CN111699191A - Heterocyclic compound and organic light emitting device including the same - Google Patents

Abstract

The present specification provides an organic light emitting device, comprising: the organic light emitting device includes a first electrode, a second electrode provided to face the first electrode, and 1 or 2 or more organic layers provided between the first electrode and the second electrode, wherein 1 or more of the organic layers include a heterocyclic compound represented by chemical formula 1.

Description

Heterocyclic compound and organic light-emitting device comprising the same

technical field

This specification claims priority to Korean Patent Application No. 10-2018-0124532 filed with the Korean Patent Office on October 18, 2018, the entire contents of which are incorporated herein.

The present specification relates to heterocyclic compounds and organic light-emitting devices comprising the same.

Background technique

In general, the organic light-emitting phenomenon refers to the phenomenon of using organic substances to convert electrical energy into light energy. An organic light-emitting device utilizing an organic light-emitting phenomenon generally has a structure including an anode and a cathode and an organic layer interposed therebetween. Here, in order to improve the efficiency and stability of the organic light-emitting device, the organic layer is usually formed of a multilayer structure composed of different substances. A transport layer, an electron injection layer, and the like are formed. For the structure of such an organic light-emitting device, if a voltage is applied between two electrodes, holes are injected from the anode to the organic layer, and electrons are injected from the cathode to the organic layer. An exciton emits light when it re-transitions to the ground state.

There is a continuing need to develop new materials for organic light-emitting devices as described above.

US Patent Application Publication No. 2004-0251816

SUMMARY OF THE INVENTION

technical issues

The present specification provides heterocyclic compounds and organic light-emitting devices including the same.

Solution to the problem

The present invention provides a heterocyclic compound represented by the following Chemical Formula 1.

[Chemical formula 1]

[Chemical formula 2]

In the above Chemical Formula 1 and Chemical Formula 2,

R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₃ , R ₅₁ to R ₅₅ , and R ₆₁ to R ₆₄ are the same or different from each other, each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted silyl group, substituted or unsubstituted phosphine oxide group, A substituted or unsubstituted amine group, a substituted or unsubstituted boron group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or combined with an adjacent substituent to form a substituted or unsubstituted ring,

2 adjacent substituent groups in the above-mentioned R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₃ , and R ₅₁ to R ₅₅ ; and the above-mentioned R ₁₁ to R ₁₄ , Two adjacent substituent groups of a substituted or unsubstituted ring formed by combining adjacent substituents among R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₃ , and R ₅₁ to R ₅₅ One or more groups in the above-mentioned chemical formula 2 are combined with the dotted line.

In addition, the present specification provides an organic light-emitting device comprising: a first electrode, a second electrode provided opposite to the first electrode, and a layer provided between the first electrode and the second electrode Or two or more organic material layers, wherein one or more of the organic material layers contain the above-mentioned heterocyclic compound.

Invention effect

The heterocyclic compound according to an embodiment of the present specification can be used as a material for an organic layer of an organic light-emitting device, and by using the heterocyclic compound, an improvement in efficiency, low driving voltage and/or lifetime characteristics can be achieved in the organic light-emitting device improvement.

The heterocyclic compound of the present specification can exhibit high efficiency characteristics in a device by having a small half-width in structure.

Description of drawings

FIG. 1 illustrates an organic light emitting device according to an embodiment of the present specification.

FIG. 2 illustrates an organic light emitting device according to an embodiment of the present specification.

FIG. 3 illustrates an organic light emitting device according to an embodiment of the present specification.

1: Substrate

2: The first electrode

3: Organic layer

4: The second electrode

5: Light-emitting layer

6: Hole injection layer

7: Hole transport layer-1

8: hole transport layer-2

9: Electron transport layer

Detailed ways

Hereinafter, the present specification will be described in more detail.

The present specification provides the heterocyclic compound represented by the above-mentioned Chemical Formula 1.

Existing spiro structures have a right-angle structure based on the central carbon atom, or a simple cyclized compound such as dimethylfluorene is used to adjust the wavelength and suppress the interaction between molecules to improve the luminous efficiency. At the limit, the use of new substances containing adamantane to control electrical and luminescent properties can improve the efficiency and lifetime of OLED devices.

In addition, in the case of the core containing boron and nitrogen, the device exhibits high efficiency characteristics by having a small half width.

In the present specification, examples of substituents are described below, but are not limited thereto.

The above term "substituted" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is a position where a hydrogen atom can be substituted, that is, a position where a substituent can be substituted. Without limitation, when two or more substituents are substituted, the two or more substituents may be the same or different from each other.

In this specification, the term "substituted or unsubstituted" refers to a group selected from the group consisting of deuterium, nitrile, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted silyl , substituted or unsubstituted alkoxy group, substituted or unsubstituted amine group, substituted or unsubstituted aryl group, and substituted or unsubstituted heterocyclic group with one or more substituents substituted, or substituted by Among the substituents exemplified above, a substituent in which two or more substituents are connected is substituted or does not have any substituents. For example, the "substituent formed by connecting two or more substituents" may be an aryl group substituted with an aryl group, an aryl group substituted with a heteroaryl group, a heterocyclic group substituted with an aryl group, or an aryl group substituted with an alkyl group. Base et al.

In this specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but preferably 1 to 30. Specifically, the number of carbon atoms is preferably 1 to 20. More specifically, the number of carbon atoms is preferably 1 to 10. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1- Ethylbutyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2- Amyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl , tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethylpropyl, 1,1- Dimethylpropyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but is preferably a cycloalkyl group having 3 to 30 carbon atoms, and more preferably a cycloalkyl group having 3 to 20 carbon atoms. Specifically, there are cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methyl Cyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., but not limited thereto.

In this specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but preferably 1 to 30 carbon atoms. Specifically, the number of carbon atoms is preferably 1 to 20. More specifically, the number of carbon atoms is preferably 1 to 10. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, new Pentyloxy, isopentyloxy, n-hexyloxy, 3,3-dimethylbutoxy, 2-ethylbutoxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy , p-methylbenzyloxy, etc., but not limited thereto.

In the present specification, the amine group may be represented by the chemical formula of -NRdRe, the above-mentioned Rd and Re are the same or different from each other, and each independently may be hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or Unsubstituted aryl group, substituted or unsubstituted heterocyclic group, etc., but not limited thereto. Further, the number of carbon atoms of the above-mentioned amine group is not limited, but is preferably 1 to 30. Specific examples of the amino group include a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a phenylamino group, a naphthylamino group, a biphenylamino group, and an anthracenylamino group. , 9-methylanthracenylamino, diphenylamino, N-phenylnaphthylamino, xylylamino, N-phenyltolylamino, triphenylamino, N-phenyl Biphenylamino, N-phenylnaphthylamino, N-biphenylnaphthylamino, N-naphthylfluorenylamino, N-phenylphenanthrenylamino, N-biphenylphenanthrenyl An amino group, an N-phenylfluorenylamino group, an N-phenylterphenylamino group, an N-phenanthrenylfluorenylamino group, an N-biphenylfluorenylamino group, and the like, but not limited thereto.

In the present specification, the silyl group may be represented by the chemical formula of -SiRaRbRc, and the aforementioned Ra, Rb and Rc are the same or different from each other, and each independently may be hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl , substituted or unsubstituted aryl, etc. The above-mentioned silyl groups specifically include trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenyl A silyl group, a diphenylsilyl group, a phenylsilyl group, etc., but not limited thereto.

基、芴基等，但并不限定于此。In the present specification, the aryl group is not particularly limited, but is preferably an aryl group having 6 to 60 carbon atoms, and more preferably an aryl group having 6 to 30 carbon atoms. The above-mentioned aryl group may be monocyclic or polycyclic. In the case where the above-mentioned aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but preferably 6 to 30 carbon atoms. More specifically, the number of carbon atoms is preferably 6 to 20. Specifically, as a monocyclic aryl group, although a phenyl group, a biphenyl group, a terphenyl group, etc. may be mentioned, it is not limited to this. When the above-mentioned aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited, but preferably 10 to 30 carbon atoms, more specifically, 10 to 20 carbon atoms. Specifically, as the polycyclic aryl group, naphthyl, anthracenyl, phenanthryl, triphenyl, pyrenyl, benzyl, perylene,

group, fluorene group, etc., but not limited to this.

When the above-mentioned fluorenyl group is substituted, the two substituents of the 9th carbon atom of the fluorenyl group may combine with each other to form a spiro ring structure such as 9,9-dimethylfluorenyl and 9,9-diphenylfluorenyl. , but not limited to this.

