KR20220052289A - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting element. The organic light emitting element comprises: a positive electrode; a negative electrode installed to face the positive electrode; and a light emitting layer provided between the positive electrode and the negative electrode. Therefore, efficiency, driving voltage, and/or a lifespan of the organic light emitting element can be increased.

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 material layer is often made of a multi-layer 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, it may be made of an electron injection layer, etc. When a voltage is applied between the two electrodes in the structure of the organic light emitting device, 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 these excitons are When it falls back to the ground state, it lights up.

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.

The present invention provides the following organic light emitting device.

anode;

a negative electrode provided to face the positive electrode; and

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

The light emitting layer is an organic light emitting device including a first compound represented by the following Chemical Formula 1 and a second compound represented by the following Chemical Formula 2:

[Formula 1]

In Formula 1,

A ₁ and A ₂ are each independently a benzene or naphthalene ring fused to a neighboring pentacyclic ring,

L is a substituted or unsubstituted C _6-60 arylene,

L ₁ and L ₂ 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 _2-20 heteroaryl containing one or more heteroatoms among substituted or unsubstituted N, O and S;

R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; 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;

When A ₁ and A ₂ are each a benzene ring, a and b are each independently an integer of 0 to 4,

When A ₁ and A ₂ are each a naphthalene ring, a and b are each independently an integer of 0 to 6,

[Formula 2]

In Formula 2,

L' is a substituted or unsubstituted C _6-60 arylene,

L ₃ and L ₄ are each independently a single bond; Or a substituted or unsubstituted C _6-60 arylene,

Ar ₃ and Ar ₄ are each independently substituted or unsubstituted C _6-60 aryl; a substituent represented by the following formula (2a); a substituent represented by the following formula 2b; or a substituent represented by the following formula 2c, provided that Ar ₃ and Ar ₄ are not fluorenyl,

In Formulas 2a to 2c,

each X is independently O, S, or N(Ar);

where Ar is hydrogen, deuterium, or substituted or unsubstituted C _6-20 aryl,

B ₁ to B ₃ are each independently a substituted or unsubstituted naphthalene ring fused to a neighboring pentacyclic ring,

R is hydrogen, deuterium, or substituted or unsubstituted C _6-20 aryl;

n is an integer from 0 to 4,

R ₃ is hydrogen or deuterium,

c is an integer from 0 to 9;

In this case, when a, b, and c are each 2 or more, the substituents in parentheses are the same or different from each other.

The above-described organic light emitting device may include two kinds of host compounds in the light emitting layer to improve efficiency, driving voltage, and/or lifespan characteristics in the organic light emitting device.

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 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 a cathode 4 are shown.

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

, 또는

는 다른 치환기에 연결되는 결합을 의미하고, D는 중수소를 의미하고, Ph는 페닐기를 의미한다. In this specification,

, or

means a bond connected to another substituent, D means deuterium, and Ph means a phenyl group.

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 substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group including at least one of N, O and S atoms, or substituted or unsubstituted with a substituent to which two or more of the above-exemplified substituents are connected it means. 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. For example, the term “substituted or unsubstituted” means “unsubstituted or at least one selected from the group consisting of deuterium, halogen, C _1-10 alkyl, C _1-10 alkoxy and C _6-20 aryl. , for example, substituted with 1 to 5 substituents. Also, as used herein, the term “substituted with one or more substituents” shall be understood to mean, for example, “substituted with 1 to 5 substituents”, or “substituted with 1 or 2 substituents”. can

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, it may be a substituent having the following structure, but is not limited thereto.

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

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably from 1 to 25 carbon atoms. Specifically, it may be a substituent having the following structure, 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 trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron group, and the like.

In the present specification, examples of the halogen group include fluoro, chloro, bromo, or iodo.

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, 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-ethylbutyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-ethyl-propyl, 1,1-dimethylpropyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, isohexyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5 -Methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2,4,4-trimethyl-1-pentyl, 2,4,4- trimethyl-2-pentyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 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 having aromaticity. 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 include, but is not limited to, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a triphenylenyl group, a pyrenyl group, a perylenyl group, a chrysenyl group, and the like.

In the present specification, the heteroaryl group is a heterocyclic group including at least one heteroatom among O, N, Si and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but is preferably from 2 to 60 carbon atoms. Examples of the heteroaryl 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, aralkenyl group, alkylaryl group, arylamine group, and arylsilyl group is the same as the above-described aryl group. 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 heteroarylamines, the description regarding heteroaryl described above 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 heteroaryl 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. In the present specification, the heterocyclic group is not a monovalent group, and the description regarding heteroaryl described above may be applied, except that it is formed by combining two substituents.

On the other hand, an organic light emitting device according to an embodiment includes an anode; a negative electrode provided to face the positive electrode; and a light emitting layer provided between the anode and the cathode, wherein the light emitting layer includes a first compound represented by Formula 1 and a second compound represented by Formula 2 above.

The organic light emitting device according to the present invention may include two types of compounds having a specific structure as a host material in the light emitting layer at the same time, thereby improving efficiency, driving voltage, and/or lifespan characteristics in the organic light emitting device.

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

positive and negative

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; LiF/Al or a multi-layered material such as 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.

electron suppression layer

The organic light emitting diode 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 suppression 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 hole-electron coupling probability, thereby increasing the efficiency of the organic light emitting diode It means a layer that plays a role in improving The electron blocking layer includes an electron blocking material, and an example of such an electron blocking material may be an arylamine-based organic 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 the hole transport ability, and the second compound functions as a P-type host material having a hole transport ability superior to the electron transport ability, 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, and the linker L is arylene. In particular, the first compound does not have L, that is, compared to the compound in which the triazinyl group is connected to the N atom of the carbazole-based core by a single bond, the electron transport ability is more improved, and the light emitting layer as it efficiently transfers electrons to the dopant material It is possible to increase the probability of electron-hole recombination in

According to one embodiment, in Formula 1,

A ₁ and A ₂ are each independently a benzene ring fused to a neighboring pentacyclic ring;

A ₁ and A ₂ are either a benzene ring fused to a neighboring pentacyclic ring, and the other is a naphthalene ring fused to a neighboring pentacyclic ring; or

A ₁ and A ₂ are each independently a naphthalene ring fused to a neighboring pentacyclic ring.

In addition, in Formula 1, a means the number of R ₁ , and is an integer of 0 to 6. Specifically, when A ₁ is a benzene ring, a is 0, 1, 2, 3, or 4, and when A ₁ is a naphthalene ring, b is 0, 1, 2, 3, 4, 5, or 6.

In addition, b denotes the number of R ₂ , and is an integer of 0 to 6. Specifically, when A ₂ is a benzene ring, b is 0, 1, 2, 3, or 4, and when A ₂ is a naphthalene ring, b is 0, 1, 2, 3, 4, 5, or 6.

In this case, a+b may be an integer of 0 to 4. Alternatively, a+b may be 0 or 1.

는 하기 화학식 1a 내지 1j 중 어느 하나로 표시될 수 있다:More specifically, in Formula 1, the substituent

may be represented by any one of the following formulas 1a to 1j:

In Formulas 1a to 1j,

a' and b' are each independently an integer of 0 to 4,

a" and b" are each independently an integer from 0 to 6,

R ₁ and R ₂ are as defined in Formula 1 above.

More specifically, in Formulas 1a to 1j,

a', b', a" and b" can each independently be 0, 1, or 2.

For example, in Formula 1a, a'+b' is 0 or 1,

In Formulas 1b to 1d, a"+b' is 0 or 1,

In Formulas 1e to 1j, a"+b" is 0 or 1.

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

In the above 1-1 to 1-10,

a' and b' are each independently an integer of 0 to 4,

a" and b" are each independently an integer from 0 to 6,

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

More specifically, in the above 1-1 to 1-10,

a', b', a" and b" can each independently be 0, 1, or 2.

For example, in Formula 1-1, a'+b' is 0 or 1,

In Formulas 1-2 to 1-4, a"+b' is 0 or 1,

In Formulas 1-5 to 1-10, a"+b" is 0 or 1.

In addition, in Formula 1, L may be unsubstituted or substituted C _6-20 aryl with one or more deuterium.

Specifically, L may be phenylene, biphenyldiyl, or naphthylene.

More specifically, L may be any one selected from the group consisting of:

.

.

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.

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:

.

.

For example, L ₁ and L ₂ are both single bonds;

one of L ₁ and L ₂ is a single bond and the other is naphthylene; or

One of L ₁ and L ₂ may be a single bond, and the other may be phenylene.

In addition, in Formula 1, Ar ₁ and Ar ₂ do not include a heteroaryl group having more than 20 carbon atoms, such as a monovalent substituent of a spiro (fluorene-xanthene) structure. An organic light emitting device employing as a host a compound including a heteroaryl group having more than 20 carbon atoms in at least one of Ar ₁ and Ar ₂ has higher efficiency and lifetime compared to an organic light emitting device employing the compound represented by Formula 1 as a host. can be significantly lowered.

