KR102507554B1 - Compound and organic light emitting device comprising the same - Google Patents

Abstract

The present specification relates to a compound represented by Formula 1 and an organic light emitting device including the same.

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 content of which is incorporated herein.

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

In general, the organic light emitting phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including a first electrode and a second electrode and an organic material layer therebetween. Here, the organic material layer is often composed of a multi-layer structure composed of different materials to increase the efficiency and stability of the organic light emitting device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. In the structure of such an organic light emitting device, when a voltage is applied between the two electrodes, holes are injected from the first electrode and electrons from the second electrode are injected into the organic material layer, and when the injected holes and electrons meet, excitons are formed. , when this exciton falls back to the ground state, it emits light.

Development of new materials for the organic light emitting device as described above has been continuously demanded.

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

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

[Formula 1]

In Formula 1,

X and Y are the same as or different from each other, and are each independently O, S or CZZ2;

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 integers from 1 to 4, respectively;

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 as 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 one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layers contains the aforementioned compound.

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

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

Hereinafter, this specification will be described in detail.

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

In the present specification, when a certain component is said to "include", it means that it may further include other components without excluding other components unless otherwise stated.

In this specification, when a member is said to be located “on” another member, this includes not only the case where a member is in contact with another 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 Chemical Formula 1 has a structure in which a benzothiophene, benzofuran group or dihydroindene is directly condensed to an indolocarbazole structure, thereby improving the rigidity of the molecule itself. stability can be improved. This has an advantage of improving the lifetime of the organic light emitting device when driving. In addition, the compound represented by Chemical Formula 1 is substituted with two or more amine groups at specific positions, which increases the oscillator strength value compared to the case where there is no amine group or only one amine group, thereby improving the luminous efficiency of the device.

Examples of substituents 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 hydrogen atom is substituted, that is, a position where the substituent can be substituted, and in the case of two or more substitutions , Two or more substituents may be the same as or different from each other.

In this specification, the term "substituted or unsubstituted" means deuterium (-D); halogen group; nitrile group; nitro group; hydroxy group; amine group; silyl group; boron group; alkoxy group; an alkyl group; cycloalkyl group; aryl group; And it means that it is substituted with one or two or more substituents selected from the group consisting of a heterocyclic group, or is substituted with a substituent in which two or more substituents from among the above exemplified substituents are connected, 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 in 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 a chemical 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 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, but is not limited thereto. don't

In the present specification, the boron group may be represented by the chemical formula -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. The boron group specifically includes a trimethyl boron group, a triethyl boron group, a tert-butyldimethyl boron group, a triphenyl boron group, a phenyl boron group, and the like, but is not limited thereto.

In the present specification, the alkyl group may be straight or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60. According to one embodiment, the number of carbon atoms of the alkyl group is 1 to 30. According to another embodiment, the number of carbon atoms of the alkyl group is 1 to 20. According to another exemplary embodiment, the number of carbon atoms of the alkyl group is 1 to 10. 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, etc., but is not limited thereto.

In the present specification, the alkoxy group may be straight chain, branched chain or cyclic chain. The number of carbon atoms in the alkoxy group is not particularly limited, but 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, etc., but is not limited thereto. .

Alkyl groups, alkoxy groups, and substituents containing other alkyl moieties described herein include both straight-chain and branched forms.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 6. 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 preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 39. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 30. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, etc. as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, triphenylenyl group, etc., 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 ring group containing one or more of N, O, P, S, Si and Se as heteroatoms, and the number of carbon atoms is not particularly limited, but preferably has 2 to 60 carbon atoms. According to one embodiment, the carbon number of the heterocyclic group is 2 to 36. 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, and an indolocarbazole group, but are not limited thereto.

In the present specification, the heterocyclic group described above may be applied except that the heteroaryl group is aromatic.

In the present specification, the amine group is -NH ₂ ; Alkylamine group; N-alkyl arylamine group; Arylamine group; N-arylheteroarylamine 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, etc., but are not limited thereto.