In this specification, a "adjacent" group may refer to a substituent substituted on the atom directly connected to the atom substituted by the substituent, the closest substituent in steric structure to the substituent, or on the Other substituents substituted on the atoms substituted by the substituents. For example, two substituents substituted at the ortho position in a benzene ring and two substituents substituted on the same carbon in an aliphatic ring can be interpreted as groups "adjacent" to each other.

In the present specification, among substituted or unsubstituted rings formed by combining with each other, "ring" refers to a hydrocarbon ring or a heterocyclic ring.

The above-mentioned hydrocarbon ring may be aromatic, aliphatic, or a condensed ring of aromatic and aliphatic groups, and may be selected from the examples of the above-mentioned cycloalkyl group or aryl group in addition to the above-mentioned divalent group.

In the present specification, the above-mentioned description about the aryl group can be applied except that the aromatic hydrocarbon ring is divalent.

In addition to the above-mentioned heterocyclic ring being divalent, the following description about the heterocyclic group can be applied.

In the present specification, as examples of the arylamine group, there are substituted or unsubstituted monoarylamine group, substituted or unsubstituted diarylamine group, or substituted or unsubstituted triarylamine group. The aryl group in the above-mentioned arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group containing two or more of the above-mentioned aryl groups may contain a monocyclic aryl group, a polycyclic aryl group, or may contain both a monocyclic aryl group and a polycyclic aryl group. For example, the aryl group in the above-mentioned arylamine group can be selected from the above-mentioned exemplification of the aryl group.

唑基、

二唑基、吡啶基、联吡啶基、嘧啶基、三嗪基、三唑基、吖啶基、哒嗪基、吡嗪基、喹啉基、喹唑啉基、喹喔啉基、酞嗪基、吡啶并嘧啶基、吡啶并吡嗪基、吡嗪并吡嗪基、异喹啉基、吲哚基、咔唑基、苯并

唑基、苯并咪唑基、苯并噻唑基、苯并咔唑基、苯并噻吩基、二苯并噻吩基、苯并呋喃基、菲咯啉基(phenanthroline)、异

唑基、噻二唑基、吩噻嗪基和二苯并呋喃基等，但并不限定于此。In the present specification, a heterocyclic group contains one or more non-carbon atoms, that is, a heteroatom. Specifically, the above-mentioned heteroatom may contain one or more atoms selected from O, N, Se, SO, SO ₂ , S, etc. . The number of carbon atoms is not particularly limited, but preferably 2 to 60 carbon atoms, more preferably 2 to 30 carbon atoms, and the above-mentioned heterocyclic group may be monocyclic or polycyclic. As examples of the above-mentioned heteroaryl groups, there are thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl,

azolyl,

oxadiazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, triazolyl, acridine, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phthalazine base, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolinyl, indolyl, carbazolyl, benzoyl

azolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, benzofuranyl, phenanthroline, iso

azolyl, thiadiazolyl, phenothiazinyl, dibenzofuranyl, etc., but not limited thereto.

According to an embodiment of the present specification, the above-mentioned R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₃ , R ₅₁ to R ₅₅ , and R ₆₁ to R ₆₄ are the same or different from each other, each independently hydrogen, deuterium, nitrile, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted silyl, substituted or unsubstituted phosphine oxide group, substituted or unsubstituted amine group, substituted or unsubstituted boron group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, or combined with adjacent substituents To form a substituted or unsubstituted ring, two adjacent substituent groups in the above-mentioned R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₃ , and R ₅₁ to R ₅₅ ; and a phase of a substituted or unsubstituted ring formed by combining adjacent substituents among the above-mentioned R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₃ , and R ₅₁ to R ₅₅ One or more of the adjacent two substituent groups are bound to the dotted line of the above-mentioned Chemical Formula 2.

The above-mentioned "two adjacent substituent groups among R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₃ , and R ₅₁ to R ₅₅ " means in the above Chemical Formula 1 2 substituents substituted with ortho. Specifically, in the above Chemical Formula 1, R ₁₁ and R ₁₂ , R ₁₂ and R ₁₃ , R ₁₃ and R ₁₄ , R ₂₁ and R ₂₂ , R ₂₂ and R ₂₃ , R ₂₃ and R ₂₄ , R ₃₁ and R 24 ₃₂ , R ₃₂ and R ₃₃ , R ₃₃ and R ₃₄ , R ₃₄ and R ₃₅ , R ₄₁ and R ₄₂ , R ₄₂ and R ₄₃ , R ₅₁ and R ₅₂ , R ₅₂ and R ₅₃ , R ₅₃ and R ₅₄ , And R ₅₄ and R ₅₅ serve as two adjacent substituents, respectively, and correspond to one group. In addition, the above-mentioned "R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₃ , and R ₅₁ to R ₅₅ are combined with adjacent substituents to form a substituted or unsubstituted "Adjacent two substituent groups on the ring" refers to the following, when R ₂₃ and R ₂₄ of Chemical Formula 1 combine with each other to form a benzene ring, the following R ₂₅ and R ₂₆ , R ₂₆ and R ₂₇ , and R ₂₇ and R ₂₈ respectively serve as two adjacent substituents, corresponding to one group.

According to an embodiment of the present specification, two adjacent substituent groups among the above-mentioned R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₃ , and R ₅₁ to R ₅₅ ; and a phase of a substituted or unsubstituted ring formed by combining adjacent substituents among the above-mentioned R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₃ , and R ₅₁ to R ₅₅ One to four groups of the adjacent two substituent groups are combined with the dotted line of the above-mentioned Chemical Formula 2.

According to an embodiment of the present specification, two adjacent substituent groups among the above-mentioned R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₃ , and R ₅₁ to R ₅₅ ; and a phase of a substituted or unsubstituted ring formed by combining adjacent substituents among the above-mentioned R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₃ , and R ₅₁ to R ₅₅ One or more of the adjacent two substituent groups are bound to the dotted line of the above-mentioned Chemical Formula 2, and the above-mentioned R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₃ , and The substituents of R ₅₁ to R ₅₅ that are not combined with Chemical Formula 2 and R ₆₁ to R ₆₄ are the same or different from each other, and are each independently hydrogen, deuterium, nitrile, halogen group, substituted or unsubstituted alkyl, substituted or Unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted silyl, substituted or unsubstituted phosphine oxide, substituted or unsubstituted amine, substituted or unsubstituted boron, A substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or combined with an adjacent substituent to form a substituted or unsubstituted ring.

In one embodiment of the present specification, the substituents not combined with Chemical Formula 2 among the above-mentioned R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₃ , and R ₅₁ to R ₅₅ and R ₆₁ to R ₆₄ are the same or different from each other, each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkyl group having 3 to 20 carbon atoms 30 cycloalkyl, substituted or unsubstituted alkoxy with 1 to 20 carbon atoms, substituted or unsubstituted silyl group with 1 to 60 carbon atoms, substituted or unsubstituted carbon number 1 to 30 Amino group, substituted or unsubstituted aryl group with 6 to 60 carbon atoms, or substituted or unsubstituted heterocyclic group with 2 to 60 carbon atoms, or combined with adjacent substituents to form substituted or unsubstituted A hydrocarbon ring having 3 to 60 carbon atoms, or a substituted or unsubstituted heterocyclic ring having 2 to 60 carbon atoms. The above-mentioned "substituted or unsubstituted" refers to a group selected from the group consisting of deuterium, nitrile group, halogen group, alkyl group with 1 to 20 carbon atoms, cycloalkyl group with 3 to 30 carbon atoms, and cycloalkyl group with 1 to 20 carbon atoms. One or more of an alkoxy group, a silyl group having 1 to 30 carbon atoms, an amine group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a heterocyclic group having 2 to 30 carbon atoms The connected substituents are substituted or unsubstituted.

In one embodiment of the present specification, the substituents not combined with Chemical Formula 2 among the above-mentioned R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₃ , and R ₅₁ to R ₅₅ and R ₆₁ to R ₆₄ are the same or different from each other, each independently hydrogen, deuterium, nitrile, halogen group, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted methoxy , substituted or unsubstituted ethoxy, substituted or unsubstituted trimethylsilyl, substituted or unsubstituted triphenylsilyl, substituted or unsubstituted diphenylamine, substituted or unsubstituted Dibenzofuranilino, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted carbazolyl , substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, or substituted or unsubstituted pyridyl, or combined with adjacent substituents to form substituted or unsubstituted carbon atoms An aromatic or aliphatic hydrocarbon ring of 3 to 30; or a substituted or unsubstituted heterocyclic ring of 2 to 30 carbon atoms containing one or more of N, O and S as a hetero atom. The above "substituted or unsubstituted" refers to a group selected from the group consisting of deuterium, nitrile, halogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted methoxy, substituted or unsubstituted Unsubstituted ethoxy, substituted or unsubstituted trimethylsilyl, substituted or unsubstituted triphenylsilyl, substituted or unsubstituted diphenylamine, substituted or unsubstituted dibenzo Furylanilino, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted A substituent in which one or more of an unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothienyl group, and a substituted or unsubstituted pyridyl group are connected is substituted or unsubstituted.

