. Synthesis of Intermediate 9-a

Intermediate 9-a was obtained by the same synthesis procedure as in Synthetic Example 10-1, except that 3-bromo-5-chloro-2-fluorophenol was used instead of 3-bromonaphthalene-2,7-diol and (3-hydroxynaphthalen-2-yl)boronic acid was used instead of (2-chloro-6-fluorophenyl)boronic acid.

Synthesis Example 11-2. Synthesis of Intermediate 9-b

Intermediate 9-b was obtained by the same synthesis as in Synthesis Example 10-2, except that intermediate 9-a was used instead of intermediate 8-a.

Synthesis Example 11-3. Synthesis of Intermediate 9-c

Intermediate 9-c was obtained by the same synthesis as in Synthesis Example 10-3, except that intermediate 9-b was used instead of intermediate 8-b.

Synthesis Example 11-4. Synthesis of Intermediate 9-d

Intermediate 9-d was obtained by the same synthesis as in Synthesis Example 10-4, except that intermediate 9-c was used instead of intermediate 8-c.

Synthesis Example 11-5. Synthesis of Intermediate 9-e

Intermediate 9-e was obtained by the same synthesis as in Synthesis Example 10-5, except that intermediate 9-d was used instead of intermediate 8-d.

Synthesis Example 11-6. Synthesis of Compound 9

Compound 9 was obtained by the same synthesis as in Synthetic Example 10-6, except that intermediate 9-e was used instead of intermediate 8-e and 9-bromo-10-(naphthalen-1-yl)anthracene was used instead of 9-bromo-10-(naphthalen-2-yl)anthracene. [M+H ⁺ ]= 597.2

12. Synthesis of compound 10

Synthesis Example 12-1. Synthesis of Intermediate 10-a

Intermediate 10-a was obtained by the same synthesis procedure as in Synthetic Example 10-1, except that 5-bromo-2-chloro-4-fluorophenol was used instead of 3-bromonaphthalene-2,7-diol and (1-hydroxynaphthalen-2-yl)boronic acid was used instead of (2-chloro-6-fluorophenyl)boronic acid.

Synthesis Example 12-2. Synthesis of Intermediate 10-b

Intermediate 10-b was obtained by the same synthesis as in Synthesis Example 10-2, except that Intermediate 10-a was used instead of Intermediate 8-a.

Synthesis Example 12-3. Synthesis of Intermediate 10-c

Intermediate 10-c was obtained by the same synthesis as in Synthesis Example 10-3, except that Intermediate 10-b was used instead of Intermediate 8-b.

Synthesis Example 12-4. Synthesis of Intermediate 10-d

Intermediate 10-d was obtained by the same synthesis as in Synthesis Example 10-4, except that intermediate 10-c was used instead of intermediate 8-c.

Synthesis Example 12-5. Synthesis of Intermediate 10-e

Intermediate 10-e was obtained by the same synthesis as in Synthesis Example 10-5, except that intermediate 10-d was used instead of intermediate 8-d.

Synthesis Example 12-6. Synthesis of Compound 10

Compound 10 was obtained by the same synthesis as in Synthesis Example 10-6, except that intermediate 10-e was used instead of intermediate 8-e. [M+H ⁺ ]= 597.2

13. Synthesis of compound 11

Synthesis Example 13-1. Synthesis of Intermediate 11-a

Intermediate 11-a was obtained by the same synthesis as in Synthesis Example 10-1, except that 4-bromonaphthalene-1,3-diol was used instead of 3-bromonaphthalene-2,7-diol.

Synthesis Example 13-2. Synthesis of Intermediate 11-b

Intermediate 11-b was obtained by the same synthesis as in Synthesis Example 10-2, except that Intermediate 11-a was used instead of Intermediate 8-a.

Synthesis Example 13-3. Synthesis of Intermediate 11-c

Intermediate 11-c was obtained by the same synthesis as in Synthesis Example 10-3, except that Intermediate 11-b was used instead of Intermediate 8-b.

Synthesis Example 13-4. Synthesis of Intermediate 11-d

Intermediate 11-d was obtained by the same synthesis as in Synthesis Example 10-4, except that intermediate 11-c was used instead of intermediate 8-c.

Synthesis Example 13-5. Synthesis of Intermediate 11-e

Intermediate 11-e was obtained by the same synthesis as in Synthesis Example 10-5, except that intermediate 11-d was used instead of intermediate 8-d.

Synthesis Example 13-6. Synthesis of Compound 11

Compound 11 was obtained by the same synthesis as in Synthetic Example 10-6, except that intermediate 11-e was used instead of intermediate 8-e and 9-{[1,1'-biphenyl]-4-yl}-10-bromoanthracene was used instead of 9-bromo-10-(naphthalen-2-yl)anthracene. [M+H ⁺ ]= 623.2

14. Synthesis of compound 12

Synthesis Example 14-1. Synthesis of Intermediate 12-a

Intermediate 12-a was obtained by the same synthesis procedure as in Synthetic Example 10-1, except that 1-bromonaphthalene-2,7-diol was used instead of 3-bromonaphthalene-2,7-diol and (5-chloro-2-fluorophenyl)boronic acid was used instead of (2-chloro-6-fluorophenyl)boronic acid.

Synthesis Example 14-2. Synthesis of Intermediate 12-b

Intermediate 12-b was obtained by the same synthesis as in Synthesis Example 10-2, except that Intermediate 12-a was used instead of Intermediate 8-a.

Synthesis Example 14-3. Synthesis of Intermediate 12-c

Intermediate 12-c was obtained by the same synthesis as in Synthesis Example 10-3, except that intermediate 12-b was used instead of intermediate 8-b.

Synthesis Example 14-4. Synthesis of Intermediate 12-d

Intermediate 12-d was obtained by the same synthesis as in Synthesis Example 14-4, except that intermediate 12-c was used instead of intermediate 8-c.

Synthesis Example 14-5. Synthesis of Intermediate 12-e

Intermediate 12-e was obtained by the same synthesis as in Synthesis Example 10-5, except that intermediate 12-d was used instead of intermediate 8-d.