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

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

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

In the present specification, an alkylamine group; N-alkyl arylamine group; Arylamine group; N-arylheteroarylamine group; The alkyl, aryl and heteroaryl groups in the N-alkylheteroarylamine group and the heteroarylamine group are the same as the above-mentioned alkyl groups, aryl groups and heteroaryl groups, respectively.

In one embodiment of the present specification, the compound represented by Chemical Formula 1 is represented by any one of Chemical 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, 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 one embodiment of the present specification, X and Y are the same as or different from each other, and are each independently O, S or CZ1Z2, 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.

In one embodiment of the present specification, the compound represented by Chemical Formula 1 is represented by any one of Chemical 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 as defined in Formula 1, Z3 and Z4 are the same as or different from each other, Each independently 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 as or different from each other.

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

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

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

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

In one 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 one 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 one 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 one 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 having 1 to 10 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

In one 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 straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.

In one 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 one embodiment of the present specification, A1 to A4 are each hydrogen; or deuterium.

In one 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 one embodiment of the present specification, R1 to R6 are the same as or different from each other, and each independently represents 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 are each independently deuterium, an alkyl group, a halohalkyl group, an alkyl group substituted with a deuterium, a halogen group, a cyano group, a cycloalkyl group, or a silyl group 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 a deuterium, an alkyl group, a halohalkyl group, an alkyl group substituted with deuterium, a halogen group, an aryl group unsubstituted or substituted 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 heavy hydrogen, methyl group, tert-butyl group, iso-propyl group, -CF ₃ , -CD ₃ , F, a phenyl group unsubstituted or substituted with heavy hydrogen, and a cyclohexyl group. It is Ki.

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; Biphenyl group unsubstituted or substituted with deuterium or 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, an iso-propyl group, a tert-butyl group, -CD ₃ , a phenyl group unsubstituted or substituted with heavy hydrogen, and a cyclohexyl group; a dibenzothiophenyl group unsubstituted or substituted with a group selected from the group consisting of a methyl group, an iso-propyl group, a tert-butyl group, -CD ₃ , a phenyl group unsubstituted or substituted with heavy hydrogen, 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 one 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 aforementioned compound.

In one embodiment of the present specification, the 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, wherein at least one layer 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, or may have a multi-layer 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, and an electron injection layer as organic material layers. However, the structure of the organic light emitting device is not limited thereto and may include fewer organic layers.

In one 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 hole transport layer includes the compound.

In one embodiment of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes the compound. Specifically, the light emitting layer may include a host and a dopant including the compound.

In one 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 electron injection layer includes the compound.

In one embodiment of the present specification, the organic material layer includes a light emitting layer, a hole injection layer, a hole transport layer. It further includes one layer or two 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 one embodiment of the present specification, the organic light emitting device includes an anode; a cathode provided to face the anode; and one or more organic material layers 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 light emitting layer and the cathode, wherein the light emitting layer includes the compound.

In one embodiment of the present specification, the organic material layer of the hole transport region may be at least one selected from the group consisting of a hole transport layer, a hole injection layer, a hole transport and hole injection layer, and an electron blocking layer.

In one embodiment of the present specification, the organic material layer of the electron transport region may be at least one selected from the group consisting of an electron transport layer, an electron injection layer, an electron transport and electron injection layer, 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 embodiment, the organic light emitting diode may be an inverted type organic light emitting diode 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 suppression layer/emission layer/hole blocking layer/electron transport layer/electron injection layer/cathode

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

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

For example, the structure of an 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 sequential stacking of 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. The structure of the organic light emitting element 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 with materials and methods known in the art, except that at least one layer of organic material layers 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 with materials and methods known in the art, except that at least one layer of organic material layers includes the compound, that is, the compound represented by Chemical Formula 1.

For example, the organic light emitting device of the present specification may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, a metal or a metal oxide having conductivity or an alloy thereof is deposited on the substrate to form 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, 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 a second electrode material, an organic material layer, and a first electrode material on a substrate.