In one embodiment of the present specification, the above-mentioned Chemical Formula 1 is represented by one of the following Chemical Formulas 1-1 to 1-7.

[Chemical formula 1-1]

[Chemical formula 1-2]

[Chemical formula 1-3]

[Chemical formula 1-4]

[Chemical formula 1-5]

[Chemical formula 1-6]

[Chemical formula 1-7]

In the above Chemical Formulas 1-1 to 1-7,

R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₃ , R ₅₁ to R ₅₅ , and R ₆₁ to R ₆₄ are the same as defined in Chemical Formulas 1 and 2,

R ₇₁ to R ₇₄ , R ₈₁ to R ₈₄ , R ₉₁ to R ₉₄ , and Ra to Re are the same or different from each other, and are each independently hydrogen, deuterium, nitrile, halogen, substituted or unsubstituted alkyl, Substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted silyl, substituted or unsubstituted phosphine oxide, substituted or unsubstituted amine, substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, or combined with an adjacent substituent to form a substituted or unsubstituted ring,

a and c are each an integer from 0 to 3,

b and f are each 0 or 1,

d and e are each an integer from 0 to 2,

When each of a, and c to e is 2 or more, the substituents in parentheses are the same or different from each other.

According to an embodiment of the present specification, the above-mentioned R ₇₁ to R ₇₄ , R ₈₁ to R ₈₄ , R ₉₁ to R ₉₄ , and Ra to Re are the same as or different from each other, and are each independently hydrogen, deuterium, nitrile group, halogen group , substituted or unsubstituted alkyl group with 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group with 3 to 30 carbon atoms, substituted or unsubstituted alkoxy group with 1 to 20 carbon atoms, substituted or unsubstituted alkoxy group with 1 to 20 carbon atoms Unsubstituted silyl group having 1 to 60 carbon atoms, substituted or unsubstituted amine group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or substituted or unsubstituted aryl group Heterocyclic group having 2 to 60 carbon atoms, or combining with adjacent substituents to form a substituted or unsubstituted hydrocarbon ring having 3 to 60 carbon atoms, or a substituted or unsubstituted hydrocarbon ring having 2 to 60 carbon atoms Heterocycle. The above-mentioned "substituted or unsubstituted" refers to a group selected from the group consisting of deuterium, nitrile group, halogen group, alkyl group with 1 to 20 carbon atoms, cycloalkyl group with 3 to 30 carbon atoms, and cycloalkyl group with 1 to 20 carbon atoms. One or more of an alkoxy group, a silyl group having 1 to 30 carbon atoms, an amine group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a heterocyclic group having 2 to 30 carbon atoms The connected substituents are substituted or unsubstituted.

In one embodiment of the present specification, the above-mentioned R ₇₁ to R ₇₄ , R ₈₁ to R ₈₄ , R ₉₁ to R ₉₄ , and Ra to Re are the same as or different from each other, and are each independently hydrogen, deuterium, nitrile, and halogen. group, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl cyclopentyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted trimethylsilyl, substituted or unsubstituted or unsubstituted triphenylsilyl, substituted or unsubstituted diphenylamino, substituted or unsubstituted dibenzofuranilino, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl or A substituted or unsubstituted pyridyl group, or combined with adjacent substituents to form a substituted or unsubstituted aromatic or aliphatic hydrocarbon ring with 3 to 30 carbon atoms; or a substituted or unsubstituted carbon number from 2 to 30 30 heterocycles containing at least one of N, O, and S as a heteroatom. The above "substituted or unsubstituted" refers to a group selected from the group consisting of deuterium, nitrile, halogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted methoxy, substituted or unsubstituted Unsubstituted ethoxy, substituted or unsubstituted trimethylsilyl, substituted or unsubstituted triphenylsilyl, substituted or unsubstituted diphenylamine, substituted or unsubstituted dibenzo Furylanilino, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted A substituent in which one or more of an unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothienyl group, and a substituted or unsubstituted pyridyl group are connected is substituted or unsubstituted.

In one embodiment of the present specification, the above-mentioned Chemical Formula 1 is represented by one of the following Chemical Formulas 2-1 to 2-5.

[Chemical formula 2-1]

[Chemical formula 2-2]

[Chemical formula 2-3]

[Chemical formula 2-4]

[Chemical formula 2-5]

In the above Chemical Formulas 2-1 to 2-5,

R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₃ , and R ₅₁ to R ₅₅ are the same as defined in Chemical Formulas 1 and 2,

X ₁ and X ₂ are the same or different from each other and are each independently O, S or NR,

R, R ₁₀₁ to R ₁₁₁ , and R ₂₀₁ to R ₂₂₈ are the same or different from each other, and are each independently hydrogen, deuterium, nitrile, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl , substituted or unsubstituted alkoxy, substituted or unsubstituted silyl, substituted or unsubstituted phosphine oxide, substituted or unsubstituted amine, substituted or unsubstituted boron, substituted or unsubstituted aryl radical, substituted or unsubstituted heterocyclyl,

n1 to n9 are each an integer from 0 to 2,

n10 and n11 are each an integer from 0 to 4,

When each of n1 to n11 is 2 or more, the substituents in parentheses are the same or different from each other.

According to an embodiment of the present specification, the above-mentioned R, R ₁₀₁ to R ₁₁₁ and R ₂₀₁ to R ₂₂₈ are the same or different from each other, and each independently represents hydrogen, deuterium, nitrile, halogen, substituted or unsubstituted carbon atoms 1 to 20 alkyl groups, substituted or unsubstituted cycloalkyl groups with 3 to 30 carbon atoms, substituted or unsubstituted alkoxy groups with 1 to 20 carbon atoms, substituted or unsubstituted 1 to 60 carbon atoms silyl group, substituted or unsubstituted amine group with 1 to 30 carbon atoms, substituted or unsubstituted aryl group with 6 to 60 carbon atoms, or substituted or unsubstituted heterocycle with 2 to 60 carbon atoms group, or combine with adjacent substituent groups to form a substituted or unsubstituted hydrocarbon ring having 3 to 60 carbon atoms, or a substituted or unsubstituted heterocyclic ring having 2 to 60 carbon atoms. The above-mentioned "substituted or unsubstituted" refers to a group selected from the group consisting of deuterium, nitrile group, halogen group, alkyl group with 1 to 20 carbon atoms, cycloalkyl group with 3 to 30 carbon atoms, and cycloalkyl group with 1 to 20 carbon atoms. One or more of an alkoxy group, a silyl group having 1 to 30 carbon atoms, an amine group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a heterocyclic group having 2 to 30 carbon atoms The connected substituents are substituted or unsubstituted.

In one embodiment of the present specification, the above-mentioned R, R ₁₀₁ to R ₁₁₁ and R ₂₀₁ to R ₂₂₈ are the same or different from each other, and are each independently hydrogen, deuterium, nitrile, halogen, substituted or unsubstituted methyl , substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentane group, substituted or unsubstituted cyclohexyl, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted trimethylsilyl, substituted or unsubstituted triphenylsilyl base, substituted or unsubstituted diphenylamino, substituted or unsubstituted dibenzofurylanilino, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl substituted or unsubstituted naphthyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, or substituted or unsubstituted pyridyl, or Combining with adjacent substituents to form a substituted or unsubstituted aromatic or aliphatic hydrocarbon ring of 3 to 30 carbon atoms; or a substituted or unsubstituted carbon number of 2 to 30 including N, O and S A heterocyclic ring with at least one of which is used as a heteroatom. The above "substituted or unsubstituted" refers to a group selected from the group consisting of deuterium, nitrile, halogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted methoxy, substituted or unsubstituted Unsubstituted ethoxy, substituted or unsubstituted trimethylsilyl, substituted or unsubstituted triphenylsilyl, substituted or unsubstituted diphenylamine, substituted or unsubstituted dibenzo Furylanilino, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted A substituent in which one or more of an unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothienyl group, and a substituted or unsubstituted pyridyl group are connected is substituted or unsubstituted.

In one embodiment of the present specification, the above-mentioned Chemical Formula 1 is any one selected from the following compounds.

