KR20200110228A - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting element with a low driving voltage, high luminous efficiency, and excellent lifetime. The organic light emitting element comprises: a first electrode; a second electrode facing the first electrode; and a light emitting layer between the first electrode and the second electrode.

Description

Organic light emitting device TECHNICAL FIELD

The present invention relates to an organic light-emitting device having a low driving voltage, high luminous efficiency, and excellent lifespan.

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

The 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-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device.For example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of such an organic light-emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. It glows when it falls back to the ground.

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

Korean Patent Publication No. 10-2000-0051826

The present invention relates to an organic light-emitting device having a low driving voltage, high luminous efficiency, and excellent lifespan.

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

The organic light-emitting device according to the present invention,

A first electrode;

A second electrode provided to face the first electrode; And

Comprising a light emitting layer provided between the first electrode and the second electrode,

The emission layer includes a first compound represented by Formula 1 below and a second compound represented by Formula 2 below,

[Formula 1]

In Formula 1,

X ₁ to X ₃ are each independently N or CH, but at least two of X ₁ to X ₃ are N,

Ar ₁ and Ar ₂ are each independently deuterium; Substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S,

Z is each independently hydrogen, or deuterium, or two adjacent ones of Z are bonded to each other to include a C _6-60 aromatic ring or any one or more heteroatoms selected from the group consisting of N, O and S Can form _2-60 heteroaromatic rings,

Here, the C _6-60 aromatic ring and the C _2-60 heteroaromatic ring are unsubstituted or substituted with deuterium,

n is an integer from 0 to 6,

A is a substituent represented by the following formula 1-1,

[Formula 1-1]

In Formula 1-1,

R ₁ to R ₄ are each independently hydrogen or deuterium, or two adjacent ones of R ₁ to R ₄ are bonded to each other to form a C _6-60 aromatic ring or any one selected from the group consisting of N, O and S Can form a C _2-60 heteroaromatic ring containing more than one heteroatom

Here, the C _6-60 aromatic ring and the C _2-60 heteroaromatic ring are unsubstituted or substituted with deuterium,

D means deuterium,

m is an integer from 0 to 6,

[Formula 2]

In Chemical Formula 2,

T ₁ to T ₄ are each independently a substituted or unsubstituted C _6-60 aromatic ring fused with a neighboring pentagonal ring; Or a substituted or unsubstituted C _2-60 heteroaromatic ring containing any one or more heteroatoms selected from the group consisting of N, O and S,

L ₁ and L ₂ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; Or substituted or unsubstituted C _2-60 heteroarylene including any one or more heteroatoms selected from the group consisting of N, O and S,

Ar ₃ and Ar ₄ are each independently a substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S.

The organic light-emitting device described above may simultaneously include the first compound and the second compound as a host material in the emission layer, thereby exhibiting low driving voltage, high luminous efficiency, and long lifespan characteristics.

1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4.
2 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron suppressing layer 7, a hole blocking layer 8, an electron injection and transport layer ( 8) and the cathode 4 shows an example of an organic light emitting device.

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

(Definition of Terms)

및

는 다른 치환기에 연결되는 결합을 의미한다.In this specification,

And

Means a bond connected to another substituent.

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Halogen group; Cyano group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or it means substituted or unsubstituted with one or more substituents selected from the group consisting of a heteroaryl group containing one or more of N, O, and S atoms, or substituted or unsubstituted with two or more substituents connected among the aforementioned substituents. . For example, "a substituent to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.

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

In the present specification, the ester group may be substituted with an oxygen of the ester group with a straight chain, 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 compound of the following structural formula, but is not limited thereto.

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

In the present specification, the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.

In the present specification, the boron group specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, and a phenyl boron group, but is not limited thereto.

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

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

In the present specification, the alkenyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. 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 is preferably 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 cycloalkyl group has 3 to 20 carbon atoms. 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 are not limited thereto.

In the present specification, the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but the monocyclic aryl group is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

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

Etc. However, it is not limited thereto.

In the present specification, heteroaryl is a heteroaryl containing at least one of O, N, Si, and S as heterogeneous elements, and the number of carbons is not particularly limited, but it is preferably 2 to 60 carbon atoms. Examples of heteroaryl include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, 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 (phenanthroline), isoxazolyl group, thiadiazolyl Group, phenothiazinyl group, dibenzofuranyl group, and the like, but are not limited thereto.

The term "aromatic ring" as used herein refers to condensation having a plurality of aromatics such as a fluorene ring as well as a condensed monocyclic or condensed polycyclic ring having only carbon as a ring-forming atom and having aromaticity in the entire molecule. It is understood that the monocyclic ring also includes a condensed polycyclic ring formed by linking adjacent substituents. At this time, the number of carbon atoms of the aromatic ring is 6 to 60, or 6 to 30, or 6 to 20, but is not limited thereto. Further, the aromatic ring may be a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a fluorene ring, and the like, but is not limited thereto.

The term "heterocyclic ring" as used herein refers to a hetero-condensed monocyclic or hetero-condensed ring containing at least one heteroatom among O, N, and S other than carbon as a ring-forming atom and having aromaticity in the entire molecule. It means a polycyclic ring. The number of carbon atoms of the hetero ring is 2 to 60, or 2 to 30, or 2 to 20, but is not limited thereto. In addition, the hetero ring may be a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and the like, but is not limited thereto.

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

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

First electrode and second electrode

An organic light-emitting device according to an embodiment includes a first electrode on a substrate and a second electrode provided opposite to the first electrode, and in this case, when the first electrode is an anode, the second electrode is a cathode and When the first electrode is a cathode, the second electrode is an anode.

Specifically, the organic light-emitting device may be a normal type organic light-emitting device in which an anode, an emission layer, and a cathode are sequentially stacked on a substrate. Alternatively, the organic light-emitting device may be an organic light-emitting device of an inverted type in which a cathode, an emission layer, and an anode are sequentially stacked on a substrate.

As the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic material layer. Specific examples of the cathode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of a metal and an oxide such as ZnO:Al or SNO ₂ :Sb; Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, and the like, but are not limited thereto.

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

Emitting layer

The organic light emitting device according to an embodiment includes a light emitting layer provided between the first electrode and the second electrode, which is a layer that emits light in a visible light region by combining holes and electrons transported from the hole transport layer and the electron transport layer, The emission layer includes a first compound represented by Formula 1 and a second compound represented by Formula 2.

In this case, in the emission layer, both the first compound and the second compound are used as host materials. Specifically, the first compound is an N-type host material, and the second compound is a P-type host material, and when the emission layer of the organic light emitting device includes the N-type host material and the P-type host material at the same time, a single material host Compared to the case of use, it can exhibit improved effects in terms of efficiency and life.

In particular, the first compound has a structure in which both an N-containing 6-membered heterocyclic group and an A substituent (benzocarbazolyl-based substituent) are bonded to one benzene ring of a dibenzothiophene-based core. The first compound having such a structure includes a compound having a structure in which an N-containing 6-membered heterocyclic group and an A substituent (benzocarbazolyl-based substituent) are each bonded to another benzene ring of a dibenzothiophene-based core, and the A substituent ( Compared to a compound in which a substituted/unsubstituted carbazolyl substituent instead of a benzocarbazolyl substituent) is bonded, stability against electrons and holes is high, and the balance between electrons and holes can be stably maintained. Accordingly, in the organic light emitting device employing the first compound, (i) an N-containing 6-membered heterocyclic group and an A substituent (benzocarbazolyl-based substituent) are each bonded to another benzene ring of a dibenzothiophene-based core. Compared to an organic light-emitting device employing a compound having a structure and a compound in which a substituted/unsubstituted carbazolyl substituent is bonded instead of the A substituent (benzocarbazolyl-based substituent), it has low driving voltage, high efficiency, and long life. Show.

