阅读说明：本技术 杂环化合物及包含其的有机发光器件 (Heterocyclic compound and organic light emitting device including the same ) 是由 尹正民 金公谦 具己洞 吴重锡 吴尚珉 于 2019-10-18 设计创作，主要内容包括：本说明书提供一种有机发光器件,其中,包括：第一电极、与上述第一电极对置而具备的第二电极、以及具备在上述第一电极与上述第二电极之间的1层或2层以上的有机物层,上述有机物层中的1层以上包含由化学式1表示的杂环化合物。(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.)

1. A heterocyclic compound represented by the following chemical formula 1:

chemical formula 1

Chemical formula 2

In the chemical formulas 1 and 2,

R₁₁to R₁₄、R₂₁To R₂₄、R₃₁To R₃₅、R₄₁To R₄₃、R₅₁To R₅₅And R₆₁To R₆₄The same or different from each other, each independently is hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted silyl group, a 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 combines with an adjacent substituent to form a substituted or unsubstituted ring,

the R is₁₁To R₁₄、R₂₁To R₂₄、R₃₁To R₃₅、R₄₁To R₄₃And R₅₁To R₅₅Adjacent 2 substituent groups; and said R₁₁To R₁₄、R₂₁To R₂₄、R₃₁To R₃₅、R₄₁To R₄₃And R₅₁To R₅₅Wherein 1 or more groups among adjacent 2 substituent groups of the substituted or unsubstituted ring formed by combining adjacent substituents are combined with the dotted line of 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 formulas 1 to 3

Chemical formulas 1 to 4

Chemical formulas 1 to 5

Chemical formulas 1 to 6

Chemical formulas 1 to 7

In the chemical formulas 1-1 to 1-7,

R₁₁to R₁₄、R₂₁To R₂₄、R₃₁To R₃₅、R₄₁To R₄₃、R₅₁To R₅₅And R₆₁To R₆₄As defined in chemical formulas 1 and 2,

R₇₁to R₇₄、R₈₁To R₈₄、R₉₁To R₉₄And Ra to Re are the same as or different from each other, and each independently is hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted silyl group, a substituted or unsubstituted phosphine oxide group, a substituted or unsubstituted amine group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, or combines with an adjacent substituent to form a substituted or unsubstituted ring,

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

b and f are each 0 or 1,

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

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

3. The heterocyclic compound according to claim 1, wherein R is₁₁To R₁₄、R₂₁To R₂₄、R₃₁To R₃₅、R₄₁To R₄₃And R₅₁To R₅₅Adjacent 2 substituent groups; and said R₁₁To R₁₄、R₂₁To R₂₄、R₃₁To R₃₅、R₄₁To R₄₃And R₅₁To R₅₅Wherein 1 to 4 groups among adjacent 2 substituent groups of the substituted or unsubstituted ring formed by combining adjacent substituents are combined with the dotted line of 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,

R₁₁to R₁₄、R₂₁To R₂₄、R₃₁To R₃₅、R₄₁To R₄₃And R₅₁To R₅₅As defined in the chemical formulas 1 and 2,

X₁and X₂Equal to or different from each other, each independently O, S or NR,

R、R₁₀₁to R₁₁₁And R₂₀₁To R₂₂₈The same or different from each other, each independently is hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted silyl group, a 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,

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

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

when n1 to n11 are each 2 or more, the substituents in parentheses may be 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 so as 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 contain the heterocyclic compound according to any one of claims 1 to 5.

7. The organic light-emitting device according to claim 6, wherein the organic layer comprises a light-emitting layer containing a host and a dopant at a mass ratio of 99.9:0.1 to 80: 20.

8. The organic light-emitting device according to claim 6, wherein the organic layer comprises a light-emitting layer containing the heterocyclic compound.

Technical Field

The present specification claims priority from korean patent application No. 10-2018-0124532, which was filed in 2018, 10, 18 and 18 to the korean patent office, the entire contents of which are incorporated herein by reference.

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

Background

In general, the organic light emitting phenomenon refers to a phenomenon of converting electric energy into light energy using an organic substance. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode and a cathode with an organic layer therebetween. Here, in order to improve the efficiency and stability of the organic light emitting device, the organic layer is often formed of a multilayer structure composed of different materials, and may be formed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, or the like. In the structure of such an organic light emitting device, if a voltage is applied between both electrodes, holes are injected from the anode into the organic layer, electrons are injected from the cathode into the organic layer, and when the injected holes and electrons meet, excitons (exiton) are formed, which emit light when they transition to the ground state again.

There is a continuing demand for the development of new materials for organic light emitting devices as described above.

U.S. patent application publication No. 2004-0251816

Disclosure of Invention

Technical subject

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

Means for solving the problems

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,

R₁₁to R₁₄、R₂₁To R₂₄、R₃₁To R₃₅、R₄₁To R₄₃、R₅₁To R₅₅And R₆₁To R₆₄The same or different from each other, each independently is hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted silyl group, a 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 combines with an adjacent substituent to form a substituted or unsubstituted ring,

r is as defined above₁₁To R₁₄、R₂₁To R₂₄、R₃₁To R₃₅、R₄₁To R₄₃And R₅₁To R₅₅Adjacent 2 substituent groups; and the above R₁₁To R₁₄、R₂₁To R₂₄、R₃₁To R₃₅、R₄₁To R₄₃And R₅₁To R₅₅Wherein 1 or more groups among adjacent 2 substituent groups of the substituted or unsubstituted ring formed by bonding adjacent substituents are bonded to the dotted line of chemical formula 2.

In addition, the present specification provides an organic light emitting device, including: the organic light-emitting device includes a first electrode, a second electrode provided so as 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 the heterocyclic compound.

Effects of the invention

The heterocyclic compound according to one 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, improvement in efficiency, low driving voltage, and/or improvement in lifetime characteristics can be achieved in the organic light-emitting device.

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

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 description.

Fig. 3 illustrates an organic light emitting device according to an embodiment of the present description.

1: substrate

2: a first electrode

3: organic material layer

4: second electrode

5: luminescent layer

6: hole injection layer

7: hole transport layer-1

8: hole transport layer-2

9: electron transport layer

Detailed Description

The present specification will be described in more detail below.

The present specification provides heterocyclic compounds represented by the above chemical formula 1.

The conventional spiro ring structure has a limit in the characteristic of improving the luminous efficiency by forming a right angle based on a carbon atom positioned at the center or by adjusting the wavelength and suppressing the interaction between molecules using a simple cyclized compound such as dimethylfluorene, and the efficiency and the lifetime of the OLED device can be improved by controlling the electrical characteristics and the luminous characteristics using a new substance including adamantane (adamantane).

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

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

The term "substituted" means that a hydrogen atom bonded to a carbon atom of a compound is substituted with another substituent, and the substituted position is not limited as long as the hydrogen atom can be substituted, that is, the substituent can be substituted, and when 2 or more substituents are substituted, 2 or more substituents may be the same as or different from each other.

