KR20210063246A - Compound and organic light emitting device comprising the same - Google Patents

Abstract

The present specification relates to a compound represented by chemical formula 1 and an organic light emitting device including the same. The present specification provides a compound represented by chemical formula 1. The organic light emitting device using the compound according to an exemplary embodiment of the present application can have a low driving voltage, high luminous efficiency, or a long lifespan.

Description

Compound and organic light emitting device including the same {COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME}

This specification claims the benefit of the filing date of Korean Patent Application No. 10-2019-0151322 filed with the Korean Intellectual Property Office on November 22, 2019, the entire contents of which are incorporated herein by reference.

The present specification relates to a compound and an organic light emitting device including the same.

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy by using an organic material. An organic light emitting device using an organic light emitting phenomenon generally has a structure including a first electrode and a second electrode and an organic material layer therebetween. Here, the organic material layer is often made of a multilayer 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. When a voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the first electrode and electrons are injected into the organic material layer at the second electrode, and excitons are formed when the injected holes and electrons meet. , when this exciton falls back to the ground state, it glows.

Development of a new material for the organic light emitting device as described above is continuously required.

The present specification provides a compound and an organic light emitting device including the same.

The present specification provides a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

X and Y are the same as or different from each other, each independently O, S or CZ1Z2,

Ring A is a benzene ring or a naphthalene ring,

A1 to A4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitro group; Hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

R1 to R6, Z1 and Z2 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

n1 to n3, m and l are each 0 or 1,

The sum of n1 to n3 is 2 or more,

a1 and a2 are each an integer of 1 to 4,

a3 is an integer from 1 to 3;

a4 is an integer from 1 to 6,

When a1 to a4 are each 2 or more, the structures in parentheses are the same or different from each other,

However, when ring A is naphthalene, m is 0,

When l is 1, ring A is a benzene ring.

In addition, the present specification is a first electrode; A second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound described above.

The organic light emitting device using the compound according to the exemplary embodiment of the present application can have a low driving voltage, high luminous efficiency, or a long lifespan.

1 illustrates a structure of an organic light emitting diode according to an exemplary embodiment.
2 illustrates a structure of an organic light emitting diode according to another exemplary embodiment.

Hereinafter, the present specification will be described in detail.

The present specification provides a compound represented by Formula 1 above.

In the present specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

In the present specification, when a member is said to be positioned "on" another member, this includes not only the case where the member is in contact with the other member, but also the case where another member exists between the two members.

According to an exemplary embodiment of the present specification, the compound represented by Formula 1 is a structure in which benzothiophene, benzofuran group, or dihydroindene is directly condensed with an indolocarbazole structure to improve the rigidity of the molecule itself. can increase the stability of This has the advantage of improving the lifespan of the organic light emitting device when driving. In addition, in the compound represented by Formula 1, two or more amine groups are substituted at specific positions, which increases the oscillator strength value compared to the case where there is no amine group or one, thereby improving the luminous efficiency of the device.

Examples of the substituent in the present specification are described below, but are not limited thereto.

The term “substitution” means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, a position where the substituent is substitutable, is , two or more substituents may be the same as or different from each other.

As used herein, the term “substituted or unsubstituted” refers to deuterium (-D); Halogen group; Nitrile group; Nitro group; Hydroxy group; Amine group; Silyl group; Boron group; Alkoxy group; Alkyl group; Cycloalkyl group; Aryl group; And it is substituted with one or two or more substituents selected from the group consisting of a heterocyclic group, two or more of the substituents exemplified above are substituted with a connected substituent, or does not have any substituents. For example, “a substituent in which two or more substituents are connected” may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.

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

In the present specification, examples of the halogen group include fluorine (-F), chlorine (-Cl), bromine (-Br), or iodine (-I).

In the present specification, the silyl group may be represented by the formula of _{-SiY a} Y _b Y _{c , wherein Y a} , Y _b and Y _c are each hydrogen; A substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group. The silyl group specifically includes, but is not limited to, a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. does not

In the present specification, the boron group may be represented by the formula of _{-BY d} Y _{e , wherein Y d} and Y _e are each hydrogen; A substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group. Specifically, the boron group includes, but is not limited to, a trimethylboron group, a triethylboron group, a tert-butyldimethylboron group, a triphenylboron group, a phenylboron group, and the like.

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

In the present specification, the alkoxy group may be a straight chain, branched chain, or cyclic chain. Although the number of carbon atoms of the alkoxy group is not particularly limited, it is preferably 1 to 20 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, and the like, but is not limited thereto. .

Substituents including an alkyl group, an alkoxy group, and other alkyl group moieties described in the present specification include all of a straight chain or a branched form.

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, there are a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, 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 carbon number of the aryl group is 6 to 39. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. The aryl group may be a monocyclic aryl group such as a phenyl group, a biphenyl group, a terphenyl group, or a quarterphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, a triphenylenyl group, and the like, but is not limited thereto.

In the present specification, the fluorene group may be substituted, and two substituents may be bonded to each other to form a spiro structure.

,

등의 스피로플루오렌기,

(9,9-디메틸플루오렌기), 및

(9,9-디페닐플루오렌기) 등의 치환된 플루오렌기가 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorene group is substituted,

,

spirofluorene groups such as

(9,9-dimethylfluorene group), and

It may be a substituted fluorene group such as (9,9-diphenylfluorene group). However, it is not limited thereto.

In the present specification, the heterocyclic group is a cyclic group including at least one of N, O, P, S, Si, and Se as hetero atoms, and the number of carbons is not particularly limited, but is preferably 2 to 60 carbon atoms. According to an exemplary embodiment, the heterocyclic group has 2 to 36 carbon atoms. Examples of the heterocyclic group include a pyridine group, a pyrrole group, a pyrimidine group, a quinoline group, a pyridazine group, a furan group, a thiophene group, an imidazole group, a pyrazole group, a dibenzofuran group, a dibenzothiophene group, A carbazole group, a benzocarbazole group, a benzonaphthofuran group, a benzonaphthothiophene group, an indenocarbazole group, an indolocarbazole group, etc., but are not limited thereto.

In the present specification, the description of the aforementioned heterocyclic group may be applied except that the heteroaryl group is aromatic.

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

In the present specification, the N-alkylarylamine group refers to an amine group in which an alkyl group and an aryl group are substituted with N of the amine group.

In the present specification, the N-arylheteroarylamine group refers to an amine group in which an aryl group and a heteroaryl group are substituted with N of the amine group.

In the present specification, the N-alkylheteroarylamine group refers to an amine group in which an alkyl group and a heteroaryl group are substituted with N of the amine group.

In the present specification, an alkylamine group; N-alkylarylamine group; Arylamine group; N-aryl heteroarylamine group; The alkyl group, the aryl group and the heteroaryl group in the N-alkylheteroarylamine group and the heteroarylamine group are the same as the examples of the alkyl group, the aryl group and the heteroaryl group, respectively.

In an exemplary embodiment of the present specification, the compound represented by Formula 1 is represented by any one of Formulas 2-1 to 2-8.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 2-7]

[Formula 2-8]

In Formulas 2-1 to 2-8, X, Y, A1 to A4, a1 to a4, R1 to R6, n1 to n3 and m are the same as defined in Formula 1, and A5 is hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitro group; Hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; or a substituted or unsubstituted heterocyclic group, a5 is an integer of 1 to 4, and when a5 is 2 or more, the structures in parentheses are the same as or different from each other.

In an exemplary embodiment of the present specification, X and Y are the same as or different from each other, each independently O, S or CZ1Z2, Z1 and Z2 are the same or different from each other, and each independently a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In an exemplary embodiment of the present specification, the compound represented by Formula 1 is represented by any one of Formulas 3-1 to 3-12.

[Chemical Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

[Formula 3-5]

[Formula 3-6]

[Formula 3-7]

[Formula 3-8]

[Formula 3-9]

[Formula 3-10]

[Formula 3-11]

[Formula 3-12]

In Formulas 3-1 to 3-12, A1 to A4, a1 to a4, R1 to R6, n1 to n3, m, Z1 and Z2 are the same as defined in Formula 1, Z3 and Z4 are the same as or different from each other, each independently a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, A5 is hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitro group; Hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; or a substituted or unsubstituted heterocyclic group, a5 is an integer of 1 to 4, and when a5 is 2 or more, the structures in parentheses are the same or different from each other.

In an exemplary embodiment of the present specification, the compound represented by Formula 1 is represented by any one of Formulas 4-1 to 4-4 below.

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

In Formulas 4-1 to 4-4, X, Y, A1 to A4, and R1 to R6 are the same as defined in Formula 1.

In one embodiment of the present specification, the sum of n1 to n3 is 2 or more.

In the exemplary embodiment of the present specification, the sum of n1 to n3 is 2.

In one embodiment of the present specification, the sum of n1 to n3 is 3.

In an exemplary embodiment of the present specification, A1 to A4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitro group; Hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In an exemplary embodiment of the present specification, A1 to A4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group.

In an exemplary embodiment of the present specification, A1 to A4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C1-C10 alkyl group; or a substituted or unsubstituted C6-C20 aryl group.

In an exemplary embodiment of the present specification, A1 to A4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted C1-C10 linear or branched alkyl group; or a substituted or unsubstituted C6-C10 aryl group.

In an exemplary embodiment of the present specification, A1 to A4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Methyl group; tert-butyl group; Or a phenyl group.

In an exemplary embodiment of the present specification, A1 to A4 are each hydrogen; Or deuterium.