Preferably, the first compound is represented by any one of the following Formulas 1A to 1D, depending on the bonding position of the N-containing 6-membered heterocyclic group in the dibenzothiophene-based core:

[Formula 1A] [Formula 1B]

[Formula 1C] [Formula 1D]

In Formulas 1A to 1D,

Description of each substituent is as defined in Chemical Formula 1.

Preferably, all of X ₁ to X ₃ are N.

Preferably, each of Z is independently hydrogen or deuterium, or two adjacent to Z may be bonded to each other to form an unsubstituted or deuterated C _6-20 aromatic ring, for example a benzene ring. .

At this time, n, which means the number of Z, is 0, 1, 2, 3, 4, 5, or 6.

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

In Formulas 1A-1 to 1D-1,

One of Z ₁ to Z ₃ is a substituent A represented by Formula 1-1, and the others are each independently hydrogen or deuterium, or two of Z ₁ to Z _{3 that} are adjacent to each other are unsubstituted or deuterium Can form a benzene ring substituted with,

Z ₄ to Z ₇ are each independently hydrogen or deuterium, or two adjacent two of Z ₄ to Z ₇ may be bonded to each other to form a benzene ring unsubstituted or substituted with deuterium,

Ar ₁ and Ar ₂ are as defined in Chemical Formula 1.

Specifically, in Chemical Formula 1A-1,

Z ₁ is A, Z ₂ and Z ₃ are each independently hydrogen or deuterium, or Z ₂ and Z ₃ are combined with each other to form a benzene ring unsubstituted or substituted with deuterium;

Z ₂ is A, and Z ₁ and Z ₃ are each independently hydrogen or deuterium; or

Z ₃ is A, and Z ₁ and Z ₂ are each independently hydrogen or deuterium, or Z ₁ and Z _{2 may} be bonded to each other to form a benzene ring unsubstituted or substituted with deuterium.

In addition, in Formula 1B-1,

Z ₁ is A, Z ₂ and Z ₃ are each independently hydrogen or deuterium, or Z ₂ and Z ₃ are combined with each other to form a benzene ring unsubstituted or substituted with deuterium;

Z ₂ is A, and Z ₁ and Z ₃ are each independently hydrogen or deuterium; or

Z ₃ is A, and Z ₁ and Z ₂ may each independently be hydrogen or deuterium.

In addition, in Formula 1C-1,

Z ₁ is A, and Z ₂ and Z ₃ are each independently hydrogen or deuterium;

Z ₂ is A, and Z ₁ and Z ₃ are each independently hydrogen or deuterium; or

Z ₃ is A, and Z ₁ and Z ₂ are each independently hydrogen or deuterium, or Z ₁ and Z _{2 may} be bonded to each other to form a benzene ring unsubstituted or substituted with deuterium.

Specifically, in Chemical Formula 1D-1,

Z ₁ is A, Z ₂ and Z ₃ are each independently hydrogen or deuterium, or Z ₂ and Z ₃ are combined with each other to form a benzene ring unsubstituted or substituted with deuterium;

Z ₂ is A, and Z ₁ and Z ₃ are each independently hydrogen or deuterium; or

Z ₃ is A, and Z ₁ and Z ₂ are each independently hydrogen or deuterium, or Z ₁ and Z _{2 may} be bonded to each other to form a benzene ring unsubstituted or substituted with deuterium.

Alternatively, the first compound may be represented by any one of the following Formulas 3-1 to 3-7:

In Formulas 3-1 to 3-7,

Each R is independently hydrogen or deuterium,

A, Ar ₁ and Ar ₂ are as defined in Chemical Formula 1.

Preferably, Ar ₁ and Ar ₂ are each independently unsubstituted or substituted with heavy hydrogen, or C _6-20 aryl C _6-20 aryl.

More preferably, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzothiophenyl, dibenzofuranyl, or carbazolyl,

Here, Ar ₁ and Ar ₂ may be unsubstituted or substituted with 1 to 5 substituents each independently selected from the group consisting of deuterium and C _6-20 aryl.

Most preferably, Ar ₁ and Ar ₂ are each independently any one selected from the group consisting of:

.

.

At this time, Ar ₁ and Ar ₂ may be the same as each other, or Ar ₁ and Ar ₂ may be different.

In addition, in the substituent A represented by Formula 1-1, R ₁ to R ₄ are each independently hydrogen or deuterium, or two adjacent to R ₁ to R ₄ are bonded to each other to be unsubstituted or deuterium It can form a substituted benzene ring.

At this time, m, which means the number of deuterium (D), is 0, 1, 2, 3, 4, 5, or 6.

For example, A is any one of the substituents represented by the following formulas a1 to a4:

.

.

Specific examples of the first compound are as follows:

.

On the other hand, the compound represented by Formula 1 may be prepared by a manufacturing method such as the following Scheme 1 as an example.

[Scheme 1]

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

Specifically, the compound represented by Formula 1 is prepared by combining starting materials SM1 and SM2 through an amine substitution reaction. This amine substitution reaction is preferably carried out in the presence of a palladium catalyst and a base. In addition, the reactor for the amine substitution reaction may be appropriately changed, and the method for preparing the compound represented by Formula 1 may be more specific in Preparation Examples to be described later.

Meanwhile, the second compound is a biscarbazole-based compound, and preferably, T ₁ to T ₄ have a structure in which each independently a C _6-20 aromatic ring. More preferably, T ₁ to T ₄ are unsubstituted or deuterium-substituted benzene rings, or unsubstituted or deuterium-substituted naphthalene rings.

Most preferably, all of T ₁ to T ₄ are benzene rings, wherein the second compound is represented by the following formula 2-1:

[Formula 2-1]

In Formula 2-1,

D means deuterium,

r and s are each independently an integer of 0 to 7,

Description of each substituent is as defined in Chemical Formula 2.

Preferably, L ₁ and L ₂ are each independently a single bond or an unsubstituted C _6-20 arylene.

More preferably, L ₁ and L ₂ are each independently a single bond, phenylene, or naphthylene.

Preferably, Ar ₃ and Ar ₄ are each independently C _6-20 aryl unsubstituted or substituted with C _1-10 alkyl or C _6-20 aryl; Or C _2-20 heteroaryl including O or S.

More preferably, Ar ₃ and Ar ₄ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, fluorenyl, spirobifluorenyl, fluoranthenyl, Dibenzothiophenyl, dibenzofuranyl,

Here, Ar ₃ and Ar ₄ may be unsubstituted or substituted with 1 to 4 substituents each independently selected from the group consisting of C _1-10 alkyl and C _6-20 aryl.

Most preferably, Ar ₃ and Ar ₄ are each independently any one selected from the group consisting of:

.

.

At this time, Ar ₃ and Ar ₄ may be the same as each other, or Ar ₃ and Ar ₄ may be different.

Preferably, the second compound is represented by the following formula 2-2:

[Formula 2-2]

In Formula 2-2,

L ₁ and L ₂ are each independently a single bond, phenylene, or naphthylene,

Ar ₃ and Ar ₄ are as defined in Chemical Formula 2.

Specific examples of the second compound are as follows:

.

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

[Scheme 2]

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

Specifically, the compound represented by Formula 2 is prepared by combining the starting materials SM3 and SM4 through a Suzuki-coupling reaction. This Suzuki-coupling reaction is preferably carried out in the presence of a palladium catalyst and a base. In addition, the reactor for the Suzuki-coupling reaction may be appropriately changed, and the method of preparing the compound represented by Formula 2 may be more specific in Preparation Examples to be described later.

The first compound and the second compound are preferably included in the light-emitting layer in a weight ratio of 99:1 to 1:99, more preferably 50:50, to implement a device having high efficiency and long life.

Meanwhile, the emission layer further includes a dopant material in addition to the host material. Examples of such dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group, and the styrylamine compound is substituted or unsubstituted As a compound in which at least one arylvinyl group is substituted on the arylamine, one or two or more substituents selected from the group consisting of an aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.

Preferably, the light emitting layer may include the following iridium complex compound as a dopant material, but is not limited thereto.