In the above specific examples, D means deuterium, Me means methyl, and Ph means phenyl.

In the present specification, when it is indicated that a certain part "includes/includes" a certain constituent element, unless otherwise stated, it means that other constituent elements may be further included, not excluded.

In this specification, when a certain member is referred to as being "on" another member, it includes not only the case where the certain member is in contact with the other member, but also the case where there are other members between the two members.

The organic light-emitting device of the present invention includes a first electrode, a second electrode provided opposite to the first electrode, and an organic layer provided between the first electrode and the second electrode in one or more layers. , one or more of the above-mentioned organic substance layers may contain the above-mentioned heterocyclic compound.

For example, the structure of the organic light emitting device of the present invention may have the structures shown in FIGS. 1 to 3 , but is not limited thereto.

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

The above-mentioned FIG. 1 illustrates the organic light-emitting device, but is not limited to this.

FIG. 2 illustrates a structure of an organic light emitting device in which a first electrode 2 , a light emitting layer 5 and a second electrode 4 are sequentially stacked on a substrate 1 .

The above-mentioned FIG. 2 illustrates an organic light-emitting device, but is not limited thereto, and additional organic substance layers may be further included between the first electrode 2 and the light-emitting layer 5 and between the light-emitting layer 5 and the second electrode 4 .

3 illustrates that a first electrode 2, a hole injection layer 6, a hole transport layer-1 (7), a hole transport layer-2 (8), a light-emitting layer 5, and an electron transport layer 9 are sequentially stacked on the substrate 1. and the structure of the organic light-emitting device of the second electrode 4 .

In one embodiment of the present invention, the organic layer includes a light-emitting layer, and the light-emitting layer includes the heterocyclic compound of Chemical Formula 1 above.

The organic light-emitting device of the present invention includes a light-emitting layer, and the light-emitting layer may contain a host and a dopant in a mass ratio of 99.9:0.1 to 90:10.

The organic light-emitting device of the present invention includes a light-emitting layer, and the light-emitting layer may contain a host and a dopant in a mass ratio of 99.5:0.5 to 95:5.

In one embodiment of the present invention, the organic substance layer includes a light-emitting layer, and the light-emitting layer includes the heterocyclic compound of Chemical Formula 1 as a dopant.

In one embodiment of the present invention, the organic layer includes a light-emitting layer, and the light-emitting layer includes the heterocyclic compound of Chemical Formula 1 as a dopant of the light-emitting layer.

In one embodiment of the present invention, the organic layer includes one or more of a hole injection layer, a hole transport layer, and a hole injection and transport layer, and the hole injection layer, the hole transport layer, and the hole One or more of the implantation and transport layers may contain the heterocyclic compound of Chemical Formula 1 above.

In one embodiment of the present invention, the organic layer includes at least one of an electron injection layer, an electron transport layer, and an electron injection and transport layer, and the electron injection layer, the electron transport layer, and the electron injection and transport layer One or more layers may contain the heterocyclic compound of the above-mentioned Chemical Formula 1.

In one embodiment of the present invention, the organic layer includes one or more of an electron blocking layer and a hole blocking layer, and the electron blocking layer and/or the hole blocking layer may contain the heterocyclic compound of the above Chemical Formula 1.

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

The organic light-emitting device of the present specification can be manufactured using materials and methods known in the technical field, except that one or more layers in the organic layer are formed using the above-mentioned heterocyclic compound.

In addition, the present specification also provides a method for producing an organic light-emitting device formed using the above-mentioned heterocyclic compound.

For example, the organic light emitting device according to the present invention can be manufactured by using a PVD (physical varpor deposition) method such as sputtering or e-beam evaporation on a substrate An anode is formed by vapor-depositing a metal or a conductive metal oxide or an alloy thereof, and then an organic layer including a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, etc., and an organic layer containing the above chemical formula are formed on the anode. The organic layer of the compound of 1 is produced by vapor-depositing a substance that can be used as a cathode on the organic layer. In addition to these methods, an organic light-emitting device can be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

As the anode material, generally, a material having a large work function is preferable in order to enable smooth injection of holes into the organic material layer. Specific examples of anode materials that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO) Metal oxides such as ZnO:Al or SnO ₂ :Sb and other metals and oxides; poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, etc., but not limited thereto.

As the above-mentioned cathode material, a material having a small work function is preferably used in order to easily inject electrons into the organic material layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or their alloys; LiF/Al, LiO ₂ /Al, etc. Layer structure substances, etc., but not limited to this.

The above-mentioned hole injecting material is a material that can inject holes well from the anode at a low voltage, and the HOMO (highest occupied molecular orbital) of the hole injecting material is preferably between the work function of the anode material and the surrounding organic material layer. between the HOMO. Specific examples of the hole injecting substance include metal porphyrines, oligothiophenes, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, perylene ( perylene) organic compounds, anthraquinone, polyaniline and polythiophene-based conductive polymers, etc., but not limited to this.

The above-mentioned hole-transporting material is a material that can receive holes from the anode or the hole injection layer and transfer them to the light-emitting layer, and is suitable for a material having a high mobility of holes. Specific examples include arylamine-based organic substances, conductive polymers, and block copolymers in which both a conjugated portion and a non-conjugated portion are present, but the present invention is not limited thereto.

唑、苯并噻唑及苯并咪唑系化合物；聚(对亚苯基亚乙烯基)(PPV)系高分子；螺环(spiro)化合物；聚芴；红荧烯等，但不仅限于此。The light-emitting substance is a substance that can receive holes and electrons from the hole transport layer and the electron transport layer, respectively, and combine them to emit light in the visible light region, and is preferably a substance with high quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxyquinoline aluminum complex (Alq ₃ ), carbazole-based compound, dimerized styryl compound; BAlq; 10-hydroxybenzoquinoline-metal compound;

azoles, benzothiazoles, and benzimidazole-based compounds; poly(p-phenylene vinylene) (PPV)-based polymers; spiro compounds; polyfluorenes; rubrene, etc., but not limited thereto.

、二茚并芘等，苯乙烯基胺化合物是在取代或未取代的芳基胺中取代有至少1个芳基乙烯基的化合物，被选自芳基、甲硅烷基、烷基、环烷基和芳基氨基中的1个或2个以上的取代基取代或未取代。具体而言，有苯乙烯基胺、苯乙烯基二胺、苯乙烯基三胺、苯乙烯基四胺等，但并不限定于此。此外，作为金属配合物，有铱配合物、铂配合物等，但并不限定于此。As the dopant material, there are aromatic compounds, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic compound is an aromatic condensed ring derivative having a substituted or unsubstituted arylamino group, such as pyrene, anthracene,

, bisindenopyrene, etc., styrylamine compounds are substituted or unsubstituted arylamines substituted with at least one arylvinyl group, and are selected from aryl, silyl, alkyl, cycloalkane One or two or more substituents in the arylamino group and the arylamino group are substituted or unsubstituted. Specifically, although styrylamine, styryl diamine, styryl triamine, styryl tetraamine, etc. are mentioned, it is not limited to these. Further, as the metal complex, there are iridium complexes, platinum complexes, and the like, but are not limited to these.

The above-mentioned electron transport layer is a layer that receives electrons from the electron injection layer and transports the electrons to the light-emitting layer, and the electron-transport material is a material that can inject electrons from the cathode well and transfer them to the light-emitting layer, and has a high mobility to electrons is appropriate. Specific examples include Al complexes of 8-hydroxyquinoline, complexes containing Alq ₃ , organic radical compounds, hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used in the prior art. In particular, examples of suitable cathode materials are the usual materials with a low work function accompanied by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, and in each case are accompanied by an aluminum layer or a silver layer.

唑、

二唑、三唑、咪唑、苝四羧酸、亚芴基甲烷、蒽酮等和它们的衍生物、金属配位化合物、以及含氮五元环衍生物等，但并不限定于此。The above-mentioned electron injection layer is a layer that injects electrons from the electrode, and is preferably a compound that has the ability to transport electrons, has the effect of injecting electrons from the cathode, has an excellent electron injection effect to the light-emitting layer or light-emitting material, and prevents the light-emitting layer The excitons generated in the compound migrate to the hole injection layer and have excellent thin film forming ability. Specifically, there are fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide,

azole,

Diazoles, triazoles, imidazoles, perylenetetracarboxylic acids, fluorenylene methanes, anthrone, etc., their derivatives, metal complexes, nitrogen-containing five-membered ring derivatives, etc., but not limited thereto.