In the present specification, the term "substituted or unsubstituted" means substituted with 1 or 2 or more substituents selected from deuterium, a nitrile group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amine group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group, or a substituent in which 2 or more substituents among the above-exemplified substituents are linked, or does not have any substituent. For example, the "substituent in which 2 or more substituents are bonded" 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, an aryl group substituted with an alkyl group, or the like.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 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 thereof include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methylbutyl group, 1-ethylbutyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl-2-pentyl group, 3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2-dimethylheptyl group, 1-ethylpropyl group, 1-dimethylpropyl group, isohexyl group, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are 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 may be mentioned, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl and the like.

In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but the number of carbon atoms is 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. Specifically, it may be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentoxy, n-hexoxy, 3-dimethylbutoxy, 2-ethylbutoxy, n-octoxy, n-nonoxy, n-decoxy, benzyloxy, p-methylbenzyloxy, etc., but is not limited thereto.

In the present specification, the amine group may be represented by the formula of — NRdRe, and Rd and Re may be the same or different from each other, and each independently may be hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or the like, but is not limited thereto. The number of carbon atoms of the amine group is not limited, but is preferably 1 to 30. Specific examples of the amine group include, but are not limited to, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a phenylamino group, a naphthylamino group, a biphenylamino group, an anthrylamino group, a 9-methylanthrylamino group, a diphenylamino group, an N-phenylnaphthylamino group, a ditolylamino group, an N-phenyltolylamino group, a triphenylamino group, an N-phenylbiphenylamino group, an N-phenylnaphthylamino group, an N-biphenylnaphthylamino group, an N-naphthylfluorenylamino group, an N-phenylphenanthrylamino group, an N-biphenylphenanthrylamino group, an N-phenylfluorenylamino group, an N-phenylterphenylamino group, an N-phenanthrenylfluorenylamino group, and an N-biphenylfluorenylamino group.

In the present specification, the silyl group may be represented by the formula of — SiRaRbRc, and the above Ra, Rb and Rc may be the same or different from each other, and each independently may be hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or the like. Specific examples of the silyl group include, but are not limited to, a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, and a phenylsilyl group.

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 aryl group may be monocyclic or polycyclic. When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 30. More specifically, the number of carbon atoms is preferably 6 to 20. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, or the like, but is not limited thereto. In the case where the above aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 10 to 30, more specifically, 10 to 20. Specifically, the polycyclic aryl group may be a naphthyl group, an anthryl group, a phenanthryl group, a triphenyl group, a pyrenyl group, a phenalenyl group, a perylenyl group, a perylene group,and a fluorenyl group, but is not limited thereto.

When the fluorenyl group is substituted, 2 substituents of the 9 th carbon atom of the fluorenyl group may be bonded to each other to form a spiro structure such as a 9, 9-dimethylfluorenyl group, a 9, 9-diphenylfluorenyl group, or the like, but the invention is not limited thereto.

In the present specification, an "adjacent" group may refer to a substituent substituted on an atom directly connected to an atom substituted with the substituent, a substituent closest in steric structure to the substituent, or another substituent substituted on an atom substituted with the substituent. For example, 2 substituents substituted in the ortho (ortho) position in the phenyl ring and 2 substituents substituted on the same carbon in the aliphatic ring may be interpreted as groups "adjacent" to each other.

In the present specification, in the substituted or unsubstituted ring formed by bonding to each other, "ring" means a hydrocarbon ring or a heterocyclic ring.

The hydrocarbon ring may be aromatic, aliphatic, or a fused ring of aromatic and aliphatic, and may be selected from the cycloalkyl groups and the aryl groups described above, in addition to the 2-valent group described above.

In the present specification, the aromatic hydrocarbon ring may have a valence of 2, and the above description about the aryl group may be applied.

The heterocyclic group may be substituted with a 2-valent heterocyclic group as described below.

In the present specification, as examples of the arylamine group, there are a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group containing 2 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 arylamine group may be selected from the examples of the aryl group.

In the present specification, the heterocyclic group contains 1 or more heteroatoms other than carbon atoms, specifically, the heteroatoms may contain 1 or more atoms selected from O, N, Se, SO₂And S, etc. The number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms, more preferably 2 to 30 carbon atoms, and the heterocyclic group may be monocyclic or polycyclic. Examples of the above-mentioned heteroaryl group include a thienyl group, a furyl group, a pyrrolyl group, an imidazolyl group, a thiazolyl group, a thienyl group,

Azolyl group,Oxadiazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, triazolyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzobenzoxazinylAzolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, benzofuranyl, phenanthrolinyl (phenanthroline), isoquinoyl

Examples of the heterocyclic group include, but are not limited to, an azole group, a thiadiazole group, a phenothiazine group, and a dibenzofuran group.

According to an embodiment of the present disclosure, R is₁₁To R₁₄、R₂₁To R₂₄、R₃₁To R₃₅、R₄₁To R₄₃、R₅₁To R₅₅And R₆₁To R₆₄The above R's are the same as or different from each other, and each independently hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted silyl group, a substituted or unsubstituted phosphinoxide 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 combine with an adjacent substituent to form a substituted or unsubstituted ring₁₁To R₁₄、R₂₁To R₂₄、R₃₁To R₃₅、R₄₁To R₄₃And R₅₁To R₅₅Adjacent 2 substituent groups; and the above R₁₁To R₁₄、R₂₁To R₂₄、R₃₁To R₃₅、R₄₁To R₄₃And R₅₁To R₅₅Wherein 1 or more groups among adjacent 2 substituent groups of the substituted or unsubstituted ring formed by bonding adjacent substituents are bonded to the dotted line of chemical formula 2.

The above-mentioned "R₁₁To R₁₄、R₂₁To R₂₄、R₃₁To R₃₅、R₄₁To R₄₃And R₅₁To R₅₅The adjacent 2 substituent groups "means 2 substituents substituted at the ortho position (ortho) in the above chemical formula 1. Specifically, in the above chemical formula 1, R₁₁And R₁₂、R₁₂And R₁₃、R₁₃And R₁₄、R₂₁And R₂₂、R₂₂And R₂₃、R₂₃And R₂₄、R₃₁And R₃₂、R₃₂And R₃₃、R₃₃And R₃₄、R₃₄And R₃₅、R₄₁And R₄₂、R₄₂And R₄₃、R₅₁And R₅₂、R₅₂And R₅₃、R₅₃And R₅₄And R₅₄And R₅₅Each of the adjacent 2 substituents corresponds to one group. Further, the above-mentioned "R" is₁₁To R₁₄、R₂₁To R₂₄、R₃₁To R₃₅、R₄₁To R₄₃And R₅₁To R₅₅The adjacent 2 substituent groups of the substituted or unsubstituted ring formed by combining the adjacent substituents in (1) means that R of chemical formula 1 is as follows₂₃And R₂₄When they are bonded to each other to form a benzene ring, the following R₂₅And R₂₆、R₂₆And R₂₇And R₂₇And R₂₈Each of the adjacent 2 substituents corresponds to one group.