In addition, the compound of Chemical Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method during the manufacture of 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, etc., but is not limited to these.

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

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

The anode is an electrode for injecting holes, and a material having a high 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, and gold or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO: Al or SnO ₂ : Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

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

The hole injection layer is a layer for injecting holes from the electrode, and the hole injection material has the ability to transport holes and has a hole injection effect in the first electrode and an excellent hole injection effect for the light emitting layer or the light emitting material, and in the light emitting layer A compound that prevents migration of generated excitons to an electron injecting layer or electron injecting material and has excellent thin film forming ability is preferred. 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 layer. Specific examples of the hole injection material include metal porphyrins, oligothiophenes, arylamine-based organic materials, hexanitrilehexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene-based organic materials. of organic matter, anthraquinone, and 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 the holes to the light emitting layer, and the hole transport material is a material capable of receiving holes from the first electrode or the hole injection layer and transferring them to the light emitting layer. This large material is suitable. Specific examples include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers having both conjugated and non-conjugated parts.

The light emitting layer may include a host material and a dopant material.

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

In one embodiment of the present specification, the host includes a compound represented by Formula 5 below.

[Formula 5]

In Formula 5,

L21 to L23 are the same as or different from each other, and each independently binds directly; 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 one 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 are PIQIr (acac) (bis (1-phenylisoquinoline) acetylacetonateiridium), PQIr (acac) (bis (1-phenylquinoline) acetylacetonate iridium), PQIr (tris (1 A phosphorescent material such as -phenylquinoline)iridium) or octaethylporphyrin platinum (PtOEP) or a fluorescent material such as Alq ₃ (tris(8-hydroxyquinolino)aluminum) may be used, but is not limited thereto. When the light emitting layer emits green light, a phosphorescent material 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 light emitting 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, distylbenzene (DSB), distryarylene (DSA), Fluorescent materials such as PFO-based polymers and PPV-based polymers may be used, but are not limited thereto.

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

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

In one 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 one 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 one 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 one embodiment of the present specification, when the dopant of the light emitting layer includes the compound represented by Formula 1 and the host of the light emitting layer includes the compound represented by Formula 5, the weight of the compound represented by Formula 5 When 100 parts by weight, the content of the compound represented by Formula 1 may be 0.01 part by weight to 30 parts by weight, specifically 0.1 part by weight to 20 parts by weight, more specifically 0.5 part 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 from the second electrode and transfer them to the light emitting layer, and has high electron mobility. this is suitable Specific examples include Al complexes of 8-hydroxyquinoline; complexes including Alq3; organic radical compounds; hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by a layer of aluminum or silver.

The electron injection layer is a layer for injecting electrons from an electrode, has the ability to transport electrons, has an excellent electron injection effect from the second electrode, a light emitting layer or a light emitting material, and has an excellent electron injection effect for excitons generated in the light emitting layer. A compound that prevents migration to the hole injection layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, etc. and their derivatives, 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)( There are o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium. Not limited to this.

The hole blocking layer is a layer that blocks 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, and the like, but are not limited thereto.

An electron blocking layer may be provided between the hole transport layer and the light emitting layer. Materials known in the art may be used for the electron blocking layer.

An organic light emitting device according to the present specification may be a top emission type, a bottom emission type, or a double side emission type depending on materials used.

The compound represented by Formula 1 of the present specification may have a core structure as shown in the following reaction schemes. Substituents may be combined by a method 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 Chemical Formula 4-1

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

-OSO ₂ R is a substituent containing a sulfone group generated as a result of the sulfonation reaction, and is a leaving group that is eliminated by the Buchwald amination reaction,

Me is a methyl group.