Examples of the aforementioned metal complex include lithium 8-quinolinate, bis(8-quinolinolato)zinc, bis(8-quinolinolato)copper, bis(8-quinolinolato)manganese, tris(8-hydroxyquinoline) Quinoline)aluminum, tris(2-methyl-8-hydroxyquinoline)aluminum, tris(8-hydroxyquinoline)gallium, bis(10-hydroxybenzo[h]quinoline)beryllium, bis(10-hydroxyl) Benzo[h]quinoline)zinc, bis(2-methyl-8-quinoline)gallium chloride, bis(2-methyl-8-quinoline)(o-cresol)gallium, bis(2-methyl) yl-8-quinoline)(1-naphthol)aluminum, bis(2-methyl-8-quinoline)(2-naphthol)gallium, etc., but not limited thereto.

二唑衍生物或三唑衍生物、菲咯啉衍生物、BCP、铝配合物(aluminum complex)等，但并不限定于此。The above-mentioned hole blocking layer is a layer that prevents holes from reaching the cathode, and can generally be formed under the same conditions as the hole injection layer. Specifically, there are

An oxadiazole derivative, a triazole derivative, a phenanthroline derivative, BCP, an aluminum complex, etc., are not limited to these.

The organic light emitting device according to the present specification may be of a top emission type, a bottom emission type or a bidirectional emission type according to the materials used.

way of implementing the invention

Hereinafter, in order to demonstrate this specification concretely, an Example is given and demonstrated in detail. However, the examples according to the present specification can be modified into various forms, and it should not be construed that the scope of the present specification is limited to the examples described in detail below. The examples in this specification are provided to more completely explain this specification to those skilled in the art.

<Production example>

Manufacturing example 1.

1)

1-Bromo-2,3-dichlorobenzene (22.6g), Intermediate A-1 (16.9g), Pd( _PtBu3 ) ₂ (0.51g), NaOtBu (19.2g) and toluene (400ml) were charged The flask was heated at 110 °C and stirred for 30 min. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether/hexane) gave Intermediate A-2 (25.5 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=315 was confirmed.

2)

A flask containing Intermediate A-2 (20.0 g), Intermediate A-3 (24.0 g), Pd( _PtBu3 ) ₂ (0.33 g), NaOtBu (12.23 g) and toluene (400 ml) was heated at 110 °C , stir for 30 minutes. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. It was purified by silica gel column chromatography (developing solution: hexane/ethyl acetate=50%/50% (volume ratio)) to obtain Intermediate A-4 (13.35 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=378 was confirmed.

3)

To a flask containing Intermediate A-4 (9.76g) and tert-butylbenzene (160ml) was added a 1.7M solution of tert-butyllithium in pentane (9.2ml) at 0°C under an argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70° C., and the mixture was stirred for 4 hours, and the pentane was distilled off. After cooling to -40°C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature, and the mixture was stirred for 4 hours. Then, it cooled to 0 degreeC again, N,N- diisopropylethylamine (6.6 ml) was added, and after stirring at normal temperature, it stirred at 80 degreeC for 4 hours. The reaction liquid was cooled to room temperature, and water and ethyl acetate were added for liquid separation, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to obtain compound 1 (3.2 g). As a result of mass spectrometry of the obtained solid, a peak at M/Z=629 was confirmed.

Manufacturing example 2.

1)

1-Bromo-2,3-dichlorobenzene (22.6g), Intermediate B-1 (19.7g), Pd( _PtBu3 ) ₂ (0.51g), NaOtBu (19.2g) and toluene (400ml) were charged The flask was heated at 110 °C and stirred for 30 min. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether/hexane) gave Intermediate B-2 (24.0 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=343 was confirmed.

2)

A flask containing Intermediate B-2 (15.0 g), Intermediate B-3 (20.7 g), Pd( _PtBu3 ) ₂ (0.22 g), NaOtBu (8.42 g) and toluene (400 ml) was heated at 110 °C , stir for 30 minutes. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. It was purified by silica gel column chromatography (developing solution: hexane/ethyl acetate=50%/50% (volume ratio)) to obtain Intermediate B-4 (17.1 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=780 was confirmed.

3)

To a flask containing Intermediate B-4 (11.6g) and tert-butylbenzene (160ml) was added a 1.7M solution of tert-butyllithium in pentane (9.2ml) at 0°C under an argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70° C., and the mixture was stirred for 4 hours, and the pentane was distilled off. After cooling to -40°C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature, and the mixture was stirred for 4 hours. Then, it cooled to 0 degreeC again, N,N- diisopropylethylamine (6.6 ml) was added, and after stirring at normal temperature, it stirred at 80 degreeC for 4 hours. The reaction liquid was cooled to room temperature, and water and ethyl acetate were added for liquid separation, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to obtain compound 2 (3.8 g). As a result of mass spectrometry of the obtained solid, a peak at M/Z=753 was confirmed.

Manufacturing example 3.

1)

1-Bromo-2,3-dichlorobenzene (22.6g), Intermediate C-1 (19.7g), Pd( _PtBu3 ) ₂ (0.51g), NaOtBu (19.2g) and toluene (400ml) were charged The flask was heated at 110 °C and stirred for 30 min. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether/hexane) gave Intermediate C-2 (24.0 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=343 was confirmed.

2)

A flask containing Intermediate C-2 (15.0 g), Intermediate C-3 (17.2 g), Pd( _PtBu3 ) ₂ (0.22 g), NaOtBu (8.42 g) and toluene (400 ml) was heated at 110 °C , stir for 30 minutes. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. It was purified by silica gel column chromatography (developing solution: hexane/ethyl acetate=50%/50% (volume ratio)) to obtain Intermediate C-4 (14.2 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=698 was confirmed.

3)

To a flask containing Intermediate C-4 (10.4g) and tert-butylbenzene (160ml) was added a 1.7M solution of tert-butyllithium in pentane (9.2ml) at 0°C under argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70° C., and the mixture was stirred for 4 hours, and the pentane was distilled off. After cooling to -40°C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature, and the mixture was stirred for 4 hours. Then, it cooled to 0 degreeC again, N,N- diisopropylethylamine (6.6 ml) was added, and after stirring at normal temperature, it stirred at 80 degreeC for 4 hours. The reaction liquid was cooled to room temperature, and water and ethyl acetate were added for liquid separation, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to obtain compound 3 (3.5 g). As a result of mass spectrometry of the obtained solid, a peak at M/Z=671 was confirmed.

Manufacturing Example 4.

1)

1-Bromo-2,3-dichlorobenzene (22.6g), Intermediate D-1 (45.5g), Pd( _PtBu3 ) ₂ (0.51g), NaOtBu (19.2g) and toluene (400ml) were charged The flask was heated at 110 °C and stirred for 30 min. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether/hexane) gave Intermediate D-2 (28.5 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=600 was confirmed.

2)

A flask containing Intermediate D-2 (26.3g), Intermediate D- ₃ (19.9g), Pd(PtBu3) ₂ (0.22g), NaOtBu (8.42g) and toluene (400ml) was heated at 110°C , stir for 30 minutes. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added, and after liquid separation, the solvent was distilled off under reduced pressure. It was purified by silica gel column chromatography (developing solution: hexane/ethyl acetate=50%/50% (volume ratio)) to obtain Intermediate D-4 (18.1 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=1018 was confirmed.

3)

To a flask containing Intermediate D-4 (15.2g) and tert-butylbenzene (160ml) was added a 1.7M solution of tert-butyllithium in pentane (9.2ml) at 0°C under an argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70° C., and the mixture was stirred for 4 hours, and the pentane was distilled off. After cooling to -40°C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature, and the mixture was stirred for 4 hours. Then, it cooled to 0 degreeC again, N,N- diisopropylethylamine (6.6 ml) was added, and after stirring at normal temperature, it stirred at 80 degreeC for 4 hours. The reaction liquid was cooled to room temperature, and water and ethyl acetate were added for liquid separation, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to obtain compound 4 (5.0 g). As a result of mass spectrometry of the obtained solid, a peak at M/Z=992 was confirmed.

Manufacturing Example 5.

1)

1-Bromo-2,3-dichlorobenzene (22.6g), Intermediate E-1 (48.3g), Pd( _PtBu3 ) ₂ (0.51g), NaOtBu (19.2g) and toluene (400ml) were charged The flask was heated at 110 °C and stirred for 30 min. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether/hexane) gave Intermediate E-2 (28.0 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=628 was confirmed.