Hole injection layer

The organic light emitting device according to an embodiment may further include a hole injection layer on the anode. The hole injection layer is made of a hole injection material, and the hole injection material has the ability to transport holes, and thus has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material. A compound that prevents migration to the electron injection layer or the electron injection material and has excellent thin film formation ability is preferable.

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

Hole transport layer

The organic light-emitting device according to an embodiment may further include a hole transport layer on the anode or on the hole injection layer formed on the anode. The hole transport layer is a layer that receives holes from an anode or a hole injection layer formed on the anode and transports holes to the emission layer, and the hole transport material included in the hole transport layer receives holes from the anode or the hole injection layer to the emission layer. As a transferable material, a material with high mobility for holes is suitable.

Specific examples of the hole transport material 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.

Electron suppression layer

The organic light-emitting device according to an embodiment may further include an electron suppression layer on the hole transport layer. The electron suppression layer is formed on the hole transport layer and is preferably provided in contact with the light emitting layer to control hole mobility and prevent excessive movement of electrons, thereby increasing the probability of hole-electron coupling, thereby increasing the efficiency of the organic light-emitting device. It refers to the layer that plays a role in improving the value. The electron-suppressing layer includes an electron-blocking material, and examples of such an electron-blocking material include a compound represented by Formula 1 or an arylamine-based organic material, but are not limited thereto.

Hole bottom

The organic balsop device according to an embodiment may further include a hole blocking layer on the emission layer. 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 increasing the probability of hole-electron coupling by controlling electron mobility and preventing excessive movement of holes. It means the layer that plays a role. The hole-blocking layer includes a hole-blocking material, and examples of such hole-blocking materials include: a subazine derivative including triazine; Triazole derivatives; Oxadiazole derivatives; Phenanthroline derivatives; A compound into which an electron withdrawing group such as a phosphine oxide derivative has been introduced may be used, but is not limited thereto.

Electron transport layer

The organic light-emitting device according to an embodiment may include an electron transport layer on the emission layer or on the hole blocking layer. The electron transport layer is a layer that receives electrons from a cathode or an electron injection layer to be described later and transports electrons to the emission layer. As an electron transport material included in the electron transport layer, electrons capable of receiving electrons from the cathode and transferring them to the emission layer Materials with high mobility are suitable.

Specific examples of the electron transport material include pyridine derivatives; Pyrimidine derivatives; Triazole derivatives; Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials that have a low work function and are followed by an aluminum layer or a silver layer. Specifically, they are cesium, barium, calcium, ytterbium, and samarium, and in each case an aluminum layer or a silver layer follows.

Electron injection layer

The organic light-emitting device according to an embodiment may further include an electron injection layer between the electron transport layer and the cathode. The electron injection layer is a layer that injects electrons from the cathode, and the electron injection material included in the electron injection layer has the ability to transport electrons, has an electron injection effect from the cathode, and excellent electron injection to the light emitting layer or the light emitting material A compound having an effect, preventing the movement of excitons generated in the light emitting layer to the hole injection layer, and having excellent thin film formation ability is preferable.

Specific examples of materials that can be used as the electron injection layer include LiF, NaCl, CsF, Li ₂ O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, tria Sol, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, and the like, derivatives thereof, metal complex compounds, and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include lithium 8-hydroxyquinolinato, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( o-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. It is not limited to this.

Meanwhile, the electron transport layer and the electron injection layer may be provided in the form of an electron injection and transport layer that simultaneously serves as an electron transport layer and an electron injection layer for transporting received electrons to the emission layer.

Organic light emitting element

According to an embodiment, the structure of an organic light-emitting device in which the first electrode is an anode and the second electrode is a cathode is illustrated in FIG. 1. 1 shows an example of an organic light-emitting device comprising 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.

According to another embodiment, the structure of an organic light-emitting device in which the first electrode is an anode and the second electrode is a cathode is illustrated in FIG. 2. 2 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron suppressing layer 7, a hole blocking layer 8, an electron injection and transport layer ( 8) and the cathode 4 shows an example of an organic light emitting device. 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 can be manufactured by sequentially stacking the above-described configurations. At this time, using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, the anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate. And, after forming each of the above-described 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 of a host and a dopant. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

In addition to such a 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.

Meanwhile, the organic light-emitting device according to the present invention may be a top emission type, a bottom emission type, or a double-sided emission type depending on the material used.

The fabrication of the organic light emitting device will be described in detail in the following examples. However, the following examples are for illustrating 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, intermediate 1-1-1 (10 g, 22.2 mmol), compound a (5.3 g, 24.4 mmol), sodium tert-butoxide (4.3 g, 44.4 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 7.3 g of compound 1-1. (Yield: 52%, MS: [M+H]+= 631)

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

In a nitrogen atmosphere, intermediate 1-2-1 (10 g, 20 mmol), compound a (4.8 g, 22 mmol), sodium tert-butoxide (3.8 g, 40 mmol) was added to 200 ml of Xylene and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 6.9 g of compound 1-2. (Yield: 51%, MS: [M+H]+= 681)

Synthesis Example 1-3: Preparation of Compound 1-3

In a nitrogen atmosphere, intermediate 1-3-1 (10 g, 16.3 mmol), compound a (3.9 g, 17.9 mmol), sodium tert-butoxide (3.1 g, 32.5 mmol) was added to 200 ml of Xylene, followed by stirring and refluxing. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 8.9 g of compound 1-3. (Yield: 69%, MS: [M+H]+= 796)

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

In a nitrogen atmosphere, intermediate 1-4-1 (10 g, 17.1 mmol), compound a (4.1 g, 18.8 mmol), sodium tert-butoxide (3.3 g, 34.2 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 7.1 g of compound 1-4. (Yield: 54%, MS: [M+H]+= 765)

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

In a nitrogen atmosphere, intermediate 1-5-1 (10 g, 17.9 mmol), compound a (4.3 g, 19.6 mmol), sodium tert-butoxide (3.4 g, 35.7 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 8.9 g of compound 1-5. (Yield: 67%, MS: [M+H]+= 741)

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

In a nitrogen atmosphere, intermediate 1-6-1 (10 g, 15.4 mmol), compound a (3.7 g, 16.9 mmol), sodium tert-butoxide (3 g, 30.8 mmol) was added to 200 ml of Xylene and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 7.4 g of compound 1-6. (Yield: 58%, MS: [M+H]+= 831)

Synthesis Example 1-7: Preparation of Compound 1-7

In a nitrogen atmosphere, intermediate 1-7-1 (10 g, 16.4 mmol), compound d (4.8 g, 18 mmol), sodium tert-butoxide (3.2 g, 32.8 mmol) was added to 200 ml of Xylene and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 7 g of compound 1-7. (Yield: 51%, MS: [M+H]+= 841)

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

In a nitrogen atmosphere, intermediate 1-8-1 (10 g, 16 mmol), compound d (4.7 g, 17.6 mmol), sodium tert-butoxide (3.1 g, 32 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 6.8 g of compound 1-8. (Yield: 50%, MS: [M+H]+= 855)

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

In a nitrogen atmosphere, intermediate 1-9-1 (10 g, 14.6 mmol), compound c (4.3 g, 16.1 mmol), sodium tert-butoxide (2.8 g, 29.2 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 6.7 g of compound 1-9. (Yield: 50%, MS: [M+H]+= 915)

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

In a nitrogen atmosphere, intermediate 1-10-1 (10 g, 17.4 mmol), compound b (5.1 g, 19.2 mmol), sodium tert-butoxide (3.3 g, 34.8 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 8.8 g of compound 1-10. (Yield: 63%, MS: [M+H]+= 805)

Synthesis Example 1-11: Preparation of Compound 1-11

In a nitrogen atmosphere, intermediate 1-11-1 (10 g, 16.5 mmol), compound a (3.9 g, 18.1 mmol), sodium tert-butoxide (3.2 g, 33 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 8.4 g of compound 1-11. (Yield: 65%, MS: [M+H]+= 787)