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

<Scheme 2> Synthesis of Chemical Formula 4-2

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

-OSO ₂ R is a substituent containing a sulfone group generated as a result of the sulfonation reaction, and is a leaving group that is eliminated by the Buchwald amination reaction,

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

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

<Scheme 3> Synthesis of Chemical Formula 4-3

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

-OSO ₂ R is a substituent containing a sulfone group generated as a result of the sulfonation reaction, and is a leaving group that is eliminated by the Buchwald amination reaction,

Me is a methyl group,

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

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

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

<Scheme 4> Synthesis of Formula 4-4

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

-OSO ₂ R is a substituent containing a sulfone group generated as a result of the sulfonation reaction, and is a leaving group that is eliminated by the Buchwald amination reaction,

Me is a methyl group,

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

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

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

Any one of Reaction Schemes 1 to 4 of the present specification and the intermediates may be appropriately combined based on common technical knowledge to prepare all of the compounds represented by Chemical Formula 1 described herein.

Hereinafter, the present specification will be described in more detail through examples. However, the following examples are only for exemplifying the present specification, and are not intended to limit the present specification.

Synthesis Example 1. Synthesis of Compound 1

go. 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 tetrakis (triphenylphosphine) palladium (0) After adding 1.2 g of [tetrakis(triphenylhosphine)palladium(0), (TTP), Pd(PPh ₃ ) ₄ ], 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, 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 1 (18 g). (Yield 76%, Mass [M+]=443)

me. Synthesis of Intermediate 2

Under a nitrogen atmosphere, 18 g of intermediate 1, 7.8 g of sodium t-butoxide (NaOtBu) and bis (tri-tert-butylphosphine) palladium (0) [Bis (tri (tert-butyl) phosphine) palladium (0 ), Pd(PtBu ₃ ) ₂ ] 0.4 g was put into 200 mL of toluene, heated at 140° C. and stirred for 6 hours. After completion of the reaction, the reaction solution was cooled to room temperature, separated by adding water and aq.NH ₄ Cl, 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

After putting 8.5 g of Intermediate 2 and 4.7 g of aluminum chloride in 200 mL of chlorobenzene (MCB) under a nitrogen atmosphere, the mixture was heated at 130° 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, 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 (6.7g). (Yield 82%, Mass [M+]=348)

After adding 150 mL of dimethylformamide (DMF) to 6.7 g of intermediate 3 and 5.3 g of 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

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 under a nitrogen atmosphere (0), Pd(PtBu ₃ ) ₂ ] 0.05 g was put into 40 mL of dioxane, 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. NaCl was added to separate the mixture, followed by 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

go. Synthesis of Intermediate 5

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

me. Synthesis of Intermediate 6

Intermediate 6 (5.3 g) was obtained in the same manner as in the synthesis method 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 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 in Synthesis Example 1. (Yield 74%, Mass [M+]=424)

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

la. Synthesis of compound 2

In the synthesis of Compound 1 of Synthesis Example 1, Compound 2 ( 3.5 g) was obtained. (Yield 62%, Mass [M+]=1321)

Synthesis Example 3. Synthesis of Compound 3

go. Synthesis of Intermediate 9

Starting material A-3 (10 g), benzofuroindole B-3 (11.6 g), sodium t-butoxide 6.0 g and bis(tri-tertbutylphosphine)palladium(0) under nitrogen atmosphere After putting 0.4 g of [Bis(tri(tert-butyl)phosphine)palladium(0), Pd(PtBu ₃ ) ₂ ] in 350 mL of toluene, the mixture was heated at 140°C and stirred for 5 hours. After completion of the reaction, the reaction solution was cooled to room temperature, separated by adding water and aq.NH ₄ Cl, 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)

me. Synthesis of Intermediate 10

Under a nitrogen atmosphere, intermediate 9 (13.6 g), sodium tert-butoxide 6.1 g and bis (tri-tert-butylphosphine) palladium (0) [Bis (tri (tert-butyl) phosphine) palladium (0 ), Pd(PtBu ₃ ) ₂ ] 0.3 g was put into 160 mL of dimethylacetamide, heated at 120° C. and stirred for 10 hours. After completion of the reaction, the reaction solution was cooled to room temperature, separated by adding water and aq.NH ₄ Cl, 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 in the same manner as in the synthesis method 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, Compound 3 ( 2.5 g) was obtained. (Yield 77%, Mass [M+]=1011)