Specifically, Ar ₁ and Ar ₂ are each independently unsubstituted or substituted with one or more deuterium C _6-20 aryl; or C _2-20 heteroaryl comprising one heteroatom of O and S unsubstituted or substituted with one or more deuterium.

More specifically, Ar ₁ and Ar ₂ may each independently be phenyl, naphthyl, biphenylyl, or dibenzofuranyl.

,

,

, 또는

일 수 있다.For example, Ar ₁ and Ar ₂ are each independently

,

,

, or

can be

, 또는

일 수 있다.In addition, one of Ar ₁ and Ar ₂ is

, or

can be

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

In addition, R ₁ and R ₂ may each independently be C _6-20 aryl or C _2-20 heteroaryl including one heteroatom among N, O and S.

Specifically, R ₁ and R ₂ may each independently be phenyl, dibenzofuranyl, or dibenzothiophenyl. More specifically, R ₁ and R ₂ may each independently be phenyl, naphthyl, or dibenzofuranyl.

For example, R ₁ and R ₂ may each independently be any one selected from the group consisting of:

.

.

On the other hand, representative examples of the first compound represented by Formula 1 are as follows:

.

Meanwhile, the first compound may be prepared by, for example, a preparation method as shown in Scheme 1 below.

[Scheme 1]

In Scheme 1, X" is halogen, preferably bromo, or chloro, and definitions of other substituents are as described above.

Specifically, the compound represented by Formula 1 may be prepared through an amine substitution reaction of the starting materials A1 and A2. The amine substitution reaction is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction may be appropriately changed. The method for preparing the compound represented by Formula 1 may be more specific in Preparation Examples to be described later.

(second compound)

The second compound is represented by Formula 2 above. Specifically, the second compound has a 9-phenanthryl group as one of the substituents of the amino group, and as the other substituent, one of substituted or unsubstituted C _6-60 aryl or substituted or unsubstituted N, O and S It is characterized by having a C _2-15 heteroaryl containing more than one heteroatom. In this case, the amino group does not have a fluorenyl group as its substituent. That is, Ar ₃ and Ar ₄ are not fluorenyl.

In particular, the second compound includes i) a compound having a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group or a 4-phenanthryl group instead of a 9-phenanthryl group as one of the substituents of the amino group, and ii) an amino group Compared to a compound having a fluorenyl group or carbazol-9-yl which is substituted or unsubstituted with one of the substituents, holes can be efficiently transferred to the dopant material, and accordingly, the first compound having excellent electron transport ability together with the light emitting layer It is possible to increase the probability of recombination of holes and electrons in

In addition, L' may be unsubstituted or substituted C _6-20 arylene with deuterium.

Specifically, L' may each independently be phenylene, biphenyldiyl, or naphthylene.

More specifically, L' may be any one selected from the group consisting of:

.

.

For example, L' may be any one selected from the group consisting of:

.

.

In addition, L ₃ and L ₄ may each independently represent a single bond, or C _6-20 arylene unsubstituted or substituted with one or more deuterium.

For example, L ₃ and L ₄ may each independently be a single bond, phenylene, biphenyldiyl, or naphthylene.

In this case, L ₃ and L ₄ may be the same as or different from each other.

In addition, in Formulas 2a to 2c,

each X is independently O, S, or N(C _6-20 aryl);

B ₁ to B ₃ may each independently be a naphthalene ring fused with a neighboring pentacyclic ring.

More specifically, each X is independently O, S, or N(phenyl);

B ₁ to B ₃ may each independently be an unsubstituted naphthalene ring fused with a neighboring pentacyclic ring.

In addition, R may be deuterium, or phenyl.

In this case, n means the number of R, and when n is 2 or more, two or more Rs are the same or different from each other. For example, n may be 0 or 1.

For example, the substituent represented by Formula 2a may be any one of the substituents represented by Formulas 2a-1 to 2a-5 below:

.

.

In addition, the substituent represented by Formula 2b may be any one of the substituents represented by the following Formulas 2b-1 to 2b-18:

.

.

In addition, the substituent represented by Formula 2c may be any one of the substituents represented by the following Formulas 2c-1 to 2c-9:

In Formulas 2c-1 to 2c-9,

X is O, S, or N(phenyl).

In one embodiment, Ar ₃ and Ar ₄ are each independently unsubstituted or substituted C _6-20 aryl with one or more substituents selected from the group consisting of deuterium, phenyl and naphthyl; a substituent represented by any one of Formulas 2a-1 to 2a-5; a substituent represented by any one of Formulas 2b-1 to 2b-18; Or it may be a substituent represented by any one of Formulas 2c-1 to 2c-9.

For example, Ar ₃ and Ar ₄ are each independently phenyl, phenylnaphthyl, biphenylyl, terphenylyl, naphthyl, naphthylphenyl, phenanthryl, triphenylenyl, and Formulas 2a-1 to 2a-5 It may be a substituent represented by any one of, or a substituent represented by any one of the following Chemical Formulas 2b-1 to 2b-4:

.

.

Here, the terphenylyl group is any one selected from the group represented by:

.

.

In this case, Ar ₃ and Ar ₄ may be the same as or different from each other.

In addition, R ₃ is hydrogen or deuterium, and c is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9 to mean the number of R ₃ . Specifically, all of R ₃ are hydrogen, or all are deuterium. For example, R ₃ is all hydrogen.

On the other hand, 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 preparation method as shown in Scheme 2 below:

[Scheme 2]

In Scheme 2, X' is halogen, preferably bromo, or chloro, and definitions of other substituents are the same as described above.

Specifically, the compound represented by Formula 1 may be prepared through an amine substitution reaction of starting materials A3 and A4. The amine substitution reaction is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction may be appropriately changed. The method for preparing the compound represented by Formula 2 may be more specific in Preparation Examples 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, the first compound and the agent in a weight ratio of 30:70 to 70:30, a weight ratio of 40:60 to 60:40, or a weight ratio of 50:50 in terms of properly maintaining the ratio of holes and electrons in the light emitting layer It is more preferable that 2 compounds are contained.

Meanwhile, the emission layer may further include a dopant material in addition to the two types of host materials. Examples of the dopant material 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 As a compound in which at least one arylvinyl group is substituted in the arylamine, 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 following compounds may be used as the dopant material, but the present invention is not limited thereto:

.

.

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 improve the efficiency of the organic light emitting device by controlling electron mobility and preventing excessive movement of holes to increase the hole-electron coupling probability 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 injection and transport layer

The electron injection and transport layer is a layer that simultaneously serves as an electron transport layer and an electron injection layer for injecting electrons from the electrode and transporting the received electrons to the emission layer, and is formed on the emission layer or the hole blocking layer. As the electron injection and 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 injection and transport material include Al complex of 8-hydroxyquinoline; complexes containing Alq ₃ ; organic radical compounds; hydroxyflavone-metal complexes; and triazine derivatives, but is not limited thereto. or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, and derivatives thereof, metal complex compounds , or may be used together with a nitrogen-containing 5-membered ring derivative, and the like, but is not limited thereto.

The electron injection and transport layer may be formed as a separate layer such as an electron injection layer and an electron transport layer. In this case, the electron transport layer is formed on the light emitting layer or the hole blocking layer, and the electron injection and transport material described above may be used as the electron transport material included in the electron transport layer. In addition, the electron injection layer is formed on the electron transport layer, and the electron injection material included in the electron injection layer is LiF, NaCl, CsF, Li ₂ O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, Thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone and their derivatives, metal complex compounds, nitrogen-containing 5-membered ring derivatives, etc. can be used.

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 FIG. 1 . 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 a cathode 4 are 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 a cathode material, an organic material layer, and an anode material on a substrate. 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 application 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.

In addition to this method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode material from a cathode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited thereto.

On the other hand, 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.

In addition, the compound according to the present invention may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.