According to an embodiment of the present disclosure, R is₁₁To R₁₄、R₂₁To R₂₄、R₃₁To R₃₅、R₄₁To R₄₃And R₅₁To R₅₅Adjacent 2 substituent groups; and the above R₁₁To R₁₄、R₂₁To R₂₄、R₃₁To R₃₅、R₄₁To R₄₃And R₅₁To R₅₅Wherein 1 to 4 groups among adjacent 2 substituent groups of the substituted or unsubstituted ring formed by combining adjacent substituents are combined with the dotted line of the above chemical formula 2.

According to an embodiment of the present disclosure, R is₁₁To R₁₄、R₂₁To R₂₄、R₃₁To R₃₅、R₄₁To R₄₃And R₅₁To R₅₅Adjacent 2 substituent groups; and the above R₁₁To R₁₄、R₂₁To R₂₄、R₃₁To R₃₅、R₄₁To R₄₃And R₅₁To R₅₅Wherein 1 or more groups among adjacent 2 substituent groups of the substituted or unsubstituted ring formed by bonding adjacent substituents are bonded to the dotted line of chemical formula 2, wherein R is as defined above₁₁To R₁₄、R₂₁To R₂₄、R₃₁To R₃₅、R₄₁To R₄₃And R₅₁To R₅₅Wherein the substituent not bound to chemical formula 2 and R₆₁To R₆₄The same or different from each other, each independently is hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted silyl group, a 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 combines with an adjacent substituent to form a substituted or unsubstituted ring.

In one embodiment of the present specification, R is₁₁To R₁₄、R₂₁To R₂₄、R₃₁To R₃₅、R₄₁To R₄₃And R₅₁To R₅₅Wherein the substituent not bound to chemical formula 2 and R₆₁To R₆₄The same as or different from each other, each independently is hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted silyl group having 1 to 60 carbon atoms, a substituted or unsubstituted amine group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms, or is combined with adjacent substituents to each other 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 "substituted or unsubstituted" means substituted or unsubstituted with 1 or more substituents selected from deuterium, a nitrile group, a halogen group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a silyl group having 1 to 30 carbon atoms, an amino 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.

In one embodiment of the present specification, R is₁₁To R₁₄、R₂₁To R₂₄、R₃₁To R₃₅、R₄₁To R₄₃And R₅₁To R₅₅Wherein the substituent not bound to chemical formula 2 and R₆₁To R₆₄The same or different from each other, each independently is hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted trimethylsilyl group, a substituted or unsubstituted triphenylsilyl group, a substituted or unsubstituted diphenylamino group, a substituted or unsubstituted dibenzofuranylanilino group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted dibenzofuranyl anilino group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenylA substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted pyridyl group, or an aromatic or aliphatic hydrocarbon ring having 3 to 30 carbon atoms which is substituted or unsubstituted and is bonded to an adjacent substituent; or a substituted or unsubstituted heterocyclic ring having 2 to 30 carbon atoms and containing 1 or more of N, O and S as a hetero atom. The above-mentioned "substituted or unsubstituted" means substituted or unsubstituted with one or more groups selected from deuterium, a nitrile group, a halogen group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted trimethylsilyl group, a substituted or unsubstituted triphenylsilyl group, a substituted or unsubstituted diphenylamino group, a substituted or unsubstituted dibenzofuranylanilino group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted phenyl group, substituted or unsubstituted dibenzothienyl and substituted or unsubstituted pyridyl are substituted or unsubstituted by 1 or more substituents bonded together.

In one embodiment of the present specification, the above chemical formula 1 is represented by one of the following chemical formulas 1-1 to 1-7.

[ chemical formula 1-1]

[ chemical formulas 1-2]

[ chemical formulas 1-3]

[ chemical formulas 1 to 4]

[ chemical formulas 1 to 5]

[ chemical formulas 1 to 6]

[ chemical formulas 1 to 7]

In the above chemical formulas 1-1 to 1-7,

R₁₁to R₁₄、R₂₁To R₂₄、R₃₁To R₃₅、R₄₁To R₄₃、R₅₁To R₅₅And R₆₁To R₆₄As defined in chemical formulas 1 and 2,

R₇₁to R₇₄、R₈₁To R₈₄、R₉₁To R₉₄And Ra to Re are the same as or different from each other, and each independently is hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted silyl group, a substituted or unsubstituted phosphine oxide group, a substituted or unsubstituted amine group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, or combines with an adjacent substituent to form a substituted or unsubstituted ring,

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

b and f are each 0 or 1,

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

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

According to an embodiment of the present disclosure, R is₇₁To R₇₄、R₈₁To R₈₄、R₉₁To R₉₄And Ra to Re are the same as or different from each other, and each independently is hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted silyl group having 1 to 60 carbon atoms, a substituted or unsubstituted amine group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms, or combines with adjacent substituents 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 "substituted or unsubstituted" means substituted or unsubstituted with 1 or more substituents selected from deuterium, a nitrile group, a halogen group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a silyl group having 1 to 30 carbon atoms, an amino 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.

In one embodiment of the present specification, R is₇₁To R₇₄、R₈₁To R₈₄、R₉₁To R₉₄And Ra to Re are the same or different from each other and each independently hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted trimethylsilyl group, a substituted or unsubstituted triphenylsilyl group, a substituted or unsubstituted diphenylamino group, a substituted or unsubstituted dibenzofuranylanilino group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted trimethylsilyl group, a substituted or unsubstituted triphenylsilyl group, a substituted or unsubstituted diphenylamino group, a substituted orA substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted pyridyl group, or a substituted or unsubstituted aromatic or aliphatic hydrocarbon ring having 3 to 30 carbon atoms which is bonded to an adjacent substituent; or a substituted or unsubstituted heterocyclic ring having 2 to 30 carbon atoms and containing 1 or more of N, O and S as a hetero atom. The above-mentioned "substituted or unsubstituted" means substituted or unsubstituted with one or more groups selected from deuterium, a nitrile group, a halogen group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted trimethylsilyl group, a substituted or unsubstituted triphenylsilyl group, a substituted or unsubstituted diphenylamino group, a substituted or unsubstituted dibenzofuranylanilino group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted phenyl group, substituted or unsubstituted dibenzothienyl and substituted or unsubstituted pyridyl are substituted or unsubstituted by 1 or more substituents bonded together.