Synthesis Example 14-6. Synthesis of Compound 12

Compound 12 was obtained by the same synthesis as in Synthetic Example 10-6, except that intermediate 12-e was used instead of intermediate 8-e and 9-bromo-10-(naphthalen-1-yl)anthracene was used instead of 9-bromo-10-(naphthalen-2-yl)anthracene. [M+H ⁺ ]= 597.3

15. Synthesis of compound 13

Synthesis Example 15-1. Synthesis of Intermediate 13-a

8-Bromonaphthalen-1-ol (100 g, 448 mmol) and phenylboronic acid (55 g, 448 mmol) were dissolved in THF (1500 ml), Pd(PPh ₃ ) ₄ (10.4 g, 9.0 mmol) and 300 ml of 2 M K ₂ CO ₃ aqueous solution were added, and the mixture was refluxed and stirred for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure, and the residue was purified using column chromatography to obtain compound 13-a (72 g, yield 73%).

Synthesis Example 15-2. Synthesis of Intermediate 13-b

Intermediate 13-a (72 g, 327 mmol) was dissolved in 1000 ml of DMF, and then N-bromosuccinimide (58 g, 327 mmol) dissolved in 100 ml of DMF was slowly added dropwise. After stirring at room temperature for 2 hours, DMF was removed by distillation under reduced pressure. Dissolved in chloroform, extracted several times with distilled water, and then distilled under reduced pressure to remove the solvent. Compound 13-b was obtained by purification using column chromatography. (69 g, yield 71%)

Synthesis Example 15-3. Synthesis of Intermediate 13-c

Intermediate 13-b (69 g, 231 mmol) and (4-chloro-2-fluorophenyl)boronic acid (40 g, 231 mmol) were dissolved in THF (800 ml), and Pd(PPh ₃ ) ₄ (5.3 g, 4.6 mmol) and 200 ml of 2 M K ₂ CO ₃ aqueous solution were added, and the mixture was stirred under reflux for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure, and the residue was purified using column chromatography to obtain compound 13-c (54 g, yield 67%).

Synthesis Example 15-4. Synthesis of Intermediate 13-d

Intermediate 13-c (54 g, 155 mmol) was dissolved in DMF (800 ml), K ₂ CO ₃ (64 g, 460 mmol) was added, and the mixture was refluxed for 2 hours. After cooling the reaction solution, it was poured into 3 L of distilled water to generate a solid. The solid was filtered, dissolved in chloroform, extracted several times with water, and the organic layer was dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure, and the residue was purified using column chromatography to obtain intermediate 13-d (34 g, 67%).

Synthesis Example 15-5. Synthesis of Intermediate 13-e

Intermediate 13-d (34 g, 103 mmol) and bis(pinacolato)diboron (32 g, 124 mmol), KOAc (20 g, 207 mmol) were added to a flask with 260 ml of dioxane and dispersed. Pd(dba) ₂ (1.18 g, 2.1 mmol), PCy3 (1.15 g, 4.1 mmol) were added, and the mixture was stirred under reflux for 24 hours. After completion of the reaction, dioxane was removed by distillation under reduced pressure. After dissolving in chloroform, the mixture was extracted three times with distilled water, and the organic layer was distilled under reduced pressure to remove chloroform. Intermediate 13-e was obtained by purification using column chromatography. (31 g, yield 71%)

Synthesis Example 15-6. Synthesis of Compound 13

Intermediate 13-e (20 g, 48 mmol) and 9-bromo-10-(phenanthren-9-yl)anthracene (20.6 g, 48 mmol) were dissolved in THF (250 ml), and bis(tri-tert-butylphosphine)palladium(0) (0.05 g, 0.09 mmol) and 50 ml of 2M _{K2CO3 aqueous} solution were added, and the mixture was stirred under reflux for 24 h. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. Compound 13 (17 g, yield 55%) was obtained by recrystallization from EA. [M+H ⁺ ]= 647.2

16. Synthesis of compound 14

Synthesis Example 16-1. Synthesis of Intermediate 14-a

Intermediate 8-b (100 g, 372 mmol) and phenylboronic acid (45 g, 372 mmol) were dissolved in THF (1200 ml), and Pd(PPh ₃ ) ₄ (8.6 g, 7.4 mmol) and 300 ml of 2 M K ₂ CO ₃ aqueous solution were added, and the mixture was stirred under reflux for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure, and the residue was purified using column chromatography to obtain compound 14-a (73 g, yield 63%).

Synthesis Example 16-2. Synthesis of Intermediate 14-b

Intermediate 14-a (73 g, 235 mmol) was dissolved in acetonitrile (1200 ml), and then K ₂ CO ₃ (107 g, 352 mmol) and nonafluorobutane-1-sulfonyl fluoride (107 g, 353 mmol) dissolved in 250 ml of distilled water were added. After stirring at room temperature for 3 hours, acetonitrile was removed by distillation under reduced pressure, and the mixture was dissolved in chloroform and extracted several times with water. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure to remove the organic solvent, and purified using column chromatography to obtain compound 14-b (97 g, yield 70%).

Synthesis Example 16-3. Synthesis of Intermediate 14-c

Intermediate 14-b (97 g, 163 mmol), bis(pinacolato)diboron (50 g, 196 mmol), KOAc (32 g, 327 mmol) were added to a flask with 400 ml of dioxane and dispersed. Pd(dba) ₂ (1.88 g, 3.3 mmol), PCy3 (1.83 g, 6.5 mmol) were added, and the mixture was stirred under reflux for 24 hours. After completion of the reaction, dioxane was removed by distillation under reduced pressure. After dissolving in chloroform, the mixture was extracted three times with distilled water, and the organic layer was distilled under reduced pressure to remove chloroform. Intermediate 14-c was obtained by purification using column chromatography. (52 g, yield 76%)

Synthesis Example 16-4. Synthesis of Intermediate 14-d

Intermediate 14-c (52 g, 124 mmol) and 1-bromo-3-chlorobenzene (24 g, 124 mmol) were dissolved in THF (400 ml), and Pd(PPh ₃ ) ₄ (2.8 g, 2.5 mmol) and 100 ml of 2 M K ₂ CO ₃ aqueous solution were added, and the mixture was stirred under reflux for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure, and the residue was purified using column chromatography to obtain compound 14-d (36 g, yield 72%).