The manufacturing of the organic light emitting device will be described in detail in Examples below. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

Synthesis Example 1-1: Preparation of compound 1-1

In a nitrogen atmosphere, Trz1 (10 g, 37.4 mmol) and sub1-1 (6.1 g, 39.2 mmol) were added to 200 mL of THF, stirred and refluxed. Thereafter, potassium carbonate (15.5 g, 112.1 mmol) was dissolved in 46 mL of water, and after sufficient stirring, Tetrakis(triphenylphosphine)palladium(0)(0.4 g, 0.4 mmol) was added. After 10 hours of reaction, the mixture 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 prepare 8.1 g of sub1-1-1. (Yield 63%, MS: [M+H] ⁺ = 344)

In a nitrogen atmosphere, sub1-1-1 (10 g, 29.1 mmol), compound A (5.1 g, 30.5 mmol), and sodium tert-butoxide (4.2 g, 43.6 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 8.4 g of Compound 1-1. (Yield 61%, MS: [M+H] ⁺ = 475)

Synthesis Example 1-2: Preparation of compound 1-2

In a nitrogen atmosphere, Trz2 (10 g, 29.1 mmol) and sub1-2 (4.8 g, 30.5 mmol) were added to 200 mL of THF, followed by stirring and reflux. After that, potassium carbonate (12.1 g, 87.3 mmol) was dissolved in 36 mL of water, and after sufficient stirring, Tetrakis(triphenylphosphine)palladium(0)(0.3 g, 0.3 mmol) was added. After 10 hours of reaction, the mixture 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 prepare 8.4 g of sub1-1-2. (yield 69%, MS: [M+H] ⁺ = 420)

In a nitrogen atmosphere, sub1-1-2 (10 g, 23.8 mmol), compound A (4.2 g, 25 mmol), and sodium tert-butoxide (3.4 g, 35.7 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 8.6 g of compound 1-2. (Yield 66%, MS: [M+H] ⁺ = 551)

Synthesis example 1-3: Preparation of compound 1-3

In a nitrogen atmosphere, Trz3 (10 g, 31.5 mmol) and sub1-1 (5.2 g, 33 mmol) were added to 200 mL of THF, stirred and refluxed. After that, potassium carbonate (13 g, 94.4 mmol) was dissolved in 39 mL of water and thoroughly stirred, and then Tetrakis(triphenylphosphine)palladium(0)(0.4 g, 0.3 mmol) was added. After the reaction for 9 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 prepare 8.7 g of sub1-1-3. (Yield 70%, MS: [M+H] ⁺ = 394)

In a nitrogen atmosphere, sub1-1-3 (10 g, 25.1 mmol), compound A (4.4 g, 26.4 mmol), and sodium tert-butoxide (3.6 g, 37.7 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 6.6 g of compound 1-3. (Yield 50%, MS: [M+H] ⁺ = 525)

Synthesis Example 1-4: Preparation of compound 1-4

In a nitrogen atmosphere, Trz4 (10 g, 27.9 mmol) and sub1-2 (4.6 g, 29.3 mmol) were added to 200 mL of THF, stirred and refluxed. After that, potassium carbonate (11.6 g, 83.8 mmol) was dissolved in 35 mL of water and thoroughly stirred, and then Tetrakis(triphenylphosphine)palladium(0)(0.3 g, 0.3 mmol) was added. After the reaction for 8 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 prepare 8.8 g of sub1-1-4. (Yield 73%, MS: [M+H] ⁺ = 434)

In a nitrogen atmosphere, sub1-1-4 (10 g, 23 mmol), compound A (4 g, 24.2 mmol), and sodium tert-butoxide (3.3 g, 34.6 mmol) were added to 100 mL of Xylene, and the mixture was stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 8.1 g of compound 1-4. (Yield 62%, MS: [M+H] ⁺ = 565)

Synthesis example 1-5: Preparation of compound 1-5

In a nitrogen atmosphere, Trz5 (10 g, 24.5 mmol) and sub1-1 (4 g, 25.7 mmol) were added to 200 mL of THF, stirred and refluxed. After that, potassium carbonate (10.2 g, 73.6 mmol) was dissolved in 30 mL of water and thoroughly stirred, and then Tetrakis(triphenylphosphine)palladium(0)(0.3 g, 0.2 mmol) was added. After 10 hours of reaction, the mixture 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 prepare 9.4 g of sub1-1-5. (yield 79%, MS: [M+H] ⁺ = 484)

In a nitrogen atmosphere, sub1-1-5 (10 g, 20.7 mmol), compound A (3.6 g, 21.7 mmol), and sodium tert-butoxide (3 g, 31 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 6.5 g of Compound 1-5. (Yield 51%, MS: [M+H] ⁺ = 615)

Synthesis example 1-6: Preparation of compound 1-6

In a nitrogen atmosphere, Trz6 (10 g, 25.4 mmol) and sub1-2 (4.2 g, 26.7 mmol) were added to 200 mL of THF, followed by stirring and reflux. Thereafter, potassium carbonate (10.5 g, 76.2 mmol) was dissolved in 32 mL of water, and after sufficient stirring, Tetrakis(triphenylphosphine)palladium(0)(0.3 g, 0.3 mmol) was added. After the reaction for 9 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 prepare 9.5 g of sub1-1-6. (Yield 80%, MS: [M+H] ⁺ = 470)

In a nitrogen atmosphere, sub1-1-6 (10 g, 21.3 mmol), compound B (5.4 g, 22.3 mmol), and sodium tert-butoxide (3.1 g, 31.9 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 8.9 g of Compound 1-6. (Yield 62%, MS: [M+H] ⁺ = 677)

Synthesis example 1-7: Preparation of compound 1-7

In a nitrogen atmosphere, Trz1 (10 g, 37.4 mmol) and sub1-3 (8.1 g, 39.2 mmol) were added to 200 mL of THF, stirred and refluxed. Thereafter, potassium carbonate (15.5 g, 112.1 mmol) was dissolved in 46 mL of water, and after sufficient stirring, Tetrakis(triphenylphosphine)palladium(0)(0.4 g, 0.4 mmol) was added. After the reaction for 9 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 prepare 9.5 g of sub1-1-7. (Yield 65%, MS: [M+H] ⁺ = 394)

In a nitrogen atmosphere, sub1-1-7 (10 g, 25.1 mmol), compound A (4.4 g, 26.4 mmol), and sodium tert-butoxide (3.6 g, 37.7 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 8.2 g of Compound 1-7. (Yield 62%, MS: [M+H] ⁺ = 525)

Synthesis example 1-8: Preparation of compound 1-8

In a nitrogen atmosphere, Trz7 (10 g, 25.4 mmol) and sub1-4 (5.5 g, 26.7 mmol) were added to 200 mL of THF, stirred and refluxed. Thereafter, potassium carbonate (10.5 g, 76.2 mmol) was dissolved in 32 mL of water, and after sufficient stirring, Tetrakis(triphenylphosphine)palladium(0)(0.3 g, 0.3 mmol) was added. After 10 hours of reaction, the mixture 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 prepare 10.3 g of sub1-1-8. (Yield 78%, MS: [M+H] ⁺ = 520)

In a nitrogen atmosphere, sub1-1-8 (10 g, 19.2 mmol), compound A (3.4 g, 20.2 mmol), and sodium tert-butoxide (2.8 g, 28.8 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 6.9 g of Compound 1-8. (Yield 55%, MS: [M+H] ⁺ = 651)

Synthesis Example 1-9: Preparation of compound 1-9

In a nitrogen atmosphere, Trz6 (10 g, 25.4 mmol) and sub1-5 (5.5 g, 26.7 mmol) were added to 200 mL of THF, stirred and refluxed. Thereafter, potassium carbonate (10.5 g, 76.2 mmol) was dissolved in 32 mL of water, and after sufficient stirring, Tetrakis(triphenylphosphine)palladium(0)(0.3 g, 0.3 mmol) was added. After the reaction for 12 hours, the mixture 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 prepare 10.5 g of sub1-1-9. (yield 80%, MS: [M+H] ⁺ = 520)

In a nitrogen atmosphere, sub1-1-9 (10 g, 19.2 mmol), compound A (3.4 g, 20.2 mmol), and sodium tert-butoxide (2.8 g, 28.8 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 7.5 g of Compound 1-9. (yield 60%, MS: [M+H] ⁺ = 651)

Synthesis Example 1-10: Preparation of compound 1-10

In a nitrogen atmosphere, Trz5 (10 g, 24.5 mmol) and sub1-3 (5.3 g, 25.7 mmol) were added to 200 mL of THF, stirred and refluxed. After that, potassium carbonate (10.2 g, 73.6 mmol) was dissolved in 30 mL of water and thoroughly stirred, and then Tetrakis(triphenylphosphine)palladium(0)(0.3 g, 0.2 mmol) 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 prepare 10.2 g of sub1-1-10. (Yield 78%, MS: [M+H] ⁺ = 534)

In a nitrogen atmosphere, sub1-1-10 (10 g, 18.7 mmol), compound A (3.3 g, 19.7 mmol), and sodium tert-butoxide (2.7 g, 28.1 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 7.2 g of Compound 1-10. (Yield 58%, MS: [M+H] ⁺ = 665)

Synthesis example 1-11: Preparation of compound 1-11

In a nitrogen atmosphere, Trz1 (10 g, 37.4 mmol) and sub1-6 (9.1 g, 39.2 mmol) were added to 200 mL of THF, followed by stirring and reflux. Thereafter, potassium carbonate (15.5 g, 112.1 mmol) was dissolved in 46 mL of water, and after sufficient stirring, Tetrakis(triphenylphosphine)palladium(0)(0.4 g, 0.4 mmol) was added. After the reaction for 12 hours, the mixture 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 prepare 11.7 g of sub1-1-11. (yield 75%, MS: [M+H] ⁺ = 420)

In a nitrogen atmosphere, sub1-1-11 (10 g, 23.8 mmol), compound A (4.2 g, 25 mmol), and sodium tert-butoxide (3.4 g, 35.7 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 7.6 g of Compound 1-11. (Yield 58%, MS: [M+H] ⁺ = 551)