In one embodiment of the present specification, the above 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 formulas 2-3]

[ chemical formulas 2-4]

[ chemical formulas 2 to 5]

In the above chemical formulas 2-1 to 2-5,

R₁₁to R₁₄、R₂₁To R₂₄、R₃₁To R₃₅、R₄₁To R₄₃And R₅₁To R₅₅As defined in chemical formulas 1 and 2,

X₁and X₂Equal to or different from each other, each independently O, S or NR,

R、R₁₀₁to R₁₁₁And R₂₀₁To R₂₂₈The same or different from each other, each independently is hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted silyl group, a 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,

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

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

when n1 to n11 are each 2 or more, the substituents in parentheses may be the same or different from each other.

According to one embodiment of the present disclosure, the R, R is₁₀₁To R₁₁₁And R₂₀₁To R₂₂₈The same or different from each other, each independently is hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbonA cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted silyl group having 1 to 60 carbon atoms, a substituted or unsubstituted amino group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms, or 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 is formed by bonding adjacent substituents to each other. The above "substituted or unsubstituted" means substituted or unsubstituted with 1 or more substituents selected from deuterium, a nitrile group, a halogen group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a silyl group having 1 to 30 carbon atoms, an amino 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.

In one embodiment of the present specification, the R, R is₁₀₁To R₁₁₁And R₂₀₁To R₂₂₈The same or different from each other, each independently is hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted trimethylsilyl group, a substituted or unsubstituted triphenylsilyl group, a substituted or unsubstituted diphenylamino group, a substituted or unsubstituted dibenzofuranylanilino group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted phenylthio group, A substituted or unsubstituted dibenzothienyl group or a substituted or unsubstituted pyridyl group, or a substituted or unsubstituted aromatic or aliphatic hydrocarbon ring having 3 to 30 carbon atoms, which is bonded to an adjacent substituent; or a substituted or unsubstituted C2-30 compound containing N, O and 1 or more of S as hetero atomsThe heterocyclic ring of (1). The above-mentioned "substituted or unsubstituted" means substituted or unsubstituted with one or more groups selected from deuterium, a nitrile group, a halogen group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted trimethylsilyl group, a substituted or unsubstituted triphenylsilyl group, a substituted or unsubstituted diphenylamino group, a substituted or unsubstituted dibenzofuranylanilino group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted phenyl group, substituted or unsubstituted dibenzothienyl and substituted or unsubstituted pyridyl are substituted or unsubstituted by 1 or more substituents bonded together.

In one embodiment of the present specification, the chemical formula 1 is any one selected from the following compounds.

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

In the present specification, when a part of "includes" a certain component is referred to, unless otherwise stated, it means that the other component may be further included without excluding the other component.

In the present specification, when it is stated that a certain member is "on" another member, it includes not only a case where the certain member is in contact with the another member but also a case where the other member exists between the two members.

The organic light emitting device of the present invention comprises: the organic light-emitting device includes a first electrode, a second electrode provided so as 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 may include the heterocyclic compound.

For example, the structure of the organic light emitting device of the present invention may have the structure shown in fig. 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 sequentially stacked on a substrate 1.

The organic light emitting device is illustrated in fig. 1, but is not limited thereto.

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 organic light emitting device illustrated in fig. 2 is not limited thereto, and an additional organic layer 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.

Fig. 3 illustrates a structure of an organic light emitting device in which 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, an electron transport layer 9, and a second electrode 4 are sequentially stacked on a substrate 1.

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.

The organic light emitting device of the present invention includes a light emitting layer, and the light emitting layer may include a host and a dopant at 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 include 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 layer includes a light emitting layer including 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 1 or more of a hole injection layer, a hole transport layer, and a hole injection and transport layer, and 1 or more of the hole injection layer, the hole transport layer, and the hole injection and transport layer may include the heterocyclic compound of chemical formula 1.

In one embodiment of the present invention, the organic layer includes 1 or more of an electron injection layer, an electron transport layer, and an electron injection and transport layer, and the 1 or more of the electron injection layer, the electron transport layer, and the electron injection and transport layer may include the heterocyclic compound of chemical formula 1.

In one embodiment of the present invention, the organic layer includes 1 or more of an electron blocking layer and a hole blocking layer, and the electron blocking layer and/or the hole blocking layer may include the heterocyclic compound of 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 art, except that 1 or more of the organic layers are formed using the heterocyclic compound.

The present specification also provides a method for manufacturing an organic light-emitting device using the heterocyclic compound.

For example, the organic light emitting device according to the present invention can be manufactured as follows: the organic el device is manufactured by depositing a metal, a metal oxide having conductivity, or an alloy thereof on a substrate by a PVD (physical vapor deposition) method such as a sputtering method or an electron beam evaporation method (e-beam evaporation) to form an anode, forming an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and the like, and an organic layer including the compound of the above chemical formula 1 on the anode, and then depositing a substance that can be used as a cathode on the organic layer. In addition to these methods, a cathode material, an organic layer, and an anode material may be sequentially deposited on a substrate to manufacture an organic light-emitting device.

The anode material is preferably a material having a large work function in order to smoothly inject holes into the organic 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 Tin Oxide (ITO), and Indium Zinc Oxide (IZO); ZnO-Al or SnO₂A combination of a metal such as Sb and an oxide; poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene]Conductive polymers such as (PEDOT), polypyrrole, and polyaniline, but the present invention is not limited thereto.

The cathode material is preferably a material having a small work function in order to easily inject electrons into the organic 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, and alloys thereof; LiF/Al or LiO₂And a multilayer structure material such as Al, but not limited thereto.

As the substance capable of injecting holes from the anode at a low voltage, the hole-injecting substance preferably has a HOMO (highest occupied molecular orbital) between the work function of the anode substance and the HOMO of the surrounding organic layer. Specific examples of the hole injecting substance include, but are not limited to, metalloporphyrin (porphyrine), oligothiophene, arylamine-based organic substances, hexanitrile-hexaazatriphenylene-based organic substances, quinacridone-based organic substances, perylene-based organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers.

The hole-transporting substance is a substance that can receive holes from the anode or the hole-injecting layer and transfer the holes to the light-emitting layer, and is preferably a substance having a high mobility to holes. Specific examples thereof include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers in which a conjugated portion and a non-conjugated portion are present simultaneously.

The light-emitting substance is a substance that can receive holes and electrons from the hole-transporting layer and the electron-transporting layer, respectively, and combine them to emit light in the visible light region, and is preferably a substance having high quantum efficiency with respect to fluorescence or phosphorescence. As an example, there is an 8-hydroxyquinoline aluminum complex (Alq)₃) Carbazole-based compounds, dimerized styryl (dimerized styryl) compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; benzo (b) isAzole, benzothiazole and benzimidazole-based compounds; poly (p-phenylene vinylene) (PPV) polymers; spiro (spiroo) compounds; a polyfluorene; rubrene, etc., but not limited thereto.

