KR20220000384A - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting element. The organic light emitting element comprises: an anode; a cathode; and a light emitting layer between the anode and the cathode. Therefore, the organic light emitting element improves a driving voltage, efficiency, and a lifespan.

Description

Organic light emitting device

The present invention relates to an organic light emitting device.

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, and excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.

An organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode. The organic layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of the organic light emitting device, when a voltage is applied between the two electrodes, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons It lights up when it falls back to the ground state.

The development of new materials for organic materials used in organic light emitting devices as described above is continuously required.

Korean Patent Publication No. 10-2000-0051826

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

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

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

The light emitting layer comprises a first compound represented by the following formula (1) and a second compound represented by the following formula (2),

Organic light emitting device:

[Formula 1]

In Formula 1,

L _{1 To} L _{3 Are} each independently a single bond; Or a substituted or unsubstituted C _6-60 arylene,

Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl; _{or C 2-60} heteroaryl containing one or more heteroatoms among substituted or unsubstituted N, O and S;

each R ₁ is independently hydrogen or deuterium; or two adjacent ones combine with each other to form an unsubstituted or deuterium substituted benzene ring, and the remainder are each independently hydrogen or deuterium;

each R ₂ is independently hydrogen or deuterium; or two adjacent ones combine with each other to form an unsubstituted or deuterium substituted benzene ring, and the remainder are each independently hydrogen or deuterium;

[Formula 2]

In Formula 2,

A is a benzene ring fused with an adjacent ring, or a naphthalene ring,

L' ₁ , L' ₂ and L' ₃ are each independently a single bond; substituted or unsubstituted C _6-60 arylene; _{Or or substituted or unsubstituted C 2-60} heteroarylene comprising at least one selected from the group consisting of N, O and S,

Ar' ₁ , Ar' ₂ and Ar' ₃ are each independently substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl comprising any one or more selected from the group consisting of N, O and S,

C ₁ and C ₂ are each bonded to _{C 3} and C ₄ of Formula 3 below,

[Formula 3]

In Formula 3,

X is O or S;

B is a benzene ring fused with an adjacent ring, or a naphthalene ring,

R' is hydrogen; heavy hydrogen; halogen; cyano; substituted or unsubstituted C _1-60 alkyl; substituted or unsubstituted C _1-60 alkoxy; substituted or unsubstituted C _2-60 alkenyl; substituted or unsubstituted C _2-60 alkynyl; substituted or unsubstituted C _3-60 cycloalkyl; substituted or unsubstituted C _6-60 aryl; _{It is C 2-60} heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,

m is an integer of 0 to 4 when B is a benzene ring, and an integer of 0 to 6 when B is a naphthalene ring.

The above-described organic light emitting device has excellent driving voltage, efficiency, and lifetime.

FIG. 1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a light emitting layer 3 , and a cathode 4 .
2 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 3, a hole blocking layer 8, an electron injection and transport layer An example of an organic light emitting device comprising (9) and a cathode (4) is shown.

Hereinafter, it will be described in more detail to help the understanding of the present invention.

또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

or

means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amino group; a phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; heteroarylamine group; arylamine group; an arylphosphine group; Or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more, or substituted or unsubstituted, two or more of the above-exemplified substituents are linked. . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the number of carbon atoms in the carbonyl group is not particularly limited, but preferably 1 to 40 carbon atoms. Specifically, a group having the following structure may be mentioned, but the present invention is not limited thereto.

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

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably from 1 to 25 carbon atoms. Specifically, a group having the following structure may be mentioned, but is not limited thereto.

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

In the present specification, the boron group specifically includes, but is not limited to, a dimethyl boron group, a diethyl boron group, a t-butylmethyl boron group, a diphenyl boron group, a phenyl boron group, and the like.

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

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

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the carbon number of the alkenyl group is 2 to 10. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but is not limited thereto.

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 an exemplary embodiment, the carbon number of the aryl group is 6 to 30. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, or a terphenyl group, 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 chrysenyl group, or a fluorenyl group, but is not limited thereto.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

etc. can be However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group including at least one of O, N, Si and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but it is preferably from 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, an acridyl group , pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadia and a jolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto.

In the present specification, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group, and the arylamine group is the same as the examples of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the example of the above-described alkyl group. In the present specification, as for heteroaryl among the heteroarylamine groups, the description of the above-described heterocyclic group may be applied. In the present specification, the alkenyl group among the aralkenyl groups is the same as the above-described examples of the alkenyl group. In the present specification, the description of the above-described aryl group may be applied, except that arylene is a divalent group. In the present specification, the description of the above-described heterocyclic group may be applied, except that heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the above-described aryl group or cycloalkyl group may be applied, except that it is formed by combining two substituents.

Hereinafter, the present invention will be described in detail for each configuration.

positive and negative

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

As the anode material, a material having a large work function is generally preferred so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, 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, but are not limited thereto.

The cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; and a multi-layered material such as LiF/Al or LiO ₂ /Al, but is not limited thereto.

hole injection layer

The organic light emitting diode according to the present invention may include a hole injection layer between the anode and the hole transport layer to be described later, if necessary.

The hole injection layer is located on the anode and injects holes from the anode, and includes a hole injection material. Such a hole injection material has the ability to transport holes, has a hole injection effect at the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, and prevents the movement of excitons generated in the light emitting layer to the electron injection layer or the electron injection material. In addition, a compound excellent in the ability to form a thin film is preferable. In particular, it is suitable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer.

Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene. organic materials, anthraquinone, polyaniline and polythiophene-based conductive polymers, and the like, but are not limited thereto.

hole transport layer

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

The hole transport layer receives holes from the anode or the hole injection layer formed on the anode and transports holes to the light emitting layer, and includes a hole transport material. As the hole transport material, a material capable of transporting holes from an anode or a hole injection layer to the light emitting layer is suitable, and a material having high hole mobility is suitable. Specific examples include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together.

electronic barrier layer

The organic light emitting device according to the present invention may include an electron blocking layer between the hole transport layer and the light emitting layer, if necessary.

The electron blocking layer is formed on the hole transport layer, preferably provided in contact with the light emitting layer, to control hole mobility and prevent excessive movement of electrons to increase the probability of hole-electron coupling by increasing the efficiency of the organic light emitting device It means a layer that plays a role in improving The electron-blocking layer includes an electron-blocking material, and an arylamine-based organic material may be used as an example of the electron-blocking material, but is not limited thereto.

light emitting layer

The organic light emitting diode according to the present invention includes a light emitting layer between an anode and a cathode, and the light emitting layer includes the first compound and the second compound as a host material. Specifically, the first compound functions as an N-type host material having an electron transport ability superior to a hole transport ability, and the second compound functions as a P-type host material having a hole transport ability superior to an electron transport ability, so that holes in the light emitting layer The ratio of to electrons can be properly maintained. Accordingly, excitons may emit light evenly throughout the light emitting layer, so that the light emitting efficiency and lifespan characteristics of the organic light emitting diode may be improved at the same time.

Hereinafter, the first compound and the second compound will be sequentially described.

(first compound)

The first compound is represented by Formula 1 above. Specifically, the first compound is a compound in which a triazinyl group _{is connected to the N atom of the carbazole-based core by a linker L 3} , and the compound is characterized in that no substituents other than hydrogen/deuterium are bonded to the carbazole-based core. In particular, the first compound has an excellent electron transport ability compared to a compound in which a substituent other than hydrogen/deuterium, for example, an aryl group or a heteroaryl group is substituted on the carbazole-based core, and as the electrons are efficiently transferred to the dopant material, the light emitting layer It is possible to increase the probability of electron-hole recombination in

In Formula 1,

R ₁ and R ₂ are each independently hydrogen or deuterium;

adjacent two of R ₁ combine with each other to form an unsubstituted or deuterium substituted benzene ring, the remainder are each independently hydrogen or deuterium, R ₂ are each independently hydrogen or deuterium;

each R ₁ is independently hydrogen or deuterium, and _{adjacent two of R 2} are bonded to each other to form an unsubstituted or deuterium substituted benzene ring, and the remainder are each independently hydrogen or deuterium; or

adjacent two of R ₁ combine with each other to form an unsubstituted or deuterium substituted benzene ring, the remainder are each independently hydrogen or deuterium, and _{adjacent two of R 2} combine with each other to unsubstituted or substituted with deuterium to form a benzene ring, and the remainder may be each independently hydrogen or deuterium.

More specifically, the first compound may be represented by any one of the following Chemical Formulas 1-1 to 1-10:

In Formulas 1-1 to 1-10,

L ₁ to L ₃ , Ar ₁ and Ar ₂ are as defined in Formula 1 above.

In addition, in Formula 1, L ₁ and L ₂ may each independently represent a single bond, or unsubstituted or C _6-20 arylene substituted with one or more deuterium.

More specifically, L ₁ and L ₂ may each independently be a single bond, phenylene, or naphthylene.

More specifically, L ₁ and L ₂ may each independently be a single bond, or any one selected from the group consisting of:

In each of the above formulas, a dotted line indicates a bonding position.

For example, L ₁ and L ₂ are both single bonds; Alternatively _{, one of L 1} and L ₂ may be a single bond, and the other may be any one selected from the group consisting of:

In each of the above formulas, a dotted line indicates a bonding position.

In addition, L ₁ and L ₂ may be the same as or different from each other.

In addition, in Formula 1, L ₃ is specifically a single bond; _{or C 6-20} arylene unsubstituted or substituted with one or more deuterium.

More specifically, L ₃ may be a single bond, phenylene, biphenyldiyl, or naphthylene.

More specifically, L ₃ may be a single bond, or any one selected from the group consisting of:

In each of the above formulas, a dotted line indicates a bonding position.

In addition, in Formula 1, Ar ₁ and Ar ₂ are each independently, unsubstituted or substituted with one or more deuterium C _6-20 aryl; or unsubstituted or substituted with one or more substituents selected from the group consisting of _{deuterium, C 1-10} alkyl and C _{6-20 aryl, C 2- containing a heteroatom of any one of N, O and S 20} heteroaryl.

Specifically, Ar ₁ and Ar ₂ are each independently phenyl, biphenyl, terphenyl, naphthyl, (phenyl) naphthyl, (naphthyl) phenyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzonaphthofuranyl, or benzonaphthothiophenyl;

Here, Ar ₁ and Ar ₂ may each independently be unsubstituted or substituted with one or more substituents selected from the group consisting of _{deuterium, C 1-10} alkyl, and C _{6-20 aryl, more specifically Ar 1} and Ar ₂ may each independently be unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, methyl, and phenyl.