Synthesis Example 1-12: Preparation of compound 1-12

In a nitrogen atmosphere, Trz3 (10 g, 31.5 mmol) and sub1-7 (7.7 g, 33 mmol) were added to 200 mL of THF, and the mixture was stirred and refluxed. After that, potassium carbonate (13 g, 94.4 mmol) was dissolved in 39 mL of water and thoroughly stirred, and then Tetrakis(triphenylphosphine)palladium(0)(0.4 g, 0.3 mmol) 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 prepare 10.6 g of sub1-1-12. (Yield 72%, MS: [M+H] ⁺ = 470)

In a nitrogen atmosphere, sub1-1-12 (10 g, 21.3 mmol), compound A (3.7 g, 22.3 mmol), and sodium tert-butoxide (3.1 g, 31.9 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 6.9 g of Compound 1-12. (Yield 54%, MS: [M+H] ⁺ = 601)

Synthesis Example 1-13: Preparation of compound 1-13

In a nitrogen atmosphere, Trz4 (10 g, 27.9 mmol) and sub1-8 (6.8 g, 29.3 mmol) were added to 200 mL of THF, followed by stirring and reflux. After that, potassium carbonate (11.6 g, 83.8 mmol) was dissolved in 35 mL of water and thoroughly stirred, and then Tetrakis(triphenylphosphine)palladium(0)(0.3 g, 0.3 mmol) was added. After the reaction for 12 hours, the mixture 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 prepare 8.5 g of sub1-1-13. (yield 60%, MS: [M+H] ⁺ = 510)

In a nitrogen atmosphere, sub1-1-13 (10 g, 20 mmol), compound A (3.5 g, 21 mmol), and sodium tert-butoxide (2.9 g, 29.9 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 7.4 g of Compound 1-13. (Yield 58%, MS: [M+H] ⁺ = 641)

Synthesis Example 1-14: Preparation of compound 1-14

In a nitrogen atmosphere, Trz6 (10 g, 25.4 mmol) and sub1-9 (6.2 g, 26.7 mmol) were added to 200 mL of THF, stirred and refluxed. Thereafter, potassium carbonate (10.5 g, 76.2 mmol) was dissolved in 32 mL of water, and after sufficient stirring, Tetrakis(triphenylphosphine)palladium(0)(0.3 g, 0.3 mmol) was added. After the reaction for 8 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 prepare 9.4 g of sub1-1-14. (Yield 68%, MS: [M+H] ⁺ = 546)

In a nitrogen atmosphere, sub1-1-14 (10 g, 18.3 mmol), compound A (3.2 g, 19.2 mmol), and sodium tert-butoxide (2.6 g, 27.5 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 6.7 g of Compound 1-14. (Yield 54%, MS: [M+H] ⁺ = 677)

Synthesis Example 1-15: Preparation of compound 1-15

In a nitrogen atmosphere, Trz7 (10 g, 25.4 mmol) and sub1-9 (6.2 g, 26.7 mmol) were added to 200 mL of THF, stirred and refluxed. Thereafter, potassium carbonate (10.5 g, 76.2 mmol) was dissolved in 32 mL of water, and after sufficient stirring, Tetrakis(triphenylphosphine)palladium(0)(0.3 g, 0.3 mmol) was added. After 10 hours of reaction, the mixture 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 prepare 9.8 g of sub1-1-15. (Yield 71%, MS: [M+H] ⁺ = 546)

In a nitrogen atmosphere, sub1-1-15 (10 g, 18.3 mmol), compound B (4.7 g, 19.2 mmol), and sodium tert-butoxide (2.6 g, 27.5 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 7.2 g of Compound 1-15. (Yield 52%, MS: [M+H] ⁺ = 753)

Synthesis Example 1-16: Preparation of compound 1-16

In a nitrogen atmosphere, Trz8 (10 g, 25.4 mmol) and sub1-1 (4.2 g, 26.7 mmol) were added to 200 mL of THF, stirred and refluxed. Thereafter, potassium carbonate (10.5 g, 76.2 mmol) was dissolved in 32 mL of water, and after sufficient stirring, Tetrakis(triphenylphosphine)palladium(0)(0.3 g, 0.3 mmol) was added. After the reaction for 12 hours, the mixture 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 prepare 8.9 g of sub1-1-16. (yield 75%, MS: [M+H] ⁺ = 470)

In a nitrogen atmosphere, sub1-1-16 (10 g, 21.3 mmol), compound C (4.9 g, 22.3 mmol), and sodium tert-butoxide (3.1 g, 31.9 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 9.3 g of Compound 1-16. (Yield 67%, MS: [M+H] ⁺ = 651)

Synthesis Example 1-17: Preparation of compound 1-17

In a nitrogen atmosphere, sub1-1-6 (10 g, 21.3 mmol), compound D (4.9 g, 22.3 mmol), and sodium tert-butoxide (3.1 g, 31.9 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 7.5 g of Compound 1-17. (Yield 54%, MS: [M+H] ⁺ = 651)

Synthesis Example 1-18: Preparation of compound 1-18

In a nitrogen atmosphere, Trz5 (10 g, 24.5 mmol) and sub1-2 (4 g, 25.7 mmol) were added to 200 mL of THF, stirred and refluxed. After that, potassium carbonate (10.2 g, 73.6 mmol) was dissolved in 30 mL of water and thoroughly stirred, and then Tetrakis(triphenylphosphine)palladium(0)(0.3 g, 0.2 mmol) was added. After 10 hours of reaction, the mixture 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 prepare 9.2 g of sub1-1-17. (Yield 78%, MS: [M+H] ⁺ = 484)

In a nitrogen atmosphere, sub1-1-17 (10 g, 20.7 mmol), compound E (4.7 g, 21.7 mmol), and sodium tert-butoxide (3 g, 31 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 7.5 g of Compound 1-18. (Yield 55%, MS: [M+H] ⁺ = 665)

Synthesis Example 1-19: Preparation of compound 1-19

In a nitrogen atmosphere, Trz7 (10 g, 25.4 mmol) and sub1-10 (6.2 g, 26.7 mmol) were placed in 200 mL of THF, stirred and refluxed. Thereafter, potassium carbonate (10.5 g, 76.2 mmol) was dissolved in 32 mL of water, and after sufficient stirring, Tetrakis(triphenylphosphine)palladium(0)(0.3 g, 0.3 mmol) 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 prepare 8.3 g of sub1-1-18. (Yield 60%, MS: [M+H] ⁺ = 546)

In a nitrogen atmosphere, sub1-1-18 (10 g, 18.3 mmol), compound C (4.2 g, 19.2 mmol), and sodium tert-butoxide (2.6 g, 27.5 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 7.7 g of Compound 1-19. (Yield 58%, MS: [M+H] ⁺ = 727)

Synthesis Example 1-20: Preparation of compound 1-20

In a nitrogen atmosphere, Trz5 (10 g, 24.5 mmol) and sub1-5 (5.3 g, 25.7 mmol) were added to 200 mL of THF, followed by stirring and reflux. After that, potassium carbonate (10.2 g, 73.6 mmol) was dissolved in 30 mL of water and thoroughly stirred, and then Tetrakis(triphenylphosphine)palladium(0)(0.3 g, 0.2 mmol) 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 prepare 8.6 g of sub1-1-19. (Yield 66%, MS: [M+H] ⁺ = 534)

In a nitrogen atmosphere, sub1-1-19 (10 g, 18.7 mmol), compound D (4.3 g, 19.7 mmol), and sodium tert-butoxide (2.7 g, 28.1 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 7.9 g of Compound 1-20. (yield 59%, MS: [M+H] ⁺ = 715)

Synthesis Example 1-21: Preparation of compound 1-21

In a nitrogen atmosphere, Trz8 (10 g, 25.4 mmol) and sub1-3 (5.5 g, 26.7 mmol) were added to 200 mL of THF, followed by stirring and reflux. Thereafter, potassium carbonate (10.5 g, 76.2 mmol) was dissolved in 32 mL of water, and after sufficient stirring, Tetrakis(triphenylphosphine)palladium(0)(0.3 g, 0.3 mmol) was added. After the reaction for 9 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 prepare 9.6 g of sub1-1-20. (Yield 73%, MS: [M+H] ⁺ = 520)

In a nitrogen atmosphere, sub1-1-20 (10 g, 19.2 mmol), compound E (4.4 g, 20.2 mmol), and sodium tert-butoxide (2.8 g, 28.8 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 8.1 g of compound 1-21. (Yield 60%, MS: [M+H] ⁺ = 701)

Synthesis Example 1-22: Preparation of compound 1-22

In a nitrogen atmosphere, Trz1 (10 g, 37.4 mmol) and sub1-11 (6.1 g, 39.2 mmol) were added to 200 mL of THF, stirred and refluxed. Thereafter, potassium carbonate (15.5 g, 112.1 mmol) was dissolved in 46 mL of water, and after sufficient stirring, Tetrakis(triphenylphosphine)palladium(0)(0.4 g, 0.4 mmol) was added. After the reaction for 8 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 prepare 7.8 g of sub1-1-21. (Yield 61%, MS: [M+H] ⁺ = 344)