Synthesis Example 16-5. Synthesis of Intermediate 14-e

Intermediate 14-d (36 g, 89 mmol), bis(pinacolato)diboron (27 g, 107 mol), KOAc (17 g, 178 mmol) were added to a flask with 250 ml of dioxane and dispersed. Pd(dba) ₂ (1.0 g, 1.8 mmol), PCy3 (1.00 g, 3.6 mmol) were added, and the mixture was stirred under reflux for 24 hours. After completion of the reaction, dioxane was removed by distillation under reduced pressure. After dissolving in chloroform, the mixture was extracted three times with distilled water, and the organic layer was distilled under reduced pressure to remove chloroform. Intermediate 14-e was obtained by purification using column chromatography. (32 g, yield 72%)

Synthesis Example 16-6. Synthesis of compound 14

Intermediate 14-e (20 g, 40 mmol) and 9-bromo-10-phenylanthracene (13.4 g, 40 mmol) were dissolved in THF (200 ml), and bis(tri-tert-butylphosphine)palladium(0) (0.04 g, 0.08 mmol) and 50 ml of 2M _K2CO3 aqueous solution were added, and the mixture was stirred under reflux for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl _acetate and dried over anhydrous magnesium sulfate. Compound 14 (16 g, yield 64%) was obtained by recrystallization from EA. [M+H ⁺ ]= 623.2

17. Synthesis of compound 15

Synthesis Example 17-1. Synthesis of Intermediate 15-a

Intermediate 7-c (50 g, 151 mmol), bis(pinacolato)diboron (46 g, 181 mol), KOAc (30 g, 302 mmol) were added to a flask with 400 ml of dioxane and dispersed. Pd(dppf)Cl2 (2.2 g, 3.0 mmol) was added and refluxed for 24 hours. After completion of the reaction, dioxane was removed by distillation under reduced pressure. After dissolving in chloroform, it was extracted three times with distilled water, and the organic layer was distilled under reduced pressure to remove chloroform. Intermediate 15-a was obtained by purification using column chromatography. (43 g, yield 75%)

Synthesis Example 17-2. Synthesis of Intermediate 15-b

Intermediate 15-a (43 g, 114 mmol) and 9-{[1,1'-biphenyl]-4-yl}-10-bromoanthracene (46.5 g, 114 mmol) were dissolved in THF (400 ml), and Pd(PPh ₃ ) ₄ (2.6 g, 2.3 mmol) and 80 ml of 2 M K ₂ CO ₃ aqueous solution were added, followed by reflux stirring for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. Compound 15-b (44 g, yield 67%) was obtained by purification by recrystallization from ethyl acetate.

Synthesis Example 17-3. Synthesis of Compound 15

Intermediate 15-b (20 g, 34 mmol) and phenylboronic acid (11.5 g, 34 mmol) were dissolved in dioxane (200 ml), and bis(tri-tert-butylphosphine)palladium(0) (0.04 g, 0.07 mmol) and 50 ml of 2M _{K2CO3 aqueous} solution were added, and the mixture was stirred under reflux for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. Compound 15 (16 g, yield 74%) was obtained by recrystallization from EA. [M+H ⁺ ]= 623.2

18. Synthesis of compound 16

Synthesis Example 18-1. Synthesis of Compound 16-a

Intermediate 12-b (50 g, 186 mmol) and phenylboronic acid (22.7 g, 186 mmol) were dissolved in dioxane (1000 ml), bis(tri-tert-butylphosphine)palladium(0) (0.19 g, 0.37 mmol) and 200 ml of 2 M K ₂ CO ₃ aqueous solution were added, and the mixture was stirred under reflux for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. Compound 16-a (45 g, yield 78%) was obtained by purification by column chromatography.

Synthesis Example 18-2. Synthesis of Intermediate 16-b

Intermediate 16-a (45 g, 145 mmol) was dissolved in acetonitrile (700 ml), and then K ₂ CO ₃ (107 g, 352 mmol) and nonafluorobutane-1-sulfonyl fluoride (66 g, 217 mmol) dissolved in 100 ml of distilled water were added. After stirring at room temperature for 3 hours, acetonitrile was removed by distillation under reduced pressure, dissolved in chloroform, and extracted several times with water. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure to remove the organic solvent, and purified using column chromatography to obtain compound 16-b (62 g, yield 72%).

Synthesis Example 18-3. Synthesis of Intermediate 16-c

Intermediate 16-b (62 g, 104 mmol), bis(pinacolato)diboron (32 g, 126 mol), KOAc (21 g, 209 mmol) were added to a flask with 250 ml of dioxane and dispersed. Pd(dba) ₂ (1.2 g, 2.1 mmol), PCy3 (1.2 g, 2.1 mmol) were added, and the mixture was stirred under reflux for 24 hours. After completion of the reaction, dioxane was removed by distillation under reduced pressure. After dissolving in chloroform, the mixture was extracted three times with distilled water, and the organic layer was distilled under reduced pressure to remove chloroform. Intermediate 16-c was obtained by purification using column chromatography. (30 g, yield 68%)

Synthesis Example 18-4. Synthesis of Compound 16

Intermediate 16-c (30 g, 71 mmol) and 9-bromo-10-(naphthalen-2-yl)anthracene (27.4 g, 71 mmol) were dissolved in THF (400 ml), and bis(tri-tert-butylphosphine)palladium(0) (0.07 g, 0.14 mmol) and 80 ml of 2M _{K2CO3 aqueous} solution were added, and the mixture was stirred under reflux for 24 h. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. Compound 16 (22 g, yield 52%) was obtained by recrystallization from EA. [M+H ⁺ ]= 597.3