More specifically, Ar ₁ and Ar ₂ are each independently phenyl, biphenyl, terphenyl naphthyl, (phenyl) naphthyl, (naphthyl) phenyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl , 9-phenylcarbazolyl, benzonaphthofuranyl, or benzonaphthothiophenyl.

More specifically, Ar ₁ and Ar ₂ may each independently be any one selected from the group consisting of:

In each of the above formulas,

X is O or S;

The dotted line indicates the bonding position.

For example, _{one of Ar 1} and Ar ₂ is phenyl, biphenyl, or naphthyl, and the other is phenyl, biphenyl, terphenyl, naphthyl, (phenyl)naphthyl, (naphthyl)phenyl, or phenane. It may be threnyl.

In another example, _{one of Ar 1} and Ar ₂ is phenyl, biphenyl, terphenyl, naphthyl, (phenyl)naphthyl, (naphthyl)phenyl, or phenanthrenyl, and the other is dibenzofuranyl , dibenzothiophenyl, 9-phenylcarbazolyl, benzonaphthofuranyl, or benzonaphthothiophenyl.

In another example, Ar ₁ and Ar ₂ may each independently be dibenzofuranyl, dibenzothiophenyl, 9-phenylcarbazolyl, benzonaphthofuranyl, or benzonaphthothiophenyl.

In addition, Ar ₁ and Ar ₂ may be the same as or different from each other.

Representative examples of the first compound represented by Formula 1 are as follows:

.

.

On the other hand, the compound represented by Formula 1 may be prepared by, for example, a preparation method as in Scheme 1 below.

[Scheme 1]

In Scheme 1, Ar ₁ , Ar ₂ , L ₁ to L ₃ , R ₁ , and R ₂ are as defined in Formula 1 above, Z ₁ is halogen, and preferably Z ₁ is chloro or bromo.

Scheme 1 is an amine substitution reaction, preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art. As an example, the manufacturing method may be more specific in Synthesis Examples to be described later.

(second compound)

The second compound is represented by Formula 2 above.

Specifically, the second compound may be represented by any one of the following Chemical Formulas 2-1 to 2-12:

In Formulas 2-1 to 2-12,

L' ₁ to L' ₃ , Ar' ₁ to Ar' ₃ , X, R' and m are as defined in Formula 2 above.

Also, L′ ₁ may be a single bond.

In addition, the L′ ₂ and L′ ₃ are each independently a single bond; _{or C 6-20} arylene unsubstituted or substituted with one or more deuterium.

Specifically, L′ ₂ and L′ ₃ may each independently be a single bond, phenylene, biphenyldiyl, or naphthylene.

More specifically, L' ₂ and L' ₃ may each independently be a single bond, or any one selected from the group consisting of:

In each of the above formulas, a dotted line indicates a bonding position.

In addition, L' ₂ and L' ₃ may be the same as or different from each other.

Also, in Formula 2, Ar′ ₁ may be phenyl.

In addition, in Formula 2, Ar' ₂ and Ar' ₃ are each independently, unsubstituted or substituted with deuterium C _6-20 aryl; Or unsubstituted or substituted with one or more substituents selected from the group consisting of _{deuterium, C 1-10} alkyl, or C _{6-20 aryl, C 2 containing a heteroatom of any one of N, O and S -20} heteroaryl.

Specifically, Ar' ₂ and Ar' ₃ are each independently phenyl, biphenyl, terphenyl, naphthyl, (phenyl)naphthyl, (naphthyl)phenyl, phenanthrenyl, (phenanthrenyl)phenyl, ( phenyl) phenanthrenyl, dibenzofuranyl, or dibenzothiophenyl;

Here, Ar′ ₂ and Ar′ ₃ may each independently be unsubstituted or substituted with one or more substituents selected from the group consisting of _{deuterium, C 1-10} alkyl, and C _{6-20 aryl, more specifically} Ar' ₂ and Ar' ₃ may each independently be unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, methyl, and phenyl.

More specifically, Ar' ₂ and Ar' ₃ are each independently phenyl, biphenyl, terphenyl, naphthyl, (phenyl)naphthyl, (naphthyl)phenyl, phenanthrenyl, (phenanthrenyl)phenyl , phenyl (phenanthrenyl), dibenzofuranyl, or dibenzothiophenyl.

More specifically, Ar' ₂ and Ar' ₃ may each independently be any one selected from the group consisting of:

In each of the above formulas,

X is O or S;

The dotted line indicates the bonding position.

For example, one of Ar′ ₂ and Ar′ ₃ is phenyl, biphenyl, naphthyl, or phenanthrenyl, and the other is phenyl, biphenyl, terphenyl, naphthyl, (phenyl)naphthyl, (naph tyl)phenyl, phenanthrenyl, (phenanthrenyl)phenyl, or (phenyl)phenanthrenyl.

In another example, _{one of Ar' 2} and Ar' ₃ is dibenzofuranyl or dibenzothiophenyl, and the other is phenyl, biphenyl, terphenyl, naphthyl, (phenyl)naphthyl, (naphthyl) phenyl, phenanthrenyl, (phenanthrenyl)phenyl, or (phenyl)phenanthrenyl.

In another example, Ar′ ₂ and Ar′ ₃ may each independently be dibenzofuranyl or dibenzothiophenyl.

Also, Ar′ ₂ and Ar′ ₃ may be the same as or different from each other.

Also, in Formula 2, R' may be hydrogen. In this case, m is an integer of 4 when B is a benzene ring, and an integer of 6 when B is a naphthalene ring.

Representative examples of the compound represented by Formula 2 are as follows:

.

.

On the other hand, the compound represented by Formula 2 may be prepared by, for example, a manufacturing method as shown in Scheme 2 below.

[Scheme 2]

In Scheme 2, Ar' ₁ , Ar' ₂ , L' ₁ to L' ₃ , C ₁ , and C ₂ are as defined in Formula 2, Z ₂ is halogen, preferably Z ₂ is chloro or bromo.

Scheme 2 is an amine substitution reaction, preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art. The manufacturing method may be more specific in a synthesis example to be described later.

In addition, the first compound and the second compound may be included in the light emitting layer in a weight ratio of 1:99 to 99:1. In this case, it is more preferable that the first compound and the second compound are included in a weight ratio of 30:70 to 70:30 in terms of maintaining an appropriate ratio of holes and electrons in the emission layer.

Meanwhile, the emission layer may further include a dopant material in addition to the two types of host materials.

The dopant material is not particularly limited as long as it is a material used in an organic light emitting device. Examples include an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periflanthene, and the like, having an arylamino group. As the styrylamine compound, a substituted or unsubstituted It is a compound in which at least one arylvinyl group is substituted in the arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but is not limited thereto. In addition, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.

More specifically, the dopant material may include, but is not limited to, compounds having the following structures:

.

.

.

.

hole blocking layer

The organic light emitting device according to the present invention may include a hole blocking layer between the light emitting layer and an electron transport layer to be described later, if necessary. The hole blocking layer is formed on the light emitting layer, preferably provided in contact with the light emitting layer, to control electron mobility and prevent excessive movement of holes to increase the hole-electron coupling probability, thereby improving the efficiency of the organic light emitting device layer that plays a role. The hole blocking layer includes a hole blocking material, and examples of the hole blocking material include azine derivatives including triazine; triazole derivatives; oxadiazole derivatives; phenanthroline derivatives; A compound into which an electron withdrawing group is introduced, such as a phosphine oxide derivative, may be used, but the present invention is not limited thereto.

electron transport layer

The organic light emitting device according to the present invention may include an electron transport layer on the light emitting layer (or on the hole blocking layer when the hole blocking layer is formed) if necessary.

The electron transport layer serves to transport electrons to the light emitting layer by receiving electrons from the electron injection layer formed on the cathode or the cathode. The electron transport layer includes an electron transport material. As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high electron mobility is suitable.

Specific examples of the electron transport material include an Al complex of 8-hydroxyquinoline; complexes containing Alq _{3 ;} organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.

electron injection layer

The organic light emitting diode according to the present invention may include an electron injection layer on the light emitting layer (or on the electron transport layer if the electron transport layer is present) if necessary.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer. It is preferable to use a compound which prevents movement to a layer and is excellent in the ability to form a thin film.

Specific examples of the material that can be used as the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preole Nylidene methane, anthrone, and the like, derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.

Examples of the metal complex compound include 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-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. Accordingly, the present invention is not limited thereto.

organic light emitting device

The structure of the organic light emitting device according to the present invention is illustrated in FIGS. 1 and 2 .

FIG. 1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a light emitting layer 3 , and a cathode 4 . In such a structure, the first compound and the second compound may be included in the emission layer.

2 is a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron blocking layer (7), a light emitting layer (3), a hole blocking layer (8), an electron injection and transport layer ( 9), and an example of an organic light emitting device including the cathode 4 is shown. In such a structure, the first compound and the second compound may be included in the emission layer.

The organic light emitting device according to the present invention may be manufactured by sequentially stacking the above-described components. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode And, after forming each of the above-mentioned layers thereon, it can be prepared by depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing the anode material on the substrate in the reverse order of the above-described configuration from the cathode material (WO 2003/012890). In addition, the light emitting layer may be formed by a solution coating method as well as a vacuum deposition method for the host and dopant. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

Meanwhile, the organic light emitting device according to the present invention may be a bottom emission device, a top emission device, or a double-sided light emitting device, and in particular, may be a bottom light emitting device requiring relatively high luminous efficiency.

Hereinafter, preferred embodiments are presented to help the understanding of the present invention. However, the following examples are only for illustrating the present invention, and the content of the present invention is not limited by the following examples.

Preparation Example 1

Synthesis of compound A-1

In a nitrogen atmosphere, 3-bromobenzofuran (10 g, 50.8 mmol) and (4-chloro-2-nitrophenyl) boronic acid (12.3 g, 60.9 mmol) were added to 200 ml of THF, followed by stirring and reflux. After that, potassium carbonate (21g, 152.3mmol) was dissolved in 63ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3g, 0.5mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.9 g of compound A-1_P1 (yield 64%, MS: [M+H]+=274).

Compound A-1_P1 (10g, 36.5mmol) was added to 100ml of triethylphosphite in a nitrogen atmosphere, stirred and refluxed. After 10 hours of reaction, the mixture was cooled to room temperature and the organic solvent was distilled under reduced pressure. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.9 g of compound A-1_P2 (yield 78%, MS: [M+H] + = 242).

Compound A-1_P2 (10g, 41.4mmol), bromobenzene (6.6g, 42.2mmol), and sodium tert-butoxide (5.2g, 53.8mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 7.6 g of Compound A-1 (yield 58%, MS: [M+H]+=318).