In an exemplary embodiment of the present specification, R1 to R6 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In an exemplary embodiment of the present specification, R1 to R6 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In an exemplary embodiment of the present specification, R1 to R6 are the same as or different from each other, and each independently deuterium, an alkyl group, a halohalo group, an alkyl group substituted with deuterium, a halogen group, a cyano group, a cycloalkyl group, a silyl substituted with an alkyl group an aryl group unsubstituted or substituted with a group selected from the group consisting of a group and an alkoxy group; or a heterocyclic group unsubstituted or substituted with a group selected from the group consisting of deuterium, an alkyl group, a halohalo group, an alkyl group substituted with deuterium, a halogen group, an aryl group substituted or unsubstituted with deuterium, and a cycloalkyl group.

In an exemplary embodiment of the present specification, R1 to R6 are the same as or different from each other, and each independently deuterium, methyl group, tert-butyl group, iso-propyl group, -CF ₃ , -CD ₃ , F, cyano group, cyclo an aryl group unsubstituted or substituted with a group selected from the group consisting of a hexyl group, a trimethylsilyl group, and a methoxy group; Or a heterocyclic ring unsubstituted or substituted with a group selected from the group consisting of deuterium, a methyl group, a tert-butyl group, an iso-propyl group, -CF ₃ , -CD ₃ , F, a phenyl group unsubstituted or substituted with deuterium, and a cyclohexyl group it's gi

In an exemplary embodiment of the present specification, R1 to R6 are the same as or different from each other, and each independently deuterium, methyl group, tert-butyl group, iso-propyl group, -CF ₃ , -CD ₃ , F, cyano group, cyclo a phenyl group unsubstituted or substituted with a group selected from the group consisting of a hexyl group, a trimethylsilyl group, and a methoxy group; a biphenyl group unsubstituted or substituted with deuterium or a tert-butyl group; a fluorenyl group substituted with a methyl group; naphthyl group; phenanthrenyl group; a dibenzofuranyl group unsubstituted or substituted with a group selected from the group consisting of a methyl group, iso-propyl group, tert-butyl group, -CD _{3 , a phenyl group unsubstituted or substituted with deuterium, and a cyclohexyl group;} a dibenzothiophenyl group unsubstituted or substituted with a group selected from the group consisting of a methyl group, iso-propyl group, tert-butyl group, -CD _{3 , a phenyl group unsubstituted or substituted with deuterium, and a cyclohexyl group;} a thiophenyl group unsubstituted or substituted with a phenyl group; quinolinyl group; benzonaphthofuranyl group; benzonaphthothiophenyl group; or a benzofluorenyl group substituted with a methyl group.

In an exemplary embodiment of the present specification, the compound represented by Formula 1 is represented by any one of the following structures.

Here, tBu is a tert-butyl group, and Me is a methyl group.

In addition, the present specification provides an organic light-emitting device including the above-described compound.

In an exemplary embodiment of the present specification, the first electrode; A second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound.

The organic material layer of the organic light emitting device of the present specification may have a single-layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

In an exemplary embodiment of the present specification, the organic material layer includes a hole injection layer or a hole transport layer, and the hole injection layer or the hole transport layer includes the compound.

In an exemplary embodiment of the present specification, the organic material layer includes an emission layer, and the emission layer includes the compound. Specifically, the emission layer may include a host and a dopant including the compound.

In an exemplary embodiment of the present specification, the organic material layer includes an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer includes the compound.

In an exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, a hole injection layer, and a hole transport layer. It further includes one or more layers selected from the group consisting of an electron transport layer, an electron injection layer, an electron blocking layer, and a hole blocking layer.

In the exemplary embodiment of the present specification, the organic light emitting device includes an anode; a cathode provided to face the anode; and at least one organic material layer provided between the anode and the cathode, wherein the organic material layer includes: a light emitting layer; a hole transport region provided between the light emitting layer and the anode; and an electron transport region provided between the emission layer and the cathode, wherein the emission layer includes the compound.

In one embodiment of the present specification, the organic material layer of the hole transport region may be one or more selected from the group consisting of a hole transport layer, a hole injection layer, a layer that transports and injects holes at the same time, and an electron blocking layer.

In an exemplary embodiment of the present specification, the organic material layer of the electron transport region may be one or more selected from the group consisting of an electron transport layer, an electron injection layer, a layer that simultaneously transports and injects electrons, and a hole blocking layer.

In another exemplary embodiment, the organic light emitting device may be a normal type organic light emitting device in which a first electrode, one or more organic material layers, and a second electrode are sequentially stacked on a substrate.

In another exemplary embodiment, the organic light emitting device may be an inverted type organic light emitting device in which a second electrode, one or more organic material layers, and a first electrode are sequentially stacked on a substrate.

The organic light-emitting device may have, for example, a stacked structure as described below, but is not limited thereto.

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

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

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

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

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

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

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

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

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

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

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

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

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

(14) anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode

(15) anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode

(16) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode

(17) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode

(18) anode / hole injection layer / hole transport layer / light emitting layer / layer that simultaneously injects and transports electrons / cathode

(19) anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode

(20) anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / cathode

(21) anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / layer that simultaneously injects and transports electrons / cathode

For example, the structure of the organic light emitting device according to an exemplary embodiment of the present specification is illustrated in FIGS. 1 and 2 .

1 illustrates a structure of an organic light emitting device in which a substrate 1, a first electrode 2, a light emitting layer 3, and a second electrode 4 are sequentially stacked.

2 is a substrate (1), a first electrode (2), a hole injection layer (5), a hole transport layer (6), a light emitting layer (3), an electron transport layer (7) and a second electrode (4) are sequentially stacked The structure of the organic light emitting device is exemplified. In such a structure, the compound may be included in the light emitting layer 3 .

The organic light emitting device of the present specification may be manufactured using materials and methods known in the art, except that at least one layer of the organic material layer includes the compound of the present specification, that is, the compound.

When the organic light-emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

The organic light emitting device of the present specification may be manufactured using materials and methods known in the art, except that at least one layer of the organic material layer includes the compound, that is, the compound represented by Formula 1 above.

For example, the organic light emitting device of the present specification may be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or a metal oxide having conductivity or an alloy thereof is deposited on a substrate to deposit the first electrode After forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, it can be prepared by depositing a material that can be used as a second electrode thereon. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing the second electrode material, the organic material layer, and the first electrode material on the substrate.

In addition, the compound of Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

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

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

The anode is an electrode for injecting holes, and 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 anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as 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.

The cathode is an electrode for injecting electrons, and the cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the 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 multilayered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

The hole injection layer is a layer for injecting holes from the electrode, and as a hole injection material, it has the ability to transport holes and has a hole injection effect in the first electrode, an excellent hole injection effect with respect to the light emitting layer or the light emitting material, and in the light emitting layer A compound that prevents the generated exciton from moving to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the first electrode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. Organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light emitting layer. The hole transport material is a material capable of transporting holes from the first electrode or hole injection layer to the light emitting layer. Mobility for holes This large material is suitable. Specific examples include an arylamine-based organic material, a conductive polymer, and a block copolymer including a conjugated portion and a non-conjugated portion, but are not limited thereto.

The emission layer may include a host material and a dopant material.

Examples of the host material for the light emitting layer include a condensed aromatic ring derivative or a heterocyclic compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic compound containing compounds include carbazole derivatives, dibenzofuran, dibenzofuran. derivatives, dibenzothiophene, dibenzothiophene derivatives, ladder-type furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

In an exemplary embodiment of the present specification, the host includes a compound represented by the following formula (5).

[Formula 5]

In Formula 5,

L21 to L23 are the same as or different from each other, and are each independently a direct bond; Or a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

R21 to R27 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Ar21 to Ar23 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

a is 0 or 1.

In an exemplary embodiment of the present specification, the host includes a compound represented by any one of the following structures.

The compound may be used as a dopant material of the light emitting layer, and an additional dopant may be further included.

Additional dopants include PIQIr(acac)(bis(1-phenylisoquinoline)acetylacetonateiridium), PQIr(acac)(bis(1-phenylquinoline)acetylacetonate iridium), PQIr(tris(1) when the light-emitting layer emits red light. -phenylquinoline)iridium), a phosphorescent material such as PtOEP (octaethylporphyrin platinum), or a _{fluorescent material such as Alq 3} (tris(8-hydroxyquinolino)aluminum) may be used, but is not limited thereto. When the emission layer emits green light, a _{phosphor such as Ir(ppy) 3} (fac tris(2-phenylpyridine)iridium) or a fluorescent material such as Alq3 (tris(8-hydroxyquinolino)aluminum) may be used as the emission dopant. However, it is not limited thereto. When the light-emitting layer emits blue light, as the light-emitting dopant, a _{phosphorescent material such as (4,6-F2ppy) 2} Irpic, spiro-DPVBi, spiro-6P, distillbenzene (DSB), distrylarylene (DSA), A fluorescent material such as a PFO-based polymer or a PPV-based polymer may be used, but is not limited thereto.

In an exemplary embodiment of the present specification, the compound is a dopant, specifically a fluorescent dopant, and more specifically a blue fluorescent dopant.

In an exemplary embodiment of the present specification, the maximum emission peak of the compound represented by Formula 1 is 420 nm to 480 nm.

In an exemplary embodiment of the present specification, the light emitting layer includes a host and a dopant in a mass ratio of 99:1 to 1:99.

In an exemplary embodiment of the present specification, the light emitting layer includes a host and a dopant in a mass ratio of 99:1 to 10:90.

In an exemplary embodiment of the present specification, the light emitting layer includes a host and a dopant in a mass ratio of 99:1 to 50:50.