Synthesis Example 4. Synthesis of Compound 4

go. Synthesis of Intermediate 13

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

me. Synthesis of Intermediate 14

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

all. Synthesis of intermediates 15 and 16

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

Intermediate 16 (4.3g) was obtained in the same manner as in the synthesis of Intermediate 4, except that Intermediate 15 (2.7g) 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, Compound 4 ( 2.1 g) was obtained. (Yield 74%, Mass [M+]=881)

Synthesis Example 5. Synthesis of Compound 5

go. 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) were used instead of benzofuroindole B-3, but the same as the synthesis method of Intermediate 9 was prepared to obtain intermediate 17 (6.8 g). (Yield 73%, Mass [M+]=439)

me. Synthesis of Intermediate 18

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

all. Synthesis of intermediates 19 and 20

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

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

la. Synthesis of compound 5

In the synthesis of Compound 1 in Synthesis Example 1, Compound 5 ( 2.5 g) was obtained. (Yield 74%, Mass [M+]=1103)

Synthesis Example 6. Synthesis of Compound 6

go. Synthesis of Intermediate 21

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

me. 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 in Synthesis Example 3. (Yield 66%, Mass [M+]=468)

all. Synthesis of intermediates 23 and 24

Intermediate 23 (3.2g) was obtained in the same manner as in the synthesis of Intermediate 3, except that Intermediate 22 (4.6g) 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 method 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, Compound 6 ( 2.3 g) was obtained. (Yield 72%, Mass [M+]=1067)

Synthesis Example 7. Synthesis of Compound 7

go. Synthesis of Intermediate 25

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

me. Synthesis of Intermediate 26

Intermediate 26 (4.3 g) was obtained in the same manner as in the synthesis of Intermediate 10, except that Intermediate 25 (7.6 g) was used instead of Intermediate 9 in the synthesis of Intermediate 10 in Synthesis Example 3. (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 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, Compound 7 ( 1.9 g) was obtained. (Yield 65%, Mass [M+]=959)

Synthesis Example 8. Synthesis of Compound 8

go. Synthesis of Intermediate 29

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

me. Synthesis of Intermediate 30

Intermediate 30 (4.1 g) was obtained in the same manner as in the synthesis method of Intermediate 10, except that Intermediate 29 (6.9 g) was used instead of Intermediate 9 in the synthesis of Intermediate 10 in Synthesis Example 3. (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 in the same manner as in the synthesis method 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, Compound 8 ( 2.0 g) was obtained. (Yield 69%, Mass [M+]=907)

Synthesis Example 9. Synthesis of Compound 9

go. Synthesis of Intermediate 33

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

me. Synthesis of Intermediate 34

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

all. Synthesis of Intermediates 35 and 36

Intermediate 35 (2.7g) was obtained in the same manner as in the synthesis of Intermediate 3, except that Intermediate 34 (3.9g) 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 in the same manner as in the synthesis method 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, Compound 9 ( 2.1 g) was obtained. (Yield 73%, Mass [M+]=963)

Synthesis Example 10. Synthesis of Compound 10

go. Synthesis of Intermediate 37

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

me. Synthesis of Intermediate 38

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

all. Synthesis of intermediates 39 and 40

Intermediate 39 (3.3g) was obtained in the same manner as in the synthesis of Intermediate 3, except that Intermediate 38 (4.3g) 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 method 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, Compound 10 ( 108 g) was obtained. (Yield 70%, Mass [M+]=899)

Synthesis Example 11. Synthesis of Compound 11

go. Synthesis of Intermediate 41

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

me. Synthesis of Intermediate 42

Intermediate 42 (3.8 g) was obtained 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 in 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)