Preparation 2

Synthesis of compound A-2

Compound A- using the same method as in Preparation Example 1, except that (5-chloro-2-nitrophenyl)boronic acid was used instead of (4-chloro-2-nitrophenyl)boronic acid as a starting material in Preparation Example 1 2 was prepared.

Preparation 3

Synthesis of compound B-1

Compound B-1 was prepared in the same manner as in Preparation Example 1, except that 1-bromonaphtho[2,1-b]furan was used as a starting material in Preparation Example 1 instead of 3-bromobenzofuran.

Preparation 4

Synthesis of compound C-1

Compound C-1 was prepared in the same manner as in Preparation Example 1, except that 3-bromonaphtho[2,3-b]furan was used as a starting material in Preparation Example 1 instead of 3-bromobenzofuran.

Preparation 5

Synthesis of compound D-1

The same method as in Preparation Example 1 was used, except that (7-chloro-1-nitronaphthalen-2-yl)boronic acid was used instead of (4-chloro-2-nitrophenyl)boronic acid as a starting material in Preparation Example 1 Thus, compound D-1 was prepared.

Preparation 6

Synthesis of compound E-1

The same method as in Preparation Example 1 was used, except that (6-chloro-3-nitronaphthalen-2-yl)boronic acid was used as a starting material in Preparation Example 1 instead of (4-chloro-2-nitrophenyl)boronic acid. Thus, compound E-1 was prepared.

Preparation 7

Synthesis of compound E-2

The same method as in Preparation Example 1 was used, except that (7-chloro-3-nitronaphthalen-2-yl)boronic acid was used instead of (4-chloro-2-nitrophenyl)boronic acid as a starting material in Preparation Example 1 Thus, compound E-2 was prepared.

Preparation 8

Synthesis of compound F-1

The same method as in Preparation Example 1 was used, except that (7-chloro-2-nitronaphthalen-1-yl)boronic acid was used as a starting material in Preparation Example 1 instead of (4-chloro-2-nitrophenyl)boronic acid. Thus, compound F-1 was prepared.

Preparation 9

Synthesis of compound g-1

In Preparation Example 1, 2-bromobenzofuran was used instead of 3-bromobenzofuran as a starting material, and (2-chloro-6-nitrophenyl)boronic acid was used instead of (4-chloro-2-nitrophenyl)boronic acid. Compound g-1 was prepared in the same manner as in Example 1.

Preparation 10

Synthesis of compound H-1

Compound H-1 was prepared in the same manner as in Preparation Example 1, except that 2-bromonaphtho[1,2-b]furan was used as a starting material in Preparation Example 1 instead of 3-bromobenzofuran.

Preparation 11

Synthesis of compound I-1

Compound I-1 was prepared in the same manner as in Preparation Example 1, except that 2-bromonaphtho[2,3-b]furan was used as a starting material in Preparation Example 1 instead of 3-bromobenzofuran.

Preparation 12

Synthesis of compound J-1

Except for using 2-bromobenzofuran instead of 3-bromobenzofuran as a starting material in Preparation Example 1, and using (4-chloro-1-nitronaphthalen-2-yl)boronic acid instead of (4-chloro-2-nitrophenyl)boronic acid And, using the same method as in Preparation Example 1, compound J-1 was prepared.

Preparation 13

Synthesis of compound J-2

Except for using 2-bromobenzofuran instead of 3-bromobenzofuran as a starting material in Preparation Example 1, and using (7-chloro-1-nitronaphthalen-2-yl)boronic acid instead of (4-chloro-2-nitrophenyl)boronic acid And, using the same method as in Preparation Example 1, compound J-2 was prepared.

Preparation 14

Synthesis of compound K-1

Except for using 2-bromobenzofuran instead of 3-bromobenzofuran as a starting material in Preparation Example 1, and using (6-chloro-3-nitronaphthalen-2-yl)boronic acid instead of (4-chloro-2-nitrophenyl)boronic acid And, using the same method as in Preparation Example 1, compound K-1 was prepared.

Preparation 15

Synthesis of compound K-2

Except for using 2-bromobenzofuran instead of 3-bromobenzofuran as a starting material in Preparation Example 1, and using (1-chloro-3-nitronaphthalen-2-yl)boronic acid instead of (4-chloro-2-nitrophenyl)boronic acid And, using the same method as in Preparation Example 1, compound K-2 was prepared.

Preparation 16

Synthesis of compound L-1

Except for using 2-bromobenzofuran instead of 3-bromobenzofuran as a starting material in Preparation Example 1, and using (6-chloro-2-nitronaphthalen-1-yl)boronic acid instead of (4-chloro-2-nitrophenyl)boronic acid Then, using the same method as in Preparation Example 1, compound L-1 was prepared.

Preparation 17

Synthesis of compound M-1

Compound M-1 was prepared in the same manner as in Preparation Example 1, except that 3-bromobenzo[b]thiophene was used instead of 3-bromobenzofuran as a starting material in Preparation Example 1.

Preparation 18

Synthesis of compound M-2

Except for using 3-bromobenzo[b]thiophene instead of 3-bromobenzofuran as a starting material in Preparation Example 1, and using (5-chloro-2-nitrophenyl)boronic acid instead of (4-chloro-2-nitrophenyl)boronic acid And, using the same method as in Preparation Example 1, compound M-2 was prepared.

Preparation 19

Synthesis of compound N-1

Compound N-1 was prepared in the same manner as in Preparation Example 1, except that 1-bromonaphtho[2,1-b]thiophene was used as a starting material in Preparation Example 1 instead of 3-bromobenzofuran.

Preparation 20

Synthesis of compound O-1

Compound O-1 was prepared in the same manner as in Preparation Example 1, except that 3-bromonaphtho[2,3-b]thiophene was used as a starting material in Preparation Example 1 instead of 3-bromobenzofuran.

Preparation 21

Synthesis of compound P-1

In Preparation Example 1, 3-bromobenzo[b]thiophene was used instead of 3-bromobenzofuran as a starting material, and (7-chloro-1-nitronaphthalen-2-yl)boronic acid was used instead of (4-chloro-2-nitrophenyl)boronic acid. Compound P-1 was prepared in the same manner as in Preparation Example 1, except that

Preparation 22

Synthesis of compound Q-1

In Preparation Example 1, 3-bromobenzo[b]thiophene was used instead of 3-bromobenzofuran as a starting material, and (6-chloro-3-nitronaphthalen-2-yl)boronic acid was used instead of (4-chloro-2-nitrophenyl)boronic acid. Compound Q-1 was prepared in the same manner as in Preparation Example 1, except that

Preparation 23

Synthesis of compound R-1

In Preparation Example 1, 3-bromobenzo[b]thiophene was used instead of 3-bromobenzofuran as a starting material, and (6-chloro-2-nitronaphthalen-1-yl)boronic acid was used instead of (4-chloro-2-nitrophenyl)boronic acid. Except for using the compound R-1 was prepared in the same manner as in Preparation Example 1.

Preparation 24

Synthesis of compound S-1

Except for using 2-bromobenzo[b]thiophene instead of 3-bromobenzofuran as a starting material in Preparation Example 1, and using (2-chloro-6-nitrophenyl)boronic acid instead of (4-chloro-2-nitrophenyl)boronic acid And, using the same method as in Preparation Example 1, compound S-1 was prepared.

Preparation 25

Synthesis of compound S-2

Except for using 2-bromobenzo[b]thiophene instead of 3-bromobenzofuran as a starting material in Preparation Example 1, and using (5-chloro-2-nitrophenyl)boronic acid instead of (4-chloro-2-nitrophenyl)boronic acid And, using the same method as in Preparation Example 1, compound S-2 was prepared.

Preparation 26

Synthesis of compound S-3

Compound S-3 was prepared in the same manner as in Preparation Example 1, except that 2-bromobenzo[b]thiophene was used instead of 3-bromobenzofuran as a starting material in Preparation Example 1.

Preparation 27

Synthesis of compound T-1

Compound T-1 was prepared in the same manner as in Preparation Example 1, except that 2-bromonaphtho[1,2-b]thiophene was used as a starting material in Preparation Example 1 instead of 3-bromobenzofuran.

Preparation 28

Synthesis of compound U-1

Compound U-1 was prepared in the same manner as in Preparation Example 1, except that 2-bromonaphtho[2,3-b]thiophene was used as a starting material in Preparation Example 1 instead of 3-bromobenzofuran.

Preparation 29

Synthesis of compound V-1

In Preparation Example 1, 2-bromobenzo[b]thiophene was used instead of 3-bromobenzofuran as a starting material, and (4-chloro-1-nitronaphthalen-2-yl)boronic acid was used instead of (4-chloro-2-nitrophenyl)boronic acid. Compound V-1 was prepared in the same manner as in Preparation Example 1, except that

Preparation 30

Synthesis of compound V-2

In Preparation Example 1, 2-bromobenzo[b]thiophene was used instead of 3-bromobenzofuran as a starting material, and (7-chloro-1-nitronaphthalen-2-yl)boronic acid was used instead of (4-chloro-2-nitrophenyl)boronic acid. Compound V-2 was prepared in the same manner as in Preparation Example 1, except that .

Preparation 31

Synthesis of compound W-1

In Preparation Example 1, 2-bromobenzo[b]thiophene was used instead of 3-bromobenzofuran as a starting material, and (1-chloro-3-nitronaphthalen-2-yl)boronic acid was used instead of (4-chloro-2-nitrophenyl)boronic acid. Compound W-1 was prepared in the same manner as in Preparation Example 1, except that

Preparation 32

Synthesis of compound X-1

In Preparation Example 1, 2-bromobenzo[b]thiophene was used instead of 3-bromobenzofuran as a starting material, and (4-chloro-2-nitronaphthalen-1-yl)boronic acid was used instead of (4-chloro-2-nitrophenyl)boronic acid. Compound X-1 was prepared in the same manner as in Preparation Example 1, except that

Preparation 33

Synthesis of compound X-2

In Preparation Example 1, 2-bromobenzo[b]thiophene was used instead of 3-bromobenzofuran as a starting material, and (7-chloro-2-nitronaphthalen-1-yl)boronic acid was used instead of (4-chloro-2-nitrophenyl)boronic acid. Compound X-1 was prepared in the same manner as in Preparation Example 1, except that

Synthesis Example 1-1

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), sub1 (25.6 g, 62.8 mmol) and Potassium Phosphate (K ₃ PO ₄ ) (38.1 g, 179.4 mmol) were placed in 200 ml of Xylene, stirred and refluxed. To the resulting mixture, bis(tri-tert-butylphosphine)palladium(0) (Pd(t-Bu ₃ P) ₂ ) (0.6 g, 1.2 mmol) was added. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was again completely dissolved in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 17.7 g of compound 1-1 (yield 55%, MS: [M+H] + = 539).