In an exemplary embodiment of the present specification, when the dopant of the emission layer includes the compound represented by Formula 1, and the host of the emission layer includes the compound represented by Formula 5, the weight of the compound represented by Formula 5 When set to 100 parts by weight, the content of the compound represented by Formula 1 may be 0.01 parts by weight to 30 parts by weight, specifically 0.1 parts by weight to 20 parts by weight, and more specifically 0.5 parts by weight to 10 parts by weight. .

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. The electron transport material is a material that can receive electrons well from the second electrode and transfer them to the light emitting layer, and has high electron mobility. This is suitable. Specific examples include Al complex of 8-hydroxyquinoline; complexes comprising Alq3; organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the second electrode, an excellent electron injection effect on the light emitting layer or the light emitting material, and A compound that prevents migration to the hole injection layer and is excellent in the ability to form a thin film is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, etc., derivatives thereof, metals complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( o-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.

The hole blocking layer is a layer that blocks the holes from reaching the cathode, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes, etc., but are not limited thereto.

An electron blocking layer may be provided between the hole transport layer and the light emitting layer. The electronic blocking layer may be a material known in the art.

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

The compound represented by Formula 1 of the present specification may have a core structure as shown in the following Reaction Formulas. Substituents may be combined by methods known in the art, and the type, position and number of substituents may be changed according to techniques known in the art.

<Scheme 1> Synthesis of Formula 4-1

In Scheme 1, X, A1 and R3 to R6 are the same as defined in Formula 1,

_{-OSO 2} R is a substituent including a sulfone group generated as a result of the sulfonation reaction, and is a living group that is released by the Buchwald amination reaction,

Me is a methyl group.

Intermediate IM-3 is synthesized by Buchwald amination of Intermediate IM-1 and Intermediate IM-2, and Intermediate IM-4 can be obtained through Heck reaction. Intermediate IM-5 containing a sulfone group can be obtained by demethylation reaction and sulfonylation in Intermediate IM-4. In the intermediate IM-5, Formula 4-1 can be obtained by Buchwald amination.

<Scheme 2> Synthesis of Formula 4-2

In Scheme 2, X, A4, R1, R2, R5 and R6 are the same as defined in Formula 1 above,

_{-OSO 2} R is a substituent including a sulfone group generated as a result of the sulfonation reaction, and is a living group that is released by the Buchwald amination reaction,

Me is a methyl group, and Hal ₁ and Hal ₂ are different and each independently a halogen group.

Intermediate IM-8 was synthesized by Suzuki coupling reaction of intermediate IM-6 and intermediate IM-7 substituted with different halogens and Buchwald amination reaction, and demethylation of intermediate IM-8 was performed. Intermediate IM-9 containing a sulfone group can be obtained by a demethylation reaction and a sulfonylation reaction. Formula 4-2 can be obtained by Buchwald amination in the intermediate IM-9.

<Scheme 3> Synthesis of Formula 4-3

In Scheme 3, X, A3, Y and R1 to R4 are the same as defined in Formula 1 above,

_{-OSO 2} R is a substituent including a sulfone group generated as a result of the sulfonation reaction, and is a living group that is released by the Buchwald amination reaction,

Me is a methyl group,

Hal ₁ and Hal ₂ are different from each other and are each independently a halogen group,

Hal ₃ and Hal ₄ are different from each other and each independently represent a halogen group.

The intermediate IM-11 was synthesized through the borylation of the intermediate IM-10, and the intermediate IM-12 was synthesized by the Suzuki coupling reaction with the intermediate IM-6 and the Buchwald amination reaction. can get Intermediate IM-13 was synthesized from Intermediate IM-12 through borylation again, and Intermediate IM-15 was subjected to Suzuki coupling reaction with Intermediate IM-14 and Buchwald amination reaction. can get Intermediate IM-16 containing a sulfone group can be obtained from intermediate IM-15 by demethylation reaction and sulfonylation reaction. Finally, Formula 4-3 can be obtained by Buchwald amination in the intermediate IM-16.

<Scheme 4> Synthesis of Formula 4-4

In Scheme 4, X, Y, A2, A3 and R1 to R4 are the same as defined in Formula 1 above,

_{-OSO 2} R is a substituent including a sulfone group generated as a result of the sulfonation reaction, and is a living group that is released by the Buchwald amination reaction,

Me is a methyl group,

Hal ₁ and Hal ₂ are different from each other and are each independently a halogen group,

Hal ₃ and Hal ₄ are different from each other and each independently represent a halogen group.

The intermediate IM-18 was synthesized through the boronation of the intermediate IM-17, and the intermediate was subjected to the Suzuki coupling reaction with the intermediate 6 (IM-6) and the Buchwald amination reaction. You can get IM-19. Intermediate IM-20 was synthesized from Intermediate IM-19 again through borylation, and Intermediate IM-21 was subjected to Suzuki coupling reaction with Intermediate IM-14 and Buchwald amination reaction. can get Intermediate IM-22 containing a sulfone group can be obtained from Intermediate IM-21 by demethylation reaction and sulfonylation reaction. Finally, Formula 4-4 can be obtained by Buchwald amination in the intermediate IM-22.

When any one of Schemes 1 to 4 of the present specification and the intermediates are appropriately combined based on common technical knowledge, all of the compounds of Formula 1 described herein can be prepared.

Hereinafter, the present specification will be described in more detail through examples. However, the following examples are only for illustrating the present specification, and not for limiting the present specification.

Synthesis Example 1. Synthesis of compound 1

end. Synthesis of Intermediate 1

In a nitrogen atmosphere, 20 g of starting material A-1, 12 g of boronic ester B-1, 11 g of potassium carbonate, 400 mL of tetrahydrofuran (THF) and 40 mL of water were added, and then tetrakis (triphenylphosphine) palladium (0) After 1.2 g of [tetrakis(triphenylhosphine)palladium(0), (TTP), Pd(PPh ₃ ) ₄ ] was added, the mixture was heated at 120° C. and stirred for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature, separated by adding water and ethyl acetate, and filtered by treatment with _{MgSO 4 (anhydrous).} The filtered solution was distilled off under reduced pressure and purified by recrystallization (ethylacetate/hexane) to obtain Intermediate 1 (18 g). (Yield 76%, Mass [M+]=443)

I. Synthesis of Intermediate 2

18 g of intermediate 1, sodium t-butoxide (NaOtBu) 7.8 g and bis(tri-tertbutylphosphine)palladium(0) [Bis(tri(tert-butyl)phosphine)palladium(0) under nitrogen atmosphere ), Pd(PtBu ₃ ) ₂ ] 0.4 g was added to 200 mL of toluene, and then heated at 140° C. and stirred for 6 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water and aq.NH ₄ Cl were added to separate the mixture, and the mixture was _{treated with MgSO 4} (anhydrous) and filtered. The filtered solution was distilled off under reduced pressure and purified by recrystallization to obtain Intermediate 2 (8.5 g). (Yield 58%, Mass [M+]=362)

All. Synthesis of intermediates 3 and 4

8.5 g of Intermediate 2 and 4.7 g of aluminum chloride [aluminum chloride] were placed in 200 mL of chlorobenzene (MCB) under a nitrogen atmosphere, and then heated at 130° C. and stirred for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the mixture, and the mixture was _{treated with MgSO 4} (anhydrous) and filtered. The filtered solution was distilled off under reduced pressure and purified by recrystallization (ethylacetate/hexane) to obtain Intermediate 3 (6.7 g). (Yield 82%, Mass [M+]=348)

After 150 mL of dimethylformamide (DMF) was added to 6.7 g of Intermediate 3 and 5.3 g of potassium carbonate [potassium carbonate], 3.8 mL of Nonafluorobutanesulfonyl fluoride was added dropwise at room temperature. After the reaction was completed by stirring for 5 hours, the reaction solution was filtered. The filtered solution was separated by adding water and ethyl acetate, and then _{treated with MgSO 4} (anhydrous) and filtered. The filtered solution was distilled off under reduced pressure and purified by recrystallization (toluene/hexane) to obtain Intermediate 4 (9.4 g). (Yield 77%, Mass [M+]=630)

la. Synthesis of compound 1

Under nitrogen atmosphere, 3.0 g of intermediate 4, 2.9 g of amine AM-1, 2.5 g of potassium phosphate and bis(tri-tertbutylphosphine)palladium(0)[Bis(tri(tert-butyl)phosphine)palladium (0), Pd(PtBu ₃ ) ₂ ] After 0.05 g of dioxane was placed in 40 mL of dioxane, it was heated at 100° C. and stirred for 28 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and water and aq. After separation by adding NaCl, MgSO ₄ (anhydrous) treatment and filtration. The filtered solution was distilled off under reduced pressure and purified by recrystallization (toluene/hexane) to obtain Compound 1 (3.1 g). (Yield 73%, Mass [M+]=897)

Synthesis Example 2. Synthesis of compound 2

end. Synthesis of Intermediate 5

Prepared in the same manner as in the synthesis of Intermediate 1, except that in the synthesis of Intermediate 1 of Synthesis Example 1, A-2 (10 g) instead of the starting material A-1 and B-2 (10.8 g) instead of the boronic ester B-1 were used Thus, intermediate 5 (10 g) was obtained. (Yield 72%, Mass [M+]=519)

I. Synthesis of Intermediate 6

Intermediate 6 (5.3 g) was obtained in the same manner as in the synthesis of Intermediate 2, except that Intermediate 5 (10 g) was used instead of Intermediate 1 in the synthesis of Intermediate 2 of Synthesis Example 1. (Yield 63%, Mass [M+]=438)