2)

A flask containing Intermediate E-2 (27.5g), Intermediate E- ₃ (20.1g), Pd(PtBu3) ₂ (0.22g), NaOtBu (8.42g) and toluene (400ml) was heated at 110°C , stir for 30 minutes. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. It was purified by silica gel column chromatography (developing solution: hexane/ethyl acetate=50%/50% (volume ratio)) to obtain Intermediate E-4 (23.0 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=1051 was confirmed.

3)

To a flask containing Intermediate E-4 (15.7g) and tert-butylbenzene (160ml) was added a 1.7M solution of tert-butyllithium in pentane (9.2ml) at 0°C under argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70° C., and the mixture was stirred for 4 hours, and the pentane was distilled off. After cooling to -40°C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature, and the mixture was stirred for 4 hours. Then, it cooled to 0 degreeC again, N,N- diisopropylethylamine (6.6 ml) was added, and after stirring at normal temperature, it stirred at 80 degreeC for 4 hours. The reaction liquid was cooled to room temperature, and water and ethyl acetate were added for liquid separation, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to obtain compound 5 (8.8 g). As a result of mass spectrometry of the obtained solid, a peak at M/Z=1025 was confirmed.

Manufacturing Example 6.

1)

1-Bromo-2,3-dichlorobenzene (22.6g), Intermediate F-1 (120.0g), Pd( _PtBu3 ) ₂ (1.02g), NaOtBu (38.4g) and toluene (800ml) were charged The flask was heated at 110 °C and stirred for 30 min. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether/hexane) gave Intermediate F-2 (50.1 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=1309 was confirmed.

2)

To a flask containing Intermediate F-2 (19.5g) and tert-butylbenzene (160ml) was added a 1.7M solution of tert-butyllithium in pentane (9.2ml) at 0°C under an argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70° C., and the mixture was stirred for 4 hours, and the pentane was distilled off. After cooling to -40°C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature, and the mixture was stirred for 4 hours. Then, it cooled to 0 degreeC again, N,N- diisopropylethylamine (6.6 ml) was added, and after stirring at normal temperature, it stirred at 80 degreeC for 4 hours. The reaction liquid was cooled to room temperature, and water and ethyl acetate were added for liquid separation, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to obtain compound 6 (9.8 g). As a result of mass spectrometry of the obtained solid, a peak at M/Z=1282 was confirmed.

Manufacturing Example 7.

1)

1-Bromo-2,3-dichlorobenzene (22.6g), Intermediate G-1 (16.9g), Pd( _PtBu3 ) ₂ (0.51g), NaOtBu (19.2g) and toluene (400ml) were charged The flask was heated at 110 °C and stirred for 30 min. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether/hexane) gave Intermediate G-2 (25.5 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=315 was confirmed.

2)

A flask containing Intermediate G-2 (13.8g), Intermediate G- ₃ (40.0g), Pd(PtBu3) ₂ (0.22g), NaOtBu (8.42g) and toluene (400ml) was heated at 110°C , stir for 30 minutes. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. It was purified by silica gel column chromatography (developing solution: hexane/ethyl acetate=50%/50% (volume ratio)) to obtain Intermediate G-4 (26.6 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=1191 was confirmed.

3)

To a flask containing Intermediate G-4 (17.7g) and tert-butylbenzene (160ml) was added a 1.7M solution of tert-butyllithium in pentane (9.2ml) at 0°C under an argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70° C., and the mixture was stirred for 4 hours, and the pentane was distilled off. After cooling to -40°C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature, and the mixture was stirred for 4 hours. Then, it cooled to 0 degreeC again, N,N- diisopropylethylamine (6.6 ml) was added, and after stirring at normal temperature, it stirred at 80 degreeC for 4 hours. The reaction liquid was cooled to room temperature, and water and ethyl acetate were added for liquid separation, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to obtain compound 7 (6.6 g). As a result of mass spectrometry of the obtained solid, a peak at M/Z=1164 was confirmed.

Manufacturing Example 8.

1)

3-Bromo-4,5-dichloro-1,1'-biphenyl (30.2 g), Intermediate H-1 (47.0 g), Pd(PtBu ₃ ) ₂ (0.51 g), NaOtBu (19.2 g) were charged g) A flask of toluene (400 ml) was heated at 110°C and stirred for 30 minutes. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether/hexane) gave Intermediate H-2 (55.9 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=691 was confirmed.

2)

A flask containing Intermediate H-2 (30.3g), Intermediate H- ₃ (9.6g), Pd(PtBu3) ₂ (0.22g), NaOtBu (8.42g) and toluene (400ml) was heated at 110°C , stir for 30 minutes. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. It was purified by silica gel column chromatography (developing solution: hexane/ethyl acetate=50%/50% (volume ratio)) to obtain Intermediate H-4 (23.7 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=874 was confirmed.

3)

To a flask containing Intermediate H-4 (13.0 g) and tert-butylbenzene (160 ml) was added a 1.7M solution of tert-butyllithium in pentane (9.2 ml) at 0°C under argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70° C., and the mixture was stirred for 4 hours, and the pentane was distilled off. After cooling to -40°C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature, and the mixture was stirred for 4 hours. Then, it cooled to 0 degreeC again, N,N- diisopropylethylamine (6.6 ml) was added, and after stirring at normal temperature, it stirred at 80 degreeC for 4 hours. The reaction liquid was cooled to room temperature, and water and ethyl acetate were added for liquid separation, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to obtain compound 8 (8.7 g). As a result of mass spectrometry of the obtained solid, a peak at M/Z=847 was confirmed.

Manufacturing Example 9.

1)

1-Bromo-2,3-dichloro-5-toluene (24.0 g), Intermediate 1-1 (37.8 g), Pd( _PtBu3 ) ₂ (0.51 g), NaOtBu (19.2 g) and toluene were charged (400ml) flask was heated at 110°C and stirred for 30 minutes. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether/hexane) gave Intermediate I-2 (40.2 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=537 was confirmed.

2)

A flask containing Intermediate 1-2 (23.5g), Intermediate 1-3 (16.5g), Pd( _PtBu3 ) ₂ (0.22g), NaOtBu (8.42g) and toluene (400ml) was heated at 110°C , stir for 30 minutes. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. It was purified by silica gel column chromatography (developing solution: hexane/ethyl acetate=50%/50% (volume ratio)) to obtain Intermediate I-4 (19.3 g). As a result of mass spectrometry measurement of the obtained solid, a peak at [M+H+]=878 was confirmed.

3)

To a flask containing Intermediate I-4 (13.1 g) and tert-butylbenzene (160 ml) was added a 1.7M solution of tert-butyllithium in pentane (9.2 ml) at 0°C under an argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70° C., and the mixture was stirred for 4 hours, and the pentane was distilled off. After cooling to -40°C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature, and the mixture was stirred for 4 hours. Then, it cooled to 0 degreeC again, N,N- diisopropylethylamine (6.6 ml) was added, and after stirring at normal temperature, it stirred at 80 degreeC for 4 hours. The reaction liquid was cooled to room temperature, and water and ethyl acetate were added for liquid separation, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to obtain compound 9 (6.9 g). As a result of mass spectrometry of the obtained solid, a peak at M/Z=851 was confirmed.

Manufacturing Example 10.

1)

1-Bromo-2,3-dichloro-5-iodobenzene (70.4 g), Intermediate J-1 (54.4 g), Pd(PPh ₃ ) ₂ (0.51 g), K ₂ CO ₃ (55.2 g) were charged g) A flask with 200 mL of water and tetrahydrofuran (1000 mL) was heated under reflux and stirred for 30 minutes. The reaction solution was cooled to room temperature, and a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and tetrahydrofuran were added for liquid separation, and then the solvent was distilled off under reduced pressure. Purification by recrystallization (ethyl acetate/hexane) gave Intermediate J-2 (73.3 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=453 was confirmed.

2)

The flask containing Intermediate J- ₂ (67.8 g), _CH3SO2OH (96 mL) and toluene (600 mL) was stirred for 5 hours. The reaction liquid was cooled to room temperature, the reaction product was poured into water, the resulting solid was filtered, and the resulting solid was purified with chloroform and ethanol to obtain Intermediate J-3 (59.9 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=435 was confirmed.

3)

A flask containing Intermediate J-3 (43.4g), Intermediate J-4 (16.9g), Pd( _PtBu3 ) ₂ (0.51g), NaOtBu (19.2g) and toluene (400ml) was heated at 110°C , stir for 30 minutes. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether/hexane) gave Intermediate J-5 (40.8 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=523 was confirmed.