Synthesis Example 1-2

In a nitrogen atmosphere, 9H-carbazole (10g, 59.8mmol), sub2 (25.6g, 62.8mmol) and Potassium Phosphate (38.1g, 179.4mmol) were added to 200ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.6g, 1.2mmol) was added to the resulting mixture. When the reaction was completed after 2 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 19 g of compound 1-2 (yield 59%, MS: [M+H] + = 539).

Synthesis Example 1-3

In a nitrogen atmosphere, 9H-carbazole (10g, 59.8mmol), sub3 (27.2g, 62.8mmol) and Potassium Phosphate (38.1g, 179.4mmol) were added to 200 ml of Xylene, stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.6g, 1.2mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 18.5 g of compound 1-3 (yield 55%, MS: [M+H] + = 564).

Synthesis Example 1-4

In a nitrogen atmosphere, 9H-carbazole (10g, 59.8mmol), sub4 (30.4g, 62.8mmol) and Potassium Phosphate (38.1g, 179.4mmol) were added to 200 ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.6g, 1.2mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 20.9 g of compound 1-4 (yield 57%, MS: [M+H] + = 615).

Synthesis Example 1-5

In a nitrogen atmosphere, 9H-carbazole (10g, 59.8mmol), sub5 (29.5g, 62.8mmol) and sodium tert-butoxide (NaOtBu) (7.5g, 77.7mmol) were added to 200 ml of Xylene and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.6g, 1.2mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 23.3 g of compound 1-5 (yield 65%, MS: [M+H]+=601).

Synthesis Example 1-6

In a nitrogen atmosphere, 9H-carbazole (10g, 59.8mmol), sub6 (29.5g, 62.8mmol), and sodium tert-butoxide (7.5g, 77.7mmol) were added to 200 ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.6g, 1.2mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 20.5 g of compound 1-6 (yield 57%, MS: [M+H]+=601).

Synthesis Example 1-7

In a nitrogen atmosphere, 9H-carbazole (10g, 59.8mmol), sub7 (27.2g, 62.8mmol), and sodium tert-butoxide (7.5g, 77.7mmol) were added to 200 ml of Xylene, stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.6g, 1.2mmol) was added to the resulting mixture. When the reaction was completed after 2 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 19.2 g of compound 1-7 (yield 57%, MS: [M+H] + = 565).

Synthesis Example 1-8

In a nitrogen atmosphere, 9H-carbazole (10g, 59.8mmol), sub8 (32.7g, 62.8mmol) and sodium tert-butoxide (7.5g, 77.7mmol) were added to 200ml of Xylene and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.6g, 1.2mmol) was added to the resulting mixture. When the reaction was completed after 2 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 26.4 g of compound 1-8 (yield 68%, MS: [M+H] + = 651).

Synthesis Example 1-9

In a nitrogen atmosphere, 9H-carbazole (10g, 59.8mmol), sub9 (30.4g, 62.8mmol) and sodium tert-butoxide (7.5g, 77.7mmol) were added to 200ml of Xylene and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.6g, 1.2mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 24.6 g of compounds 1-9 (yield 67%, MS: [M+H] + = 615).

Synthesis Example 1-10

In a nitrogen atmosphere, 9H-carbazole (10g, 59.8mmol), sub10 (30.4g, 62.8mmol) and sodium tert-butoxide (7.5g, 77.7mmol) were added to 200 ml of Xylene and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.6g, 1.2mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 23.5 g of compound 1-10 (yield 64%, MS: [M+H] + = 615).

Synthesis Example 1-11

In a nitrogen atmosphere, 9H-carbazole (10g, 59.8mmol), sub11 (27.2g, 62.8mmol) and sodium tert-butoxide (7.5g, 77.7mmol) were added to 200 ml of Xylene, stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.6g, 1.2mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 17.5 g of compound 1-11 (yield 52%, MS: [M+H] + = 565).

Synthesis Example 1-12

In a nitrogen atmosphere, 9H-carbazole (10g, 59.8mmol), sub12 (27.9g, 62.8mmol), and sodium tert-butoxide (7.5g, 77.7mmol) were added to 200 ml of Xylene and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.6g, 1.2mmol) was added to the resulting mixture. When the reaction was completed after 2 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 18.2 g of compound 1-12 (yield 53%, MS: [M+H] + = 575).

Synthesis Example 1-13

In a nitrogen atmosphere, 9H-carbazole (10g, 59.8mmol), sub13 (29.5g, 62.8mmol) and sodium tert-butoxide (7.5g, 77.7mmol) were added to 200 ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.6g, 1.2mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 19.4 g of compound 1-13 (yield 54%, MS: [M+H]+=601).

Synthesis Example 1-14

In a nitrogen atmosphere, 9H-carbazole (10g, 59.8mmol), sub14 (35.1g, 62.8mmol) and sodium tert-butoxide (7.5g, 77.7mmol) were added to 200 ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.6g, 1.2mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 28.4 g of compound 1-14 (yield 69%, MS: [M+H]+=690).

Synthesis Example 1-15

In a nitrogen atmosphere, 9H-carbazole (10g, 59.8mmol), sub15 (31g, 62.8mmol) and sodium tert-butoxide (7.5g, 77.7mmol) were added to 200 ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.6g, 1.2mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 26.1 g of compound 1-15 (yield 70%, MS: [M+H] + = 625).

Synthesis Example 1-16

In a nitrogen atmosphere, 9H-carbazole (10g, 59.8mmol), sub16 (31.4g, 62.8mmol) and sodium tert-butoxide (7.5g, 77.7mmol) were added to 200 ml of Xylene, stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.6g, 1.2mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 22.2 g of compound 1-16 (yield 59%, MS: [M+H]+=631).

Synthesis Example 1-17

In a nitrogen atmosphere, 9H-carbazole (10g, 59.8mmol), sub17 (26.4g, 62.8mmol) and sodium tert-butoxide (7.5g, 77.7mmol) were added to 200 ml of Xylene, stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.6g, 1.2mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 18.1 g of compound 1-17 (yield 55%, MS: [M+H]+=551).

Synthesis Example 1-18

In a nitrogen atmosphere, 9H-carbazole (10g, 59.8mmol), sub18 (32g, 62.8mmol) and sodium tert-butoxide (7.5g, 77.7mmol) were added to 200 ml of Xylene, stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.6g, 1.2mmol) was added to the resulting mixture. When the reaction was completed after 2 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was again completely dissolved in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 24.5 g of compound 1-18 (yield 64%, MS: [M+H]+=641).

Synthesis Example 1-19

In a nitrogen atmosphere, 9H-carbazole (10g, 59.8mmol), sub19 (31.1g, 62.8mmol), and sodium tert-butoxide (7.5g, 77.7mmol) were added to 200 ml of Xylene, stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.6g, 1.2mmol) was added to the resulting mixture. When the reaction was completed after 2 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 25.1 g of compound 1-19 (yield 67%, MS: [M+H] + = 627).

Synthesis Example 1-20

In a nitrogen atmosphere, 9H-carbazole (10g, 59.8mmol), sub20 (33g, 62.8mmol) and sodium tert-butoxide (7.5g, 77.7mmol) were added to 200 ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.6g, 1.2mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 20 g of compound 1-20 (yield 51%, MS: [M+H] + = 657).

Synthesis Example 1-21

In a nitrogen atmosphere, 7H-benzo[c]carbazole (10g, 46mmol), sub21 (18.1g, 48.3mmol), and Potassium Phosphate (29.3g, 138.1mmol) were added to 200 ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.5g, 0.9mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 14.3 g of compound 1-21 (yield 56%, MS: [M+H] + = 555).

Synthesis Example 1-22

In a nitrogen atmosphere, 7H-benzo[c]carbazole (10g, 46mmol), sub7 (21g, 48.3mmol) and sodium tert-butoxide (5.7g, 59.8mmol) were added to 200 ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.5g, 0.9mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 14.7 g of compound 1-22 (yield 52%, MS: [M+H] + = 615).

Synthesis Example 1-23

In a nitrogen atmosphere, 7H-benzo[c]carbazole (10g, 46mmol), sub22 (26.9g, 48.3mmol), and sodium tert-butoxide (5.7g, 59.8mmol) were added to 200 ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.5g, 0.9mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 22 g of compound 1-23 (yield 65%, MS: [M+H]+=737).

Synthesis Example 1-24

In a nitrogen atmosphere, 7H-benzo[c]carbazole (10g, 46mmol), sub23 (16.6g, 48.3mmol) and sodium tert-butoxide (5.7g, 59.8mmol) were added to 200ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.5g, 0.9mmol) was added to the resulting mixture. When the reaction was completed after 2 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was again completely dissolved in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 12.1 g of compound 1-24 (yield 50%, MS: [M+H] + = 525).

Synthesis Example 1-25

In a nitrogen atmosphere, 7H-benzo[c]carbazole (10g, 46mmol), sub24 (16.6g, 48.3mmol) and sodium tert-butoxide (5.7g, 59.8mmol) were added to 200ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.5g, 0.9mmol) was added to the resulting mixture. When the reaction was completed after 2 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 12.5 g of compound 1-25 (yield 52%, MS: [M+H]+=525).

Synthesis Example 1-26

In a nitrogen atmosphere, 7H-benzo[c]carbazole (10g, 46mmol), sub25 (25.1g, 48.3mmol) and sodium tert-butoxide (5.7g, 59.8mmol) were added to 200ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.5g, 0.9mmol) was added to the resulting mixture. When the reaction was completed after 2 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 20.3 g of compound 1-26 (yield 63%, MS: [M+H] + = 701).

Synthesis Example 1-27

In a nitrogen atmosphere, 7H-benzo[c]carbazole (10g, 46mmol), sub26 (25.4g, 48.3mmol) and sodium tert-butoxide (5.7g, 59.8mmol) were added to 200ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.5g, 0.9mmol) was added to the resulting mixture. When the reaction was completed after 2 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 18.2 g of compound 1-27 (yield 56%, MS: [M+H]+=707).

Synthesis Example 1-28

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10g, 46mmol), sub27 (17.8g, 48.3mmol) and Potassium Phosphate (29.3g, 138.1mmol) were added to 200ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.5g, 0.9mmol) was added to the resulting mixture. When the reaction was completed after 2 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 16.9 g of compound 1-28 (yield 67%, MS: [M+H]+=549).