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

In a nitrogen atmosphere, intermediate 1-12-1 (10 g, 19 mmol), compound a (4.5 g, 20.9 mmol), sodium tert-butoxide (3.7 g, 38 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 7.1 g of compound 1-12. (Yield: 53%, MS: [M+H]+= 707)

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

In a nitrogen atmosphere, intermediate 1-13-1 (10 g, 15.4 mmol), compound a (3.7 g, 16.9 mmol), sodium tert-butoxide (3 g, 30.8 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 6.8 g of compound 1-13. (Yield: 53%, MS: [M+H]+= 831)

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

In a nitrogen atmosphere, intermediate 1-14-1 (10 g, 20 mmol), compound b (5.9 g, 22 mmol), sodium tert-butoxide (3.8 g, 40 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 7.9 g of compound 1-14. (Yield: 54%, MS: [M+H]+= 731)

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

In a nitrogen atmosphere, intermediate 1-15-1 (10 g, 15.3 mmol), compound c (4.5 g, 16.9 mmol), sodium tert-butoxide (2.9 g, 30.7 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 9.3 g of compound 1-15. (Yield: 69%, MS: [M+H]+= 883)

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

In a nitrogen atmosphere, intermediate 1-16-1 (10 g, 14.4 mmol), compound a (3.4 g, 15.8 mmol), sodium tert-butoxide (2.8 g, 28.7 mmol) was added to 200 ml of Xylene, followed by stirring and refluxing. After this, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 6.4 g of compound 1-16. (Yield: 51%, MS: [M+H]+= 877)

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

In a nitrogen atmosphere, intermediate 1-17-1 (10 g, 20 mmol), compound a (4.8 g, 22 mmol), sodium tert-butoxide (3.8 g, 40 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 7.9 g of compound 1-17. (Yield: 58%, MS: [M+H]+= 681)

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

In a nitrogen atmosphere, intermediate 1-18-1 (10 g, 16 mmol), compound b (4.7 g, 17.6 mmol), sodium tert-butoxide (3.1 g, 31.9 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 7.2 g of compound 1-18. (Yield: 53%, MS: [M+H]+= 857)

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

In a nitrogen atmosphere, intermediate 1-19-1 (10 g, 15.2 mmol), compound c (4.5 g, 16.8 mmol), sodium tert-butoxide (2.9 g, 30.5 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 8.5 g of compound 1-19. (Yield: 63%, MS: [M+H]+= 887)

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

In a nitrogen atmosphere, intermediate 1-20-1 (10 g, 15.2 mmol), compound d (4.5 g, 16.8 mmol), sodium tert-butoxide (2.9 g, 30.5 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 7.4 g of compound 1-20. (Yield: 55%, MS: [M+H]+= 887)

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

In a nitrogen atmosphere, intermediate 1-21-1 (10 g, 19 mmol), compound a (4.5 g, 20.9 mmol), sodium tert-butoxide (3.7 g, 38 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 9.4 g of compound 1-21. (Yield: 70%, MS: [M+H]+= 707)

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

In a nitrogen atmosphere, intermediate 1-22-1 (10 g, 22.2 mmol), compound a (5.3 g, 24.4 mmol), sodium tert-butoxide (4.3 g, 44.4 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 7.1 g of compound 1-22. (Yield: 51%, MS: [M+H]+= 631)

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

In a nitrogen atmosphere, intermediate 1-23-1 (10 g, 16.2 mmol), compound a (3.9 g, 17.9 mmol), sodium tert-butoxide (3.1 g, 32.5 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 6.8 g of compound 1-23. (Yield: 53%, MS: [M+H]+= 797)

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

In a nitrogen atmosphere, intermediate 1-24-1 (10 g, 16 mmol), compound b (4.7 g, 17.6 mmol), sodium tert-butoxide (3.1 g, 31.9 mmol) was added to 200 ml of Xylene and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 8.3 g of compound 1-24. (Yield: 61%, MS: [M+H]+= 857)

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

In a nitrogen atmosphere, intermediate 1-25-1 (10 g, 15 mmol), compound d (4.4 g, 16.5 mmol), sodium tert-butoxide (2.9 g, 30 mmol) was added to 200 ml of Xylene and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 8.7 g of compounds 1-25. (Yield: 65%, MS: [M+H]+= 897)

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

In a nitrogen atmosphere, intermediate 1-26-1 (10 g, 20 mmol), compound a (4.8 g, 22 mmol), sodium tert-butoxide (3.8 g, 40 mmol) was added to 200 ml of Xylene and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 6.9 g of compound 1-26. (Yield: 51%, MS: [M+H]+= 681)

Synthesis Example 1-27: Preparation of Compound 1-27

In a nitrogen atmosphere, intermediate 1-27-1 (10 g, 16.7 mmol), compound a (4 g, 18.3 mmol), sodium tert-butoxide (3.2 g, 33.3 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 6.6 g of compound 1-27. (Yield: 51%, MS: [M+H]+= 781)

Synthesis Example 1-28: Preparation of Compound 1-28

In a nitrogen atmosphere, intermediate 1-28-1 (10 g, 15.4 mmol), compound c (4.5 g, 16.9 mmol), sodium tert-butoxide (3 g, 30.8 mmol) was added to 200 ml of Xylene and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 7 g of compound 1-28. (Yield: 52%, MS: [M+H]+= 881)

Synthesis Example 1-29: Preparation of Compound 1-29

In a nitrogen atmosphere, intermediate 1-29-1 (10 g, 16.7 mmol), compound a (4 g, 18.3 mmol), sodium tert-butoxide (3.2 g, 33.3 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 6.9 g of compound 1-29. (Yield: 53%, MS: [M+H]+= 781)

Synthesis Example 1-30: Preparation of Compound 1-30

In a nitrogen atmosphere, intermediates 1-30-1 (10 g, 14 mmol), compound a (3.4 g, 15.4 mmol), sodium tert-butoxide (2.7 g, 28.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 7.1 g of compound 1-30. (Yield: 57%, MS: [M+H]+= 893)

Synthesis Example 1-31: Preparation of Compound 1-31

In a nitrogen atmosphere, intermediate 1-31-1 (10 g, 22.2 mmol), compound a (5.3 g, 24.4 mmol), sodium tert-butoxide (4.3 g, 44.4 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 7.8 g of compound 1-31. (Yield: 56%, MS: [M+H]+= 631)

Synthesis Example 1-32: Preparation of Compound 1-32

In a nitrogen atmosphere, intermediate 1-32-1 (10 g, 16.6 mmol), compound a (4 g, 18.3 mmol), sodium tert-butoxide (3.2 g, 33.3 mmol) was added to 200 ml of Xylene and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 8.1 g of compound 1-32. (Yield: 62%, MS: [M+H]+= 783)

Synthesis Example 1-33: Preparation of Compound 1-33

In a nitrogen atmosphere, intermediate 1-33-1 (10 g, 19 mmol), compound a (4.6 g, 20.9 mmol), sodium tert-butoxide (3.7 g, 38.1 mmol) was added to 200 ml of Xylene and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 7 g of compound 1-33. (Yield: 52%, MS: [M+H]+= 707)

Synthesis example 1-34: Preparation of compound 1-34

In a nitrogen atmosphere, intermediate 1-34-1 (10 g, 18.2 mmol), compound a (4.4 g, 20 mmol), sodium tert-butoxide (3.5 g, 36.4 mmol) was added to 200 ml of Xylene, followed by stirring and refluxing. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 8.2 g of compound 1-34. (Yield: 62%, MS: [M+H]+= 731)

Synthesis Example 1-35: Preparation of compound 1-35

In a nitrogen atmosphere, intermediate 1-35-1 (10 g, 15.6 mmol), compound d (4.6 g, 17.2 mmol), sodium tert-butoxide (3 g, 31.3 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 9.4 g of compound 1-35. (Yield: 69%, MS: [M+H]+= 871)