As the dopant material, there are an aromatic compound, a styrylamine compound, a boron complex, a fluoranthene compound, a metal complex, and the like. Specifically, the aromatic compound is an aromatic fused ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, perylene, and the like having an arylamino group,

And diindenopyrene, and the like, and the styrylamine compound is a compound substituted with at least 1 arylvinyl group in a substituted or unsubstituted arylamine, and is substituted or unsubstituted with 1 or 2 or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamine group. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltrimethylamine, and styryltretramine. Furthermore, as metal complexesThere are iridium complexes, platinum complexes, and the like, but the present invention is not limited thereto.

The electron transporting layer is a layer that receives electrons from the electron injecting layer and transports the electrons to the light emitting layer, and the electron transporting substance is a substance that can inject electrons well from the cathode and transfer the electrons to the light emitting layer, and is preferably a substance having a high mobility to electrons. Specific examples thereof include Al complexes of 8-hydroxyquinoline and Al complexes containing Alq₃The complex of (a), an organic radical compound, a hydroxyflavone-metal complex, etc., but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in the art. Examples of suitable cathodes are, in particular, the customary substances having a low work function and accompanied by an aluminum or silver layer. In particular cesium, barium, calcium, ytterbium and samarium, in each case accompanied by an aluminum or silver layer.

The electron injection layer is a layer for injecting electrons from the electrode, and is preferably a compound of: a compound having an ability to transport electrons, having an effect of injecting electrons from a cathode, having an excellent electron injection effect with respect to a light-emitting layer or a light-emitting material, preventing excitons generated in the light-emitting layer from migrating to a hole-injecting layer, and having an excellent thin-film-forming ability. Specifically, there are fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, and the like,Azole,

Oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, and the like, and derivatives thereof, metal complex compounds, nitrogen-containing five-membered ring derivatives, and the like, but are not limited thereto.

Examples of the metal complex include lithium 8-quinolinolato, zinc bis (8-quinolinolato), copper bis (8-quinolinolato), manganese bis (8-quinolinolato), aluminum tris (2-methyl-8-quinolinolato), and gallium tris (8-quinolinolato), bis (10-hydroxybenzo [ h ] quinoline) beryllium, bis (10-hydroxybenzo [ h ] quinoline) zinc, bis (2-methyl-8-quinoline) gallium chloride, bis (2-methyl-8-quinoline) (o-cresol) gallium, bis (2-methyl-8-quinoline) (1-naphthol) aluminum, bis (2-methyl-8-quinoline) (2-naphthol) gallium, and the like, but are not limited thereto.

The hole-blocking layer is a layer that prevents holes from reaching the cathode and can be formed under the same conditions as those of the hole-injecting layer. Specifically, there are

An oxadiazole derivative or a triazole derivative, a phenanthroline derivative, BCP, an aluminum complex (aluminum complex), and the like, but the present invention is not limited thereto.

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

Modes for carrying out the invention

Hereinafter, in order to specifically explain the present specification, the details are explained by referring to examples. However, the embodiments described herein may be modified into various forms, and the scope of the present description is not to be construed as being limited to the embodiments described in detail below. The embodiments of the present description are provided to more fully describe the present description to those skilled in the art.

< production example >

Production example 1.

1)

The reaction mixture was charged with 1-bromo-2, 3-dichlorobenzene (22.6g), intermediate A-1(16.9g), Pd (PtBu)₃)₂A flask of (0.51g), NaOtBu (19.2g) and toluene (400ml) was heated at 110 ℃ and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and then the solvent was distilled off under reduced pressure. Purification was performed by recrystallization (methyl t-butyl ether/hexane), whereby intermediate A-2(25.5g) was obtained. Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak at 315.

2)

The intermediate A-2(20.0g), intermediate A-3(24.0g), Pd (PtBu) were charged₃)₂A flask of (0.33g), NaOtBu (12.23g) and toluene (400ml) was heated at 110 ℃ and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and then the solvent was distilled off under reduced pressure. Purification was performed by silica gel column chromatography (developing solution: hexane/ethyl acetate 50%/50% (volume ratio)) to obtain intermediate a-4(13.35 g). Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak at 378.

3)

To a flask containing intermediate A-4(9.76g) and tert-butylbenzene (160ml) was added 1.7M t-butyllithium pentane solution (9.2ml) under argon at 0 ℃. After the end of the dropwise addition, the temperature was raised to 70 ℃ and the mixture was stirred for 4 hours, and the pentane was distilled off. Cooled to-40 ℃, boron tribromide (1.6ml) was added, the temperature was raised to room temperature, and stirring was carried out for 4 hours. Then, the mixture was cooled to 0 ℃ again, N-diisopropylethylamine (6.6ml) was added thereto, and the mixture was stirred at room temperature and then at 80 ℃ for 4 hours. The reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the reaction solution, 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/Z629 was confirmed.

Production example 2.

1)

The reaction mixture was charged with 1-bromo-2, 3-dichlorobenzene (22.6g), intermediate B-1(19.7g), Pd (PtBu)₃)₂A flask of (0.51g), NaOtBu (19.2g) and toluene (400ml) was heated at 110 ℃ and stirredFor 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and then the solvent was distilled off under reduced pressure. Purification was performed by recrystallization (methyl t-butyl ether/hexane), whereby intermediate B-2(24.0g) was obtained. Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak at 343.

2)

The intermediate B-2(15.0g), the intermediate B-3(20.7g) and Pd (PtBu) were charged₃)₂A flask of (0.22g), NaOtBu (8.42g) and toluene (400ml) was heated at 110 ℃ and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and then the solvent was distilled off under reduced pressure. Purification was performed by silica gel column chromatography (developing solution: hexane/ethyl acetate 50%/50% (volume ratio)) to obtain intermediate B-4(17.1 g). Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak 780.

3)

To a flask containing intermediate B-4(11.6g) and tert-butylbenzene (160ml) was added 1.7M t-butyllithium pentane solution (9.2ml) under argon at 0 ℃. After the end of the dropwise addition, the temperature was raised to 70 ℃ and the mixture was stirred for 4 hours, and the pentane was distilled off. Cooled to-40 ℃, boron tribromide (1.6ml) was added, and the mixture was stirred at room temperature for 4 hours. Then, the mixture was cooled to 0 ℃ again, N-diisopropylethylamine (6.6ml) was added thereto, and the mixture was stirred at room temperature and then at 80 ℃ for 4 hours. The reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the reaction solution, 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/Z753 was confirmed.

Production example 3.

1)

The reaction mixture was charged with 1-bromo-2, 3-dichlorobenzene (22.6g), intermediate C-1(19.7g), Pd (PtBu)₃)₂A flask of (0.51g), NaOtBu (19.2g) and toluene (400ml) was heated at 110 ℃ and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and then the solvent was distilled off under reduced pressure. Purification was performed by recrystallization (methyl t-butyl ether/hexane), whereby intermediate C-2(24.0g) was obtained. Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak at 343.