In a nitrogen atmosphere, sub1-1-21 (10 g, 29.1 mmol), compound F (8.2 g, 30.5 mmol), and sodium tert-butoxide (4.2 g, 43.6 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 11.4 g of compound 1-22. (Yield 68%, MS: [M+H] ⁺ = 575)

Synthesis Example 1-23: Preparation of compound 1-23

In a nitrogen atmosphere, sub1-1-16 (10 g, 21.3 mmol), compound G (6 g, 22.3 mmol), and sodium tert-butoxide (3.1 g, 31.9 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 8 g of compound 1-23. (Yield 54%, MS: [M+H] ⁺ = 701)

Synthesis Example 1-24: Preparation of compound 1-24

In a nitrogen atmosphere, Trz3 (10 g, 31.5 mmol) and sub1-3 (6.8 g, 33 mmol) were added to 200 mL of THF, followed by stirring and reflux. After that, potassium carbonate (13 g, 94.4 mmol) was dissolved in 39 mL of water and thoroughly stirred, and then Tetrakis(triphenylphosphine)palladium(0)(0.4 g, 0.3 mmol) was added. After the reaction for 9 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 prepare 10.6 g of sub1-1-22. (yield 76%, MS: [M+H] ⁺ = 444)

In a nitrogen atmosphere, sub1-1-22 (10 g, 22.5 mmol), compound H (6.3 g, 23.7 mmol), and sodium tert-butoxide (3.2 g, 33.8 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 10.2 g of compound 1-24. (Yield 67%, MS: [M+H] ⁺ = 675)

Synthesis Example 1-25: Preparation of compound 1-25

In a nitrogen atmosphere, Trz2 (10 g, 29.1 mmol) and sub1-12 (7.1 g, 30.5 mmol) were added to 200 mL of THF, followed by stirring and reflux. After that, potassium carbonate (12.1 g, 87.3 mmol) was dissolved in 36 mL of water, and after sufficient stirring, Tetrakis(triphenylphosphine)palladium(0)(0.3 g, 0.3 mmol) 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 prepare 11.4 g of sub1-1-23. (yield 79%, MS: [M+H] ⁺ = 496)

In a nitrogen atmosphere, sub1-1-23 (10 g, 20.2 mmol), compound G (5.7 g, 21.2 mmol), and sodium tert-butoxide (2.9 g, 30.2 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 8.5 g of Compound 1-25. (Yield 58%, MS: [M+H] ⁺ = 727)

Synthesis Example 1-26: Preparation of compound 1-26

In a nitrogen atmosphere, Trz5 (10 g, 24.5 mmol) and sub1-8 (6 g, 25.7 mmol) were added to 200 mL of THF, followed by stirring and reflux. After that, potassium carbonate (10.2 g, 73.6 mmol) was dissolved in 30 mL of water and thoroughly stirred, and then Tetrakis(triphenylphosphine)palladium(0)(0.3 g, 0.2 mmol) was added. After the reaction for 9 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 prepare 11 g of sub1-1-24. (yield 80%, MS: [M+H] ⁺ = 560)

In a nitrogen atmosphere, sub1-1-24 (10 g, 17.9 mmol), compound F (5 g, 18.7 mmol), and sodium tert-butoxide (2.6 g, 26.8 mmol) were added to 100 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 8.3 g of compound 1-26. (yield 59%, MS: [M+H] ⁺ = 791)

Synthesis Example 2-1: Preparation of compound 2-1

In a nitrogen atmosphere, sub2-1 (10 g, 38.9 mmol) and sub2-2 (6.7 g, 42.8 mmol) were added to 200 mL of THF, stirred and refluxed. After that, potassium carbonate (16.1 g, 116.7 mmol) was dissolved in 48 mL of water, and after sufficient stirring, Tetrakis(triphenylphosphine)palladium(0)(0.4 g, 0.4 mmol) was added. After the reaction for 12 hours, the mixture 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 prepare 8.9 g of sub2-1-1. (yield 79%, MS: [M+H] ⁺ = 289)

In a nitrogen atmosphere, sub2-1-1 (10 g, 34.6 mmol), amine1 (14.5 g, 36.4 mmol), and sodium tert-butoxide (8.3 g, 86.6 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 13.9 g of Compound 2-1. (Yield 62%, MS: [M+H] ⁺ = 650)

Synthesis Example 2-2: Preparation of compound 2-2

In a nitrogen atmosphere, sub2-1-1 (10 g, 34.6 mmol), amine2 (14.5 g, 36.4 mmol), and sodium tert-butoxide (8.3 g, 86.6 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 13.9 g of Compound 2-2. (Yield 62%, MS: [M+H] ⁺ = 650)

Synthesis Example 2-3: Preparation of compound 2-3

In a nitrogen atmosphere, sub2-1-1 (10 g, 34.6 mmol), amine3 (11.7 g, 36.4 mmol), and sodium tert-butoxide (8.3 g, 86.6 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 mmol) was added. After 5 hours, when the reaction was completed, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 13.1 g of compound 2-3. (Yield 66%, MS: [M+H] ⁺ = 574)

Synthesis Example 2-4: Preparation of compound 2-4

In a nitrogen atmosphere, sub2-1-1 (10 g, 34.6 mmol), amine4 (14.5 g, 36.4 mmol), and sodium tert-butoxide (8.3 g, 86.6 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound 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 concentrated compound was purified by silica gel column chromatography to obtain 13.5 g of Compound 2-4. (yield 60%, MS: [M+H] ⁺ = 650)

Synthesis Example 2-5: Preparation of compound 2-5

In a nitrogen atmosphere, sub2-1-1 (10 g, 34.6 mmol), amine5 (16.3 g, 36.4 mmol), and sodium tert-butoxide (8.3 g, 86.6 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 13.6 g of Compound 2-5. (Yield 56%, MS: [M+H] ⁺ = 700)

Synthesis Example 2-6: Preparation of compound 2-6

In a nitrogen atmosphere, sub2-1-1 (10 g, 34.6 mmol), amine6 (14.5 g, 36.4 mmol), and sodium tert-butoxide (8.3 g, 86.6 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 11.9 g of Compound 2-6. (Yield 53%, MS: [M+H] ⁺ = 650)

Synthesis Example 2-7: Preparation of compound 2-7

In a nitrogen atmosphere, sub2-1-1 (10 g, 34.6 mmol), amine7 (14.5 g, 36.4 mmol), and sodium tert-butoxide (8.3 g, 86.6 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 12.8 g of Compound 2-7. (Yield 57%, MS: [M+H] ⁺ = 650)

Synthesis Example 2-8: Preparation of compound 2-8

In a nitrogen atmosphere, sub2-1-1 (10 g, 34.6 mmol), amine8 (14.4 g, 36.4 mmol), and sodium tert-butoxide (8.3 g, 86.6 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 14.8 g of Compound 2-8. (Yield 66%, MS: [M+H] ⁺ = 648)

Synthesis Example 2-9: Preparation of compound 2-9

In a nitrogen atmosphere, sub2-1-1 (10 g, 34.6 mmol), amine9 (12.6 g, 36.4 mmol), and sodium tert-butoxide (8.3 g, 86.6 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 13.4 g of Compound 2-9. (Yield 65%, MS: [M+H] ⁺ = 598)

Synthesis Example 2-10: Preparation of compound 2-10

In a nitrogen atmosphere, sub2-1 (10 g, 38.9 mmol) and sub2-3 (6.7 g, 42.8 mmol) were added to 200 mL of THF, stirred and refluxed. After that, potassium carbonate (16.1 g, 116.7 mmol) was dissolved in 48 mL of water, and after sufficient stirring, Tetrakis(triphenylphosphine)palladium(0)(0.4 g, 0.4 mmol) was added. After the reaction for 12 hours, the mixture 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 prepare 9 g of sub2-1-2. (yield 80%, MS: [M+H] ⁺ = 289)

In a nitrogen atmosphere, sub2-1-2 (10 g, 34.6 mmol), amine10 (14.4 g, 36.4 mmol), and sodium tert-butoxide (8.3 g, 86.6 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 13.7 g of Compound 2-10. (Yield 61%, MS: [M+H] ⁺ = 648)

Synthesis Example 2-11: Preparation of compound 2-11

In a nitrogen atmosphere, amine11 (10 g, 59.1 mmol), sub2-1-1 (35.8 g, 124.1 mmol), and sodium tert-butoxide (19.9 g, 206.8 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.9 g, 1.8 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 27.1 g of Compound 2-11. (Yield 68%, MS: [M+H] ⁺ = 674)