Synthesis Example 1-29

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10g, 46mmol), sub28 (20.3g, 48.3mmol) and sodium tert-butoxide (5.7g, 59.8mmol) were added to 200ml of Xylene and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.5g, 0.9mmol) was added to the resulting mixture. When the reaction was completed after 2 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 19.3 g of compound 1-29 (yield 70%, MS: [M+H]+=601).

Synthesis Example 1-30

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10g, 46mmol), sub29 (21.7g, 48.3mmol) and sodium tert-butoxide (5.7g, 59.8mmol) were added to 200ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.5g, 0.9mmol) was added to the resulting mixture. When the reaction was completed after 2 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 17.7 g of compound 1-30 (yield 61%, MS: [M+H]+=631).

Synthesis Example 1-31

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10g, 46mmol), sub30 (24.6g, 48.3mmol) and sodium tert-butoxide (5.7g, 59.8mmol) were added to 200ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.5g, 0.9mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 20 g of compound 1-31 (yield 63%, MS: [M+H] + = 690).

Synthesis Example 1-32

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10g, 46mmol), sub31 (25.1g, 48.3mmol) and sodium tert-butoxide (5.7g, 59.8mmol) were added to 200ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.5g, 0.9mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 21.3 g of compound 1-32 (yield 66%, MS: [M+H] + = 701).

Synthesis Example 1-33

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10g, 46mmol), sub32 (19g, 48.3mmol) and sodium tert-butoxide (5.7g, 59.8mmol) were added to 200ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.5g, 0.9mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 14 g of compound 1-33 (yield 53%, MS: [M+H]+=575).

Synthesis Example 1-34

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10g, 46mmol), sub33 (22.7g, 48.3mmol) and sodium tert-butoxide (5.7g, 59.8mmol) were added to 200ml of Xylene and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.5g, 0.9mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 15.3 g of compound 1-34 (yield 51%, MS: [M+H] + = 651).

Synthesis Example 1-35

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10g, 46mmol), sub17 (20.3g, 48.3mmol) and sodium tert-butoxide (5.7g, 59.8mmol) were added to 200ml of Xylene and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.5g, 0.9mmol) was added to the resulting mixture. When the reaction was completed after 2 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 18.2 g of compound 1-35 (yield 66%, MS: [M+H]+=601).

Synthesis Example 1-36

In a nitrogen atmosphere, 11H-benzo[a]carbazole (10g, 46mmol), sub34 (22.7g, 48.3mmol), and sodium tert-butoxide (5.7g, 59.8mmol) were added to 200ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.5g, 0.9mmol) was added to the resulting mixture. When the reaction was completed after 2 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 15 g of compound 1-36 (yield 50%, MS: [M+H] + = 651).

Synthesis Example 1-37

In a nitrogen atmosphere, 11H-benzo[a]carbazole (10g, 46mmol), sub35 (21.7g, 48.3mmol), and sodium tert-butoxide (5.7g, 59.8mmol) were added to 200ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.5g, 0.9mmol) was added to the resulting mixture. When the reaction was completed after 2 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 20.3 g of compound 1-37 (yield 70%, MS: [M+H] + = 631).

Synthesis Example 1-38

In a nitrogen atmosphere, 11H-benzo[a]carbazole (10g, 46mmol), sub36 (27.1g, 48.3mmol), and sodium tert-butoxide (5.7g, 59.8mmol) were added to 200ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.5g, 0.9mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 20.4 g of compound 1-38 (yield 60%, MS: [M+H]+=741).

Synthesis Example 1-39

In a nitrogen atmosphere, 11H-benzo[a]carbazole (10g, 46mmol), sub37 (25.4g, 48.3mmol), and sodium tert-butoxide (5.7g, 59.8mmol) were added to 200ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.5g, 0.9mmol) was added to the resulting mixture. When the reaction was completed after 2 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 17.9 g of compound 1-39 (yield 55%, MS: [M+H]+=707).

Synthesis Examples 1-40

In a nitrogen atmosphere, 11H-benzo[a]carbazole (10g, 46mmol), sub38 (24.6g, 48.3mmol), and sodium tert-butoxide (5.7g, 59.8mmol) were added to 200ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.5g, 0.9mmol) was added to the resulting mixture. When the reaction was completed after 2 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 15.9 g of compound 1-40 (yield 50%, MS: [M+H] + = 691).

Synthesis Example 1-41

In a nitrogen atmosphere, 7H-dibenzo[b,g]carbazole (10g, 37.4mmol), sub39 (14.7g, 39.3mmol), Potassium Phosphate (23.8g, 112.2mmol) was added to 200ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.7mmol) was added to the resulting mixture. When the reaction was completed after 2 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 11.5 g of compound 1-41 (yield 51%, MS: [M+H]+=605).

Synthesis Example 1-42

In a nitrogen atmosphere, 7H-dibenzo[b,g]carbazole (10g, 37.4mmol), sub40 (19g, 39.3mmol), and sodium tert-butoxide (4.7g, 48.6mmol) were added to 200ml of Xylene and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.7mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 13.9 g of compound 1-42 (yield 52%, MS: [M+H] + = 715).

Synthesis Example 1-43

In a nitrogen atmosphere, 6H-dibenzo[b,h]carbazole (10g, 37.4mmol), sub41 (14.1g, 39.3mmol), and Potassium Phosphate (23.8g, 112.2mmol) were added to 200ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.7mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 13.6 g of compound 1-43 (yield 62%, MS: [M+H] + = 589).

Synthesis Example 1-44

In a nitrogen atmosphere, 6H-dibenzo[b,h]carbazole (10g, 37.4mmol), sub42 (19.6g, 39.3mmol), and sodium tert-butoxide (4.7g, 48.6mmol) were added to 200ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.7mmol) was added to the resulting mixture. When the reaction was completed after 2 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 19.1 g of compound 1-44 (yield 70%, MS: [M+H]+=731).

Synthesis Example 1-45

In a nitrogen atmosphere, 13H-dibenzo[a,h]carbazole (10g, 37.4mmol), sub43 (16g, 39.3mmol), and Potassium Phosphate (23.8g, 112.2mmol) were added to 200ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.7mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 14.1 g of compound 1-45 (yield 59%, MS: [M+H] + = 639).

Synthesis Example 1-46

In a nitrogen atmosphere, 13H-dibenzo[a,h]carbazole (10g, 37.4mmol), sub44 (17.7g, 39.3mmol), and sodium tert-butoxide (4.7g, 48.6mmol) were added to 200ml of Xylene and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.7mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 13.7 g of compound 1-46 (yield 54%, MS: [M+H]+=681).

Synthesis Example 1-47

In a nitrogen atmosphere, 7H-dibenzo[c,g]carbazole (10g, 37.4mmol), sub45 (14.1g, 39.3mmol), and Potassium Phosphate (23.8g, 112.2mmol) were added to 200ml of Xylene, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.7mmol) was added to the resulting mixture. When the reaction was completed after 3 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 12.1 g of compound 1-47 (yield 55%, MS: [M+H]+=589).

Synthesis Example 2-1

Formula A-1 (10g, 31.5mmol), amine1 (10.3g, 32.1mmol) and sodium tert-butoxide (3.9g, 40.9mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 10.6 g of compound 2-1 (yield 56%, MS: [M+H] + = 603).

Synthesis Example 2-2

Formula A-2 (10g, 31.5mmol), amine2 (10.8g, 32.1mmol), and sodium tert-butoxide (3.9g, 40.9mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 13.6 g of compound 2-2 (yield 70%, MS: [M+H] + = 617).

Synthesis Example 2-3

Formula B-1 (10g, 27.2mmol), amine3 (8.2g, 27.7mmol), and sodium tert-butoxide (3.4g, 35.3mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 11.4 g of compound 2-3 (yield 67%, MS: [M+H] + = 627).

Synthesis Example 2-4

Formula B-1 (10g, 27.2mmol), amine1 (8.9g, 27.7mmol), and sodium tert-butoxide (3.4g, 35.3mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 9.4 g of compound 2-4 (yield 53%, MS: [M+H]+=653).

Synthesis Example 2-5

Formula C-1 (10g, 27.2mmol), amine4 (10.3g, 27.7mmol), and sodium tert-butoxide (3.4g, 35.3mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 10.1 g of compound 2-5 (yield 53%, MS: [M+H]+=703).

Synthesis Example 2-6

Formula E-1 (10g, 27.2mmol), amine5 (8.2g, 27.7mmol), and sodium tert-butoxide (3.4g, 35.3mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 11.2 g of compound 2-6 (yield 66%, MS: [M+H] + = 627).

Synthesis Example 2-7

Formula E-2 (10g, 27.2mmol), amine6 (6.8g, 27.7mmol), and sodium tert-butoxide (3.4g, 35.3mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 8 g of compound 2-7 (yield 51%, MS: [M+H] + = 577).

Synthesis Example 2-8

Formula F-1 (10g, 27.2mmol), amine6 (6.8g, 27.7mmol), and sodium tert-butoxide (3.4g, 35.3mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 11 g of compound 2-8 (yield 70%, MS: [M+H] + = 577).

Synthesis Example 2-9

Formula G-1 (10g, 31.5mmol), amine7 (12.1g, 32.1mmol), and sodium tert-butoxide (3.9g, 40.9mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 11.6 g of compound 2-9 (yield 56%, MS: [M+H] + = 657).

Synthesis Example 2-10

Formula H-1 (10g, 27.2mmol), amine6 (6.8g, 27.7mmol), and sodium tert-butoxide (3.4g, 35.3mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 8 g of compound 2-10 (yield 51%, MS: [M+H] + = 577).

Synthesis Example 2-11

Formula J-1 (10g, 27.2mmol), amine8 (10.3g, 27.7mmol), and sodium tert-butoxide (3.4g, 35.3mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 12.2 g of compound 2-11 (yield 64%, MS: [M+H] + = 703).

Synthesis Example 2-12

Formula J-2 (10g, 27.2mmol), amine9 (9.6g, 27.7mmol), and sodium tert-butoxide (3.4g, 35.3mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 12.9 g of compound 2-12 (yield 70%, MS: [M+H] + = 676).

Synthesis Example 2-13

Formula K-1 (10g, 27.2mmol), amine10 (7.5g, 27.7mmol), and sodium tert-butoxide (3.4g, 35.3mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 9.8 g of compound 2-13 (yield 60%, MS: [M+H]+=601).

Synthesis Example 2-14

Formula K-2 (10g, 27.2mmol), amine6 (6.8g, 27.7mmol), and sodium tert-butoxide (3.4g, 35.3mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 8.3 g of compound 2-14 (yield 53%, MS: [M+H] + = 577).

Synthesis Example 2-15

Formula L-1 (10g, 27.2mmol), amine11 (8.2g, 27.7mmol), and sodium tert-butoxide (3.4g, 35.3mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 9.2 g of compound 2-15 (yield 54%, MS: [M+H] + = 627).