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

la. Synthesis of compound 11

In the synthesis of Compound 1 of Synthesis Example 1, Compound 11 ( 2.4 g) was obtained. (Yield 70%, Mass [M+]=1129)

Synthesis Example 12. Synthesis of Compound 12

go. Synthesis of Intermediate 45

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

me. Synthesis of Intermediate 46

Intermediate 46 (3.7 g) was obtained 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 in 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 (4.2g) was obtained in the same manner as in the synthesis of Intermediate 4, except that Intermediate 47 (2.6g) 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, Compound 12 ( 1.6 g) was obtained. (Yield 72%, Mass [M+]=738)

Synthesis Example 13. Synthesis of Compound 13

go. Synthesis of Intermediate 49

In the synthesis of Intermediate 9 of Synthesis Example 3, except for using A-4 (5.0 g) instead of starting material A-3 and benzothioindole B-13 (10.8 g) instead of Benzofuroindole B-3, the Intermediate 49 (6.5 g) was obtained in the same manner as in the synthesis method. (Yield 69%, Mass [M+]=444)

me. 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 in 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, Compound 13 ( 2.1 g) was obtained. (Yield 74%, Mass [M+]=899)

Synthesis Example 14. Synthesis of Compound 14

go. Synthesis of Intermediate 53

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

me. Synthesis of Intermediate 53

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

all. Synthesis of intermediates 55 and 56

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

Intermediate 56 (4.2 g) was obtained in the same manner as in the synthesis of Intermediate 4, except that Intermediate 55 (2.8 g) 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, Compound 14 ( 1.8 g) was obtained. (Yield 72%, Mass [M+]=839)

Synthesis Example 15. Synthesis of Compound 15

go. Synthesis of Intermediate 57

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

me. Synthesis of Intermediate 58

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

all. Synthesis of intermediates 59 and 60

Intermediate 59 (2.6 g) was obtained 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 in Synthesis Example 1. (Yield 71%, Mass [M+]=390)

Intermediate 60 (3.9g) was obtained in the same manner as in the synthesis of Intermediate 4, except that Intermediate 59 (2.6g) 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, Compound 15 ( 2.1 g) was obtained. (Yield 80%, Mass [M+]=839)

Synthesis Example 16. Synthesis of Compound 16

go. 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) were used instead of benzofuroindole B-3, but the same as the synthesis method of Intermediate 9 was prepared to obtain intermediate 61 (7.6 g). (Yield 71%, Mass [M+]=511)

me. Synthesis of Intermediate 62

Intermediate 62 (4.4 g) was obtained in the same manner as in the synthesis method of Intermediate 10, except that Intermediate 61 (7.6 g) was used instead of Intermediate 9 in the synthesis of Intermediate 10 in 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, Compound 16 ( 2.9 g) was obtained. (Yield 75%, Mass [M+]=1299)

Synthesis Example 17. Synthesis of Compound 17

go. Synthesis of Intermediates 65 and 66

Under a nitrogen atmosphere, after adding starting material A-7 (5.0 g), boronic ester B-17 5.2 g, potassium carbonate 3.5 g, tetrahydrofuran 130 mL and water 13 mL, tetrakis (triphenylphosphine) palladium ( 0) After adding 0.4 g of [tetrakis(triphenylhosphine)palladium(0)] Pd(PPh ₃ ) ₄ , the mixture was 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 potassium carbonate 2.3 g were added, followed by further stirring for 4 hours. After the reaction was completed, the reaction solution was cooled to room temperature, separated by adding water and ethyl acetate, 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 66 (6.2g). (Yield 79%, Mass [M+]=471)

me. Synthesis of Intermediate 67

Under a nitrogen atmosphere, intermediate 66 (6.2 g), sodium t-butoxide 3.8 g, bis (tri-tert-butylphosphine) palladium (0) [Bis (tri (tert-butyl) phosphine) palladium (0 ), Pd(PtBu ₃ ) ₂ ] was put into 65 mL of toluene, heated at 140° C., and stirred for 6 hours. After completion of the reaction, the reaction solution was cooled to room temperature, separated by adding water and aq.NH ₄ Cl, 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