Synthesis Example 2-12: Preparation of compound 2-12

In a nitrogen atmosphere, amine12 (10 g, 40.8 mmol), sub2-1-1 (24.7 g, 85.6 mmol), and sodium tert-butoxide (13.7 g, 142.7 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 17.7 g of Compound 2-12. (Yield 58%, MS: [M+H] ⁺ = 750)

Synthesis Example 2-13: Preparation of compound 2-13

In a nitrogen atmosphere, amine13 (10 g, 51.7 mmol), sub2-1-2 (31.4 g, 108.7 mmol), and sodium tert-butoxide (17.4 g, 181.1 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0)(0.8 g, 1.6 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 23.5 g of compound 2-13. (Yield 65%, MS: [M+H] ⁺ = 698)

Synthesis Example 2-14: Preparation of compound 2-14

In a nitrogen atmosphere, sub2-1 (10 g, 38.9 mmol) and sub2-4 (9.9 g, 42.8 mmol) were added to 200 mL of THF, stirred and refluxed. After that, potassium carbonate (16.1 g, 116.7 mmol) was dissolved in 48 mL of water, and after sufficient stirring, Tetrakis(triphenylphosphine)palladium(0)(0.4 g, 0.4 mmol) was added. After the reaction for 8 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 prepare 10.9 g of sub2-1-3. (yield 77%, MS: [M+H] ⁺ = 365)

In a nitrogen atmosphere, amine14 (10 g, 45.6 mmol), sub2-1-3 (34.9 g, 95.8 mmol), and sodium tert-butoxide (15.3 g, 159.6 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0)(0.7 g, 1.4 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 22 g of compound 2-14. (Yield 55%, MS: [M+H] ⁺ = 876)

Synthesis Example 2-15: Preparation of compound 2-15

In a nitrogen atmosphere, sub2-1-1 (10 g, 34.6 mmol), amine15 (12.2 g, 36.4 mmol), and sodium tert-butoxide (8.3 g, 86.6 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 11.8 g of Compound 2-15. (Yield 58%, MS: [M+H] ⁺ = 588)

Synthesis Example 2-16: Preparation of compound 2-16

In a nitrogen atmosphere, sub2-1-1 (10 g, 34.6 mmol), amine16 (15 g, 36.4 mmol), and sodium tert-butoxide (8.3 g, 86.6 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 14.7 g of Compound 2-16. (Yield 64%, MS: [M+H] ⁺ = 664)

Synthesis Example 2-17: Preparation of compound 2-17

In a nitrogen atmosphere, sub2-1-1 (10 g, 34.6 mmol), amine17 (14 g, 36.4 mmol), and sodium tert-butoxide (8.3 g, 86.6 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 11.7 g of Compound 2-17. (Yield 53%, MS: [M+H] ⁺ = 638)

Synthesis Example 2-18: Preparation of compound 2-18

In a nitrogen atmosphere, sub2-1-1 (10 g, 34.6 mmol), amine18 (12.8 g, 36.4 mmol), and sodium tert-butoxide (8.3 g, 86.6 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 14.4 g of Compound 2-18. (yield 69%, MS: [M+H] ⁺ = 604)

Synthesis Example 2-19: Preparation of compound 2-19

In a nitrogen atmosphere, sub2-1-1 (10 g, 34.6 mmol), amine19 (14.6 g, 36.4 mmol), and sodium tert-butoxide (8.3 g, 86.6 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 13.3 g of Compound 2-19. (yield 59%, MS: [M+H] ⁺ = 654)

Synthesis Example 2-20: Preparation of compound 2-20

In a nitrogen atmosphere, sub2-1-1 (10 g, 34.6 mmol), amine20 (12.8 g, 36.4 mmol), and sodium tert-butoxide (8.3 g, 86.6 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 12.1 g of Compound 2-20. (Yield 58%, MS: [M+H] ⁺ = 604)

Synthesis Example 2-21: Preparation of compound 2-21

In a nitrogen atmosphere, sub2-1-1 (10 g, 34.6 mmol), amine21 (15.4 g, 36.4 mmol), and sodium tert-butoxide (8.3 g, 86.6 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 14.8 g of compound 2-21. (Yield 63%, MS: [M+H] ⁺ = 677)

Synthesis Example 2-22: Preparation of compound 2-22

In a nitrogen atmosphere, sub2-1-1 (10 g, 34.6 mmol), amine22 (15.4 g, 36.4 mmol), and sodium tert-butoxide (8.3 g, 86.6 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 16.2 g of compound 2-22. (yield 69%, MS: [M+H] ⁺ = 677)

Synthesis Example 2-23: Preparation of compound 2-23

In a nitrogen atmosphere, sub2-1-2 (10 g, 34.6 mmol), amine23 (15.8 g, 36.4 mmol), and sodium tert-butoxide (8.3 g, 86.6 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 13.6 g of compound 2-23. (Yield 57%, MS: [M+H] ⁺ = 688)

Synthesis Example 2-24: Preparation of compound 2-24

In a nitrogen atmosphere, sub2-1-2 (10 g, 34.6 mmol), amine24 (13.1 g, 36.4 mmol), and sodium tert-butoxide (8.3 g, 86.6 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 14.2 g of compound 2-24. (Yield 67%, MS: [M+H] ⁺ = 612)

Synthesis Example 2-25: Preparation of compound 2-25

In a nitrogen atmosphere, amine25 (10 g, 38.6 mmol), sub2-1-1 (23.4 g, 81 mmol), and sodium tert-butoxide (13 g, 135 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 15.6 g of Compound 2-15. (Yield 53%, MS: [M+H] ⁺ = 764)

Synthesis Example 2-26: Preparation of compound 2-26

In a nitrogen atmosphere, sub2-1-1 (10 g, 34.6 mmol), amine26 (14 g, 36.4 mmol), and sodium tert-butoxide (8.3 g, 86.6 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 11.9 g of compound 2-26. (Yield 54%, MS: [M+H] ⁺ = 638)

Synthesis Example 2-27: Preparation of compound 2-27

In a nitrogen atmosphere, sub2-1-1 (10 g, 34.6 mmol), amine27 (17.3 g, 36.4 mmol), and sodium tert-butoxide (8.3 g, 86.6 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 14.6 g of compound 2-27. (Yield 58%, MS: [M+H] ⁺ = 727)

Synthesis Example 2-28: Preparation of compound 2-28

In a nitrogen atmosphere, sub2-1-1 (10 g, 34.6 mmol), amine28 (14 g, 36.4 mmol), and sodium tert-butoxide (8.3 g, 86.6 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 11.9 g of compound 2-28. (Yield 54%, MS: [M+H] ⁺ = 638)

Synthesis Example 2-29: Preparation of compound 2-29

In a nitrogen atmosphere, sub2-1 (10 g, 38.9 mmol) and sub2-5 (8.8 g, 42.8 mmol) were added to 200 mL of THF, stirred and refluxed. After that, potassium carbonate (16.1 g, 116.7 mmol) was dissolved in 48 mL of water, and after sufficient stirring, Tetrakis(triphenylphosphine)palladium(0)(0.4 g, 0.4 mmol) was added. After the reaction for 9 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 prepare 8.8 g of sub2-1-4. (Yield 67%, MS: [M+H] ⁺ = 339)

In a nitrogen atmosphere, sub2-1-4 (10 g, 29.5 mmol), amine26 (11.9 g, 31 mmol), and sodium tert-butoxide (7.1 g, 73.8 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 12.8 g of compound 2-29. (Yield 63%, MS: [M+H] ⁺ = 688)

Synthesis Example 2-30: Preparation of compound 2-30

In a nitrogen atmosphere, sub2-1-4 (10 g, 29.5 mmol), amine29 (14.2 g, 31 mmol), and sodium tert-butoxide (7.1 g, 73.8 mmol) were added to 300 mL of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. Upon completion of the reaction after 5 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved again 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 concentrated compound was purified by silica gel column chromatography to obtain 12.4 g of Compound 2-30. (Yield 55%, MS: [M+H] ⁺ = 762)

Comparative Example 1: Preparation of an organic light emitting device

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. At this time, 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 the ITO for 30 minutes, ultrasonic washing 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, and after drying, it was 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.

The following HI-1 compound was formed as a hole injection layer on the thus prepared ITO transparent electrode 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 EB-1 deposition layer, the host material, compound 1-1 prepared in Synthesis Example 1-1, and the dopant material, the following Dp-7 compound were vacuum-deposited in a weight ratio of 98:2 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 x 10 ^- By maintaining ⁷ to 5 x 10 ^-6 torr, an organic light emitting diode was manufactured.

Comparative Examples 2 to 15

An organic light emitting device was manufactured in the same manner as in Comparative Example 1, except that the compound shown in Table 1 was used instead of Compound 1-1 in the organic light emitting device of Comparative Example 1.

Examples 1-104

In the organic light emitting device of Comparative Example 1, instead of Compound 1-1, the compound represented by Formula 1 as the first host and the compound represented by Formula 2 as the second host were mixed in a weight ratio of 1:1. An organic light emitting diode was manufactured in the same manner as in Comparative Example 1, except that it was used by vapor deposition.