All. Synthesis of intermediates 7 and 8

Intermediate 7 (3.8 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 3, except that Intermediate 6 (5.3 g) was used instead of Intermediate 2 in the synthesis of Intermediate 3 of Synthesis Example 1. (Yield 74%, Mass [M+]=424)

Intermediate 8 (4.5 g) was obtained in the same manner as in the synthesis of Intermediate 4, except that Intermediate 7 (3.8 g) was used instead of Intermediate 3 in the synthesis of Intermediate 4 of Synthesis Example 1. (Yield 71%, Mass [M+]=706)

la. Synthesis of compound 2

In the synthesis of Compound 1 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Compound 1, except that Intermediate 8 (3.0 g) instead of Intermediate 4 and AM-2 (4.0 g) instead of AM-1 as an amine were used. 3.5 g) was obtained. (Yield 62%, Mass [M+]=1321)

Synthesis Example 3. Synthesis of compound 3

end. Synthesis of Intermediate 9

Under nitrogen atmosphere, starting material A-3 (10 g), benzofuroindole B-3 (11.6 g), sodium tert-butoxide [sodium t-butoxide] 6.0 g and bis(tri-tertbutylphosphine)palladium (0) [Bis(tri(tert-butyl)phosphine)palladium(0), Pd(PtBu ₃ ) ₂ ] 0.4 g was placed in 350 mL of toluene, and then heated at 140° C. and stirred for 5 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water and aq.NH ₄ Cl were added to separate the mixture, and the mixture was _{treated with MgSO 4} (anhydrous) and filtered. The filtered solution was distilled off under reduced pressure and purified by recrystallization to obtain Intermediate 9 (13.6 g). (Yield 75%, Mass [M+]=428)

I. Synthesis of Intermediate 10

Intermediate 9 (13.6 g), sodium tert-butoxide 6.1 g and bis(tri-tertbutylphosphine)palladium(0)[Bis(tri(tert-butyl)phosphine)palladium(0) under nitrogen atmosphere ), Pd(PtBu ₃ ) ₂ ] 0.3g was put in 160 mL of dimethylacetamide, and then heated at 120° C. and stirred for 10 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water and aq.NH ₄ Cl were added to separate the mixture, and the mixture was _{treated with MgSO 4} (anhydrous) and filtered. The filtered solution was distilled off under reduced pressure and purified by recrystallization (toluene/hexane) to obtain Intermediate 10 (7.9 g). (Yield 63%, Mass [M+]=392)

All. Synthesis of intermediates 11 and 12

Intermediate 11 (5.0 g) was obtained in the same manner as in the synthesis of Intermediate 3, except that Intermediate 10 (7.9 g) was used instead of Intermediate 2 in the synthesis of Intermediate 3 of Synthesis Example 1. (Yield 68%, Mass [M+]=364)

Intermediate 12 (8.1 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 4, except that Intermediate 11 (5.0 g) was used instead of Intermediate 3 in the synthesis of Intermediate 4 of Synthesis Example 1. (Yield 63%, Mass [M+]=928)

la. Synthesis of compound 3

In the synthesis of Compound 1 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Compound 1, except that Intermediate 12 (3.0 g) instead of Intermediate 4 and AM-3 (2.2 g) instead of AM-1 as an amine were used. 2.5 g) was obtained. (Yield 77%, Mass [M+]=1011)

Synthesis Example 4. Synthesis of compound 4

end. Synthesis of Intermediate 13

In the synthesis of Intermediate 9 of Synthesis Example 3, the same as the synthesis method of Intermediate 9 except that A-4 (5.0 g) instead of the starting material A-3 and B-4 (5.8 g) instead of benzofuroindole B-3 were used was prepared to obtain Intermediate 13 (6.8 g). (Yield 75%, Mass [M+]=428)

I. Synthesis of Intermediate 14

In the synthesis of Intermediate 10 of Synthesis Example 3, it was prepared in the same manner as in the synthesis of Intermediate 10, except that Intermediate 13 (6.8 g) was used instead of Intermediate 9 to obtain Intermediate 14 (3.8 g). (Yield 61%, Mass [M+]=392)

All. Synthesis of intermediates 15 and 16

In the synthesis of Intermediate 3 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Intermediate 3, except that Intermediate 14 (3.8 g) was used instead of Intermediate 2 to obtain Intermediate 15 (2.7 g). (Yield 77%, Mass [M+]=364)

Intermediate 16 (4.3 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 4, except that Intermediate 15 (2.7 g) was used instead of Intermediate 3 in the synthesis of Intermediate 4 of Synthesis Example 1. (Yield 62%, Mass [M+]=928)

la. Synthesis of compound 4

In the synthesis of Compound 1 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Compound 1, except that Intermediate 16 (3.0 g) instead of Intermediate 4 and AM-4 (1.8 g) instead of AM-1 as an amine were used. 2.1 g) was obtained. (Yield 74%, Mass [M+]=881)

Synthesis Example 5. Synthesis of compound 5

end. Synthesis of intermediate 17

In the synthesis of Intermediate 9 of Synthesis Example 3, A-5 (5.0 g) instead of starting material A-3 and B-5 (7.0 g) instead of benzofuroindole B-3 in the synthesis of Intermediate 9 are the same as the synthesis method of Intermediate 9 to obtain intermediate 17 (6.8 g). (Yield 73%, Mass [M+]=439)

I. Synthesis of Intermediate 18

In the synthesis of Intermediate 10 of Synthesis Example 3, intermediate 18 (4.6 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 10, except that Intermediate 17 (6.8 g) was used instead of Intermediate 9. (Yield 66%, Mass [M+]=448)

All. Synthesis of intermediates 19 and 20

Intermediate 19 (3.4 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 3, except that Intermediate 18 (4.6 g) was used instead of Intermediate 2 in the synthesis of Intermediate 3 of Synthesis Example 1. (Yield 79%, Mass [M+]=420)

In the synthesis of Intermediate 4 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Intermediate 4 except that Intermediate 19 (3.4 g) was used instead of Intermediate 3 to obtain Intermediate 20 (6.1 g). (Yield 77%, Mass [M+]=984)

la. Synthesis of compound 5

In the synthesis of Compound 1 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Compound 1, except that Intermediate 20 (3.0 g) instead of Intermediate 4 and AM-5 (2.2 g) instead of AM-1 as an amine were used. 2.5 g) was obtained. (Yield 74%, Mass [M+]=1103)

Synthesis Example 6. Synthesis of compound 6

end. Synthesis of Intermediate 21

In the synthesis of Intermediate 9 of Synthesis Example 3, the same as the synthesis method of Intermediate 9 except that A-4 (5.0 g) instead of the starting material A-3 and B-6 (7.4 g) instead of benzofuroindole B-3 were used was prepared to obtain Intermediate 21 (7.5 g). (Yield 71%, Mass [M+]=504)

I. Synthesis of Intermediate 22

Intermediate 22 (4.6 g) was obtained in the same manner as in the synthesis of Intermediate 10, except that Intermediate 21 (7.5 g) was used instead of Intermediate 9 in the synthesis of Intermediate 10 of Synthesis Example 3. (Yield 66%, Mass [M+]=468)

All. Synthesis of intermediates 23 and 24

Intermediate 23 (3.2 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 3, except that Intermediate 22 (4.6 g) was used instead of Intermediate 2 in the synthesis of Intermediate 3 of Synthesis Example 1. (Yield 74%, Mass [M+]=440)

Intermediate 24 (5.3 g) was obtained in the same manner as in the synthesis of Intermediate 4, except that Intermediate 23 (3.2 g) was used instead of Intermediate 3 in the synthesis of Intermediate 4 of Synthesis Example 1. (Yield 73%, Mass [M+]=1004)

la. Synthesis of compound 6

In the synthesis of Compound 1 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Compound 1, except that Intermediate 24 (3.0 g) instead of Intermediate 4 and AM-6 (2.0 g) instead of AM-1 as an amine were used. 2.3 g) was obtained. (Yield 72%, Mass [M+]=1067)

Synthesis Example 7. Synthesis of compound 7

end. Synthesis of Intermediate 25

In the synthesis of Intermediate 9 of Synthesis Example 3, A-6 (5.0 g) instead of starting material A-3 and B-7 (8.2 g) instead of benzofuroindole B-3 were used in the synthesis of Intermediate 9. The same as the synthesis method of Intermediate 9 was prepared to obtain Intermediate 25 (7.6 g). (Yield 66%, Mass [M+]=484)

I. Synthesis of Intermediate 26

In the synthesis of Intermediate 10 of Synthesis Example 3, intermediate 26 (4.3 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 10, except that Intermediate 25 (7.6 g) was used instead of Intermediate 9. (Yield 61%, Mass [M+]=448)

All. Synthesis of intermediates 27 and 28

Intermediate 27 (3.0 g) was obtained in the same manner as in the synthesis of Intermediate 3, except that Intermediate 26 (4.3 g) was used instead of Intermediate 2 in the synthesis of Intermediate 3 of Synthesis Example 1. (Yield 74%, Mass [M+]=420)

Intermediate 28 (4.8 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 4, except that Intermediate 27 (3.0 g) was used instead of Intermediate 3 in the synthesis of Intermediate 4 of Synthesis Example 1. (Yield 68%, Mass [M+]=984)

la. Synthesis of compound 7

In the synthesis of Compound 1 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Compound 1, except that Intermediate 28 (3.0 g) instead of Intermediate 4 and AM-7 (1.8 g) instead of AM-1 as an amine were used. 1.9 g) was obtained. (Yield 65%, Mass [M+]=959)