19. Synthesis of compound 17

Synthesis Example 19-1. Synthesis of Intermediate 17-a

9-Phenylanthracene (50 g) and AlCl ₃ (10 g) were added to C ₆ D ₆ (1000 ml) and stirred for 2 hours. After the reaction was completed, D ₂ O (75 ml) was added and stirred for 30 minutes, and then trimethylamine (6 ml) was added dropwise. The reaction solution was transferred to a separatory funnel and extracted with water and toluene. The extract was dried over MgSO ₄ and recrystallized from ethyl acetate to obtain intermediate 17-a. (36 g, yield 72%)

Synthesis Example 19-2. Synthesis of Intermediate 17-b

Intermediate 17-a (36 g, 128 mmol) was dissolved in 500 ml of DMF, and then N-bromosuccinimide (22.8 g, 128 mmol) dissolved in 100 ml of DMF was slowly added dropwise. After stirring at room temperature for 2 hours, 1000 ml of water was added dropwise. When a solid was formed, it was filtered, dissolved in chloroform, and extracted several times with distilled water. Intermediate 17-b was obtained by recrystallization from ethyl acetate. (31 g, yield 67%)

Synthesis Example 19-3. Synthesis of compound 17

Intermediate 2-d (23.4 g, 56 mmol) and intermediate 17-b (20 g, 56 mmol) were dissolved in THF (300 ml), and bis(tri-tert-butylphosphine)palladium(0) (0.06 g, 0.11 mmol) and 60 ml of 2M _{K2CO3 aqueous} solution were added, and the mixture was stirred under reflux for 24 h. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The compound 17 (22 g, yield 71%) was obtained by recrystallization from EA. [M+H ⁺ ]= 560.3

20. Synthesis of compound 18

Synthesis Example 20-1. Synthesis of Intermediate 18-a

Compound 18-a was obtained by the same synthesis as in Synthetic Example 19-1, except that 9-(naphthalen-2-yl)anthracene was used instead of 9-phenylanthracene.

Synthesis Example 20-2. Synthesis of Intermediate 18-b

Compound 18-b was obtained by the same synthesis as in Synthetic Example 19-2, except that intermediate 18-a was used instead of intermediate 17-a.

Synthesis Example 20-3. Synthesis of compound 18

Compound 18 was obtained through the same synthesis as in Synthetic Example 19-3, except that intermediate 3-d was used instead of intermediate 2-b, and intermediate 18-b was used instead of intermediate 17-b.

21. Synthesis of compound 19

Synthesis Example 21-1. Synthesis of Compound 19

Compound 19 was obtained by the same synthesis as in Synthesis Example 19-1, except that compound 7 was used instead of 9-phenyl anthracene.

22. Synthesis of compound 20

Synthesis Example 22-1. Synthesis of Compound 20

Compound 20 was obtained by the same synthesis as in Synthetic Example 19-1, except that compound 12 was used instead of 9-phenyl anthracene.

23. Synthesis of compound 21

<23-a> Synthesis of intermediate 21-a

Under a nitrogen atmosphere, 1-bromo-3-(tert-butyl)-5-chlorobenzene (50 g, 202 mmol), 4a,9a-dimethyl-2,3,4,4a,9,9a-hexahydro-1H-carbazole (41 g, 202 mmol), sodium tert-butoxide (29.1 g, 303 mmol), and bis(tri-tert-butylphosphine)palladium(0) (2.06 g, 4.0 mmol) were added to 700 ml of toluene and stirred under reflux for 6 hours. After the reaction was completed, extraction was performed and the mixture was purified by using an ethyl acetate:hexane column to obtain intermediate 21-a (47 g, yield 63%).

<23-b> Synthesis of intermediate 21-b

Under a nitrogen atmosphere, 21-a (47 g, 128 mmol), 5-(tert-butyl)phenyl)-[1,1'-biphenyl]-2-amine (28.8 g, 128 mmol), sodium-tert-butoxide (24.5 g, 255 mmol), and bis(tri-tert-butylphosphine)palladium(0) (1.31 g, 2.6 mmol) were added to 400 ml of toluene and stirred under reflux for 12 hours. After the reaction was completed, extraction was performed, and the product was purified using an ethyl acetate:hexane column and recrystallized to obtain intermediate 21-b (41 g, yield 58%).

<23-c> Synthesis of intermediate 21-c

Under a nitrogen atmosphere, 21-b (41 g, 74 mmol), 1-bromo-3-chlorobenzene (14.1 g, 74 mmol), sodium-tert-butoxide (10.6 g, 110 mmol), and bis(tri-tert-butylphosphine)palladium(0) (0.75 g, 1.5 mmol) were added to 300 ml of toluene and stirred under reflux for 6 hours. After the reaction was completed, extraction was performed, and the mixture was purified using an ethyl acetate:hexane column and recrystallized to obtain intermediate 21-c (34 g, yield 69%).

<23-d> Synthesis of intermediate 21-d

Under a nitrogen atmosphere, 21-c (34 g, 51 mmol) was dissolved in 500 ml of dichlorobenzene, and then 9.73 ml of boron triiodide was added. The temperature was raised to 160 degrees and stirred for 3 hours. After completion of the reaction, dichlorobenzene was removed by distillation under reduced pressure, and then extracted with ethyl acetate/water. After purification with an ethyl acetate:hexane column, intermediate 21-d was obtained through recrystallization (8.9 g, yield 26%).

<23-e> Synthesis of compound 21

Under a nitrogen atmosphere, 21-d (8.9 g, 13 mmol), diphenylamine (3.9 g, 13 mmol), sodium-tert-butoxide (2.53 g 26 mmol), and bis(tri-tert-butylphosphine)palladium(0) (0.13 g, 0.26 mmol) were added to 50 ml of toluene and stirred under reflux for 12 hours. After the reaction was completed, extraction was performed, and the resultant was purified using an ethyl acetate:hexane column and recrystallized to obtain compound 21 (5.9 g, yield 56%). MS[M+H]+ = 808.5

24. Synthesis of compound 22

<24-a> Synthesis of intermediate 22-a

Under a nitrogen atmosphere, 1,3-Dibromo-5-chlorobenzene (50 g, 185 mmol), 4a,9a-dimethyl-2,3,4,4a,9,9a-hexahydro-1H-carbazole (74.5 g, 370 mmol), sodium-tert-butoxide (44.4 g, 462 mmol), and bis(tri-tert-butylphosphine)palladium(0) (1.89 g, 3.7 mmol) were added to 600 ml of toluene and stirred under reflux for 6 hours. After the reaction was completed, extraction was performed and the mixture was purified by an ethyl acetate:hexane column to obtain intermediate 22-a (57 g, yield 60%).