4)

A flask containing Intermediate J-5 (22.9g), Intermediate J-6 (8.6g), Pd( _PtBu3 ) ₂ (0.22g), NaOtBu (8.42g) and toluene (400ml) was heated at 110°C , stir for 30 minutes. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. It was purified by silica gel column chromatography (developing solution: hexane/ethyl acetate=50%/50% (volume ratio)) to obtain Intermediate J-7 (19.4 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=684 was confirmed.

5)

To a flask containing Intermediate J-7 (10.2g) and tert-butylbenzene (160ml) was added a 1.7M solution of tert-butyllithium in pentane (9.2ml) at 0°C under argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70° C., and the mixture was stirred for 4 hours, and the pentane was distilled off. After cooling to -40°C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature, and the mixture was stirred for 4 hours. Then, it cooled to 0 degreeC again, N,N- diisopropylethylamine (6.6 ml) was added, and after stirring at normal temperature, it stirred at 80 degreeC for 4 hours. The reaction liquid was cooled to room temperature, and water and ethyl acetate were added for liquid separation, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to obtain compound 10 (6.5 g). As a result of mass spectrometry of the obtained solid, a peak at M/Z=657 was confirmed.

Manufacturing Example 11.

1)

1-Bromo-2,3-dichloro-5-iodobenzene (70.4 g), Intermediate K-1 (58.0 g), Pd(PPh ₃ ) ₂ (0.51 g), K ₂ CO ₃ (55.2 g) were charged g) A flask with 200 mL of water and tetrahydrofuran (1000 mL) was heated under reflux and stirred for 30 minutes. The reaction solution was cooled to room temperature, and a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and tetrahydrofuran were added for liquid separation, and then the solvent was distilled off under reduced pressure. Purification by recrystallization (ethyl acetate/hexane) gave Intermediate K-2 (73.3 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=471 was confirmed.

2)

The flask containing Intermediate K- ₂ (70.5 g), _CH3SO2OH (96 mL) and toluene (600 mL) was stirred for 5 hours. The reaction solution was cooled to room temperature, the reaction product was poured into water, the resulting solid was filtered, and the resulting solid was purified with chloroform and ethanol to obtain Intermediate K-3 (61.0 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=453 was confirmed.

3)

A flask containing Intermediate K-3 (45.2g), Intermediate K-4 (52.6g), Pd( _PtBu3 ) ₂ (1.02g), NaOtBu (38.4g) and toluene (400ml) was heated at 110°C , stir for 30 minutes. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether/hexane) gave Intermediate K-5 (40.5 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=862 was confirmed.

4)

To a flask containing Intermediate K-5 (12.8g) and tert-butylbenzene (160ml) was added a 1.7M solution of tert-butyllithium in pentane (9.2ml) at 0°C under argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70° C., and the mixture was stirred for 4 hours, and the pentane was distilled off. After cooling to -40°C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature, and the mixture was stirred for 4 hours. Then, it cooled to 0 degreeC again, N,N- diisopropylethylamine (6.6 ml) was added, and after stirring at normal temperature, it stirred at 80 degreeC for 4 hours. The reaction liquid was cooled to room temperature, and water and ethyl acetate were added for liquid separation, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to obtain compound 11 (4.8 g). As a result of mass spectrometry of the obtained solid, a peak at M/Z=835 was confirmed.

Manufacturing Example 12.

1)

2-Bromo-3,4-dichloro-1-iodobenzene (70.4 g), intermediate L-1 (54.4 g), Pd(PPh ₃ ) ₂ (0.51 g), K ₂ CO ₃ (55.2 g) were charged g) A flask with 200 mL of water and tetrahydrofuran (1000 mL) was heated under reflux and stirred for 30 minutes. The reaction solution was cooled to room temperature, and a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and tetrahydrofuran were added for liquid separation, and then the solvent was distilled off under reduced pressure. Purification by recrystallization (ethyl acetate/hexane) gave Intermediate L-2 (68.1 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=453 was confirmed.

2)

The flask containing Intermediate L- ₂ (67.8 g), _CH3SO2OH (96 mL) and toluene (600 mL) was stirred for 5 hours. The reaction solution was cooled to room temperature, the reaction product was poured into water, the resulting solid was filtered, and the resulting solid was purified with chloroform and ethanol to obtain Intermediate L-3 (60.1 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=435 was confirmed.

3)

A flask containing Intermediate L-3 (43.4g), Intermediate L-4 (40.6g), Pd( _PtBu3 ) ₂ (0.51g), NaOtBu (19.2g) and toluene (400ml) was heated at 110°C , stir for 30 minutes. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether/hexane) gave Intermediate L-5 (37.9 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=759 was confirmed.

4)

A flask containing Intermediate L-5 (33.2g), Intermediate L-6 (17.8g), Pd( _PtBu3 ) ₂ (0.22g), NaOtBu (8.42g) and toluene (400ml) was heated at 110°C , stir for 30 minutes. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. It was purified by silica gel column chromatography (developing solution: hexane/ethyl acetate=50%/50% (volume ratio)) to obtain Intermediate L-7 (18.8 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=1129 was confirmed.

5)

To a flask containing Intermediate L-7 (16.8 g) and tert-butylbenzene (160 ml) was added a 1.7M solution of tert-butyllithium in pentane (9.2 ml) at 0°C under argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70° C., and the mixture was stirred for 4 hours, and the pentane was distilled off. After cooling to -40°C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature, and the mixture was stirred for 4 hours. Then, it cooled to 0 degreeC again, N,N- diisopropylethylamine (6.6 ml) was added, and after stirring at normal temperature, it stirred at 80 degreeC for 4 hours. The reaction liquid was cooled to room temperature, and water and ethyl acetate were added for liquid separation, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to obtain compound 12 (6.9 g). As a result of mass spectrometry of the obtained solid, a peak at M/Z=1102 was confirmed.

Manufacturing Example 13.

1)

It was charged with 3-bromo-4,5-dichlorophenol (24.2g), intermediate M-1 (16.9g), Pd( _PtBu3 ) ₂ (0.51g), NaOtBu (19.2g) and toluene (400ml) The flask was heated and stirred at 110 °C for 30 min. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether/hexane) gave Intermediate M-2 (28.1 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=331 was confirmed.

2)

A flask containing Intermediate M-2 (14.5g), Intermediate M- ₃ (16.5g), Pd(PtBu3) ₂ (0.22g), NaOtBu (8.42g) and toluene (400ml) was heated at 110°C , stir for 30 minutes. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. It was purified by silica gel column chromatography (developing solution: hexane/ethyl acetate=50%/50% (volume ratio)) to obtain Intermediate M-4 (17.9 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=672 was confirmed.

3)

To a flask containing Intermediate M-4 (10.0 g) and tert-butylbenzene (160 ml) was added a 1.7M solution of tert-butyllithium in pentane (9.2 ml) at 0°C under argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70° C., and the mixture was stirred for 4 hours, and the pentane was distilled off. After cooling to -40°C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature, and the mixture was stirred for 4 hours. Then, it cooled to 0 degreeC again, N,N- diisopropylethylamine (6.6 ml) was added, and after stirring at normal temperature, it stirred at 80 degreeC for 4 hours. The reaction liquid was cooled to room temperature, and water and ethyl acetate were added for liquid separation, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to give Intermediate M-5 (4.8 g). As a result of mass spectrometry of the obtained solid, a peak at M/Z=645 was confirmed.

4)

Intermediate M-5 (4.1 g), nonafluorobutane-1-sulfonyl fluoride (2.2 g) and potassium carbonate (1.5 g) were dissolved in acetonitrile (40 ml), heated to 50°C, and stirred for 4 hours. After cooling to normal temperature, distilled water was thrown in, and potassium carbonate was removed, and the intermediate body M-6 (5.5g) was obtained.

5)

A flask containing Intermediate M-6 (13.8 g), Intermediate M-7 (6.4 g), Pd( _PtBu3 ) ₂ (0.10 g), NaOtBu (3.0 g) and toluene (100 ml) was heated at 110 °C , stir for 30 minutes. The reaction liquid was cooled to room temperature, a saturated solution of NH ₄ Cl (sat.aq. NH ₄ Cl) and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. It was purified by silica gel column chromatography (developing solution: hexane/ethyl acetate=50%/50% (volume ratio)) to obtain Compound 13 (11.2 g). As a result of mass spectrometry of the obtained solid, a peak at [M+H+]=1055 was confirmed.

<Experimental example>

Example 1.