2)

The intermediate C-2(15.0g), intermediate C-3(17.2g), Pd (PtBu) were charged₃)₂A flask of (0.22g), NaOtBu (8.42g) and toluene (400ml) was heated at 110 ℃ and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and then the solvent was distilled off under reduced pressure. Purification was performed by silica gel column chromatography (developing solution: hexane/ethyl acetate 50%/50% (volume ratio)) to obtain intermediate C-4(14.2 g). Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak at 698.

3)

To a flask containing intermediate C-4(10.4g) and tert-butylbenzene (160ml) was added 1.7M t-butyllithium pentane solution (9.2ml) under argon at 0 ℃. After the end of the dropwise addition, the temperature was raised to 70 ℃ and the mixture was stirred for 4 hours, and the pentane was distilled off. Cooled to-40 ℃, boron tribromide (1.6ml) was added, the temperature was raised to room temperature, and stirring was carried out for 4 hours. Then, the mixture was cooled to 0 ℃ again, N-diisopropylethylamine (6.6ml) was added thereto, and the mixture was stirred at room temperature and then at 80 ℃ for 4 hours. The reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the reaction solution, 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/Z671 was confirmed.

Production example 4.

1)

The reaction mixture was charged with 1-bromo-2, 3-dichlorobenzene (22.6g), intermediate D-1(45.5g), Pd (PtBu)₃)₂A flask of (0.51g), NaOtBu (19.2g) and toluene (400ml) was heated at 110 ℃ and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and then the solvent was distilled off under reduced pressure. Purification was performed by recrystallization (methyl t-butyl ether/hexane), whereby intermediate D-2(28.5g) was obtained. Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak at 600.

2)

The intermediate D-2(26.3g), the intermediate D-3(19.9g) and Pd (PtBu) were charged₃)₂A flask of (0.22g), NaOtBu (8.42g) and toluene (400ml) was heated at 110 ℃ and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and after separation, the solvent was distilled off under reduced pressure. Purification was performed by silica gel column chromatography (developing solution: hexane/ethyl acetate 50%/50% (volume ratio)) to obtain intermediate D-4(18.1 g). Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak at 1018.

3)

To a flask containing intermediate D-4(15.2g) and tert-butylbenzene (160ml) was added 1.7M t-butyllithium pentane solution (9.2ml) under argon at 0 ℃. After the end of the dropwise addition, the temperature was raised to 70 ℃ and the mixture was stirred for 4 hours, and the pentane was distilled off. Cooled to-40 ℃, boron tribromide (1.6ml) was added, the temperature was raised to room temperature, and stirring was carried out for 4 hours. Then, the mixture was cooled to 0 ℃ again, N-diisopropylethylamine (6.6ml) was added thereto, and the mixture was stirred at room temperature and then at 80 ℃ for 4 hours. The reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the reaction solution, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to the solution to obtain compound 4(5.0 g). As a result of mass spectrometry of the obtained solid, a peak at M/Z992 was confirmed.

Production example 5.

1)

The reaction mixture was charged with 1-bromo-2, 3-dichlorobenzene (22.6g), intermediate E-1(48.3g), Pd (PtBu)₃)₂A flask of (0.51g), NaOtBu (19.2g) and toluene (400ml) was heated at 110 ℃ and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and then the solvent was distilled off under reduced pressure. Purification was performed by recrystallization (methyl t-butyl ether/hexane), whereby intermediate E-2(28.0g) was obtained. Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak at 628.

2)

The intermediate E-2(27.5g), intermediate E-3(20.1g), Pd (PtBu) were charged₃)₂A flask of (0.22g), NaOtBu (8.42g) and toluene (400ml) was heated at 110 ℃ and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and then the solvent was distilled off under reduced pressure. Chromatography on silica gel column (developing solution: hexane/ethyl acetate)Purification of the ester 50%/50% (v/v)) gave intermediate E-4(23.0 g). Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak at 1051.

3)

To a flask containing intermediate E-4(15.7g) and tert-butylbenzene (160ml) was added 1.7M t-butyllithium pentane solution (9.2ml) under argon at 0 ℃. After the end of the dropwise addition, the temperature was raised to 70 ℃ and the mixture was stirred for 4 hours, and the pentane was distilled off. Cooled to-40 ℃, boron tribromide (1.6ml) was added, the temperature was raised to room temperature, and stirring was carried out for 4 hours. Then, the mixture was cooled to 0 ℃ again, N-diisopropylethylamine (6.6ml) was added thereto, and the mixture was stirred at room temperature and then at 80 ℃ for 4 hours. The reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the reaction solution, 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/Z1025 was confirmed.

Production example 6.

1)

The reaction mixture was charged with 1-bromo-2, 3-dichlorobenzene (22.6g), intermediate F-1(120.0g), Pd (PtBu)₃)₂A flask of (1.02g), NaOtBu (38.4g) and toluene (800ml) was heated at 110 ℃ and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and then the solvent was distilled off under reduced pressure. Purification was performed by recrystallization (methyl t-butyl ether/hexane), whereby intermediate F-2(50.1g) was obtained. Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]1309 peak.

2)

To a flask containing intermediate F-2(19.5g) and tert-butylbenzene (160ml) was added 1.7M t-butyllithium pentane solution (9.2ml) under argon at 0 ℃. After the end of the dropwise addition, the temperature was raised to 70 ℃ and the mixture was stirred for 4 hours, and the pentane was distilled off. Cooled to-40 ℃, boron tribromide (1.6ml) was added, the temperature was raised to room temperature, and stirring was carried out for 4 hours. Then, the mixture was cooled to 0 ℃ again, N-diisopropylethylamine (6.6ml) was added thereto, and the mixture was stirred at room temperature and then at 80 ℃ for 4 hours. The reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the reaction solution, 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/Z1282 was confirmed.

Production example 7.

1)

The reaction mixture was charged with 1-bromo-2, 3-dichlorobenzene (22.6G), intermediate G-1(16.9G), Pd (PtBu)₃)₂A flask of (0.51g), NaOtBu (19.2g) and toluene (400ml) was heated at 110 ℃ and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and then the solvent was distilled off under reduced pressure. Purification was performed by recrystallization (methyl t-butyl ether/hexane), whereby intermediate G-2(25.5G) was obtained. Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak at 315.

2)

The intermediate G-2(13.8G), intermediate G-3(40.0G), Pd (PtBu) were charged₃)₂A flask of (0.22g), NaOtBu (8.42g) and toluene (400ml) was heated at 110 ℃ and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and then the solvent was distilled off under reduced pressure. Column chromatography over silica gel (developing solution: hexane/ethyl acetate 50%/50%(volume ratio)) was purified, thereby obtaining intermediate G-4 (26.6G). Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak at 1191.