<24-b> Synthesis of intermediate 22-b

Under a nitrogen atmosphere, 22-a (57 g, 112 mmol) was dissolved in 1000 ml of dichlorobenzene, and 21.3 ml of boron triiodide was added. The temperature was raised to 160 degrees and stirred for 3 hours. After completion of the reaction, dichlorobenzene was removed by distillation under reduced pressure, and then extracted with ethyl acetate/water. After purification with an ethyl acetate:hexane column, intermediate 22-b was obtained through recrystallization (12.3 g, yield 21%).

<24-c> Synthesis of compound 22

Under a nitrogen atmosphere, 22-b (12.3 g, 24 mmol), diphenylamine (4.0 g, 24 mmol), sodium-tert-butoxide (4.6 g 47 mol), and bis(tri-tert-butylphosphine)palladium(0) (0.24 0.47 mmol) were added to 80 ml of toluene and stirred under reflux for 12 hours. After the reaction was completed, extraction was performed, and the resultant was purified by an ethyl acetate:hexane column and recrystallized to obtain compound 22 (9.3 g, yield 60%). MS[M+H]+ = 652.4

25. Synthesis of compound 23

<25-a> Synthesis of intermediate 23-a

Under a nitrogen atmosphere, 1-bromo-3,5-dichlorobenzene (50 g, 221 mmol), 9,9'-dimethyl-9,10-dihydroacridine (46.3 g, 221 mmol), sodium tert-butoxide (31.9 g, 332 mmol), and bis(tri-tert-butylphosphine)palladium(0) (2.3 g, 4.4 mmol) were added to 750 ml of toluene and stirred under reflux for 6 hours. After the reaction was completed, extraction was performed and the mixture was purified by an ethyl acetate:hexane column to obtain 23-a (53 g, yield 67%).

<25-b> Synthesis of intermediate 23-b

Under a nitrogen atmosphere, 23-a (53 g, 148 mmol), 5-(tert-butyl)-N-(3-(tert-butyl)phenyl)-[1,1'-biphenyl]-2-amine (52.5 g, 148 mmol), sodium-tert-butoxide (28.4 g, 296 mmol), and bis(tri-tert-butylphosphine)palladium(0) (1.51 g, 3.0 mmol) were added to 500 ml of toluene and stirred under reflux for 12 hours. After the reaction was completed, extraction was performed and the mixture was purified by an ethyl acetate:hexane column to obtain 23-b (59 g, yield 59%).

<25-c> Synthesis of intermediate 23-c

Under a nitrogen atmosphere, compound 23-b (59 g, 87 mmol) was dissolved in 900 ml of dichlorobenzene, and then 16.7 ml of boron triiodide was added. The temperature was raised to 160 degrees and stirred for 3 hours. After completion of the reaction, dichlorobenzene was removed by distillation under reduced pressure, and then extracted with ethyl acetate/water. After purification with an ethyl acetate:hexane column, 23-c was obtained through recrystallization (11.7 g, yield 20%).

<25-d> Synthesis of compound 23

Under a nitrogen atmosphere, compound 23-c (11.7 g, 17 mmol), diphenylamine (2.9 g, 17 mmol), sodium-tert-butoxide (3.3 g 34 mmol), and bis(tri-tert-butylphosphine)palladium(0) (0.17 g, 0.34 mmol) were added to 60 ml of toluene and stirred under reflux for 12 hours. After the reaction was completed, extraction was performed, and the resultant was purified using an ethyl acetate:hexane column and recrystallized to obtain compound 23 (9.3 g, yield 67%). MS[M+H]+ = 816.4

26. Synthesis of compound 24

<26-a> Synthesis of intermediate 24-a

Intermediate 24-a was obtained by the same synthesis procedure as in Synthetic Example 23-a, except that 1-bromo-3-chloro-5-methylbenzene was used instead of 1-bromo-3-(tert-butyl)-5-chlorobenzene.

<26-b> Synthesis of intermediate 24-b

Intermediate 24-b was obtained by the same synthesis procedure as in Synthetic Example 23-b, except that 24-a was used instead of 21-a and dibenzo[b,d]furan-1-amine was used instead of 5-(tert-butyl)phenyl)-[1,1'-biphenyl]-2-amine.

<26-c> Synthesis of intermediate 24-c

Intermediate 24-c was obtained by the same synthesis except that 24-b was used instead of 21-b in Synthesis Example 23-c.

<26-d> Synthesis of intermediate 24-d

Intermediate 24-d was obtained by the same synthesis procedure except that 24-c was used instead of 21-c in Synthetic Example 23-d.

<26-e> Synthesis of compound 24

Compound 24 was obtained by the same synthesis method as in Synthetic Example 23-e, except that 24-d was used instead of compound 21-d and bis(4-(tert-butyl)phenyl)amine was used instead of diphenylamine. MS[M+H]+ = 836.5

27. Synthesis of compound 25

<27-a> Synthesis of intermediate 25-a

Intermediate 25-a was obtained by the same synthesis procedure as in Synthetic Example 25-a, except that 4a,9a-dimethyl-2,3,4,4a,9,9a-hexahydro-1H-carbazole was used instead of 9,9'-dimethyl-9,10-dihydroacridine.

<27-b> Synthesis of intermediate 25-b

Intermediate 25-b was obtained by the same synthesis procedure as in Synthetic Example 25-b, except that 25-a was used instead of 23-a and 9H-carbazole was used instead of 5-(tert-butyl)-N-(3-(tert-butyl)phenyl)-[1,1'-biphenyl]-2-amine.