Here, the structures of the compounds used in Examples and Comparative Examples 2 to 15 are summarized as follows.

Comparative Examples 16 to 47

In the organic light-emitting device of Comparative Example 1, in the same manner as in Comparative Example 1, except that the compound of the first host and the second host described in Table 5 below was used by co-deposition in a weight ratio of 1:1 instead of Compound 1 An organic light emitting device was manufactured. Here, the structures of the comparative compounds RH1 to RH8 are as follows.

Experimental Example 1: Evaluation of device characteristics

When a current was applied to the organic light emitting devices manufactured in Examples 1 to 104 and Comparative Examples 1 to 47, voltage, efficiency, and lifetime were measured (based on 10 mA/cm ² ), and the results are shown in Table 1 to 5. Here, the lifetime T95 means the time it takes for the luminance to decrease from the initial luminance (5,000 nits) to 95%.

division matter Efficiency (cd/A) Life T95 (hr) luminous color Comparative Example 1 compound 1-1 18.2 183 Red Comparative Example 2 compound 1-2 19.4 162 Red Comparative Example 3 compound 1-3 19.2 161 Red Comparative Example 4 compound 1-5 19.5 198 Red Comparative Example 5 compound 1-7 18.7 169 Red Comparative Example 6 compounds 1-9 19.8 194 Red Comparative Example 7 compounds 1-10 18.9 182 Red Comparative Example 8 compound 1-11 18.7 164 Red Comparative Example 9 compound 1-13 18.8 166 Red Comparative Example 10 compound 1-15 17.2 161 Red Comparative Example 11 compound 1-17 18.4 179 Red Comparative Example 12 compound 1-19 17.5 152 Red Comparative Example 13 compound 1-20 18.7 164 Red Comparative Example 14 compound 1-21 18.1 162 Red Comparative Example 15 compounds 1-25 18.6 153 Red

division 1st host 2nd host drive voltage
(V) Efficiency (cd/A) Life T95 (hr) luminous color Example 1 compound 1-1 compound 2-1 3.51 23.2 262 Red Example 2 compound 1-1 compound 2-6 3.44 22.1 245 Red Example 3 compound 1-1 compound 2-9 3.42 24.0 284 Red Example 4 compound 1-1 compound 2-16 3.46 23.0 266 Red Example 5 compound 1-2 compound 2-3 3.67 22.9 221 Red Example 6 compound 1-2 compound 2-8 3.72 21.7 238 Red Example 7 compound 1-2 compound 2-14 3.71 21.2 221 Red Example 8 compound 1-2 compound 2-28 3.79 22.3 249 Red Example 8 compound 1-3 compound 2-2 3.77 22.4 220 Red Example 10 compound 1-3 compound 2-4 3.76 21.5 210 Red Example 11 compound 1-3 compound 2-13 3.70 21.7 249 Red Example 12 compound 1-3 compound 2-22 3.72 21.2 222 Red Example 13 compound 1-4 compound 2-1 3.62 20.2 257 Red Example 14 compound 1-4 compound 2-9 3.75 21.3 226 Red Example 15 compound 1-4 compound 2-14 3.74 22.4 220 Red Example 16 compound 1-4 compound 2-22 3.76 20.6 242 Red Example 17 compound 1-5 compound 2-5 3.57 24.5 259 Red Example 18 compound 1-5 compound 2-12 3.46 23.1 270 Red Example 19 compound 1-5 compound 2-21 3.46 25.3 292 Red Example 20 compound 1-5 compound 2-24 3.45 25.2 256 Red Example 21 compound 1-6 compound 2-5 3.73 21.8 235 Red Example 22 compound 1-6 compound 2-11 3.77 21.5 245 Red Example 23 compound 1-6 compound 2-17 3.82 23.4 234 Red Example 24 compound 1-6 compound 2-25 3.81 22.3 247 Red Example 25 compound 1-7 compound 2-3 3.87 21.5 229 Red Example 26 compound 1-7 compound 2-11 3.78 21.3 221 Red Example 27 compound 1-7 compound 2-18 3.72 20.2 249 Red Example 28 compound 1-7 compound 2-26 3.76 22.9 236 Red Example 29 compounds 1-8 compound 2-4 3.79 25.8 268 Red Example 30 compounds 1-8 compound 2-19 3.82 24.3 281 Red Example 31 compounds 1-8 compound 2-27 3.79 23.1 262 Red Example 32 compounds 1-8 compound 2-30 3.82 24.2 271 Red Example 33 compounds 1-9 compound 2-6 3.80 22.3 235 Red Example 34 compounds 1-9 compound 2-12 3.81 21.2 245 Red Example 35 compounds 1-9 compound 2-16 3.78 21.8 226 Red Example 36 compounds 1-9 compound 2-29 3.72 20.4 237 Red Example 37 compounds 1-10 compound 2-9 3.65 22.6 248 Red Example 38 compounds 1-10 compound 2-15 3.76 20.1 232 Red Example 39 compounds 1-10 compound 2-22 3.63 20.3 244 Red Example 40 compounds 1-10 compound 2-26 3.61 21.2 235 Red

division 1st host 2nd host drive voltage
(V) Efficiency (cd/A Life T95 (hr) luminous color Example 41 compound 1-11 compound 2-8 3.61 20.1 241 Red Example 42 compound 1-11 compound 2-17 3.52 20.9 250 Red Example 43 compound 1-11 compound 2-18 3.56 20.2 262 Red Example 44 compound 1-11 compound 2-25 3.54 20.8 241 Red Example 45 compound 1-12 compound 2-7 3.62 21.7 260 Red Example 46 compound 1-12 compound 2-13 3.68 21.4 266 Red Example 47 compound 1-12 compound 2-24 3.61 21.7 244 Red Example 48 compound 1-12 compound 2-30 3.59 21.5 266 Red Example 49 compound 1-13 compound 2-11 3.62 23.2 236 Red Example 50 compound 1-13 compound 2-14 3.69 22.2 246 Red Example 51 compound 1-13 compound 2-19 3.61 21.4 235 Red Example 52 compound 1-13 compound 2-20 3.71 20.5 252 Red Example 53 compound 1-14 compound 2-10 3.62 21.9 264 Red Example 54 compound 1-14 compound 2-20 3.83 21.5 255 Red Example 55 compound 1-14 compound 2-23 3.94 22.4 241 Red Example 56 compound 1-14 compound 2-28 3.72 22.2 231 Red Example 57 compound 1-15 compound 2-5 3.56 21.7 262 Red Example 58 compound 1-15 compound 2-19 3.62 22.1 273 Red Example 59 compound 1-15 compound 2-21 3.64 21.3 257 Red Example 60 compound 1-15 compound 2-29 3.52 22.2 286 Red Example 61 compound 1-16 compound 2-2 3.78 21.5 239 Red Example 62 compound 1-16 compound 2-12 3.74 20.1 244 Red Example 63 compound 1-16 compound 2-18 3.63 20.1 246 Red Example 64 compound 1-16 compound 2-29 3.65 20.2 234 Red Example 65 compound 1-17 compound 2-1 3.56 21.3 252 Red Example 66 compound 1-17 compound 2-2 3.44 23.3 255 Red Example 67 compound 1-17 compound 2-6 3.43 21.2 225 Red Example 68 compound 1-17 compound 2-17 3.51 22.1 237 Red Example 69 compound 1-18 compound 2-6 3.62 23.2 240 Red Example 70 compound 1-18 compound 2-15 3.78 21.2 262 Red Example 71 compound 1-18 compound 2-21 3.65 22.3 265 Red Example 72 compound 1-18 compound 2-29 3.60 21.5 241 Red Example 73 compound 1-19 compound 2-5 3.42 22.1 232 Red Example 74 compound 1-19 compound 2-13 3.43 21.7 241 Red Example 75 compound 1-19 compound 2-19 3.44 21.2 234 Red Example 76 compound 1-19 compound 2-22 3.55 21.6 257 Red Example 77 compound 1-20 compound 2-8 3.62 23.5 268 Red Example 78 compound 1-20 compound 2-16 3.42 23.5 275 Red Example 79 compound 1-20 compound 2-20 3.51 24.3 234 Red Example 80 compound 1-20 compound 2-23 3.54 22.2 243 Red