Synthesis Example 8. Synthesis of compound 8

end. Synthesis of Intermediate 29

In the synthesis of Intermediate 9 of Synthesis Example 3, A-4 (5.0 g) instead of the starting material A-3 and benzothioindole B-8 (10.8 g) instead of benzofuroindole B-3 were used in the synthesis of Intermediate 9. It was prepared in the same manner as in the synthesis method to obtain Intermediate 29 (6.9 g). (Yield 74%, Mass [M+]=444)

I. Synthesis of Intermediate 30

In the synthesis of Intermediate 10 of Synthesis Example 3, intermediate 30 (4.1 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 10, except that Intermediate 29 (6.9 g) was used instead of Intermediate 9. (Yield 65%, Mass [M+]=408)

All. Synthesis of intermediates 31 and 32

Intermediate 31 (3.0 g) was obtained in the same manner as in the synthesis of Intermediate 3, except that Intermediate 30 (4.1 g) was used instead of Intermediate 2 in the synthesis of Intermediate 3 of Synthesis Example 1. (Yield 79%, Mass [M+]=380)

Intermediate 32 (5.3 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 4 except that Intermediate 31 (3.0 g) was used instead of Intermediate 3 in the synthesis of Intermediate 4 of Synthesis Example 1. (Yield 71%, Mass [M+]=944)

la. Synthesis of compound 8

In the synthesis of Compound 1 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Compound 1, except that Intermediate 32 (3.0 g) instead of Intermediate 4 and AM-8 (1.8 g) instead of AM-1 as an amine were used. 2.0 g) was obtained. (Yield 69%, Mass [M+]=907)

Synthesis Example 9. Synthesis of compound 9

end. Synthesis of Intermediate 33

In the synthesis of Intermediate 9 of Synthesis Example 3, A-4 (5.0 g) instead of the starting material A-3, benzothioindole B-9 (7.3 g) instead of benzofuroindole B-3 was used. It was prepared in the same manner as in the synthesis method to obtain Intermediate 33 (7.1 g). (Yield 67%, Mass [M+]=501)

I. Synthesis of Intermediate 34

In the synthesis of Intermediate 10 of Synthesis Example 3, intermediate 34 (3.9 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 10, except that Intermediate 33 (7.1 g) was used instead of Intermediate 9. (Yield 59%, Mass [M+]=464)

All. Synthesis of intermediates 35 and 36

Intermediate 35 (2.7 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 3, except that Intermediate 34 (3.9 g) was used instead of Intermediate 2 in the synthesis of Intermediate 3 of Synthesis Example 1. (Yield 74%, Mass [M+]=436)

Intermediate 36 (4.6 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 4, except that Intermediate 35 (2.7 g) was used instead of Intermediate 3 in the synthesis of Intermediate 4 of Synthesis Example 1. (Yield 74%, Mass [M+]=1000)

la. Synthesis of compound 9

In the synthesis of Compound 1 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Compound 1, except that Intermediate 36 (3.0 g) instead of Intermediate 4 and AM-8 (1.7 g) instead of AM-1 as an amine were used. 2.1 g) was obtained. (Yield 73%, Mass [M+]=963)

Synthesis Example 10. Synthesis of compound 10

end. Synthesis of Intermediate 37

In the synthesis of Intermediate 9 of Synthesis Example 3, A-4 (5.0 g) instead of starting material A-3, benzothioindole B-10 (8.3 g) instead of benzofuroindole B-3 was used in the synthesis of Intermediate 9. It was prepared in the same manner as in the synthesis method to obtain Intermediate 37 (7.0 g). (Yield 61%, Mass [M+]=549)

I. Synthesis of Intermediate 38

Intermediate 38 (4.3 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 10, except that Intermediate 37 (7.0 g) was used instead of Intermediate 9 in the synthesis of Intermediate 10 of Synthesis Example 3. (Yield 66%, Mass [M+]=512)

All. Synthesis of intermediates 39 and 40

Intermediate 39 (3.3 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 3, except that Intermediate 38 (4.3 g) was used instead of Intermediate 2 in the synthesis of Intermediate 3 of Synthesis Example 1. (Yield 81%, Mass [M+]=484)

Intermediate 40 (5.5 g) was obtained in the same manner as in the synthesis of Intermediate 4 except that Intermediate 39 (3.3 g) was used instead of Intermediate 3 in the synthesis of Intermediate 4 of Synthesis Example 1. (Yield 77%, Mass [M+]=1048)

la. Synthesis of compound 10

In the synthesis of Compound 1 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Compound 1, except that Intermediate 40 (3.0 g) instead of Intermediate 4 and AM-9 (1.3 g) instead of AM-1 as an amine were used. 108 g) was obtained. (Yield 70%, Mass [M+]=899)

Synthesis Example 11. Synthesis of compound 11

end. Synthesis of Intermediate 41

In the synthesis of Intermediate 9 of Synthesis Example 3, A-4 (5.0 g) instead of starting material A-3 and benzothioindole B-11 (7.0 g) instead of benzofuroindole B-3 were used in the synthesis of Intermediate 9. It was prepared in the same manner as in the synthesis method to obtain Intermediate 41 (7.4 g). (Yield 72%, Mass [M+]=487)

I. Synthesis of Intermediate 42

Intermediate 42 (3.8 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 10, except that Intermediate 41 (7.4 g) was used instead of Intermediate 9 in the synthesis of Intermediate 10 of Synthesis Example 3. (Yield 56%, Mass [M+]=450)

All. Synthesis of intermediates 43 and 44

Intermediate 43 (2.6 g) was obtained in the same manner as in the synthesis of Intermediate 3, except that Intermediate 42 (3.8 g) was used instead of Intermediate 2 in the synthesis of Intermediate 3 of Synthesis Example 1. (Yield 73%, Mass [M+]=422)

In the synthesis of Intermediate 4 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Intermediate 4 except that Intermediate 43 (2.6 g) was used instead of Intermediate 3 to obtain Intermediate 44 (4.1 g). (Yield 67%, Mass [M+]=986)

la. Synthesis of compound 11

In the synthesis of Compound 1 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Compound 1, except that Intermediate 44 (3.0 g) instead of Intermediate 4 and AM-10 (2.3 g) instead of AM-1 as an amine were used. 2.4 g) was obtained. (Yield 70%, Mass [M+]=1129)

Synthesis Example 12. Synthesis of compound 12

end. Synthesis of Intermediate 45

In the synthesis of Intermediate 9 of Synthesis Example 3, A-4 (5.0 g) instead of the starting material A-3 and benzothioindole B-12 (7.3 g) instead of benzofuroindole B-3 were used in the synthesis of Intermediate 9. It was prepared in the same manner as in the synthesis method to obtain Intermediate 45 (6.5 g). (Yield 62%, Mass [M+]=501)

I. Synthesis of Intermediate 46

Intermediate 46 (3.7 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 10, except that Intermediate 45 (6.5 g) was used instead of Intermediate 9 in the synthesis of Intermediate 10 of Synthesis Example 3. (Yield 61%, Mass [M+]=464)

All. Synthesis of intermediates 47 and 48

Intermediate 47 (2.6 g) was obtained in the same manner as in the synthesis of Intermediate 3, except that Intermediate 46 (3.7 g) was used instead of Intermediate 2 in the synthesis of Intermediate 3 of Synthesis Example 1. (Yield 75%, Mass [M+]=436)

Intermediate 48 (4.2 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 4, except that Intermediate 47 (2.6 g) was used instead of Intermediate 3 in the synthesis of Intermediate 4 of Synthesis Example 1. (Yield 70%, Mass [M+]=1000)

la. Synthesis of compound 12

In the synthesis of Compound 1 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Compound 1, except that Intermediate 48 (3.0 g) instead of Intermediate 4 and AM-11 (1.0 g) instead of AM-1 as an amine were used. 1.6 g) was obtained. (Yield 72%, Mass [M+]=738)

Synthesis Example 13. Synthesis of compound 13

end. Synthesis of Intermediate 49

In the synthesis of Intermediate 9 of Synthesis Example 3, A-4 (5.0 g) instead of the starting material A-3 and benzothioindole B-13 (10.8 g) instead of benzofuroindole B-3 were used in the synthesis of Intermediate 9. It was prepared in the same manner as in the synthesis method to obtain intermediate 49 (6.5 g). (Yield 69%, Mass [M+]=444)

I. Synthesis of Intermediate 50

Intermediate 50 (3.6 g) was obtained in the same manner as in the synthesis of Intermediate 10, except that Intermediate 49 (6.5 g) was used instead of Intermediate 9 in the synthesis of Intermediate 10 of Synthesis Example 3. (Yield 60%, Mass [M+]=408)

All. Synthesis of intermediates 51 and 52

Intermediate 51 (2.5 g) was obtained in the same manner as in the synthesis of Intermediate 3, except that Intermediate 50 (3.6 g) was used instead of Intermediate 2 in the synthesis of Intermediate 3 of Synthesis Example 1. (Yield 75%, Mass [M+]=380)

Intermediate 52 (4.3 g) was obtained in the same manner as in the synthesis of Intermediate 4, except that Intermediate 51 (2.5 g) was used instead of Intermediate 3 in the synthesis of Intermediate 4 of Synthesis Example 1. (Yield 70%, Mass [M+]=944)

la. Synthesis of compound 13

In the synthesis of Compound 1 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Compound 1, except that Intermediate 52 (3.0 g) instead of Intermediate 4 and AM-12 (1.8 g) instead of AM-1 as an amine were used. 2.1 g) was obtained. (Yield 74%, Mass [M+]=899)