<27-c> Synthesis of intermediate 25-c

Intermediate 25-c was obtained by the same synthesis process except that 25-b was used instead of 23-b in Synthetic Example 25-c.

<27-d> Synthesis of compound 25

Compound 25 was obtained by the same synthesis method except that 25-c was used instead of 23-c in Synthetic Example 25-d and bis(4-(tert-butyl)phenyl)amine was used instead of diphenylamine. MS[M+H]+ = 730.4

28. Synthesis of compound 26

<28-a> Synthesis of intermediate 26-a

Intermediate 26-a was obtained by the same synthesis procedure as in Synthetic Example 25-a, except that 1-bromo-3-chloro-5-methylbenzene was used instead of 1-bromo-3,5-dichlorobenzene and 10H-spiro[acridine-9,9'-fluorene] was used instead of 9,9'-dimethyl-9,10-dihydroacridine.

<28-b> Synthesis of intermediate 26-b

Intermediate 26-b was obtained by the same synthesis procedure except that 26-a was used instead of 23-a in Synthetic Example 25-b.

<28-c> Synthesis of compound 26

Compound 26 was obtained by the same synthesis method except that 26-b was used instead of compound 23-b in Synthesis Example 25-c. MS[M+H]+ = 785.4

29. Synthesis of compound 27

<29-a> Synthesis of intermediate 27-a

50 g of 4a,9a-dimethyl-2,3,4,4a,9,9a-hexahydro-1H-carbazole, 10 g of 5% Pt/C, 300 ml of toluene, and 700 ml of D2O were placed in an autoclave, and then hydrogen was charged. After the temperature was increased to 180 degrees, the reaction was performed for 24 hours. After completion of the reaction, the catalyst was filtered through a Celite pad and then extracted. The mixture was purified by an ethyl acetate:hexane column to obtain intermediate 27-a. (29 g, yield 57%)

<29-b> Synthesis of intermediate 27-b

Intermediate 27-b was obtained by the same synthesis procedure as in Synthetic Example 29-a, except that N-(4-(tert-butyl)phenyl)-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-amine was used instead of 4a,9a-dimethyl-2,3,4,4a,9,9a-hexahydro-1H-carbazole.

<29-c> Synthesis of intermediate 27-c

Intermediate 27-c was obtained by the same synthesis procedure as in Synthetic Example 25-a, except that 27-a was used instead of 9,9'-dimethyl-9,10-dihydroacridine.

<29-d> Synthesis of intermediate 27-d

Intermediate 27-d was obtained by the same synthesis procedure as in Synthetic Example 25-b, except that 27-c was used instead of 23-a and 27-b was used instead of 5-(tert-butyl)-N-(3-(tert-butyl)phenyl)-[1,1'-biphenyl]-2-amine.

<29-e> Synthesis of intermediate 27-e

Intermediate 27-e was obtained by the same synthesis procedure except that 27-d was used instead of 23-b in Synthetic Example 25-c.

<29-f> Synthesis of compound 27

Compound 27 was obtained by the same synthesis method except that 28-e was used instead of compound 23-c in Synthetic Example 25-d and bis(phenyl-d5)amine was used instead of diphenylamine. MS[M+H]+ = 805.6

30. Synthesis of compound 28

<30-a> Synthesis of intermediate 28-a

Intermediate 28-a was obtained by the same synthesis procedure as in Synthetic Example 29-a, except that N-(4-(tert-butyl)phenyl)-[1,1'-biphenyl]-4-amine was used instead of 4a,9a-dimethyl-2,3,4,4a,9,9a-hexahydro-1H-carbazole.

<30-b> Synthesis of intermediate 28-b

Intermediate 28-b was obtained by the same synthesis procedure as in Synthetic Example 25-a, except that 1-bromo-3-chloro-5-(methyl-d3)benzene was used instead of 1-bromo-3,5-dichlorobenzene, and Intermediate 28-a was used instead of 9,9'-dimethyl-9,10-dihydroacridine.

<30-c> Synthesis of intermediate 28-c

Intermediate 28-c was obtained by the same synthesis procedure as in Synthetic Example 25-b, except that 28-b was used instead of 23-a, and 4a,9a-dimethyl-2,3,4,4a,9,9a-hexahydro-1H-carbazole was used instead of 5-(tert-butyl)-N-(3-(tert-butyl)phenyl)-[1,1'-biphenyl]-2-amine.

<30-d> Synthesis of compound 28

Compound 28 was obtained by the same synthesis except that 28-d was used instead of 23-b in Synthesis Example 25-c. MS[M+H]+ = 614.7

<Example>

<Comparative Example>

Example 1

A glass substrate coated with a 150 nm thick ITO (indium tin oxide) film was placed in distilled water containing a detergent and ultrasonically cleaned. At this time, a Fischer Co. product was used as the detergent, and distilled water filtered twice through a Millipore Co. filter was used as the distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was performed twice with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, and after drying, it was transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using nitrogen plasma and then transported to a vacuum deposition device. On the ITO transparent electrode thus prepared, the following HAT-CN compound was thermally vacuum deposited to a thickness of 5 nm to form a hole injection layer. Then, HTL1 was thermally vacuum deposited to a thickness of 100 nm, and then HTL2 was thermally vacuum deposited to a thickness of 10 nm to form a hole transport layer. Then, the compound 1 as a host and the compound 21 as a dopant (weight ratio 95:5) were simultaneously vacuum deposited to form a 20 nm thick emitting layer. Then, ETL was vacuum deposited to a thickness of 20 nm to form an electron transport layer. Then, LiF was vacuum deposited to a thickness of 0.5 nm to form an electron injection layer. Then, aluminum was deposited to a thickness of 100 nm to form a cathode, thereby manufacturing an organic light-emitting device.

The structures of the compounds used in the examples are as follows.

Examples 2 to 45 and Comparative Examples 1 to 17

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the compounds described in Table 1 below were used instead of Compound 1 and Compound 21 as the host and dopant of the light-emitting layer, respectively. At this time, among the structures below, the compounds represented by Chemical Formula 1, Chemical Formula 202, and 203 of the present invention were manufactured through the same process as Synthesis Examples 1 to 30 described above, respectively.