Synthesis Example 1-36: Preparation of Compound 1-36

In a nitrogen atmosphere, intermediate 1-36-1 (10 g, 22.3 mmol), compound c (6.5 g, 24.5 mmol), sodium tert-butoxide (4.3 g, 44.5 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 8 g of compound 1-36. (Yield: 53%, MS: [M+H]+= 681)

Synthesis Example 1-37: Preparation of Compound 1-37

In a nitrogen atmosphere, intermediate 1-37-1 (10 g, 18.2 mmol), compound b (5.4 g, 20 mmol), and sodium tert-butoxide (3.5 g, 36.4 mmol) were added to 200 ml of Xylene, followed by stirring and refluxing. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 37 9 g of compound 1-37. (Yield: 63%, MS: [M+H]+= 781)

Synthesis Example 1-38: Preparation of Compound 1-38

In a nitrogen atmosphere, intermediate 1-38-1 (10 g, 14.7 mmol), compound c (4.3 g, 16.2 mmol), sodium tert-butoxide (2.8 g, 29.4 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 8.6 g of compound 1-38. (Yield: 64%, MS: [M+H]+= 913)

Synthesis Example 1-39: Preparation of Compound 1-39

In a nitrogen atmosphere, intermediate 1-39-1 (10 g, 16 mmol), compound b (4.7 g, 17.6 mmol), sodium tert-butoxide (3.1 g, 32 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 9.3 g of compound 1-39. (Yield: 68%, MS: [M+H]+= 857)

Synthesis Example 1-40: Preparation of Compound 1-40

In a nitrogen atmosphere, intermediate 1-40-1 (10 g, 18.2 mmol), compound a (4.4 g, 20 mmol), sodium tert-butoxide (3.5 g, 36.4 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 8 g of compound 1-40. (Yield: 60%, MS: [M+H]+= 731)

Synthesis Example 1-41: Preparation of Compound 1-41

In a nitrogen atmosphere, intermediate 1-41-1 (10 g, 16.5 mmol), compound d (4.9 g, 18.2 mmol), sodium tert-butoxide (3.2 g, 33.1 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 8.2 g of compound 1-41. (Yield: 59%, MS: [M+H]+= 837)

Synthesis Example 1-42: Preparation of Compound 1-42

In a nitrogen atmosphere, intermediate 1-42-1 (10 g, 14.4 mmol), compound c (4.2 g, 15.8 mmol), sodium tert-butoxide (2.8 g, 28.8 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, 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 prepare 7.1 g of compound 1-42. (Yield: 53%, MS: [M+H]+= 927)

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

In a nitrogen atmosphere, intermediate 2-1-1 (10g, 25.2mmol) and intermediate 2-1-2 (8g, 27.7mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.9g, 100.7mmol) was dissolved in water and added. After sufficient stirring, reflux was performed, and then bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 3 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 compound 2-1. (Yield: 64%, MS: [M+H]+= 561)

Synthesis example 2-2: Preparation of compound 2-2

In a nitrogen atmosphere, intermediate 2-2-1 (10g, 25.2mmol) and intermediate 2-2-2 (8g, 27.7mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.9g, 100.7mmol) was dissolved in water and added. After sufficient stirring, reflux was performed, and then bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 4 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 compound 2-2. (Yield: 66%, MS: [M+H]+= 637)

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

In a nitrogen atmosphere, add Intermediate 2-3-1 (10g, 25.2mmol) and Intermediate 2-3-2 (10.1g, 27.7mmol) to 200 ml of THF, stir, and dissolve potassium carbonate (13.9g, 100.7mmol) in water. The mixture was added, stirred sufficiently, and refluxed, and then bis (tri-tert-butylphosphine) palladium(0) (0.1g, 0.3mmol) was added. After the reaction for 4 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 compound 2-3. (Yield: 56%, MS: [M+H]+= 637)

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

In a nitrogen atmosphere, intermediate 2-4-1 (10g, 25.2mmol) and intermediate 2-4-2 (9.3g, 27.7mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.9g, 100.7mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis (tri-tert-butylphosphine) palladium(0) (0.1g, 0.3mmol) was added. After 2 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 compound 2-4. (Yield: 51%, MS: [M+H]+= 611)

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

In a nitrogen atmosphere, intermediate 2-5-1 (10g, 25.2mmol) and intermediate 2-5-2 (10.1g, 27.7mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.9g, 100.7mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis (tri-tert-butylphosphine) palladium(0) (0.1g, 0.3mmol) was added. After the reaction for 4 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.4 g of compound 2-5. (Yield: 65%, MS: [M+H]+= 637)

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

In a nitrogen atmosphere, intermediate 2-6-1 (10g, 25.2mmol) and intermediate 2-6-2 (11.4g, 27.7mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.9g, 100.7mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis (tri-tert-butylphosphine) palladium(0) (0.1g, 0.3mmol) was added. After 2 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 compound 2-6. (Yield: 61%, MS: [M+H]+= 687)

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

In a nitrogen atmosphere, intermediate 2-7-1 (10g, 22.4mmol) and intermediate 2-7-2 (10.2g, 24.6mmol) were added to 200 ml of THF, stirred, and potassium carbonate (12.4g, 89.5mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 3 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 compound 2-7. (Yield: 67%, MS: [M+H]+= 737)

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

In a nitrogen atmosphere, intermediate 2-8-1 (10g, 17.9mmol) and intermediate 2-8-2 (5.6g, 19.7mmol) were added to 200 ml of THF, stirred, and potassium carbonate (9.9g, 71.5mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 3 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 compound 2-8. (Yield: 60%, MS: [M+H]+= 723)

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

In a nitrogen atmosphere, intermediate 2-9-1 (10g, 21.1mmol) and intermediate 2-9-2 (6.7g, 23.3mmol) were added to 200 ml of THF, stirred, and potassium carbonate (11.7g, 84.6mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 3 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.4 g of compound 2-9. (Yield: 55%, MS: [M+H]+= 637)

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

In a nitrogen atmosphere, intermediate 2-10-1 (10g, 27mmol) and intermediate 2-10-2 (10g, 29.6mmol) were added to 200 ml of THF, stirred, and potassium carbonate (14.9g, 107.8mmol) was dissolved in water and added. After sufficiently stirring and refluxing, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added. After 2 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 compound 2-10. (Yield: 70%, MS: [M+H]+= 585)

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

In a nitrogen atmosphere, intermediate 2-11-1 (10g, 27mmol) and intermediate 2-11-2 (11.5g, 29.6mmol) were added to 200 ml of THF, stirred, and potassium carbonate (14.9g, 107.8mmol) was dissolved in water and added. After sufficient stirring, reflux was performed, and then bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After 2 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.5 g of compound 2-11. (Yield: 67%, MS: [M+H]+= 635)

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

In a nitrogen atmosphere, intermediate 2-12-1 (10g, 23.8mmol) and intermediate 2-12-2 (8.8g, 26.1mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.1g, 95mmol) was dissolved in water and added. Then, after sufficiently stirring, refluxed, and then bis (tri-tert-butylphosphine) palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 3 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.4 g of compound 2-12. (Yield: 69%, MS: [M+H]+= 635)

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

In a nitrogen atmosphere, intermediate 2-13-1 (10g, 24.3mmol) and intermediate 2-13-2 (11.1g, 26.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.5g, 97.3mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After 2 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 compound 2-13. (Yield: 53%, MS: [M+H]+= 701)

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

In a nitrogen atmosphere, intermediate 2-14-1 (10g, 24.3mmol) and intermediate 2-14-2 (7.7g, 26.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.5g, 97.3mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 3 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 compound 2-14. (Yield: 64%, MS: [M+H]+= 575)

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

In a nitrogen atmosphere, intermediate 2-15-1 (10g, 24.3mmol) and intermediate 2-15-2 (9g, 26.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.5g, 97.3mmol) was dissolved in water and added. Then, after sufficiently stirring, refluxed, and then bis (tri-tert-butylphosphine) palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 4 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 compound 2-15. (Yield: 55%, MS: [M+H]+= 625)