Synthesis Example 2-16

Formula M-1 (10g, 30mmol), amine12 (12.1g, 30.6mmol), and sodium tert-butoxide (3.7g, 38.9mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 14.3 g of compound 2-16 (yield 69%, MS: [M+H]+=695).

Synthesis Example 2-17

Formula M-2 (10g, 30mmol), amine13 (10.2g, 30.6mmol), and sodium tert-butoxide (3.7g, 38.9mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 11 g of compound 2-17 (yield 58%, MS: [M+H]+=633).

Synthesis Example 2-18

Formula N-1 (10g, 26mmol), amine6 (6.5g, 26.6mmol), and sodium tert-butoxide (3.3g, 33.9mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 10.3 g of compound 2-18 (yield 67%, MS: [M+H]+=593).

Synthesis Example 2-19

Formula O-1 (10g, 26mmol), amine6 (6.5g, 26.6mmol), and sodium tert-butoxide (3.3g, 33.9mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 8.9 g of compound 2-19 (yield 58%, MS: [M+H]+=593).

Synthesis Example 2-20

Formula O-1 (10g, 26mmol), amine14 (8.5g, 26.6mmol), and sodium tert-butoxide (3.3g, 33.9mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 11 g of compound 2-20 (yield 63%, MS: [M+H] + = 669).

Synthesis Example 2-21

Formula Q-1 (10g, 26mmol), amine15 (4.5g, 26.6mmol), and sodium tert-butoxide (3.3g, 33.9mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 7.7 g of compound 2-21 (yield 57%, MS: [M+H] + = 517)

Synthesis Example 2-22

Formula R-1 (10g, 26mmol), amine16 (9.2g, 26.6mmol), and sodium tert-butoxide (3.3g, 33.9mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 9.7 g of compound 2-22 (yield 54%, MS: [M+H]+=693).

Synthesis Example 2-23

Formula R-2 (10g, 26mmol), amine17 (9.9g, 26.6mmol), and sodium tert-butoxide (3.3g, 33.9mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 12.9 g of compound 2-23 (yield 69%, MS: [M+H]+= 719)

Synthesis Example 2-24

Formula S-1 (10g, 30mmol), amine18 (12.3g, 30.6mmol), and sodium tert-butoxide (3.7g, 38.9mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 11.3 g of compound 2-24 (yield 54%, MS: [M+H] + = 699).

Synthesis Example 2-25

Formula S-2 (10g, 30mmol), amine19 (8.4g, 30.6mmol), and sodium tert-butoxide (3.7g, 38.9mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 9.1 g of compound 2-25 (yield 53%, MS: [M+H]+=573).

Synthesis Example 2-26

Formula S-3 (10g, 30mmol), amine20 (12.9g, 30.6mmol), and sodium tert-butoxide (3.7g, 38.9mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 14 g of compound 2-26 (yield 65%, MS: [M+H] + = 719).

Synthesis Example 2-27

Formula T-1 (10g, 26mmol), amine21 (10.6g, 26.6mmol), and sodium tert-butoxide (3.3g, 33.9mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 12.8 g of compound 2-27 (yield 66%, MS: [M+H]+= 745).

Synthesis Example 2-28

Formula U-1 (10g, 26mmol), amine22 (8.5g, 26.6mmol), and sodium tert-butoxide (3.3g, 33.9mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 8.9 g of compound 2-28 (yield 51%, MS: [M+H]+=669).

Synthesis Example 2-29

Formula V-1 (10g, 26mmol), amine6 (6.5g, 26.6mmol), and sodium tert-butoxide (3.3g, 33.9mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 10 g of compound 2-29 (yield 65%, MS: [M+H] + = 593).

Synthesis Example 2-30

Formula V-2 (10g, 26mmol), amine23 (10.5g, 26.6mmol), and sodium tert-butoxide (3.3g, 33.9mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 10.8 g of compound 2-30 (yield 56%, MS: [M+H] + = 743).

Synthesis Example 2-31

Formula W-1 (10g, 26mmol), amine24 (8.5g, 26.6mmol), and sodium tert-butoxide (3.3g, 33.9mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 10.3 g of compound 2-31 (yield 59%, MS: [M+H]+=669).

Synthesis Example 2-32

Formula X-1 (10g, 26mmol), amine6 (6.5g, 26.6mmol), and sodium tert-butoxide (3.3g, 33.9mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 9.4 g of compound 2-32 (yield 61%, MS: [M+H]+=593).

Synthesis Example 2-33

Formula X-2 (10g, 26mmol), amine26 (9.2g, 26.6mmol), and sodium tert-butoxide (3.3g, 33.9mmol) were added to 200ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added to the resulting mixture. When the reaction was completed after 5 hours, the resulting reactant was cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The resulting concentrate was purified by silica gel column chromatography to obtain 11.4 g of compound 2-33 (yield 63%, MS: [M+H]+=693).

Example 1

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. In this case, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

On the thus prepared ITO transparent electrode, the following HI-1 compound was formed as a hole injection layer to a thickness of 1150 Å, but the following A-1 compound was p-doped at a concentration of 1.5%. The following HT-1 compound was vacuum-deposited on the hole injection layer to form a hole transport layer having a thickness of 800 Å. Then, the following EB-1 compound was vacuum-deposited to a thickness of 150 Å on the hole transport layer to form an electron blocking layer. Next, on the electronic blocking layer, the compound 1-1 prepared in Synthesis Example 1-1 as a first host, the compound 2-1 prepared in Synthesis Example 2-1 as a second host, and the following as a dopant The Dp-7 compound was vacuum-deposited at a weight ratio of 49:49:2 to form a red light emitting layer having a thickness of 400 Å. A hole blocking layer was formed by vacuum-depositing the following HB-1 compound to a thickness of 30 Å on the light emitting layer. Then, on the hole blocking layer, the following ET-1 compound and the following LiQ compound were vacuum-deposited at a weight ratio of 2:1 to form an electron injection and transport layer to a thickness of 300 Å. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1,000 Å on the electron injection and transport layer.

In the above process, the deposition rate of organic material was maintained at 0.4~0.7Å/sec, the deposition rate of lithium fluoride of the negative electrode was maintained at 0.3Å/sec, and the deposition rate of aluminum was maintained at 2Å/sec, and the vacuum degree during deposition was 2×10 ^-7 ~ ^{By maintaining 5} ×10 -6 torr, an organic light emitting device was manufactured.

Examples 2 to 205

The organic light emitting device in the same manner as in Example 1, except for using the first and second host compounds shown in Tables 1 to 6 below instead of the first and second hosts in the organic light emitting device of Example 1 was manufactured

Comparative Examples 1 to 30

Example 1, except for using the first host (compounds B-1 to B-3) and the second host shown in Table 7 below instead of the first and second hosts in the organic light emitting device of Example 1 An organic light emitting device was manufactured in the same manner as described above.

Comparative Examples 31 to 63

Except for using the first host and the second host (compounds C-1 to C-3) shown in Table 8 below instead of the first and second hosts in the organic light emitting device of Example 1, Example 1 and An organic light emitting device was manufactured in the same manner.

Compounds B-1 to B-3 and compounds C-1 to C-3 used in Comparative Examples 1 to 63 are as follows:

Experimental example

When a current was applied to the organic light emitting diodes prepared in Examples and Comparative Examples, driving voltage and efficiency were measured, respectively, and the results are shown in Tables 1 to 8 below (based on 15 mA/cm ² ). In addition, the lifetime T95 means the time it takes for the luminance to decrease to 95% from the initial luminance (6,000 nits).

1st host 2nd host Driving voltage (V) Efficiency (cd/A) Life T95 (hr) luminous color Example 1 compound 1-1 compound 2-1 3.62 20.81 184 Red Example 2 compound 2-6 3.59 19.65 187 Red Example 3 compound 2-11 3.64 21.48 175 Red Example 4 compound 2-15 3.60 20.19 179 Red Example 5 compound 2-19 3.65 22.67 183 Red Example 6 compound 1-2 compound 2-2 3.64 21.98 171 Red Example 7 compound 2-7 3.60 21.40 182 Red Example 8 compound 2-12 3.63 22.95 183 Red Example 9 compound 2-16 3.59 20.02 188 Red Example 10 compound 2-21 3.57 19.75 180 Red Example 11 compound 1-3 compound 2-3 3.86 18.87 191 Red Example 12 compound 2-9 3.88 18.61 205 Red Example 13 compound 2-13 3.86 18.67 190 Red Example 14 compound 2-17 3.85 18.87 187 Red Example 15 compound 2-24 3.75 18.61 203 Red Example 16 compound 1-4 compound 2-5 3.83 18.39 204 Red Example 17 compound 2-10 3.78 18.37 200 Red Example 18 compound 2-14 3.89 18.38 198 Red Example 19 compound 2-18 3.81 18.95 197 Red Example 20 compound 2-25 3.76 18.64 207 Red Example 21 compound 1-5 compound 2-1 3.95 17.07 180 Red Example 22 compound 2-6 3.95 18.34 166 Red Example 23 compound 2-11 3.94 17.39 171 Red Example 24 compound 2-15 3.92 17.11 166 Red Example 25 compound 2-19 3.91 17.11 168 Red Example 26 compound 1-6 compound 2-2 3.95 18.50 172 Red Example 27 compound 2-7 3.98 18.48 166 Red Example 28 compound 2-12 3.96 17.23 175 Red Example 29 compound 2-16 3.99 18.38 179 Red Example 30 compound 2-21 3.97 17.33 170 Red Example 31 compound 1-7 compound 2-3 3.80 19.30 221 Red Example 32 compound 2-9 3.82 19.19 228 Red Example 33 compound 2-13 3.88 19.73 206 Red Example 34 compound 2-17 3.89 19.09 219 Red Example 35 compound 2-24 3.86 20.21 222 Red