的厚度被涂布成薄膜的玻璃基板放入溶解有洗涤剂的蒸馏水中，利用超声波进行洗涤。这时，洗涤剂使用菲希尔公司(Fischer Co.)制品，蒸馏水使用了利用密理博公司(Millipore Co.)制造的过滤器(Filter)过滤两次的蒸馏水。将ITO洗涤30分钟后，用蒸馏水重复两次而进行10分钟超声波洗涤。在蒸馏水洗涤结束后，用异丙醇、丙酮、甲醇的溶剂进行超声波洗涤并干燥后，输送至等离子体清洗机。此外，利用氧等离子体，将上述基板清洗5分钟后，将基板输送至真空蒸镀机。ITO (indium tin oxide, indium tin oxide) with

The thickness of the glass substrate coated as a thin film is put into distilled water in which detergent is dissolved, and washed with ultrasonic waves. At this time, a Fischer Co. product was used as the detergent, and distilled water filtered twice by a Millipore Co. filter was used for the distilled water. After washing with ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropanol, acetone, and methanol, followed by drying, and then transported to a plasma cleaning machine. Moreover, after the said board|substrate was wash|cleaned for 5 minutes by oxygen plasma, the board|substrate was conveyed to a vacuum vapor deposition machine.

的厚度进行热真空蒸镀而形成空穴注入层。在上述空穴注入层上，作为第一空穴传输层，将下述化合物HT-A真空蒸镀成

接着，作为第二空穴传输层，将下述化合物HT-B蒸镀成

将作为主体的BH-A和作为掺杂剂的化合物1以95:5的重量比进行真空蒸镀而形成

厚度的发光层。On the ITO transparent electrode thus prepared, the following compound HAT was added to

A hole injection layer was formed by thermal vacuum evaporation. On the above hole injection layer, as the first hole transport layer, the following compound HT-A was vacuum-evaporated into a

Next, as the second hole transport layer, the following compound HT-B was vapor-deposited into

Formed by vacuum evaporation of BH-A as the host and compound 1 as the dopant at a weight ratio of 95:5

thickness of the light-emitting layer.

在上述同时进行电子注入和电子传输的层上，依次将氟化锂(LiF)以

的厚度、将铝以

的厚度进行蒸镀而形成阴极，从而制造了有机发光器件。Next, as a layer for simultaneous electron injection and electron transport, the following compound ET-A and the following compound Liq were vapor-deposited at a ratio of 1:1.

On the above-mentioned layer for simultaneous electron injection and electron transport, lithium fluoride (LiF) was sequentially added to

thickness, aluminum to

A cathode was formed by vapor deposition with a thickness of 100 Å, thereby fabricating an organic light-emitting device.

/sec，阴极的氟化锂维持

/sec的蒸镀速速，铝维持

/sec的蒸镀速度，在蒸镀时，真空度维持1×10^-7至5×10^-8托，从而制作了有机发光器件。During the above process, the evaporation rate of organic substances is maintained

/sec, lithium fluoride maintenance at the cathode

/sec vapor deposition rate, aluminum maintains

At the vapor deposition rate of /sec, the vacuum degree was maintained at 1×10 ⁻⁷ to 5×10 ⁻⁸ Torr during the vapor deposition, thereby producing an organic light-emitting device.

Examples 2 to 14

An organic light-emitting device was produced by the same method as in Example 1, except that the host and dopant compounds described in Table 1 below were used as the light-emitting layer substances in the above-mentioned Example 1.

Comparative Examples 1 to 4

An organic light-emitting device was produced by the same method as in Example 1, except that the host and dopant compounds described in Table 1 below were used as the light-emitting layer substances in the above-mentioned Example 1.

Examples 15 to 19 and Comparative Example 5

An organic light-emitting device was produced by the same method as in Example 1, except that the host and dopant compounds described in Table 1 below were used as the light-emitting layer substances in the above-mentioned Example 1. Specifically for the main body, the first main body and the second main body were used in a weight ratio of 1:1 in place of the BH-A of Example 1.

The driving voltage and the efficiency at a current density of 10 mA/cm ² were measured for the organic light-emitting devices fabricated according to the above-mentioned Examples 1 to 19 and Comparative Examples 1 to 5, and it was measured that at a current density of 20 mA/cm ² , relative to the initial brightness, Time required at 97% (T97). The results are shown in Table 1 below.

[Table 1]

As shown in Table 1 above, it was confirmed that the devices of Examples 1 to 19 using the compound having the structure of Chemical Formula 1 had characteristics of lower voltage, higher efficiency, and longer life than the devices of Comparative Examples 1 to 5 .

Claims (8)

1. A heterocyclic compound represented by the following Chemical Formula 1: Chemical formula 1

Chemical formula 2

In the Chemical Formula 1 and Chemical Formula 2, R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₃ , R ₅₁ to R ₅₅ , and R ₆₁ to R ₆₄ are the same or different from each other, each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted silyl group, substituted or unsubstituted phosphine oxide group, A substituted or unsubstituted amine group, a substituted or unsubstituted boron group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, or combined with an adjacent substituent to form a substituted or unsubstituted ring , 2 adjacent substituent groups among the R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₃ , and R ₅₁ to R ₅₅ ; and the R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₃ , and the adjacent two substituents of the substituted or unsubstituted ring formed by combining adjacent substituents of R ₅₁ to R ₅₅ One or more of the groups are bound to the dotted line of the above-mentioned Chemical Formula 2. 2. The heterocyclic compound according to claim 1, wherein the chemical formula 1 is represented by any one of the following chemical formulae 1-1 to 1-7: Chemical formula 1-1

Chemical formula 1-2

Chemical formula 1-3

Chemical formula 1-4

Chemical formula 1-5

Chemical formula 1-6

Chemical formula 1-7

In the Chemical Formulas 1-1 to 1-7, R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₃ , R ₅₁ to R ₅₅ , and R ₆₁ to R ₆₄ are the same as defined in Chemical Formulas 1 and 2, R ₇₁ to R ₇₄ , R ₈₁ to R ₈₄ , R ₉₁ to R ₉₄ , and Ra to Re are the same or different from each other, and are each independently hydrogen, deuterium, nitrile, halogen, substituted or unsubstituted alkyl, Substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted silyl, substituted or unsubstituted phosphine oxide, substituted or unsubstituted amine, substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, or combined with an adjacent substituent to form a substituted or unsubstituted ring, a and c are each an integer from 0 to 3, b and f are each 0 or 1, d and e are each an integer from 0 to 2, When each of a, and c to e is 2 or more, the substituents in parentheses are the same or different from each other. 3. The heterocyclic compound according to claim 1, wherein the adjacent ones of R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₃ , and R ₅₁ to R ₅₅ 2 substituent groups; and the adjacent substituents in the R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₃ , and R ₅₁ to R ₅₅ are combined to form 1 to 4 groups of the adjacent 2 substituent groups of the substituted or unsubstituted ring are combined with the dotted line of the Chemical Formula 2. 4. The heterocyclic compound according to claim 1, wherein the chemical formula 1 is represented by any one of the following chemical formulae 2-1 to 2-5: Chemical formula 2-1

Chemical formula 2-2

Chemical formula 2-3

Chemical formula 2-4

Chemical formula 2-5

In the Chemical Formulas 2-1 to 2-5, R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₃ , and R ₅₁ to R ₅₅ are the same as defined in the Chemical Formulas 1 and 2, X ₁ and X ₂ are the same or different from each other and are each independently O, S or NR, R, R ₁₀₁ to R ₁₁₁ , and R ₂₀₁ to R ₂₂₈ are the same or different from each other, and are each independently hydrogen, deuterium, nitrile, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl , substituted or unsubstituted alkoxy, substituted or unsubstituted silyl, substituted or unsubstituted phosphine oxide, substituted or unsubstituted amine, substituted or unsubstituted boron, substituted or unsubstituted aryl radical, substituted or unsubstituted heterocyclyl, n1 to n9 are each an integer from 0 to 2, n10 and n11 are each an integer from 0 to 4, When each of n1 to n11 is 2 or more, the substituents in parentheses are the same or different from each other. 5. The heterocyclic compound according to claim 1, wherein the chemical formula 1 is any one selected from the following compounds:

6. An organic light-emitting device comprising: a first electrode, a second electrode provided opposite to the first electrode, and a layer provided between the first electrode and the second electrode Or two or more organic substance layers, one or more of the organic substance layers containing the heterocyclic compound of any one of claims 1 to 5. 7 . The organic light-emitting device of claim 6 , wherein the organic layer comprises a light-emitting layer including a host and a dopant in a mass ratio of 99.9:0.1 to 80:20. 8 . 8 . The organic light-emitting device of claim 6 , wherein the organic layer comprises a light-emitting layer, and the light-emitting layer includes the heterocyclic compound. 9 .

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