Synthesis Example 14. Synthesis of compound 14

end. Synthesis of intermediate 53

In the synthesis of Intermediate 9 of Synthesis Example 3, A-6 (5.0 g) instead of the starting material A-3 and benzothioindole B-14 (8.2 g) instead of benzofuroindole B-3 were used in the synthesis of Intermediate 9. It was prepared in the same manner as in the synthesis method to obtain Intermediate 53 (7.3 g). (Yield 65%, Mass [M+]=501)

I. Synthesis of intermediate 53

In the synthesis of Intermediate 10 of Synthesis Example 3, it was prepared in the same manner as in the synthesis of Intermediate 10, except that Intermediate 53 (7.3 g) was used instead of Intermediate 9 to obtain Intermediate 54 (4.2 g). (Yield 62%, Mass [M+]=464)

All. Synthesis of intermediates 55 and 56

In the synthesis of Intermediate 3 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Intermediate 3, except that Intermediate 54 (4.2g) was used instead of Intermediate 2 to obtain Intermediate 55 (2.8g). (Yield 71%, Mass [M+]=436)

Intermediate 56 (4.2g) was obtained by preparing in the same manner as in the synthesis of Intermediate 4 except that Intermediate 55 (2.8g) was used instead of Intermediate 3 in the synthesis of Intermediate 4 of Synthesis Example 1. (Yield 65%, Mass [M+]=1000)

la. Synthesis of compound 14

In the synthesis of Compound 1 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Compound 1, except that Intermediate 56 (3.0 g) instead of Intermediate 4 and AM-13 (1.3 g) instead of AM-1 as an amine were used. 1.8 g) was obtained. (Yield 72%, Mass [M+]=839)

Synthesis Example 15. Synthesis of compound 15

end. Synthesis of Intermediate 57

In the synthesis of Intermediate 9 of Synthesis Example 3, the same as the synthesis method of Intermediate 9, except that A-4 (5.0 g) instead of the starting material A-3 and B-15 (6.3 g) instead of benzofuroindole B-3 were used was prepared to give Intermediate 57 (7.1 g). (Yield 74%, Mass [M+]=454)

I. Synthesis of Intermediate 58

In the synthesis of Intermediate 10 of Synthesis Example 3, intermediate 58 (3.9 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 10, except that Intermediate 57 (7.1 g) was used instead of Intermediate 9. (Yield 60%, Mass [M+]=418)

All. Synthesis of Intermediate 59 and 60

Intermediate 59 (2.6 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 3, except that Intermediate 58 (3.9 g) was used instead of Intermediate 2 in the synthesis of Intermediate 3 of Synthesis Example 1. (Yield 71%, Mass [M+]=390)

Intermediate 60 (3.9 g) was obtained in the same manner as in the synthesis of Intermediate 4, except that Intermediate 59 (2.6 g) was used instead of Intermediate 3 in the synthesis of Intermediate 4 of Synthesis Example 1. (Yield 61%, Mass [M+]=954)

la. Synthesis of compound 15

In the synthesis of Compound 1 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Compound 1, except that Intermediate 60 (3.0 g) instead of Intermediate 4 and AM-14 (1.5 g) instead of AM-1 as an amine were used in the synthesis of Compound 15 ( 2.1 g) was obtained. (Yield 80%, Mass [M+]=839)

Synthesis Example 16. Synthesis of compound 16

end. Synthesis of Intermediate 61

In the synthesis of Intermediate 9 of Synthesis Example 3, A-4 (5.0 g) instead of starting material A-3 and B-16 (7.5 g) instead of benzofuroindole B-3 were used in the synthesis of Intermediate 9. was prepared to obtain Intermediate 61 (7.6 g). (Yield 71%, Mass [M+]=511)

I. Synthesis of Intermediate 62

Intermediate 62 (4.4 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 10, except that Intermediate 61 (7.6 g) was used instead of Intermediate 9 in the synthesis of Intermediate 10 of Synthesis Example 3. (Yield 62%, Mass [M+]=474)

All. Synthesis of intermediates 63 and 64

Intermediate 63 (3.0 g) was obtained in the same manner as in the synthesis of Intermediate 3, except that Intermediate 62 (4.4 g) was used instead of Intermediate 2 in the synthesis of Intermediate 3 of Synthesis Example 1. (Yield 72%, Mass [M+]=446)

Intermediate 64 (5.1 g) was obtained in the same manner as in the synthesis of Intermediate 4, except that Intermediate 63 (3.0 g) was used instead of Intermediate 3 in the synthesis of Intermediate 4 of Synthesis Example 1. (Yield 75%, Mass [M+]=1010)

la. Synthesis of compound 16

In the synthesis of Compound 1 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Compound 1, except that Intermediate 64 (3.0 g) instead of Intermediate 4 and AM-15 (2.6 g) instead of AM-1 as an amine were used. 2.9 g) was obtained. (Yield 75%, Mass [M+]=1299)

Synthesis Example 17. Synthesis of compound 17

end. Synthesis of intermediates 65 and 66

In a nitrogen atmosphere, after adding the starting material A-7 (5.0 g), boronic ester B-17 5.2 g, potassium carbonate 3.5 g 130 mL tetrahydrofuran and 13 mL water, tetrakis (triphenylphosphine) palladium ( 0) [tetrakis(triphenylhosphine)palladium(0)] Pd(PPh ₃ ) ₄ 0.4 g was added, and then heated at 120° C. and stirred for 2 hours. After the starting material disappeared and Intermediate 65 was confirmed, boronic ester B-18 (5.5 g) and 2.3 g of potassium carbonate were added, followed by further stirring for 4 hours. After the reaction was completed, the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the mixture, and then, MgSO ₄ (anhydrous) was treated and filtered. The filtered solution was distilled off under reduced pressure and purified by recrystallization (ethylacetate/hexane) to obtain an intermediate 66 (6.2 g). (Yield 79%, Mass [M+]=471)

I. Synthesis of Intermediate 67

Intermediate 66 (6.2 g), sodium t-butoxide 3.8 g, bis(tri-tertbutylphosphine)palladium(0) [Bis(tri(tert-butyl)phosphine)palladium(0) under nitrogen atmosphere ), Pd(PtBu ₃ ) ₂ ] After 0.13 g of toluene was added to 65 mL of toluene, it was heated at 140° C. and stirred for 6 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water and aq.NH ₄ Cl were added to separate the mixture, and the mixture was _{treated with MgSO 4} (anhydrous) and filtered. The filtered solution was distilled off under reduced pressure and purified by recrystallization to obtain Intermediate 67 (4.1 g). (Yield 78%, Mass [M+]=398)

All. Synthesis of intermediates 68 and 69

In the synthesis of Intermediate 3 of Synthesis Example 1, intermediate 68 (2.8 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 3, except that Intermediate 67 (4.1 g) was used instead of Intermediate 2. (Yield 73%, Mass [M+]=370)

In the synthesis of Intermediate 4 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Intermediate 4, except that Intermediate 68 (2.8 g) was used instead of Intermediate 3 to obtain Intermediate 69 (5.1 g). (Yield 72%, Mass [M+]=934)

la. Synthesis of compound 17

In the synthesis of Compound 1 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Compound 1, except that Intermediate 69 (3.0 g) instead of Intermediate 4 and AM-16 (1.6 g) instead of AM-1 as an amine were used. 2.0 g) was obtained. (Yield 74%, Mass [M+]=837)

Synthesis Example 18. Synthesis of compound 18

end. Synthesis of intermediates 70 and 71

In the synthesis of Intermediate 65 of Synthesis Example 17, except that B-19 (5.5 g) was used instead of boronic ester B-17, it was prepared in the same manner as in the synthesis of Intermediate 65 to confirm Intermediate 70, and then in the synthesis of Intermediate 66 Intermediate 71 (6.5 g) was obtained in the same manner as in the synthesis of Intermediate 66, except that Intermediate 70 (5.5 g) was used instead of Intermediate 65. (Yield 80%, Mass [M+]=487)

I. Synthesis of Intermediate 72

Intermediate 72 (4.1 g) was obtained in the same manner as in the synthesis of Intermediate 67, except that Intermediate 71 (6.5 g) was used instead of Intermediate 66 in the synthesis of Intermediate 67 of Synthesis Example 17. (Yield 74%, Mass [M+]=414)

All. Synthesis of intermediates 73 and 74

Intermediate 73 (3.0 g) was obtained in the same manner as in the synthesis of Intermediate 3, except that Intermediate 72 (4.1 g) was used instead of Intermediate 2 in the synthesis of Intermediate 3 of Synthesis Example 1. (Yield 78%, Mass [M+]=386)

In the synthesis of Intermediate 4 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Intermediate 4, except that Intermediate 73 (3.0 g) was used instead of Intermediate 3 to obtain Intermediate 74 (5.1 g). (Yield 69%, Mass [M+]=950)

la. Synthesis of compound 18

In the synthesis of Compound 1 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Compound 1, except that Intermediate 74 (3.0 g) instead of Intermediate 4 and AM-17 (1.7 g) instead of AM-1 as an amine were used. 2.1 g) was obtained. (Yield 74%, Mass [M+]=903)

Synthesis Example 19. Synthesis of compound 19

end. Synthesis of intermediates 75 and 76

In the synthesis of Intermediate 65 of Synthesis Example 17, starting material A-7 (5.0 g) and boronic ester B-17 (5.2 g) were prepared in the same manner as in the synthesis of Intermediate 65 to confirm Intermediate 75, followed by Intermediate Intermediate 76 (6.1 g) was obtained in the same manner as in the synthesis of Intermediate 66, except that Intermediate 75 (5.5 g) was used instead of Intermediate 65 in the synthesis of 66. (Yield 77%, Mass [M+]=471)