division 1st host 2nd host drive voltage
(V) Efficiency (cd/A) Life T95 (hr) luminous color Example 81 compound 1-21 compound 2-9 3.62 21.4 265 Red Example 82 compound 1-21 compound 2-11 3.64 23.8 246 Red Example 83 compound 1-21 compound 2-14 3.62 23.7 255 Red Example 84 compound 1-21 compound 2-25 3.64 22.6 264 Red Example 85 compound 1-22 compound 2-4 3.56 21.2 273 Red Example 86 compound 1-22 compound 2-10 3.61 21.8 284 Red Example 87 compound 1-22 compound 2-12 3.77 23.3 287 Red Example 88 compound 1-22 compound 2-30 3.62 22.2 276 Red Example 89 compound 1-23 compound 2-4 3.54 23.4 268 Red Example 90 compound 1-23 compound 2-14 3.62 24.7 265 Red Example 91 compound 1-23 compound 2-16 3.68 21.4 272 Red Example 92 compound 1-23 compound 2-24 3.66 21.5 266 Red Example 93 compound 1-24 compound 2-4 3.65 23.2 261 Red Example 94 compound 1-24 compound 2-9 3.52 22.8 258 Red Example 95 compound 1-24 compound 2-15 3.43 23.5 259 Red Example 96 compound 1-24 compound 2-23 3.44 22.3 242 Red Example 97 compounds 1-25 compound 2-2 3.51 24.2 251 Red Example 98 compounds 1-25 compound 2-8 3.44 23.4 245 Red Example 99 compounds 1-25 compound 2-13 3.55 24.7 245 Red Example 100 compounds 1-25 compound 2-24 3.56 23.4 216 Red Example 101 compound 1-26 compound 2-10 3.62 22.3 276 Red Example 102 compound 1-26 compound 2-18 3.61 22.5 264 Red Example 103 compound 1-26 compound 2-22 3.52 23.2 268 Red Example 104 compound 1-26 compound 2-28 3.58 22.1 248 Red

division 1st host 2nd host Driving voltage (V) Efficiency (cd/) Life T95 (hr) luminous color Comparative Example 16 compound 1-2 RH1 3.95 18.2 181 Red Comparative Example 17 compound 1-4 RH1 3.92 18.6 192 Red Comparative Example 18 compound 1-12 RH1 4.04 19.1 194 Red Comparative Example 19 compound 1-19 RH1 3.95 19.5 181 Red Comparative Example 20 compound 1-1 RH2 4.11 18.4 177 Red Comparative Example 21 compound 1-3 RH2 4.19 19.2 178 Red Comparative Example 22 compound 1-15 RH2 4.02 19.1 169 Red Comparative Example 23 compound 1-21 RH2 4.00 18.8 192 Red Comparative Example 24 compound 1-3 RH3 3.93 19.2 204 Red Comparative Example 25 compound 1-4 RH3 4.14 19.5 202 Red Comparative Example 26 compound 1-15 RH3 4.01 19.2 197 Red Comparative Example 27 compound 1-21 RH3 3.92 18.6 208 Red Comparative Example 28 compound 1-6 RH4 3.92 18.7 161 Red Comparative Example 29 compounds 1-8 RH4 3.95 17.7 179 Red Comparative Example 30 compound 1-11 RH4 3.92 17.9 172 Red Comparative Example 31 compound 1-21 RH4 3.94 16.2 167 Red Comparative Example 32 RH5 compound 2-1 4.01 17.5 186 Red Comparative Example 33 RH5 compound 2-7 4.09 17.3 209 Red Comparative Example 34 RH5 compound 2-12 3.92 18.5 198 Red Comparative Example 35 RH5 compound 2-28 3.87 18.3 200 Red Comparative Example 36 RH6 compound 2-4 3.97 17.5 181 Red Comparative Example 37 RH6 compound 2-10 3.94 18.7 172 Red Comparative Example 38 RH6 compound 2-17 3.93 17.1 193 Red Comparative Example 39 RH6 compound 2-24 4.06 16.7 184 Red Comparative Example 40 RH7 compound 2-2 4.11 17.4 205 Red Comparative Example 41 RH7 compound 2-7 4.17 16.6 191 Red Comparative Example 42 RH7 compound 2-16 4.11 18.2 192 Red Comparative Example 43 RH7 compound 2-29 4.08 17.4 206 Red Comparative Example 44 RH8 compound 2-6 4.29 18.7 198 Red Comparative Example 45 RH8 compound 2-14 4.16 19.5 182 Red Comparative Example 46 RH8 compound 2-23 4.25 18.8 185 Red Comparative Example 47 RH8 compound 2-25 4.23 18.2 174 Red

As shown in Tables 1 to 5, the organic light emitting device of an embodiment in which the first compound represented by Formula 1 and the second compound represented by Formula 2 were simultaneously used as the host material of the light emitting layer were represented by Formulas 1 and 2 It exhibited superior driving voltage, luminous efficiency and lifespan characteristics compared to the organic light emitting device of Comparative Example employing only one of the indicated compounds or not using both.

In particular, the device according to the embodiment includes the devices of Comparative Examples 32 to 47 employing the comparative compounds RH5 to RH8 as a first host and the compound represented by Formula 2 as a second host, and the compound represented by Formula 1, All of the driving voltage, efficiency, and lifespan characteristics were improved compared to all of the devices of Comparative Examples 16 to 31 in which the first host and the comparative compounds RH1 to RH4 were used as the second host. Through this, it is confirmed that when the combination of the first compound represented by Formula 1 and the second compound represented by Formula 2 is used as a cohost, energy transfer from the red light emitting layer to the red dopant is effectively achieved. This can be determined because the first compound has high stability to electrons and holes, and as the amount of holes increases as the second compound is used at the same time, a more stable balance of electrons and holes in the red light emitting layer is maintained. is judged as

Therefore, it was confirmed that when the first compound and the second compound were simultaneously employed as the host material of the organic light emitting device, the driving voltage, luminous efficiency, and lifespan characteristics of the organic light emitting device could be improved. In general, considering that the luminous efficiency and lifespan characteristics of the organic light emitting device have a trade-off relationship with each other, the organic light emitting device employing the combination of the compounds of the present invention has significantly improved device characteristics compared to the comparative example device. can be seen to indicate

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 (15)

anode;
a negative electrode provided to face the positive electrode; and
a light emitting layer provided 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,
A ₁ and A ₂ are each independently a benzene or naphthalene ring fused to a neighboring pentacyclic ring,
L is a substituted or unsubstituted C _6-60 arylene,
L ₁ and L ₂ 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 _2-20 heteroaryl containing one or more heteroatoms among substituted or unsubstituted N, O and S;
R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; 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;
When A ₁ and A ₂ are each a benzene ring, a and b are each independently an integer of 0 to 4,
When A ₁ and A ₂ are each a naphthalene ring, a and b are each independently an integer of 0 to 6,
[Formula 2]

In Formula 2,
L' is a substituted or unsubstituted C _6-60 arylene,
L ₃ and L ₄ are each independently a single bond; Or a substituted or unsubstituted C _6-60 arylene,
Ar ₃ and Ar ₄ are each independently substituted or unsubstituted C _6-60 aryl; a substituent represented by the following formula (2a); a substituent represented by the following formula 2b; or a substituent represented by the following formula 2c, provided that Ar ₃ and Ar ₄ are not fluorenyl,

In Formulas 2a to 2c,
each X is independently O, S, or N(Ar);
where Ar is hydrogen, deuterium, or substituted or unsubstituted C _6-20 aryl,
B ₁ to B ₃ are each independently a substituted or unsubstituted naphthalene ring fused to a neighboring pentacyclic ring,
R is hydrogen, deuterium, or substituted or unsubstituted C _6-20 aryl;
n is an integer from 0 to 4,
R ₃ is hydrogen or deuterium,
c is an integer from 0 to 9;
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 the above 1-1 to 1-10,
a' and b' are each independently an integer of 0 to 4,
a" and b" are each independently an integer from 0 to 6,
L, L ₁ , L ₂ , Ar ₁ , Ar ₂ , R ₁ and R ₂ are as defined in claim 1 .
According to claim 1,
L is phenylene, biphenyldiyl, or naphthylene;
organic light emitting device.
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,
Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, naphthyl, or dibenzofuranyl;
organic light emitting device.
According to claim 1,
R ₁ and R ₂ are each independently phenyl, naphthyl, or dibenzofuranyl;
organic light emitting device.
According to claim 1,
a+b is 0 or 1,
organic light emitting device.
According to claim 1,
The first compound is any one selected from the group consisting of
Organic light emitting device:

.
According to claim 1,
L' is phenylene, biphenyldiyl, or naphthylene;
organic light emitting device.
10. The method of claim 9,
L' is any one selected from the group consisting of
Organic light emitting device:

.
According to claim 1,
L ₃ and L ₄ are each independently a single bond, phenylene, biphenyldiyl, or naphthylene,
organic light emitting device.
According to claim 1,
In Formulas 2a to 2c,
each X is independently O, S, or N(phenyl);
B ₁ to B ₃ are each independently an unsubstituted naphthalene ring fused with a neighboring pentacyclic ring,
organic light emitting device.
According to claim 1,
Ar ₃ and Ar ₄ are each independently phenyl, phenylnaphthyl, biphenylyl, terphenylyl, naphthyl, naphthylphenyl, phenanthryl, triphenylenyl, represented by any one of Formulas 2a-1 to 2a-5 a substituent, or a substituent represented by any one of the following formulas 2b-1 to 2b-4,
Organic light emitting device:

.
According to claim 1,
R ₃ 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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