1st host 2nd host Driving voltage (V) Efficiency (cd/A) Life T95 (hr) luminous color Example 36 compound 1-8 compound 2-5 3.81 19.09 219 Red Example 37 compound 2-10 3.88 19.64 212 Red Example 38 compound 2-14 3.81 19.72 227 Red Example 39 compound 2-18 3.81 19.44 208 Red Example 40 compound 2-25 3.87 19.71 213 Red Example 41 compound 1-9 compound 2-1 3.89 19.89 187 Red Example 42 compound 2-6 3.87 19.69 192 Red Example 43 compound 2-11 3.86 19.81 190 Red Example 44 compound 2-15 3.85 19.47 182 Red Example 45 compound 2-19 3.87 19.38 204 Red Example 46 compound 1-10 compound 2-2 3.88 19.29 190 Red Example 47 compound 2-7 3.82 20.10 184 Red Example 48 compound 2-12 3.87 19.81 182 Red Example 49 compound 2-16 3.80 19.76 203 Red Example 50 compound 2-21 3.80 20.17 182 Red Example 51 compound 1-11 compound 2-3 3.76 18.39 199 Red Example 52 compound 2-9 3.88 19.06 199 Red Example 53 compound 2-13 3.86 18.13 185 Red Example 54 compound 2-17 3.81 18.18 202 Red Example 55 compound 2-24 3.89 18.93 193 Red Example 56 compound 1-12 compound 2-5 3.86 18.80 185 Red Example 57 compound 2-10 3.80 18.13 188 Red Example 58 compound 2-14 3.88 18.86 190 Red Example 59 compound 2-18 3.85 18.87 191 Red Example 60 compound 2-25 3.76 19.00 189 Red Example 61 compound 1-13 compound 2-1 3.61 20.13 176 Red Example 62 compound 2-6 3.57 20.92 186 Red Example 63 compound 2-11 3.59 19.52 183 Red Example 64 compound 2-15 3.63 20.56 180 Red Example 65 compound 2-19 3.55 21.17 173 Red Example 66 compound 1-14 compound 2-2 3.60 22.09 184 Red Example 67 compound 2-7 3.57 22.55 179 Red Example 68 compound 2-12 3.59 21.22 170 Red Example 69 compound 2-16 3.61 22.21 180 Red Example 70 compound 2-21 3.58 22.70 178 Red

1st host 2nd host Driving voltage (V) Efficiency (cd/A) Life T95 (hr) luminous color Example 71 compound 1-15 compound 2-3 3.59 20.72 189 Red Example 72 compound 2-9 3.62 20.77 172 Red Example 73 compound 2-13 3.62 22.98 179 Red Example 74 compound 2-17 3.63 23.00 187 Red Example 75 compound 2-24 3.63 20.74 170 Red Example 76 compound 1-16 compound 2-5 3.64 22.90 171 Red Example 77 compound 2-10 3.58 20.43 179 Red Example 78 compound 2-14 3.65 20.86 190 Red Example 79 compound 2-18 3.55 22.10 182 Red Example 80 compound 2-25 3.64 21.61 174 Red Example 81 compound 1-17 compound 2-1 3.98 17.82 168 Red Example 82 compound 2-6 3.93 17.43 178 Red Example 83 compound 2-11 3.92 18.39 169 Red Example 84 compound 2-15 3.99 17.37 176 Red Example 85 compound 2-19 3.92 17.66 168 Red Example 86 compound 1-18 compound 2-2 3.96 17.15 173 Red Example 87 compound 2-7 3.97 17.11 169 Red Example 88 compound 2-12 3.99 17.56 171 Red Example 89 compound 2-16 3.92 17.52 180 Red Example 90 compound 2-21 3.98 17.92 166 Red Example 91 compound 1-19 compound 2-3 3.82 19.62 191 Red Example 92 compound 2-9 3.89 20.33 209 Red Example 93 compound 2-13 3.87 20.19 202 Red Example 94 compound 2-17 3.80 19.09 208 Red Example 95 compound 2-24 3.85 20.05 190 Red Example 96 compound 1-20 compound 2-5 3.88 20.27 181 Red Example 97 compound 2-10 3.85 19.67 189 Red Example 98 compound 2-14 3.84 19.23 196 Red Example 99 compound 2-18 3.83 19.87 203 Red Example 100 compound 2-25 3.82 19.52 195 Red Example 101 compound 1-21 compound 2-1 3.83 18.52 198 Red Example 102 compound 2-6 3.75 18.99 188 Red Example 103 compound 2-11 3.85 19.29 201 Red Example 104 compound 2-15 3.80 19.15 186 Red Example 105 compound 2-19 3.78 18.30 202 Red

1st host 2nd host Driving voltage (V) Efficiency (cd/A) Life T95 (hr) luminous color Example 106 compound 1-23 compound 2-2 3.79 19.17 187 Red Example 107 compound 2-7 3.75 18.57 194 Red Example 108 compound 2-12 3.81 18.79 191 Red Example 109 compound 2-16 3.89 18.70 192 Red Example 110 compound 2-21 3.75 18.26 187 Red Example 111 compound 1-25 compound 2-3 3.62 21.78 179 Red Example 112 compound 2-9 3.57 21.06 180 Red Example 113 compound 2-13 3.65 20.56 179 Red Example 114 compound 2-17 3.61 21.06 185 Red Example 115 compound 2-24 3.62 19.67 186 Red Example 116 compound 1-26 compound 2-5 3.56 22.37 188 Red Example 117 compound 2-10 3.65 20.04 187 Red Example 118 compound 2-14 3.56 20.05 182 Red Example 119 compound 2-18 3.55 22.46 173 Red Example 120 compound 2-25 3.61 19.77 177 Red Example 121 compound 1-27 compound 2-1 3.94 18.29 174 Red Example 122 compound 2-6 3.98 18.17 167 Red Example 123 compound 2-11 3.95 18.20 167 Red Example 124 compound 2-15 3.92 17.73 175 Red Example 125 compound 2-19 3.90 18.03 176 Red Example 126 compound 1-28 compound 2-2 3.86 19.21 189 Red Example 127 compound 2-7 3.87 19.72 193 Red Example 128 compound 2-12 3.86 19.99 186 Red Example 129 compound 2-16 3.81 19.22 193 Red Example 130 compound 2-21 3.87 19.41 187 Red Example 131 compound 1-32 compound 2-3 3.89 19.52 194 Red Example 132 compound 2-9 3.85 19.08 207 Red Example 133 compound 2-13 3.88 20.11 197 Red Example 134 compound 2-17 3.81 20.37 185 Red Example 135 compound 2-24 3.82 19.92 193 Red Example 136 compound 1-33 compound 2-5 3.87 18.38 186 Red Example 137 compound 2-10 3.75 18.31 187 Red Example 138 compound 2-14 3.87 18.00 190 Red Example 139 compound 2-18 3.86 19.17 190 Red Example 140 compound 2-25 3.79 19.02 201 Red

1st host 2nd host Driving voltage (V) Efficiency (cd/A) Life T95 (hr) luminous color Example 141 compound 1-34 compound 2-1 3.87 18.88 185 Red Example 142 compound 2-6 3.87 18.88 201 Red Example 143 compound 2-11 3.83 18.19 205 Red Example 144 compound 2-15 3.87 18.59 188 Red Example 145 compound 2-19 3.88 18.23 204 Red Example 146 compound 1-35 compound 2-2 3.55 22.76 189 Red Example 147 compound 2-7 3.57 20.53 184 Red Example 148 compound 2-12 3.56 21.25 183 Red Example 149 compound 2-16 3.61 22.05 185 Red Example 150 compound 2-21 3.56 20.54 184 Red Example 151 compound 1-36 compound 2-3 3.63 21.53 172 Red Example 152 compound 2-9 3.55 19.82 170 Red Example 153 compound 2-13 3.59 21.29 187 Red Example 154 compound 2-17 3.55 22.07 183 Red Example 155 compound 2-24 3.65 20.37 189 Red Example 156 compound 1-37 compound 2-5 3.59 22.76 189 Red Example 157 compound 2-10 3.57 20.53 184 Red Example 158 compound 2-14 3.56 21.25 183 Red Example 159 compound 2-18 3.61 22.05 185 Red Example 160 compound 2-25 3.56 20.54 184 Red Example 161 compound 1-38 compound 2-1 3.63 21.53 172 Red Example 162 compound 2-6 3.55 19.82 170 Red Example 163 compound 2-11 3.59 21.29 187 Red Example 164 compound 2-15 3.55 22.07 183 Red Example 165 compound 2-19 3.65 20.37 189 Red Example 166 compound 1-39 compound 2-2 3.85 19.13 196 Red Example 167 compound 2-7 3.87 19.53 190 Red Example 168 compound 2-12 3.83 19.42 209 Red Example 169 compound 2-16 3.81 19.58 202 Red Example 170 compound 2-21 3.80 19.79 202 Red Example 171 compound 1-41 compound 2-3 3.89 19.71 210 Red Example 172 compound 2-9 3.84 19.82 200 Red Example 173 compound 2-13 3.87 19.58 204 Red Example 174 compound 2-17 3.86 20.41 198 Red Example 175 compound 2-24 3.89 19.77 186 Red

1st host 2nd host Driving voltage (V) Efficiency (cd/A) Life T95 (hr) luminous color Example 176 compound 1-42 compound 2-5 3.95 18.34 166 Red Example 177 compound 2-10 3.92 18.36 168 Red Example 178 compound 2-14 3.95 17.61 165 Red Example 179 compound 2-18 3.97 17.09 166 Red Example 180 compound 2-25 3.98 17.85 168 Red Example 181 compound 1-43 compound 2-1 3.97 18.47 179 Red Example 182 compound 2-6 3.94 17.76 179 Red Example 183 compound 2-11 3.97 18.29 179 Red Example 184 compound 2-15 3.98 17.38 169 Red Example 185 compound 2-19 3.95 17.98 165 Red Example 186 compound 1-44 compound 2-2 3.81 19.79 205 Red Example 187 compound 2-7 3.88 19.23 206 Red Example 188 compound 2-12 3.87 19.31 199 Red Example 189 compound 2-16 3.88 19.44 197 Red Example 190 compound 2-21 3.84 19.78 201 Red Example 191 compound 1-45 compound 2-3 3.80 19.86 205 Red Example 192 compound 2-9 3.85 19.08 186 Red Example 193 compound 2-13 3.88 19.70 197 Red Example 194 compound 2-17 3.85 19.99 181 Red Example 195 compound 2-24 3.89 20.27 199 Red Example 196 compound 1-46 compound 2-5 3.76 18.67 198 Red Example 197 compound 2-10 3.88 18.72 195 Red Example 198 compound 2-14 3.86 19.32 190 Red Example 199 compound 2-18 3.81 18.22 186 Red Example 200 compound 2-25 3.85 19.46 194 Red Example 201 compound 1-47 compound 2-1 3.79 18.68 205 Red Example 202 compound 2-6 3.78 18.68 193 Red Example 203 compound 2-11 3.83 19.03 201 Red Example 204 compound 2-15 3.77 18.79 191 Red Example 205 compound 2-19 3.76 18.44 185 Red