I. Synthesis of Intermediate 77

Intermediate 77 (3.9 g) was obtained in the same manner as in the synthesis of Intermediate 67, except that Intermediate 76 (6.1 g) was used instead of Intermediate 66 in the synthesis of Intermediate 67 of Synthesis Example 17. (Yield 76%, Mass [M+]=398)

All. Synthesis of intermediates 78 and 79

In the synthesis of Intermediate 3 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Intermediate 3 except that Intermediate 77 (3.9 g) was used instead of Intermediate 2 to obtain Intermediate 78 (2.6 g). (Yield 72%, Mass [M+]=370)

In the synthesis of Intermediate 4 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Intermediate 4 except that Intermediate 78 (2.6 g) was used instead of Intermediate 3 to obtain Intermediate 79 (4.6 g). (Yield 70%, Mass [M+]=934)

la. Synthesis of compound 19

In the synthesis of Compound 1 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Compound 1, except that Intermediate 79 (3.0 g) instead of Intermediate 4 and AM-18 (2.7 g) instead of AM-1 as an amine were used. 2.7 g) was obtained. (Yield 71%, Mass [M+]=1177)

Synthesis Example 20. Synthesis of compound 20

end. Synthesis of Intermediate 80

In the synthesis of Intermediate 1 of Synthesis Example 1, A-8 (5.0 g) instead of starting material A-1 and B-17 (4.6 g) instead of boronic ester B-1 were used in the synthesis of Intermediate 1 in the same manner as in the synthesis method of Intermediate 1 prepared to obtain Intermediate 80 (4.6 g). (Yield 71%, Mass [M+]=444)

I. Synthesis of Intermediate 81

*

Intermediate 81 (3.0 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 2, except that Intermediate 80 (4.6 g) was used instead of Intermediate 1 in the synthesis of Intermediate 2 of Synthesis Example 1. (Yield 71%, Mass [M+]=408)

All. Synthesis of intermediates 82 and 83

Intermediate 82 (2.1 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 3, except that Intermediate 81 (3.0 g) was used instead of Intermediate 2 in the synthesis of Intermediate 3 of Synthesis Example 1. (Yield 75%, Mass [M+]=380)

In the synthesis of Intermediate 4 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Intermediate 4 except that Intermediate 82 (2.1g) was used instead of Intermediate 3 to obtain Intermediate 83 (4.2g). (Yield 80%, Mass [M+]=944)

la. Synthesis of compound 20

In the synthesis of Compound 1 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Compound 1, except that Intermediate 83 (3.0 g) instead of Intermediate 4 and AM-19 (2.1 g) instead of AM-1 as an amine were used. 2.4 g) was obtained. (Yield 74%, Mass [M+]=1015)

Synthesis Example 21. Synthesis of compound 21

end. Synthesis of Intermediate 84

In a nitrogen atmosphere, after adding the starting material A-8 (5.0 g), boronic ester B-18 11 g, potassium carbonate 6.8 g, tetrahydrofuran 120 mL and water 12 mL, tetrakis (triphenylphosphine) palladium ( 0) [tetrakis(triphenylhosphine)palladium(0), Pd(PPh ₃ ) ₄ ] 0.4 g was added, heated at 120° C. and stirred for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature, separated by adding water and ethyl acetate, and filtered by treatment with _{MgSO 4 (anhydrous).} The filtered solution was distilled off under reduced pressure and purified by recrystallization (ethylacetate/hexane) to obtain Intermediate 84 (7.0 g). (Yield 79%, Mass [M+]=543)

I. Synthesis of Intermediate 85

Intermediate 85 (4.5 g) was obtained in the same manner as in the synthesis of Intermediate 67, except that Intermediate 84 (7.0 g) was used instead of Intermediate 66 in the synthesis of Intermediate 67 of Synthesis Example 17. (Yield 74%, Mass [M+]=470)

All. Synthesis of intermediates 86 and 87

Intermediate 86 (3.2 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 3, except that Intermediate 85 (4.5 g) was used instead of Intermediate 2 in the synthesis of Intermediate 3 of Synthesis Example 1. (Yield 76%, Mass [M+]=442)

In the synthesis of Intermediate 4 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Intermediate 4, except that Intermediate 86 (3.2 g) was used instead of Intermediate 3 to obtain Intermediate 87 (5.5 g). (Yield 75%, Mass [M+]=1006)

la. Synthesis of compound 21

In the synthesis of Compound 1 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Compound 1, except that Intermediate 87 (3.0 g) instead of Intermediate 4 and AM-20 (1.0 g) instead of AM-1 as an amine were used. 1.6 g) was obtained. (Yield 71%, Mass [M+]=755)

Synthesis Example 22. Synthesis of compound 22

end. Synthesis of intermediates 88 and 89

In the synthesis of Intermediate 65 of Synthesis Example 17, in the same manner as in the synthesis of Intermediate 65, except that A-9 (5.0 g) instead of the starting material A-7 and B-20 (4.4 g) instead of boronic ester B-17 were used. After preparing and confirming Intermediate 88, it was prepared in the same manner as in the synthesis of Intermediate 66 except that Intermediate 88 (4.4 g) was used instead of Intermediate 65 in the synthesis of Intermediate 66 to obtain Intermediate 89 (6.0 g). (Yield 81%, Mass [M+]=527)

I. Synthesis of Intermediate 90

Intermediate 90 (3.9 g) was obtained in the same manner as in the synthesis of Intermediate 67, except that Intermediate 89 (6.0 g) was used instead of Intermediate 66 in the synthesis of Intermediate 67 of Synthesis Example 17. (Yield 75%, Mass [M+]=454)

All. Synthesis of intermediates 91 and 92

Intermediate 91 (2.6 g) was obtained in the same manner as in the synthesis of Intermediate 3, except that Intermediate 90 (3.9 g) was used instead of Intermediate 2 in the synthesis of Intermediate 3 of Synthesis Example 1. (Yield 71%, Mass [M+]=426)

In the synthesis of Intermediate 4 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Intermediate 4 except that Intermediate 91 (2.6 g) was used instead of Intermediate 3 to obtain Intermediate 92 (4.3 g). (Yield 71%, Mass [M+]=990)

la. Synthesis of compound 22

In the synthesis of Compound 1 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Compound 1, except that Intermediate 92 (3.0 g) instead of Intermediate 4 and AM-21 (1.6 g) instead of AM-1 as an amine were used. 2.2 g) was obtained. (Yield 78%, Mass [M+]=929)

Synthesis Example 23. Synthesis of compound 23

end. Synthesis of Intermediate 93

Intermediate 93 (7.1 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 84, except that A-10 (5.0 g) was used instead of starting material A-8 in the synthesis of Intermediate 84 of Synthesis Example 21. (Yield 83%, Mass [M+]=563)

I. Synthesis of Intermediate 94

Intermediate 94 (4.2g) was obtained in the same manner as in the synthesis of Intermediate 67, except that Intermediate 93 (7.1g) was used instead of Intermediate 66 in the synthesis of Intermediate 67 of Synthesis Example 17. (Yield 68%, Mass [M+]=490)

All. Synthesis of intermediates 95 and 96

Intermediate 95 (3.1 g) was obtained in the same manner as in the synthesis of Intermediate 3, except that Intermediate 94 (4.2 g) was used instead of Intermediate 2 in the synthesis of Intermediate 3 of Synthesis Example 1. (Yield 78%, Mass [M+]=462)

Intermediate 96 (5.6 g) was obtained in the same manner as in the synthesis of Intermediate 4, except that Intermediate 95 (3.1 g) was used instead of Intermediate 3 in the synthesis of Intermediate 4 of Synthesis Example 1. (Yield 81%, Mass [M+]=1026)

la. Synthesis of compound 23

In the synthesis of Compound 1 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Compound 1, except that Intermediate 96 (3.0 g) instead of Intermediate 4 and AM-22 (1.0 g) instead of AM-1 as an amine were used. 1.6 g) was obtained. (Yield 70%, Mass [M+]=777)

Synthesis Example 24. Synthesis of compound 24

end. Synthesis of Intermediate 97

In the synthesis of Intermediate 84 of Synthesis Example 21, in the same manner as in the synthesis of Intermediate 84, except that A-10 (5.0 g) instead of starting material A-8 and B-17 (9.9 g) instead of boronic ester B-18 were used. prepared to give Intermediate 97 (6.5 g). (Yield 80%, Mass [M+]=531)

I. Synthesis of Intermediate 98

Intermediate 98 (4.3 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 67, except that Intermediate 97 (6.5 g) was used instead of Intermediate 66 in the synthesis of Intermediate 67 of Synthesis Example 17. (Yield 77%, Mass [M+]=458)

All. Synthesis of intermediates 99 and 100

Intermediate 99 (3.1 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 3, except that Intermediate 98 (4.3 g) was used instead of Intermediate 2 in the synthesis of Intermediate 3 of Synthesis Example 1. (Yield 76%, Mass [M+]=430)

Intermediate 100 (5.7 g) was obtained by preparing in the same manner as in the synthesis of Intermediate 4, except that Intermediate 99 (3.1 g) was used instead of Intermediate 3 in the synthesis of Intermediate 4 of Synthesis Example 1. (Yield 79%, Mass [M+]=994)

la. Synthesis of compound 24

In the synthesis of Compound 1 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Compound 1, except that Intermediate 100 (3.0 g) instead of Intermediate 4 and AM-23 (1.5 g) instead of AM-1 as an amine were used. 2.1 g) was obtained. (Yield 79%, Mass [M+]=883)