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

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

la. Synthesis of compound 17

In the synthesis of Compound 1 in Synthesis Example 1, Compound 17 ( 2.0 g) was obtained. (Yield 74%, Mass [M+]=837)

Synthesis Example 18. Synthesis of Compound 18

go. 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, Intermediate 70 was prepared in the same manner as in the synthesis method of Intermediate 65, and then in the synthesis of Intermediate 66 Intermediate 71 (6.5 g) was obtained in the same manner as in the synthesis method of Intermediate 66, except that Intermediate 70 (5.5 g) was used instead of Intermediate 65. (Yield 80%, Mass [M+]=487)

me. 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 method 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)

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

la. Synthesis of compound 18

In the synthesis of Compound 1 of Synthesis Example 1, Compound 18 ( 2.1 g) was obtained. (Yield 74%, Mass [M+]=903)

Synthesis Example 19. Synthesis of Compound 19

go. 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 method of Intermediate 65, and then Intermediate 75 was confirmed. 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 Intermediate 66. (Yield 77%, Mass [M+]=471)

me. 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

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

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

la. Synthesis of compound 19

In the synthesis of Compound 1 of Synthesis Example 1, Compound 19 ( 2.7 g) was obtained. (Yield 71%, Mass [M+]=1177)

Synthesis Example 20. Synthesis of Compound 20

go. Synthesis of Intermediate 80

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

me. Synthesis of Intermediate 81

*

Intermediate 81 (3.0 g) was obtained 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 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)

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

la. Synthesis of compound 20

In the synthesis of Compound 1 of Synthesis Example 1, Compound 20 ( 2.4 g) was obtained. (Yield 74%, Mass [M+]=1015)

Synthesis Example 21. Synthesis of Compound 21

go. Synthesis of Intermediate 84

Under a nitrogen atmosphere, after adding 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) After adding 0.4 g of [tetrakis(triphenylhosphine)palladium(0), Pd(PPh ₃ ) ₄ ], 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, 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 84 (7.0 g). (Yield 79%, Mass [M+]=543)

me. 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 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)

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

la. Synthesis of compound 21

In the synthesis of Compound 1 of Synthesis Example 1, Compound 21 ( 1.6 g) was obtained. (Yield 71%, Mass [M+]=755)

Synthesis Example 22. Synthesis of Compound 22

go. Synthesis of intermediates 88 and 89

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

me. 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)

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

la. Synthesis of compound 22

Compound 22 ( 2.2 g) was obtained. (Yield 78%, Mass [M+]=929)

Synthesis Example 23. Synthesis of Compound 23

go. Synthesis of Intermediate 93

Intermediate 93 (7.1 g) was obtained 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 in Synthesis Example 21. (Yield 83%, Mass [M+]=563)

me. Synthesis of Intermediate 94

Intermediate 94 (4.2 g) was obtained in the same manner as in the synthesis of Intermediate 67, except that Intermediate 93 (7.1 g) 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 method 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

Compound 23 ( 1.6 g) was obtained. (Yield 70%, Mass [M+]=777)

Synthesis Example 24. Synthesis of Compound 24

go. Synthesis of Intermediate 97

In the synthesis of Intermediate 84 of Synthesis Example 21, the synthesis method of Intermediate 84 was the same 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. was prepared to obtain intermediate 97 (6.5 g). (Yield 80%, Mass [M+]=531)

me. Synthesis of Intermediate 98

Intermediate 98 (4.3g) was obtained in the same manner as in the synthesis of Intermediate 67, except that Intermediate 97 (6.5g) 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 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 in Synthesis Example 1. (Yield 76%, Mass [M+]=430)