3)

To a flask containing intermediate G-4(17.7G) and tert-butylbenzene (160ml) was added 1.7M t-butyllithium pentane solution (9.2ml) under argon at 0 ℃. After the end of the dropwise addition, the temperature was raised to 70 ℃ and the mixture was stirred for 4 hours, and the pentane was distilled off. Cooled to-40 ℃, boron tribromide (1.6ml) was added, the temperature was raised to room temperature, and stirring was carried out for 4 hours. Then, the mixture was cooled to 0 ℃ again, N-diisopropylethylamine (6.6ml) was added thereto, and the mixture was stirred at room temperature and then at 80 ℃ for 4 hours. The reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the reaction solution, 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 1164 was confirmed.

Production example 8.

1)

The reaction mixture containing 3-bromo-4, 5-dichloro-1, 1' -biphenyl (30.2g), intermediate H-1(47.0g), Pd (PtBu)₃)₂A flask of (0.51g), NaOtBu (19.2g) and toluene (400ml) was heated at 110 ℃ and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and then the solvent was distilled off under reduced pressure. Purification was performed by recrystallization (methyl t-butyl ether/hexane) to obtain intermediate H-2(55.9 g). Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak 691.

2)

The intermediate H-2(30.3g), intermediate H-3(9.6g), Pd (PtBu) were charged₃)₂A flask of (0.22g), NaOtBu (8.42g) and toluene (400ml) was heated at 110 ℃ and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and then the solvent was distilled off under reduced pressure. Purification was performed by silica gel column chromatography (developing solution: hexane/ethyl acetate 50%/50% (volume ratio)) to obtain intermediate H-4(23.7 g). Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak at 874.

3)

To a flask containing intermediate H-4(13.0g) and tert-butylbenzene (160ml) was added 1.7M t-butyllithium pentane solution (9.2ml) under argon at 0 ℃. After the end of the dropwise addition, the temperature was raised to 70 ℃ and the mixture was stirred for 4 hours, and the pentane was distilled off. Cooled to-40 ℃, boron tribromide (1.6ml) was added, the temperature was raised to room temperature, and stirring was carried out for 4 hours. Then, the mixture was cooled to 0 ℃ again, N-diisopropylethylamine (6.6ml) was added thereto, and the mixture was stirred at room temperature and then at 80 ℃ for 4 hours. The reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the reaction solution, 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/Z847 was confirmed.

Production example 9.

1)

The reaction mixture was charged with 1-bromo-2, 3-dichloro-5-toluene (24.0g), intermediate I-1(37.8g), Pd (PtBu)₃)₂A flask of (0.51g), NaOtBu (19.2g) and toluene (400ml) was heated at 110 ℃ and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and then the solvent was distilled off under reduced pressure. By recrystallization of (methyl tert-butyl)Ether/hexane) to give intermediate I-2(40.2 g). Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak 537.

2)

The intermediate I-2(23.5g), intermediate I-3(16.5g), Pd (PtBu) were charged₃)₂A flask of (0.22g), NaOtBu (8.42g) and toluene (400ml) was heated at 110 ℃ and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and then the solvent was distilled off under reduced pressure. Purification was performed by silica gel column chromatography (developing solution: hexane/ethyl acetate 50%/50% (volume ratio)) to obtain intermediate I-4(19.3 g). Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak at 878.

3)

To a flask containing intermediate I-4(13.1g) and tert-butylbenzene (160ml) was added 1.7M t-butyllithium pentane solution (9.2ml) under argon at 0 ℃. After the end of the dropwise addition, the temperature was raised to 70 ℃ and the mixture was stirred for 4 hours, and the pentane was distilled off. Cooled to-40 ℃, boron tribromide (1.6ml) was added, the temperature was raised to room temperature, and stirring was carried out for 4 hours. Then, the mixture was cooled to 0 ℃ again, N-diisopropylethylamine (6.6ml) was added thereto, and the mixture was stirred at room temperature and then at 80 ℃ for 4 hours. The reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the reaction solution, 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/Z851 was confirmed.

Production example 10.

1)

The mixture was charged with 1-bromo-2, 3-dichloro-5-iodobenzene (70.4g), intermediate J-1(54.4g), Pd (PPh)₃)₂(0.51g)、K₂CO₃A flask of (55.2g) and 200mL of tetrahydrofuran (1000mL) as water was heated under reflux and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and tetrahydrofuran, and the solvent was distilled off under reduced pressure. Purification was performed by recrystallization (ethyl acetate/hexane) to give intermediate J-2(73.3 g). Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]The peak at 453.

2)

Will contain intermediate J-2(67.8g), CH₃SO₂A flask of OH (96mL) and toluene (600mL) was stirred for 5 hours. The reaction solution was cooled to room temperature, and after the reaction was poured into water, the resultant solid was filtered, and the resultant solid was purified with chloroform and ethanol, thereby obtaining intermediate J-3(59.9 g). Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak at 435.

3)

The intermediate J-3(43.4g), intermediate J-4(16.9g), Pd (PtBu) were charged₃)₂A flask of (0.51g), NaOtBu (19.2g) and toluene (400ml) was heated at 110 ℃ and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and then the solvent was distilled off under reduced pressure. Purification was performed by recrystallization (methyl t-butyl ether/hexane), thereby obtaining intermediate J-5(40.8 g). Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]The peak at 523.

4)

The intermediate J-5(22.9g), intermediate J-6(8.6g) and Pd (PtBu) are charged₃)₂A flask of (0.22g), NaOtBu (8.42g) and toluene (400ml) was heated at 110 ℃ and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and then the solvent was distilled off under reduced pressure. Purification was performed by silica gel column chromatography (developing solution: hexane/ethyl acetate 50%/50% (volume ratio)) to obtain intermediate J-7(19.4 g). Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak 684.

5)

To a flask containing intermediate J-7(10.2g) and tert-butylbenzene (160ml) was added 1.7M t-butyllithium pentane solution (9.2ml) under argon at 0 ℃. After the end of the dropwise addition, the temperature was raised to 70 ℃ and the mixture was stirred for 4 hours, and the pentane was distilled off. Cooled to-40 ℃, boron tribromide (1.6ml) was added, the temperature was raised to room temperature, and stirring was carried out for 4 hours. Then, the mixture was cooled to 0 ℃ again, N-diisopropylethylamine (6.6ml) was added thereto, and the mixture was stirred at room temperature and then at 80 ℃ for 4 hours. The reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the reaction solution, 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/Z657 was confirmed.

Production example 11.

1)

The mixture was charged with 1-bromo-2, 3-dichloro-5-iodobenzene (70.4g), intermediate K-1(58.0g), Pd (PPh)₃)₂(0.51g)、K₂CO₃A flask of (55.2g) and 200mL of tetrahydrofuran (1000mL) as water was heated under reflux and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. N)H₄Cl) and tetrahydrofuran, and the solvent was distilled off under reduced pressure. Purification was performed by recrystallization (ethyl acetate/hexane) to give intermediate K-2(73.3 g). Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak at 471.