Synthesis Example 25. Synthesis of compound 25

end. Synthesis of Intermediate 101

Intermediate 101 (7.4) was obtained in the same manner as in the synthesis of Intermediate 84, except that A-11 (5.0 g) was used instead of starting material A-8 in the synthesis of Intermediate 84 of Synthesis Example 21. (Yield 76%, Mass [M+]=487)

I. Synthesis of Intermediate 102

Intermediate 102 (4.7g) was obtained by preparing in the same manner as in the synthesis of Intermediate 67, except that Intermediate 101 (7.4g) was used instead of Intermediate 66 in the synthesis of Intermediate 67 of Synthesis Example 17. (Yield 75%, Mass [M+]=414)

All. Synthesis of intermediates 103 and 104

Intermediate 103 (3.6 g) was obtained in the same manner as in the synthesis of Intermediate 3, except that Intermediate 102 (4.7 g) was used instead of Intermediate 2 in the synthesis of Intermediate 3 of Synthesis Example 1. (Yield 82%, Mass [M+]=386)

In the synthesis of Intermediate 4 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Intermediate 4, except that Intermediate 103 (3.6 g) was used instead of Intermediate 3 to obtain Intermediate 104 (7.1 g). (Yield 80%, Mass [M+]=950)

la. Synthesis of compound 25

In the synthesis of Compound 1 of Synthesis Example 1, it was prepared in the same manner as in the synthesis of Compound 1, except that Intermediate 104 (3.0 g) instead of Intermediate 4 and AM-9 (1.4 g) instead of AM-1 as an amine were used. 1.8 g) was obtained. (Yield 71%, Mass [M+]=801)

Example 1

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1,500 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and 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.

A hole injection layer was formed by thermal vacuum deposition of the following compound HAT to a thickness of 50 Å on the ITO transparent electrode prepared as described above. The following compound HT-A was vacuum deposited on the hole injection layer to form a first hole transport layer having a thickness of 1100 Å, and then the compound HT-B was vacuum deposited to form a second hole transport layer having a thickness of 100 Å. Compound BH-A as a light emitting host and Compound 1 as a dopant were vacuum-deposited in a weight ratio of 97:3 on the second hole transport layer to form a light emitting layer having a thickness of 200 Å.

On the light emitting layer, the following compound ET-A and compound LiQ were vacuum-deposited in a 1:1 weight ratio to form a first electron transport layer to a thickness of 200 Å. [LiF] was vacuum-deposited on the first electron transport layer to form a second electron transport layer to a thickness of 100 Å. A cathode was formed by depositing aluminum to a thickness of 1000 Å on the second electron transport layer.

In the above process, the deposition rate of the organic material was maintained at 1.0 Å, the lithium fluoride of the negative electrode was 0.3 Å and the aluminum maintained the deposition rate of 2.0 to 5.0 Å, and the vacuum degree during deposition was 5 × 10 ^-8 to 1 × 10 ^{- By maintaining 7} torr, an organic light emitting device was manufactured.

Examples 2 to 25 and Comparative Examples 1 to 9

In Example 1, each organic light emitting device was manufactured in the same manner as in Example 1, except that the dopant of Table 1 was used instead of Compound 1 of the light emitting layer.

Experimental example

^{When a current density of 10 mA/cm 2} is applied to the organic light emitting devices fabricated in Examples 1 to 25 and Comparative Examples 1 to 9, respectively, voltage, efficiency, and lifetime (T) when a current density of ^{20 mA/cm 2 is applied} ₉₇ ) and the results are shown in Table 1 below. At this time, T97 denotes a time required for the luminance to decrease to 97% when the initial luminance at a current density of 20 mA/cm ^{2 is 100%.}

Host dopant Luminous Efficiency
(Cd/A) Lifetime, T ₉₇ (h) Example 1 BH-A Compound 1 4.06 70 Example 2 BH-A Compound 2 4.03 68 Example 3 BH-A Compound 3 4.06 71 Example 4 BH-A Compound 4 4.27 72 Example 5 BH-A Compound 5 4.17 72 Example 6 BH-A Compound 6 4.10 69 Example 7 BH-A Compound 7 4.20 73 Example 8 BH-A Compound 8 4.24 75 Example 9 BH-A Compound 9 4.30 73 Example 10 BH-A Compound 10 4.38 71 Example 11 BH-A Compound 11 4.20 74 Example 12 BH-A Compound 12 4.38 72 Example 13 BH-A Compound 13 4.10 49 Example 14 BH-A Compound 14 4.03 71 Example 15 BH-A Compound 15 4.20 70 Example 16 BH-A compound 16 4.06 72 Comparative Example 1 BH-A BD-A 2.10 56 Comparative Example 2 BH-A BD-B 2.52 60 Comparative Example 3 BH-A BD-C 2.87 59 Comparative Example 4 BH-A BD-F 2.45 57 Comparative Example 5 BH-A BD-I 2.98 51 Example 17 BH-B compound 17 4.31 68 Example 18 BH-B compound 18 4.34 70 Example 19 BH-B compound 19 4.27 68 Example 20 BH-B compound 20 4.31 72 Example 21 BH-B compound 21 4.41 76 Example 22 BH-B compound 22 4.31 71 Example 23 BH-B compound 23 4.48 76 Example 24 BH-B compound 24 4.30 71 Example 25 BH-B compound 25 4.36 74 Comparative Example 6 BH-B BD-D 2.45 56 Comparative Example 7 BH-B BD-E 2.80 58 Comparative Example 8 BH-B BD-G 3.08 54 Comparative Example 9 BH-B BD-H 3.50 53

Through Table 1, a compound having a structure in which benzothiophene, benzofuran group or dihydroindene is directly condensed to the indolocarbazole structure represented by Formula 1 of the present specification and substituted with two or more amine groups in the core Examples 1 to 25 in which are applied to the dopant of the light emitting layer of the organic light emitting device are Comparative Examples 1 to 9 in which a compound that is not directly condensed to the indolocarbazole structure or an amine group is not substituted in the core is applied to the dopant of the light emitting layer of the organic light emitting device It can be confirmed that the luminous efficiency and lifespan are superior to those of the compound of

1: substrate
2: first electrode
3: light emitting layer
4: second electrode
5: hole injection layer
6: first hole transport layer
7: second hole transport layer
8: first electron transport layer
9: Second electron transport layer

Claims (14)

Compound represented by the following formula (1):
[Formula 1]

In Formula 1,
X and Y are the same as or different from each other, each independently O, S or CZ1Z2,
Ring A is a benzene ring or a naphthalene ring,
A1 to A4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitro group; Hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
R1 to R6, Z1 and Z2 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
n1 to n3, m and l are each 0 or 1,
The sum of n1 to n3 is 2 or more,
a1 and a2 are each an integer of 1 to 4,
a3 is an integer from 1 to 3;
a4 is an integer from 1 to 6,
When a1 to a4 are each 2 or more, the structures in parentheses are the same or different from each other,
However, when ring A is naphthalene, m is 0,
When l is 1, ring A is a benzene ring. The method according to claim 1, wherein the compound represented by Formula 1 is a compound represented by any one of the following Formulas 2-1 to 2-8:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 2-7]

[Formula 2-8]

In Formulas 2-1 to 2-8,
X, Y, A1 to A4, a1 to a4, R1 to R6, n1 to n3 and m are as defined in Formula 1,
A5 is hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitro group; Hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
a5 is an integer from 1 to 4,
When a5 is 2 or more, the structures in parentheses are the same or different from each other. The method according to claim 1, wherein the compound represented by Formula 1 is a compound represented by any one of the following Formulas 3-1 to 3-12:
[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

[Formula 3-5]

[Formula 3-6]

[Formula 3-7]

[Formula 3-8]

[Formula 3-9]

[Formula 3-10]

[Formula 3-11]

[Formula 3-12]

In Formulas 3-1 to 3-12,
A1 to A4, a1 to a4, R1 to R6, n1 to n3, m, Z1 and Z2 are the same as defined in Formula 1,
Z3 and Z4 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
A5 is hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitro group; Hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
a5 is an integer from 1 to 4,
When a5 is 2 or more, the structures in parentheses are the same or different from each other. The compound of claim 1, wherein the sum of n1 to n3 is 2. The method according to claim 1, A1 to A4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; Or a compound that is a substituted or unsubstituted aryl group. The method according to claim 1, R1 to R6 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a compound that is a substituted or unsubstituted heterocyclic group. The compound according to claim 1, wherein the maximum emission peak of the compound represented by Formula 1 is 420 nm to 480 nm. The method according to claim 1, wherein the compound represented by Formula 1 is a compound represented by any one of the following structures:

A first electrode; A second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode,
At least one of the organic material layers is an organic light-emitting device comprising the compound according to any one of claims 1 to 8. The method of claim 9,
The organic material layer is an organic light emitting device comprising a light emitting layer including the compound. The method of claim 10,
The light emitting layer is an organic light emitting device comprising a host and a dopant including the compound. The organic light-emitting device of claim 11 , wherein the host comprises a compound represented by the following Chemical Formula 5:
[Formula 5]

In Formula 5,
L21 to L23 are the same as or different from each other, and are each independently a direct bond; Or a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
R21 to R27 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
Ar21 to Ar23 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
a is 0 or 1. The organic light-emitting device of claim 11 , wherein the host comprises a compound represented by any one of the following structures:

. The method of claim 10,
The organic material layer further comprises one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an electron blocking layer and a hole blocking layer.

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