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

In a nitrogen atmosphere, intermediate 2-16-1 (10g, 24.3mmol) and intermediate 2-16-2 (11.1g, 26.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.5g, 97.3mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After 2 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2 g of compound 2-16. (Yield: 66%, MS: [M+H]+= 701)

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

In a nitrogen atmosphere, intermediate 2-17-1 (10g, 24.3mmol) and intermediate 2-17-2 (10.1g, 26.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.5g, 97.3mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 3 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10 g of compound 2-17. (Yield: 62%, MS: [M+H]+= 665)

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

In a nitrogen atmosphere, intermediate 2-18-1 (10g, 24.3mmol) and intermediate 2-18-2 (10.5g, 26.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.5g, 97.3mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After 2 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 compound 2-18. (Yield: 59%, MS: [M+H]+= 681)

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

In a nitrogen atmosphere, intermediate 2-19-1 (10g, 24.3mmol) and intermediate 2-19-2 (10.5g, 26.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.5g, 97.3mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 3 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 compound 2-19. (Yield: 69%, MS: [M+H]+= 681)

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

In a nitrogen atmosphere, intermediate 2-20-1 (10g, 23.4mmol) and intermediate 2-20-2 (9.4g, 25.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (12.9g, 93.7mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After 2 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 compound 2-20. (Yield: 58%, MS: [M+H]+= 667)

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

In a nitrogen atmosphere, intermediate 2-21-1 (10g, 23.4mmol) and intermediate 2-21-2 (10.6g, 25.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (12.9g, 93.7mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 4 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.7 g of compound 2-21. (Yield: 64%, MS: [M+H]+= 717)

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

In a nitrogen atmosphere, intermediate 2-22-1 (10g, 23.4mmol) and intermediate 2-22-2 (11.3g, 25.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (12.9g, 93.7mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 3 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 compound 2-22. (Yield: 52%, MS: [M+H]+= 743)

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

In a nitrogen atmosphere, intermediate 2-23-1 (10g, 23.4mmol) and intermediate 2-23-2 (10.1g, 25.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (12.9g, 93.7mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 4 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.1 g of compound 2-23. (Yield: 56%, MS: [M+H]+= 697)

Comparative example 1: Fabrication of an organic light emitting device

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

The HI-1 compound was formed as a hole injection layer on the prepared ITO transparent electrode to a thickness of 1150Å, but the following compound A-1 was p-doping 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 800Å. Subsequently, an electron suppressing layer was formed by vacuum depositing the following EB-1 compound with a film thickness of 150Å on the hole transport layer.

Subsequently, the compound 1-1 prepared in Preparation Example 1-1 and the following Dp-7 compound were vacuum-deposited at a weight ratio of 98:2 on the EB-1 deposition film to form a red light emitting layer having a thickness of 400Å.

A hole blocking layer was formed by vacuum depositing the following HB-1 compound with a film thickness of 30Å on the emission layer. Subsequently, the following ET-1 compound and the following LiQ compound were vacuum-deposited at a weight ratio of 2:1 on the hole blocking layer to form an electron injection and transport layer with a thickness of 300Å. Lithium fluoride (LiF) at a thickness of 12Å and aluminum at a thickness of 1,000Å were sequentially deposited on the electron injection and transport layer to form a negative electrode.

In the above process, the deposition rate of organic matter was maintained at 0.4~0.7Å/sec, the deposition rate of lithium fluoride at the cathode was 0.3Å/sec, and the deposition rate of aluminum was 2Å/sec, and the vacuum degree during deposition was 2×10 ^-7 ~ An organic light-emitting device was manufactured by maintaining 5x10 ^-6 torr.

Comparative example 2 to Comparative example 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 below was used instead of compound 1-1 in the organic light-emitting device of Comparative Example 1.

Example 1 to Example 120

In the organic light-emitting device of Comparative Example 1, instead of compound 1-1, the first host described in Tables 2 to 4 was used by co-depositing the compound of Formula 1 and the compound of Formula 2 as a second host in a weight ratio of 1:1. Then, an organic light-emitting device was manufactured in the same manner as in Comparative Example 1.

Comparative example 16 to Comparative example 63

In the organic light-emitting device of Comparative Example 1, instead of compound 1-1, a 1:1 co-deposition of the compound of Formula 2 to the first host described in Tables 5 and 6 below and the compound of Comparative Compound C-1 to C-12 and the second host An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except for using it.

Experimental example 1: element characteristics evaluation

When a current was applied to the organic light-emitting devices prepared in Examples 1 to 120 and Comparative Examples 1 to 63, voltage, efficiency, and lifetime were measured (15 mA/cm ² basis) and the results are shown in Table 1 below. It is shown in to 6. The lifetime T95 refers to the time it takes for the luminance to decrease from the initial luminance (10,000 nit) to 95%.

division Host Driving voltage (V) Efficiency (cd/A) Life T95(hr) Luminous color Comparative Example 1 Compound 1-1 3.91 16.0 141 Red Comparative Example 2 Compound 1-2 3.84 16.1 143 Red Comparative Example 3 Compound 1-3 3.76 17.5 141 Red Comparative Example 4 Compound 1-12 3.97 16.3 144 Red Comparative Example 5 Compound 1-13 3.93 16.1 147 Red Comparative Example 6 Compound 1-14 3.94 16.1 140 Red Comparative Example 7 Compound 1-22 4.02 16.5 141 Red Comparative Example 8 Compound 1-23 3.98 15.3 145 Red Comparative Example 9 Compound 1-24 4.04 16.1 137 Red Comparative Example 10 Compound 1-32 3.82 16.3 134 Red Comparative Example 11 Compound 1-33 3.98 17.4 153 Red Comparative Example 12 Compound 1-34 3.91 17.2 151 Red Comparative Example 13 Compound 1-36 3.94 18.4 157 Red Comparative Example 14 Compound 1-37 3.92 17.7 157 Red Comparative Example 15 Compound 1-40 3.93 18.7 160 Red

division Host 1 2nd host Driving
Voltage(V) Efficiency (cd/A) Life T95(hr) Luminous color Example 1 Compound 1-1 Compound 2-1 3.99 21.3 241 Red Example 2 Compound 2-2 3.97 20.4 234 Red Example 3 Compound 2-8 3.98 20.4 230 Red Example 4 Compound 2-19 3.99 21.7 227 Red Example 5 Compound 1-2 Compound 2-1 3.88 20.7 225 Red Example 6 Compound 2-2 3.91 20.6 206 Red Example 7 Compound 2-8 3.94 20.4 209 Red Example 8 Compound 2-19 3.92 20.3 212 Red Example 8 Compound 1-3 Compound 2-1 3.88 21.4 218 Red Example 10 Compound 2-2 3.85 19.4 220 Red Example 11 Compound 2-8 3.86 19.5 212 Red Example 12 Compound 2-19 3.90 20.1 215 Red Example 13 Compound 1-5 Compound 2-1 3.84 20.0 210 Red Example 14 Compound 2-2 3.82 21.1 219 Red Example 15 Compound 2-8 3.91 19.9 227 Red Example 16 Compound 2-19 3.90 20.8 203 Red Example 17 Compound 1-7 Compound 2-1 3.92 21.0 200 Red Example 18 Compound 2-2 3.90 20.1 218 Red Example 19 Compound 2-8 3.94 19.7 221 Red Example 20 Compound 2-19 3.99 20.6 220 Red Example 21 Compound 1-8 Compound 2-1 3.90 19.4 203 Red Example 22 Compound 2-2 3.91 19.3 200 Red Example 23 Compound 2-8 3.94 20.5 202 Red Example 24 Compound 2-19 3.95 20.7 199 Red Example 25 Compound 1-12 Compound 2-1 4.01 20.3 186 Red Example 26 Compound 2-2 4.05 20.2 203 Red Example 27 Compound 2-8 4.03 20.7 200 Red Example 28 Compound 2-19 4.05 20.4 209 Red Example 29 Compound 1-13 Compound 2-1 4.03 18.8 204 Red Example 30 Compound 2-2 4.07 19.1 210 Red Example 31 Compound 2-8 4.04 19.6 201 Red Example 32 Compound 2-19 4.03 20.1 212 Red Example 33 Compound 1-14 Compound 2-1 4.05 19.3 205 Red Example 34 Compound 2-2 4.10 19.5 198 Red Example 35 Compound 2-8 4.12 19.0 199 Red Example 36 Compound 2-19 4.09 19.7 203 Red Example 37 Compound 1-15 Compound 2-1 4.08 19.3 210 Red Example 38 Compound 2-2 4.06 19.0 216 Red Example 39 Compound 2-8 4.10 18.4 204 Red Example 40 Compound 2-19 4.12 19.0 201 Red