In the organic light-emitting devices manufactured in Examples 1 to 45 and Comparative Examples 1 to 17, the driving voltage and luminous efficiency were measured at a current density of 10 mA/cm ² , and the time (LT) for reaching 95% of the initial luminance was measured at a current density of 20 mA/cm ² , and the results are shown in the table below.

No. Host Dopant Vop Cd/A LT (95%) Example 1 Compound 1 Compound 21 3.82 6.91 172 Example 2 Compound 1 Compound 22 3.85 6.85 180 Example 3 Compound 2 Compound 21 3.63 6.87 191 Example 4 Compound 2 Compound 25 3.66 6.92 185 Example 5 Compound 2 Compound 27 3.62 6.94 243 Example 6 Compound 3 Compound 23 3.76 7.03 186 Example 7 Compound 3 Compound 24 3.71 7.02 190 Example 8 Compound 3 Compound 28 3.79 7.06 255 Example 9 Compound 4 Compound 26 3.56 6.85 175 Example 10 Compound 4 Compound 27 3.60 6.88 221 Example 11 Compound 5 Compound 22 3.78 7.05 162 Example 12 Compound 5 Compound 23 3.75 7.04 175 Example 13 Compound 5 Compound 27 3.71 7.07 233 Example 14 Compound 6 Compound 24 3.81 6.95 176 Example 15 Compound 6 Compound 25 3.88 6.92 180 Example 16 Compound 7 Compound 26 3.79 7.03 179 Example 17 Compound 7 Compound 28 3.77 7.09 241 Example 18 Compound 8 Compound 21 3.74 7.02 192 Example 19 Compound 8 Compound 23 3.79 7.05 187 Example 20 Compound 9 Compound 22 3.85 7.10 175 Example 21 Compound 9 Compound 26 3.82 7.08 173 Example 22 Compound 10 Compound 24 3.75 7.03 169 Example 23 Compound 10 Compound 25 3.77 7.01 173 Example 24 Compound 11 Compound 21 3.81 6.95 181 Example 25 Compound 11 Compound 28 3.79 6.98 233 Example 26 Compound 12 Compound 22 3.75 7.06 173 Example 27 Compound 12 Compound 23 3.78 7.04 177 Example 28 Compound 13 Compound 24 3.82 7.07 168 Example 29 Compound 13 Compound 26 3.85 7.09 171 Example 30 Compound 14 Compound 25 3.79 6.97 175 Example 31 Compound 14 Compound 27 3.75 7.01 223 Example 32 Compound 15 Compound 21 3.82 6.95 183 Example 33 Compound 15 Compound 28 3.78 7.02 237 Example 34 Compound 16 Compound 24 3.75 7.03 179 Example 35 Compound 16 Compound 27 3.79 7.07 245 Example 36 Compound 17 Compound 22 3.61 6.98 285 Example 37 Compound 17 Compound 25 3.66 6.92 295 Example 38 Compound 17 Compound 28 3.70 6.93 332 Example 39 Compound 18 Compound 23 3.75 7.01 280 Example 40 Compound 18 Compound 24 3.71 7.02 299 Example 41 Compound 18 Compound 28 3.79 7.06 341 Example 42 Compound 19 Compound 26 3.80 7.02 357 Example 43 Compound 19 Compound 27 3.78 7.03 452 Example 44 Compound 20 Compound 21 3.79 7.05 352 Example 45 Compound 20 Compound 22 3.75 7.06 346 Comparative Example 1 BH-A Compound 21 4.26 6.43 102 Comparative Example 2 BH-B Compound 23 4.11 6.35 110 Comparative Example 3 BH-B Compound 25 4.13 6.41 106 Comparative Example 4 BH-C Compound 26 4.01 6.51 116 Comparative Example 5 BH-C Compound 27 3.99 6.53 151 Comparative Example 6 Compound 1 BD-A 4.03 6.32 88 Comparative Example 7 Compound 8 BD-B 3.99 6.25 99 Comparative Example 8 Compound 13 BD-C 4.02 6.40 103 Comparative Example 9 Compound 16 BD-D 4.10 6.35 95 Comparative Example 10 Compound 3 BD-E 4.02 6.24 75 Comparative Example 11 Compound 6 BD-F 4.15 6.27 88 Comparative Example 12 Compound 9 BD-G 4.21 6.33 81 Comparative Example 13 Compound 11 BD-H 4.16 6.29 79 Comparative Example 14 Compound 5 BD-I 4.17 6.16 85 Big Kyoye 15 Compound 15 BD-J 4.20 6.35 73 Comparative Example 16 BH-A BD-A 4.31 6.31 83 Comparative Example 17 BH-C BD-C 4.09 6.29 92

From the above table, it can be confirmed that the organic light-emitting devices of Examples 1 to 45 have lower driving voltages and superior efficiency and lifespan compared to the organic light-emitting devices of Comparative Examples 1 to 17. In particular, Examples 36 to 45 showed that the lifespan was further improved by deuterium substitution in Chemical Formula 1, and Examples 5, 8, 10, 13, 17, 25, 31, 33, 35, 38, 41, and 43 showed that the lifespan was further improved by deuterium substitution in Chemical Formula 2.

When compared with Comparative Examples 1 to 3 that used host BH-A and BH-B that do not use benzonaphthofuran as in Chemical Formula 1 of the present invention, Examples 1 to 45 show superior effects in terms of voltage, efficiency, and lifespan by using a host material containing benzonaphthofuran.

Specifically, comparing Comparative Example 1 with Examples 1, 3, and 18, Examples 1, 3, and 18, which use a host including benzonaphthofuran, show the effects of low voltage, high efficiency, and long life, despite the common use of compound 21 as a dopant.

Comparative example material BH-C contains benzonaphthofuran, but unlike the present invention, it contains unsubstituted benzonaphthofuran. Comparative examples 4 and 5 using BH-C as a host are disadvantageous in terms of voltage, efficiency, and lifespan compared to examples 5, 9, 10, 13, 16, 42, and 43 that use the same dopant and use a compound containing only substituted benzonaphthofuran as the host. This shows that in addition to the host material simply containing benzonaphthofuran, whether or not benzonaphthofuran is substituted has a different effect when applied to a device.