2)

The intermediate K-2(70.5g) and CH are charged₃SO₂A flask of OH (96mL) and toluene (600mL) was stirred for 5 hours. The reaction solution was cooled to room temperature, and after the reaction mixture was poured into water, the resultant solid was filtered, and the resultant solid was purified with chloroform and ethanol, thereby obtaining intermediate K-3(61.0 g). Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]The peak at 453.

3)

The intermediate K-3(45.2g), the intermediate K-4(52.6g) and Pd (PtBu) are charged₃)₂A flask of (1.02g), NaOtBu (38.4g) and toluene (400ml) was heated at 110 ℃ and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and then the solvent was distilled off under reduced pressure. Purification was performed by recrystallization (methyl t-butyl ether/hexane), whereby intermediate K-5(40.5g) was obtained. Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak at 862.

4)

To a flask containing intermediate K-5(12.8g) and tert-butylbenzene (160ml) was added 1.7M t-butyllithium pentane solution (9.2ml) under argon at 0 ℃. After the end of the dropwise addition, the temperature was raised to 70 ℃ and the mixture was stirred for 4 hours, and the pentane was distilled off. Cooled to-40 ℃, boron tribromide (1.6ml) was added, the temperature was raised to room temperature, and stirring was carried out for 4 hours. Then, the mixture was cooled to 0 ℃ again, N-diisopropylethylamine (6.6ml) was added thereto, and the mixture was stirred at room temperature and then at 80 ℃ for 4 hours. The reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the reaction solution, 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/Z835 was confirmed.

Production example 12.

1)

The mixture was charged with 2-bromo-3, 4-dichloro-1-iodobenzene (70.4g), intermediate L-1(54.4g), Pd (PPh)₃)₂(0.51g)、K₂CO₃A flask of (55.2g) and 200mL of tetrahydrofuran (1000mL) as water was heated under reflux and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and tetrahydrofuran, and the solvent was distilled off under reduced pressure. Purification was performed by recrystallization (ethyl acetate/hexane) to obtain intermediate L-2(68.1 g). Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]The peak at 453.

2)

Will contain intermediate L-2(67.8g), CH₃SO₂A flask of OH (96mL) and toluene (600mL) was stirred for 5 hours. The reaction solution was cooled to room temperature, and after the reaction mixture was poured into water, the resultant solid was filtered, and the resultant solid was purified with chloroform and ethanol, thereby obtaining intermediate L-3(60.1 g). Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak at 435.

3)

The intermediate L-3(43.4g), intermediate L-4(40.6g), Pd (PtBu) were charged₃)₂A flask of (0.51g), NaOtBu (19.2g) and toluene (400ml) was heated at 110 ℃ and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and then the solvent was distilled off under reduced pressure. Purification was performed by recrystallization (methyl t-butyl ether/hexane), whereby intermediate L-5(37.9g) was obtained. Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak at 759.

4)

The intermediate L-5(33.2g), intermediate L-6(17.8g), Pd (PtBu) were charged₃)₂A flask of (0.22g), NaOtBu (8.42g) and toluene (400ml) was heated at 110 ℃ and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and then the solvent was distilled off under reduced pressure. Purification was performed by silica gel column chromatography (developing solution: hexane/ethyl acetate 50%/50% (volume ratio)) to obtain intermediate L-7(18.8 g). Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak 1129.

5)

To a flask containing intermediate L-7(16.8g) and tert-butylbenzene (160ml) was added 1.7M t-butyllithium pentane solution (9.2ml) under argon at 0 ℃. After the end of the dropwise addition, the temperature was raised to 70 ℃ and the mixture was stirred for 4 hours, and the pentane was distilled off. Cooled to-40 ℃, boron tribromide (1.6ml) was added, the temperature was raised to room temperature, and stirring was carried out for 4 hours. Then, the mixture was cooled to 0 ℃ again, N-diisopropylethylamine (6.6ml) was added thereto, and the mixture was stirred at room temperature and then at 80 ℃ for 4 hours. The reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the reaction solution, 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/Z1102 was confirmed.

Production example 13.

1)

The mixture containing 3-bromo-4, 5-dichlorophenol (24.2g), intermediate M-1(16.9g) and Pd (PtBu)₃)₂A flask of (0.51g), NaOtBu (19.2g) and toluene (400ml) was heated and stirred at 110 ℃ for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and then the solvent was distilled off under reduced pressure. Purification was performed by recrystallization (methyl t-butyl ether/hexane), whereby intermediate M-2(28.1g) was obtained. Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak at 331.

2)

The intermediate M-2(14.5g), intermediate M-3(16.5g) and Pd (PtBu) are charged₃)₂A flask of (0.22g), NaOtBu (8.42g) and toluene (400ml) was heated at 110 ℃ and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and then the solvent was distilled off under reduced pressure. Purification was performed by silica gel column chromatography (developing solution: hexane/ethyl acetate 50%/50% (volume ratio)) to obtain intermediate M-4(17.9 g). Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak at 672.

3)

To a flask containing intermediate M-4(10.0g) and tert-butylbenzene (160ml) was added 1.7M t-butyllithium pentane solution (9.2ml) under argon at 0 ℃. After the end of the dropwise addition, the temperature was raised to 70 ℃ and the mixture was stirred for 4 hours, and the pentane was distilled off. Cooled to-40 ℃, boron tribromide (1.6ml) was added, the temperature was raised to room temperature, and stirring was carried out for 4 hours. Then, the mixture was cooled to 0 ℃ again, N-diisopropylethylamine (6.6ml) was added thereto, and the mixture was stirred at room temperature and then at 80 ℃ for 4 hours. The reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the reaction solution, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to the solution to obtain intermediate M-5(4.8 g). As a result of mass spectrometry of the obtained solid, a peak at M/Z645 was confirmed.

4)

Intermediate M-5(4.1g), nonafluorobutane-1-sulfonylfluoride (2.2g) and potassium carbonate (1.5g) were dissolved in acetonitrile (40ml), heated to 50 ℃ and then stirred for 4 hours. After cooling to normal temperature, distilled water was poured in to remove potassium carbonate, thereby obtaining intermediate M-6(5.5 g).

5)

The intermediate M-6(13.8g), intermediate M-7(6.4g) and Pd (PtBu) are charged₃)₂A flask of (0.10g), NaOtBu (3.0g) and toluene (100ml) was heated at 110 ℃ and stirred for 30 minutes. Cooling the reaction solution to room temperature, and adding NH₄Saturated solution of Cl (sat. aq. NH)₄Cl) and toluene, and then the solvent was distilled off under reduced pressure. Purification was performed by silica gel column chromatography (developing solution: hexane/ethyl acetate 50%/50% (volume ratio)) to obtain compound 13(11.2 g). Mass spectrometric determination of the solid obtained confirms that the solid is at [ M + H +]Peak at 1055.

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