division Host 1 2nd host Driving
Voltage(V) Efficiency (cd/A) Life T95(hr) Luminous color Example 41 Compound 1-16 Compound 2-1 4.11 18.1 197 Red Example 42 Compound 2-2 4.08 19.3 199 Red Example 43 Compound 2-8 4.10 19.6 203 Red Example 44 Compound 2-19 4.12 19.1 201 Red Example 45 Compound 1-22 Compound 2-9 4.13 18.6 205 Red Example 46 Compound 2-10 4.09 19.0 199 Red Example 47 Compound 2-12 4.12 19.2 198 Red Example 48 Compound 2-16 4.14 19.0 210 Red Example 49 Compound 1-23 Compound 2-9 4.07 17.8 197 Red Example 50 Compound 2-10 4.10 17.9 204 Red Example 51 Compound 2-12 4.05 18.0 207 Red Example 52 Compound 2-16 4.08 18.2 206 Red Example 53 Compound 1-24 Compound 2-9 4.13 18.3 208 Red Example 54 Compound 2-10 4.11 18.9 207 Red Example 55 Compound 2-12 4.15 19.1 203 Red Example 56 Compound 2-16 4.14 19.2 194 Red Example 57 Compound 1-25 Compound 2-9 4.15 18.1 191 Red Example 58 Compound 2-10 4.13 18.0 201 Red Example 59 Compound 2-12 4.14 18.7 203 Red Example 60 Compound 2-16 4.17 19.0 208 Red Example 61 Compound 1-26 Compound 2-9 4.18 18.7 205 Red Example 62 Compound 2-10 4.19 18.6 204 Red Example 63 Compound 2-12 4.14 18.9 203 Red Example 64 Compound 2-16 4.15 18.0 211 Red Example 65 Compound 1-27 Compound 2-9 4.11 18.7 216 Red Example 66 Compound 2-10 4.13 18.6 214 Red Example 67 Compound 2-12 4.15 18.9 210 Red Example 68 Compound 2-16 4.17 18.0 208 Red Example 69 Compound 1-29 Compound 2-9 4.18 18.0 207 Red Example 70 Compound 2-10 4.21 18.7 206 Red Example 71 Compound 2-12 4.19 18.4 201 Red Example 72 Compound 2-16 4.18 18.9 197 Red Example 73 Compound 1-30 Compound 2-9 4.20 18.5 191 Red Example 74 Compound 2-10 4.17 18.3 198 Red Example 75 Compound 2-12 4.15 19.1 204 Red Example 76 Compound 2-16 4.16 19.4 206 Red Example 77 Compound 1-31 Compound 2-9 4.19 19.3 190 Red Example 78 Compound 2-10 4.21 19.2 196 Red Example 79 Compound 2-12 4.15 19.3 194 Red Example 80 Compound 2-16 4.13 18.8 208 Red

division Host 1 2nd host Driving
Voltage(V) Efficiency (cd/A) Life T95(hr) Luminous color Example 81 Compound 1-32 Compound 2-3 3.94 20.3 226 Red Example 82 Compound 2-4 3.97 21.3 211 Red Example 83 Compound 2-14 3.92 23.3 234 Red Example 84 Compound 2-21 3.96 22.7 227 Red Example 85 Compound 1-33 Compound 2-3 3.93 22.4 256 Red Example 86 Compound 2-4 3.95 23.6 267 Red Example 87 Compound 2-14 3.97 22.9 248 Red Example 88 Compound 2-21 3.96 22.5 272 Red Example 89 Compound 1-34 Compound 2-3 3.90 24.7 238 Red Example 90 Compound 2-4 3.91 24.6 222 Red Example 91 Compound 2-14 3.95 24.6 218 Red Example 92 Compound 2-21 3.97 24.3 231 Red Example 93 Compound 1-35 Compound 2-3 3.93 22.9 225 Red Example 94 Compound 2-4 3.97 22.4 219 Red Example 95 Compound 2-14 4.01 23.6 224 Red Example 96 Compound 2-21 3.98 22.7 216 Red Example 97 Compound 1-36 Compound 2-3 3.99 22.8 217 Red Example 98 Compound 2-4 3.97 23.0 205 Red Example 99 Compound 2-14 3.99 24.1 215 Red Example 100 Compound 2-21 3.95 22.8 224 Red Example 101 Compound 1-37 Compound 2-3 4.03 22.0 231 Red Example 102 Compound 2-4 3.99 21.7 244 Red Example 103 Compound 2-14 4.05 21.6 249 Red Example 104 Compound 2-21 4.02 22.0 271 Red Example 105 Compound 1-38 Compound 2-3 3.90 25.3 268 Red Example 106 Compound 2-4 3.95 25.4 248 Red Example 107 Compound 2-14 3.93 25.7 251 Red Example 108 Compound 2-21 3.97 25.0 255 Red Example 109 Compound 1-39 Compound 2-3 3.95 22.8 203 Red Example 110 Compound 2-4 3.98 21.9 201 Red Example 111 Compound 2-14 3.96 21.7 197 Red Example 112 Compound 2-21 3.99 21.3 205 Red Example 113 Compound 1-40 Compound 2-3 3.81 22.7 277 Red Example 114 Compound 2-4 3.85 22.9 285 Red Example 115 Compound 2-14 3.84 23.6 279 Red Example 116 Compound 2-21 3.80 23.8 288 Red Example 117 Compound 1-42 Compound 2-3 3.90 25.0 271 Red Example 118 Compound 2-4 3.87 24.9 265 Red Example 119 Compound 2-14 3.84 25.0 269 Red Example 120 Compound 2-21 3.89 24.5 258 Red