The effects of using dopant materials BD-1 to BD-J having a core structure different from the chemical formulas 202 and 203 of the present invention or using an amine compound instead of a boron-based organic compound are described in Comparative Examples 6 to 15.

In particular, compared with Comparative Examples 6 to 15 and Examples 1, 2, 6, 7, 11, 12, 24, 25, 32 and 33, which differ only in the dopant material, Examples 1, 2, 6, 7, 11, 12, 24, 25, 32 and 33, which include the material of Chemical Formula 2 of the present invention, exhibit lower voltage, higher efficiency and longer lifespan, and thus can be confirmed to be advantageous when applied to devices.

1: Substrate
2: First electrode
3: Organic layer
4: Second electrode
5: Hole injection layer
6: Hole transport layer
7: Emissive layer
8: Electron transport layer
9: Electron injection layer

Claims (12)

An organic light-emitting device comprising a first electrode; a second electrode provided opposite the first electrode; and at least one organic layer provided between the first electrode and the second electrode, wherein at least one layer of the organic layers comprises a compound of the following chemical formula 1 and a compound of the following chemical formula 202, or an organic light-emitting device comprising a compound of any one of the following chemical formulas 2-6, and 2-9 to 2-13 and a compound of the following chemical formula 1:
[Chemical Formula 1]

[Chemical formula 202]

[Chemical Formula 2-6]

[Chemical Formula 2-9]

[Chemical Formula 2-10]

[Chemical Formula 2-11]

[Chemical Formula 2-12]

[Chemical Formula 2-13]

In the above chemical formula 1, chemical formula 202, chemical formula 2-6, and chemical formulas 2-9 to 2-13,
Ar1 is a substituted or unsubstituted aryl group; a substituted or unsubstituted hydrocarbon ring group; or a substituted or unsubstituted heteroaryl group,
L is a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group,
R1 to R8 are the same as or different from each other, and are each independently hydrogen; deuterium; a nitrile group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group,
R9 is deuterium; a nitrile group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group,
Y1 to Y3 are the same or different from each other, and are each independently C or Si,
R11 to R14, and Z1 to Z6 are the same as or different from each other, and are each independently hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heterocyclic group; or a substituted or unsubstituted amine group, or are combined with adjacent substituents to form a substituted or unsubstituted ring,
Ar21 to Ar24 are the same as or different from each other, and are each independently hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heterocyclic group; or a substituted or unsubstituted amine group, or are combined with adjacent substituents to form a substituted or unsubstituted monocyclic hydrocarbon ring or a substituted or unsubstituted bicyclic heterocycle,
R15 to R21 are the same as or different from each other and are each hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group,
However, if Y1 is C, Z1 and Z2 combine with each other to form a substituted or unsubstituted ring,
When Y1 is S, Z1 and Z2 are hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heterocyclic group; or a substituted or unsubstituted amine group, or are bonded to each other with adjacent substituents to form a substituted or unsubstituted ring,
a is an integer from 0 to 9, and when a is plural, R9 is the same or different, and at least one of the plural R9 is not deuterium,
r1 is an integer from 0 to 4,
r2 and r3 are integers from 0 to 3, respectively,
When r1 is plural, R11 is equal to or different from each other,
When r2 is plural, R12 is equal to or different from each other,
When r3 is plural, R13 is equal to or different from each other,
r4 is an integer from 0 to 5,
When r4 is plural, R14 is equal to or different from each other,
r5, r7, r8, and r10 are each integers from 0 to 4,
When r5 is plural, R15 is equal to or different from each other,
When r7 is plural, R17 is equal to or different from each other,
When r8 is plural, R18 is equal to or different from each other,
When r10 is plural, R20 is equal to or different from each other,
r6 and r9 are integers from 0 to 8, respectively.
When r6 is plural, R16 is equal to or different from each other,
When r9 is plural, R19 is equal to or different from each other,
r11 is an integer from 0 to 4,
When r11 is plural, R21 is equal to or different from each other,
p1 is 1. In claim 1, the chemical formula 202 is an organic light-emitting device having the following chemical formula 2-3:
[Chemical Formula 2-3]

In the chemical formula 2-3 above, R11 to R14, Y1, r1 to r4, Z1 and Z2 are as defined in the chemical formula 202 above,
R17 are the same or different from each other and are each hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group,
r7 is an integer from 0 to 4,
When r7 is plural, R17 is equal to or different from each other. delete delete An organic light-emitting device according to claim 1, wherein Z1 and Z2 are combined with each other to form a ring. An organic light-emitting device according to claim 1, wherein R9 is an aryl group having 6 to 30 carbon atoms, which is unsubstituted or substituted with deuterium. An organic light-emitting device according to claim 1, wherein Ar1 is an aryl group having 6 to 30 carbon atoms substituted or unsubstituted with deuterium, an aryl group having 6 to 30 carbon atoms substituted or unsubstituted with an aryl group, or a heteroaryl group having 6 to 30 carbon atoms substituted or unsubstituted with an aryl group. An organic light-emitting device according to claim 1, wherein R13 is an alkyl group having 1 to 10 carbon atoms, unsubstituted or substituted with an aryl group having 6 to 30 carbon atoms; or an amine group substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms. An organic light-emitting device according to claim 1, wherein R1 to R8 are deuterium. In claim 1, the organic light-emitting device wherein the chemical formula 1 is one selected from the following compounds:






















In claim 1, the organic light-emitting device wherein the chemical formula 202, chemical formula 2-6, and chemical formulas 2-9 to 13 are any one selected from the following compounds:





An organic light-emitting device according to claim 1, wherein the organic layer includes a light-emitting layer, and the light-emitting layer includes a compound of the chemical formula 1 and a compound of the chemical formula 202, or includes a compound of any one of the chemical formulas 2-6 and 2-9 to 2-13 and a compound of the chemical formula 1.