1st host 2nd host Driving voltage (V) Efficiency (cd/A) Life T95 (hr) luminous color Comparative Example 1 compound B-1 compound 2-1 4.32 16.03 128 Red Comparative Example 2 compound 2-6 4.28 15.88 131 Red Comparative Example 3 compound 2-11 4.24 15.74 128 Red Comparative Example 4 compound 2-15 4.30 16.66 109 Red Comparative Example 5 compound 2-19 4.29 16.14 133 Red Comparative Example 6 compound 2-2 4.20 16.52 129 Red Comparative Example 7 compound 2-7 4.33 16.55 128 Red Comparative Example 8 compound 2-12 4.29 15.89 133 Red Comparative Example 9 compound 2-16 4.34 16.90 127 Red Comparative Example 10 compound 2-21 4.34 15.63 120 Red Comparative Example 11 compound B-2 compound 2-3 4.24 14.92 140 Red Comparative Example 12 compound 2-9 4.10 14.73 152 Red Comparative Example 13 compound 2-13 4.09 14.40 150 Red Comparative Example 14 compound 2-17 4.13 14.89 149 Red Comparative Example 15 compound 2-24 4.05 14.29 152 Red Comparative Example 16 compound 2-5 4.04 14.15 152 Red Comparative Example 17 compound 2-10 4.07 14.22 140 Red Comparative Example 18 compound 2-14 4.13 14.69 150 Red Comparative Example 19 compound 2-18 4.07 14.83 141 Red Comparative Example 20 compound 2-25 4.05 14.32 142 Red Comparative Example 21 compound B-3 compound 2-1 4.07 16.46 133 Red Comparative Example 22 compound 2-6 4.09 16.01 143 Red Comparative Example 23 compound 2-11 4.05 15.97 139 Red Comparative Example 24 compound 2-15 4.14 15.02 135 Red Comparative Example 25 compound 2-19 4.08 16.36 148 Red Comparative Example 26 compound 2-2 4.03 15.54 144 Red Comparative Example 27 compound 2-7 4.14 16.20 146 Red Comparative Example 28 compound 2-12 4.12 16.27 131 Red Comparative Example 29 compound 2-16 4.07 15.49 136 Red Comparative Example 30 compound 2-21 4.07 15.61 145 Red

1st host 2nd host Driving voltage (V) Efficiency (cd/A) Life T95 (hr) luminous color Comparative Example 31 compound 1-1 compound C-1 4.10 16.21 149 Red Comparative Example 32 compound 1-4 4.11 15.71 133 Red Comparative Example 33 compound 1-7 4.12 16.15 154 Red Comparative Example 34 compound 1-13 4.03 16.09 132 Red Comparative Example 35 compound 1-19 4.05 15.77 150 Red Comparative Example 36 compound 1-23 4.06 16.51 155 Red Comparative Example 37 compound 1-28 4.05 15.21 147 Red Comparative Example 38 compound 1-32 4.08 16.40 141 Red Comparative Example 39 compound 1-38 4.06 16.67 131 Red Comparative Example 40 compound 1-41 4.15 16.11 130 Red Comparative Example 41 compound 1-44 4.30 15.16 91 Red Comparative Example 42 compound 1-2 compound C-2 4.18 14.27 127 Red Comparative Example 43 compound 1-5 4.07 14.17 103 Red Comparative Example 44 compound 1-8 4.14 14.29 126 Red Comparative Example 45 compound 1-15 4.09 14.29 106 Red Comparative Example 46 compound 1-20 4.08 14.32 100 Red Comparative Example 47 compound 1-25 4.02 14.35 125 Red Comparative Example 48 compound 1-30 4.03 14.45 124 Red Comparative Example 49 compound 1-35 4.01 14.46 119 Red Comparative Example 50 compound 1-39 4.15 14.90 110 Red Comparative Example 51 compound 1-42 4.06 14.96 113 Red Comparative Example 52 compound 1-45 4.26 15.81 114 Red Comparative Example 53 compound 1-3 compound C-3 4.50 10.35 106 Red Comparative Example 54 compound 1-6 4.30 12.49 86 Red Comparative Example 55 compound 1-9 4.43 9.69 77 Red Comparative Example 56 compound 1-17 4.45 10.01 74 Red Comparative Example 57 compound 1-22 4.35 11.66 96 Red Comparative Example 58 compound 1-26 4.42 11.72 69 Red Comparative Example 59 compound 1-31 4.35 12.05 68 Red Comparative Example 60 compound 1-36 4.49 12.70 96 Red Comparative Example 61 compound 1-40 4.45 9.52 103 Red Comparative Example 62 compound 1-43 4.43 11.54 62 Red Comparative Example 63 compound 1-47 4.26 15.80 122 Red

The organic light emitting device of the embodiment in which a red light emitting layer is formed by co-depositing the first compound of Formula 1 and the second compound of Formula 2 according to the present invention comprises compounds B-1 to B-3 and the second compound of the present invention The organic light emitting devices of Comparative Examples 1 to 30 in which a red light emitting layer was formed by co-deposition, and the organic light emitting devices of Comparative Examples 31 to 63 in which the compounds C-1 to C-3 and the first compound of the present invention were co-deposited to form a red light emitting layer. Compared with the light emitting device, the driving voltage is reduced, and the efficiency and lifespan characteristics are improved.

From this, it can be seen that energy transfer from the host in the red light emitting layer to the red dopant was well achieved by using the first compound of Formula 1 and the second compound of Formula 2 as hosts in combination. In addition, the organic light-emitting device of the above example exhibited significantly improved lifespan characteristics while maintaining high efficiency compared to the comparative example. This is because, by using the combination of the first compound of Formula 1 and the second compound of Formula 2, the balance of electrons and holes in the light emitting layer is stably achieved, and thus electrons and holes are combined to form excitons evenly throughout the light emitting layer. to be.

In conclusion, it can be confirmed that when the first compound of Formula 1 and the second compound of Formula 2 of the present invention are used in combination as a host of the red light emitting layer, the driving voltage, luminous efficiency and lifespan characteristics of the organic light emitting device can be improved, Considering that the luminous efficiency and lifespan characteristics of the organic light emitting device have a trade-off relationship with each other in general, it can be seen that the organic light emitting device of the embodiment exhibits significantly improved device characteristics compared to the device of the comparative example.

1: Substrate 2: Anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: electron blocking layer 8: hole blocking layer
9: Electron injection and transport layer

Claims (14)

anode; cathode; and a light emitting layer between the anode and the cathode,
The light emitting layer comprises a first compound represented by the following formula (1) and a second compound represented by the following formula (2),
Organic light emitting device:
[Formula 1]

In Formula 1,
L _{1 To} L _{3 Are} each independently a single bond; Or a substituted or unsubstituted C _6-60 arylene,
Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl; _{or C 2-60} heteroaryl containing one or more heteroatoms among substituted or unsubstituted N, O and S;
each R ₁ is independently hydrogen or deuterium; or two adjacent ones combine with each other to form an unsubstituted or deuterium substituted benzene ring, and the remainder are each independently hydrogen or deuterium;
each R ₂ is independently hydrogen or deuterium; or two adjacent ones combine with each other to form an unsubstituted or deuterium substituted benzene ring, and the remainder are each independently hydrogen or deuterium;
[Formula 2]

In Formula 2,
A is a benzene ring fused with an adjacent ring, or a naphthalene ring,
L' ₁ , L' ₂ and L' ₃ are each independently a single bond; substituted or unsubstituted C _6-60 arylene; _{Or or substituted or unsubstituted C 2-60} heteroarylene comprising at least one selected from the group consisting of N, O and S,
Ar' ₁ , Ar' ₂ and Ar' ₃ are each independently substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl comprising any one or more selected from the group consisting of N, O and S,
C ₁ and C ₂ are each bonded to _{C 3} and C ₄ of Formula 3 below,
[Formula 3]

In Formula 3,
X is O or S;
B is a benzene ring fused with an adjacent ring, or a naphthalene ring,
R' is hydrogen; heavy hydrogen; halogen; cyano; substituted or unsubstituted C _1-60 alkyl; substituted or unsubstituted C _1-60 alkoxy; substituted or unsubstituted C _2-60 alkenyl; substituted or unsubstituted C _2-60 alkynyl; substituted or unsubstituted C _3-60 cycloalkyl; substituted or unsubstituted C _6-60 aryl; _{It is C 2-60} heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,
m is an integer of 0 to 4 when B is a benzene ring, and an integer of 0 to 6 when B is a naphthalene ring.
According to claim 1,
The first compound is represented by any one of the following formulas 1-1 to 1-10,
Organic light emitting device:

In Formulas 1-1 to 1-10,
L ₁ to L ₃ , Ar ₁ and Ar ₂ are as defined in claim 1.
According to claim 1,
L ₁ and L ₂ are each independently a single bond, phenylene, or naphthylene,
organic light emitting device.
According to claim 1,
L ₃ is a single bond, phenylene, biphenyldiyl, or naphthylene,
organic light emitting device.
According to claim 1,
Ar ₁ and Ar ₂ are each independently phenyl, biphenyl, terphenyl, naphthyl, (phenyl) naphthyl, (naphthyl) phenyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzo naphthofuranyl, or benzonaphthothiophenyl;
Here, Ar ₁ and Ar ₂ are each independently unsubstituted or substituted with one or more substituents selected from the group consisting of _{deuterium, C 1-10} alkyl and C _{6-20 aryl,}
organic light emitting device.
6. The method of claim 5,
Ar ₁ and Ar ₂ are each independently any one selected from the group consisting of
Organic light emitting device:

In each of the above formulas,
X is O or S;
The dotted line indicates the bonding position.
According to claim 1,
The first compound is any one selected from the group consisting of
Organic light emitting device:

.
According to claim 1,
The formula 2 is represented by any one selected from the group consisting of the following formulas 2-1 to 2-12,
Organic light emitting device:

In Formulas 2-1 to 2-12,
L' ₁ to L' ₃ , Ar' ₁ to Ar' ₃ , X, R' and m are as defined in claim 1.
According to claim 1,
L' ₁ is a single bond,
organic light emitting device.
According to claim 1,
L' ₂ and L' ₃ are each independently a single bond, phenylene, biphenyldiyl, or naphthylene;
organic light emitting device.
According to claim 1,
Ar' ₁ is phenyl,
organic light emitting device.
According to claim 1,
Ar' ₂ and Ar' ₃ are each independently phenyl, biphenyl, terphenyl, naphthyl, (phenyl) naphthyl, (naphthyl) phenyl, phenanthrenyl, (phenanthrenyl) phenyl, (phenyl) phenanthre nyl, dibenzofuranyl, or dibenzothiophenyl;
organic light emitting device.
According to claim 1,
R' is hydrogen;
organic light emitting device.
According to claim 1,
The second compound is any one selected from the group consisting of
Organic light emitting device:

.

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