division Host 1 2nd host Driving
Voltage(V) Efficiency (cd/A) Life T95(hr) Luminous color Comparative Example 16 Compound C-1 Compound 2-1 4.02 12.7 128 Red Comparative Example 17 Compound 2-2 4.03 12.3 123 Red Comparative Example 18 Compound 2-8 3.99 12.4 120 Red Comparative Example 19 Compound 2-19 4.01 12.5 111 Red Comparative Example 20 Compound C-2 Compound 2-1 4.05 13.6 116 Red Comparative Example 21 Compound 2-2 3.99 13.8 120 Red Comparative Example 22 Compound 2-8 4.10 13.7 127 Red Comparative Example 23 Compound 2-19 3.97 13.2 104 Red Comparative Example 24 Compound C-3 Compound 2-1 4.02 14.1 119 Red Comparative Example 25 Compound 2-2 4.00 14.5 121 Red Comparative Example 26 Compound 2-8 4.07 13.4 121 Red Comparative Example 27 Compound 2-19 3.99 14.3 134 Red Comparative Example 28 Compound C-4 Compound 2-1 4.01 13.7 115 Red Comparative Example 29 Compound 2-2 4.11 14.6 103 Red Comparative Example 30 Compound 2-8 4.13 13.4 101 Red Comparative Example 31 Compound 2-19 4.08 12.8 109 Red Comparative Example 32 Compound C-5 Compound 2-9 4.12 14.0 108 Red Comparative Example 33 Compound 2-10 4.13 13.3 103 Red Comparative Example 34 Compound 2-12 4.15 14.1 110 Red Comparative Example 35 Compound 2-16 4.10 14.4 111 Red Comparative Example 36 Compound C-6 Compound 2-9 4.02 15.9 104 Red Comparative Example 37 Compound 2-10 4.00 14.8 105 Red Comparative Example 38 Compound 2-12 4.10 14.9 107 Red Comparative Example 39 Compound 2-16 4.04 14.5 114 Red Comparative Example 40 Compound C-7 Compound 2-9 3.97 14.0 111 Red Comparative Example 41 Compound 2-10 3.95 14.1 113 Red Comparative Example 42 Compound 2-12 4.98 15.5 108 Red Comparative Example 43 Compound 2-16 3.99 14.3 111 Red Comparative Example 44 Compound C-8 Compound 2-9 4.01 16.5 108 Red Comparative Example 45 Compound 2-10 4.05 15.2 106 Red Comparative Example 46 Compound 2-12 4.11 15.5 105 Red Comparative Example 47 Compound 2-16 4.13 15.3 104 Red Comparative Example 48 Compound C-9 Compound 2-3 4.05 15.7 107 Red Comparative Example 49 Compound 2-4 4.07 14.5 106 Red Comparative Example 50 Compound 2-14 4.06 14.9 104 Red Comparative Example 51 Compound 2-21 4.05 14.0 108 Red Comparative Example 52 Compound C-10 Compound 2-3 4.10 13.9 115 Red Comparative Example 53 Compound 2-4 4.12 13.3 113 Red Comparative Example 54 Compound 2-14 4.11 13.7 104 Red Comparative Example 55 Compound 2-21 4.15 14.5 107 Red

division Host 1 2nd host Driving
Voltage(V) Efficiency (cd/A) Life T95(hr) Luminous color Comparative Example 56 Compound C-11 Compound 2-3 4.07 14.3 110 Red Comparative Example 57 Compound 2-4 4.11 14.0 114 Red Comparative Example 58 Compound 2-14 4.08 14.1 110 Red Comparative Example 59 Compound 2-21 4.09 15.8 118 Red Comparative Example 60 Compound C-12 Compound 2-9 4.17 13.2 111 Red Comparative Example 61 Compound 2-10 4.15 13.0 115 Red Comparative Example 62 Compound 2-12 4.18 14.2 122 Red Comparative Example 63 Compound 2-16 4.11 14.3 118 Red

As shown in the above table, the organic light-emitting device of the 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 emission layer is a compound represented by Formulas 1 and 2 Compared to the organic light-emitting device of Comparative Example in which only one of or neither is employed, the same or superior luminous efficiency, low driving voltage, and remarkably improved lifetime characteristics are exhibited.

Specifically, the device according to the example exhibited higher efficiency and longer life than the device of the comparative example employing the compound represented by Formula 1 as a single host. In addition, the device according to the embodiment has improved efficiency and lifespan characteristics compared to the device of Comparative Example employing Comparative Examples Compounds C-1 to C-12 as a first host and a compound represented by Formula 2 as a second host. Became. Through this, when the combination of the first compound represented by Formula 1 and the second compound represented by Formula 2 was used as a cohost, it was confirmed that energy was effectively transferred to the red dopant in the red light emitting layer. This can be determined because the first compound has high stability against electrons and holes, and also because the amount of holes increased as the second compound was used simultaneously, and a more stable balance of electrons and holes was maintained in the red light emitting layer. It is judged as.

Accordingly, it was confirmed that when the first compound and the second compound are simultaneously employed as host materials of the organic light-emitting device, driving voltage, luminous efficiency, and/or lifetime characteristics of the organic light-emitting device can be improved. In general, when considering that the luminous efficiency and lifetime characteristics of the organic light-emitting device have a trade-off relationship with each other, the organic light-emitting device employing a combination of the compounds of the present invention has significantly improved device characteristics compared to the comparative example device. It can be seen as representing.

1: substrate 2: anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: electron suppression layer 8: hole blocking layer
9: electron injection and transport layer

Claims (12)

A first electrode;
A second electrode provided to face the first electrode; And
Including a light emitting layer provided between the first electrode and the second electrode,
The emission layer comprises a first compound represented by the following formula 1 and a second compound represented by the following formula 2,
Organic light emitting element:
[Formula 1]

In Formula 1,
X ₁ to X ₃ are each independently N or CH, but at least two of X ₁ to X ₃ are N,
Ar ₁ and Ar ₂ are each independently deuterium; Substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S,
Z is each independently hydrogen, or deuterium, or two adjacent ones of Z are bonded to each other to include a C _6-60 aromatic ring or any one or more heteroatoms selected from the group consisting of N, O and S Can form _2-60 heteroaromatic rings,
Here, the C _6-60 aromatic ring and the C _2-60 heteroaromatic ring are unsubstituted or substituted with deuterium,
n is an integer from 0 to 6,
A is a substituent represented by the following formula 1-1,
[Formula 1-1]

In Formula 1-1,
R ₁ to R ₄ are each independently hydrogen or deuterium, or two adjacent ones of R ₁ to R ₄ are bonded to each other to form a C _6-60 aromatic ring or any one selected from the group consisting of N, O and S Can form a C _2-60 heteroaromatic ring containing more than one heteroatom
Here, the C _6-60 aromatic ring and the C _2-60 heteroaromatic ring are unsubstituted or substituted with deuterium,
D means deuterium,
m is an integer from 0 to 6,
[Formula 2]

In Chemical Formula 2,
T ₁ to T ₄ are each independently a substituted or unsubstituted C _6-60 aromatic ring; Or a substituted or unsubstituted C _2-60 heteroaromatic ring containing any one or more heteroatoms selected from the group consisting of N, O and S,
L ₁ and L ₂ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; Or substituted or unsubstituted C _2-60 heteroarylene including any one or more heteroatoms selected from the group consisting of N, O and S,
Ar ₃ and Ar ₄ are each independently a substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S.
The method of claim 1,
X ₁ to X ₃ are all N,
Organic light emitting device.
The method of claim 1,
The first compound is represented by any one of the following Formulas 3-1 to 3-7,
Organic light emitting element:

In Formulas 3-1 to 3-7,
Each R is independently hydrogen or deuterium,
A, Ar ₁ and Ar ₂ are as defined in claim 1.
The method of claim 1,
Ar ₁ and Ar ₂ are each independently, any one selected from the group consisting of,
Organic light emitting element:

.
The method of claim 1,
A is any one of the substituents represented by the following formulas a1 to a4,
Organic light emitting element:

.

The method of claim 1,
The first compound is any one selected from the group consisting of,
Organic light emitting element:

.
The method of claim 1,
The second compound is represented by the following formula 2-1,
Organic light emitting element:
[Formula 2-1]

In Formula 2-1,
D means deuterium,
r and s are each independently an integer of 0 to 7,
Descriptions of L ₁ , L ₂ , Ar ₃ and Ar ₄ are as defined in claim 1.
The method of claim 1,
L ₁ and L ₂ are each independently a single bond, phenylene, or naphthylene,
Organic light emitting device.
The method of claim 1,
Ar ₃ and Ar ₄ are each independently, any one selected from the group consisting of,
Organic light emitting element:

.
The method of claim 1,
The second compound is represented by the following formula 2-2,
Organic light emitting element:
[Formula 2-2]

In Formula 2-2,
L ₁ and L ₂ are each independently a single bond, phenylene, or naphthylene,
Ar ₃ and Ar ₄ are as defined in claim 1.
The method of claim 1,
The second compound is any one selected from the group consisting of,
Organic light emitting element:

.
The method of claim 1,
The first compound and the second compound are included in a weight ratio of 99:1 to 1:99,
Organic light emitting device.

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