Intermediate 100 (5.7 g) was obtained 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 in Synthesis Example 1. (Yield 79%, Mass [M+]=994)

la. Synthesis of Compound 24

In the synthesis of Compound 1 of Synthesis Example 1, Compound 24 ( 2.1 g) was obtained. (Yield 79%, Mass [M+]=883)

Synthesis Example 25. Synthesis of Compound 25

go. 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)

me. Synthesis of Intermediate 102

Intermediate 102 (4.7g) was obtained 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)

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

la. Synthesis of compound 25

In the synthesis of Compound 1 of Synthesis Example 1, Compound 25 ( 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 put in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product of Fischer Co. was used as a detergent, and distilled water filtered through a second filter of a product of Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was performed twice with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with solvents such as isopropyl alcohol, acetone, and methanol, and after drying, transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transferred to a vacuum deposition machine.

A hole injection layer was formed by thermally vacuum depositing the 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. On the second hole transport layer, Compound BH-A as a light emitting host and Compound 1 as a dopant were vacuum deposited at a weight ratio of 97:3 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 weight ratio of 1:1 to form a first electron transport layer with a thickness of 200 Å. [LiF] was vacuum deposited on the first electron transport layer to form a second electron transport layer with 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 deposition rate of lithium fluoride on the negative electrode was 0.3 Å, and the deposition rate of aluminum was 2.0 to 5.0 Å, and the vacuum level during deposition was 5 × 10 ^-8 to 1 × 10 ^- Maintaining ⁷ torr, an organic light emitting device was fabricated.

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 in Table 1 was used instead of Compound 1 of the light emitting layer.

Experimental example

When a current density of 10 mA/cm ² was applied to the organic light emitting devices prepared in Examples 1 to 25 and Comparative Examples 1 to 9, respectively, voltage, efficiency, and lifetime when a current density of 20 mA/cm ² was applied (T ₉₇ ) was measured and the results are shown in Table 1 below. At this time, T97 means the 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) Life, 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 a benzothiophene, benzofuran group or dihydroindene is condensed directly to the indolocarbazole structure represented by Formula 1 of the present specification and substituted with two or more amine groups in the core Comparative Examples 1 to 9 in which a compound not directly condensed into the indolocarbazole structure or in which an amine group is not substituted in the core was applied to the dopant of the light emitting layer of the organic light emitting device. It can be seen that the result of superior luminous efficiency and lifespan than 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)

A compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
X and Y are the same as or different from each other, and are each independently O, S or CZZ2;
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; A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms;
Z1 and Z2 are methyl groups,
R1 to R6 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms,
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 integers from 1 to 4, respectively;
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 as 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 compound according to claim 1, wherein 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 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, structures in parentheses are the same as or different from each other. The compound according to claim 1, wherein the compound represented by Formula 1 is represented by any one of 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 Chemical Formulas 3-1 to 3-12,
A1 to A4, a1 to a4, R1 to R6, n1 to n3, m, Z1 and Z2 are 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, structures in parentheses are the same as or different from each other. The compound according to claim 1, wherein the sum of n1 to n3 is 2. delete delete The compound of claim 1, wherein the compound represented by Formula 1 has a maximum emission peak of 420 nm to 480 nm. The compound according to claim 1, wherein the compound represented by Formula 1 is 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,
An organic light emitting device characterized in that at least one layer of the organic material layer contains the compound according to any one of claims 1 to 4, 7 and 8. The method of claim 9,
The organic material layer is an organic light emitting device comprising a light emitting layer containing the compound. The method of claim 10,
The light emitting layer is an organic light emitting device comprising a host and a dopant containing the compound. The organic light emitting device of claim 11, wherein the host includes a compound represented by Formula 5 below:
[Formula 5]

In Formula 5,
L21 to L23 are the same as or different from each other, and each independently binds directly; 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; The organic light emitting device of claim 11, wherein the host includes a compound represented by any one of the following structures:

. The method of claim 10,
The organic material layer further comprises one or two 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.

Images