Novel compound and organic light-emitting device comprising same

Abstract

The present invention relates to a novel compound and an organic light emitting device comprising the same.

Description

Technical Field

[0001] Cross-references to related applications

[0002] This application claims priority based on Korean Patent Application No. 10-2023-0018204 filed on February 10, 2023 and Korean Patent Application No. 10-2024-0019676 filed on February 8, 2024, and incorporates all the contents disclosed in the documents of the Korean patent applications as part of this specification.

[0003] The present invention relates to novel compounds and organic light-emitting devices comprising the same. Background Art

[0004] Generally speaking, the organic light-emitting phenomenon refers to the phenomenon of converting electrical energy into light energy using organic substances. Organic light-emitting devices using the organic light-emitting phenomenon have wide viewing angles, excellent contrast, fast response time, and excellent brightness, driving voltage, and response speed characteristics, so a lot of research is being carried out.

[0005] An organic light-emitting device generally has a structure including an anode and a cathode and an organic layer located between the anode and the cathode. In order to improve the efficiency and stability of the organic light-emitting device, the organic layer is usually formed by a multilayer structure composed of different substances, for example, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, etc. For such an organic light-emitting device structure, if a voltage is applied between the two electrodes, holes are injected from the anode into the organic layer, and electrons are injected from the cathode into the organic layer. When the injected holes and electrons meet, excitons are formed, and when the excitons transition back to the ground state, light is emitted.

[0006] As for organic substances used for organic light-emitting devices as described above, development of new materials continues to be required.

[0007] Prior art literature

[0008] Patent Literature

[0009] (Patent Document 1) Korean Patent Publication No. 10-2000-0051826 Summary of the invention

[0010] Technical issues

[0011] The invention relates to a novel organic light-emitting material and an organic light-emitting device comprising the same.

[0012] Solution to the problem

[0013] The present invention provides a compound represented by the following Chemical Formula 1:

[0014] [Chemical formula 1]

[0015]

[0016] In the above chemical formula 1,

[0017] Ar1 is phenyl, dibenzofuranyl, dibenzothiophenyl, Ar1 is substituted or unsubstituted,

[0018] Ar2 is naphthyl, naphthylphenyl, phenyl substituted by -Si(Q1)(Q2)(Q3), dibenzofuranyl, dibenzothiophenyl, Ar2 is substituted or unsubstituted,

[0019] Wherein, Q1, Q2 and Q3 are each independently hydrogen, deuterium, C 1-10 Alkyl or C 6-20 Aryl,

[0020] L1 and L2 are each independently a single bond, a phenylene group, a biphenyl diyl group or a naphthalene diyl group, and the above phenylene group, biphenyl diyl group and naphthalene diyl group are each independently unsubstituted or substituted with one or more deuterium groups,

[0021] However, L1-Ar1 and L2-Ar2 are different from each other.

[0022] L3 is a single bond,

[0023] R1 to R3 are each independently hydrogen or deuterium,

[0024] a1 is an integer from 1 to 8,

[0025] a2 and a3 are each independently an integer from 1 to 4,

[0026] The compound represented by the above Chemical Formula 1 is substituted with at least 2 deuteriums.

[0027] In addition, the present invention provides an organic light-emitting device, which includes: a first electrode, a second electrode arranged opposite to the first electrode, and one or more organic layers arranged between the first electrode and the second electrode, and one or more of the organic layers contains the compound represented by the above chemical formula 1.

[0028] Effects of the Invention

[0029] The compound represented by the above chemical formula 1 can be used as a material for an organic layer of an organic light-emitting device, in which improved efficiency, lower driving voltage and / or improved life characteristics can be achieved. In particular, the compound represented by the above chemical formula 1 can be used as a material for light emission, electron transport and / or electron injection. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 An example of an organic light-emitting device composed of a substrate 1 , an anode 2 , a light-emitting layer 3 , and a cathode 4 is shown.

[0031] Figure 2 An example of an organic light-emitting device composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light-emitting layer 3, a hole blocking layer 8, an electron injection and transport layer 9, and a cathode 4 is shown. DETAILED DESCRIPTION

[0032] In the following, the present invention will be described in more detail to help understanding the present invention.

[0033] The present invention provides a compound represented by the above Chemical Formula 1.

[0034] In this manual, and "D" represents a bond to other substituents, and "D" represents deuterium.

[0035] In the present specification, the term "substituted or unsubstituted" refers to a group selected from deuterium; a halogen group; a cyano group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; an alkylthio group Arylthio Alkylsulfonyl Arylsulfonyl Silyl; boryl; alkyl; cycloalkyl; alkenyl; aryl; aralkyl; aralkenyl; alkylaryl; alkylamino; aralkylamino; heteroarylamino; arylamino; arylphosphino; or substituted or unsubstituted with one or more substituents in a heterocyclic group containing one or more N, O and S atoms, or substituted or unsubstituted with a substituent formed by connecting two or more substituents among the substituents exemplified above. For example, a "substituent formed by connecting two or more substituents" can be a biphenyl group. That is, a biphenyl group can be an aryl group, and can also be interpreted as a substituent formed by connecting two phenyl groups. As an example, the term "substituted or unsubstituted" can be understood as "unsubstituted or substituted with a substituent selected from deuterium, halogen, cyano, C 1-10 Alkyl, C 1-10 Alkoxy and C 6-20In the present specification, the term “substituted with one or more substituents in the aryl group” or “unsubstituted or substituted with one or more substituents selected from deuterium, halogen, cyano, methyl, ethyl, phenyl and naphthyl” may be understood as “substituted with 1 to the maximum number of replaceable hydrogen atoms”. Alternatively, in the present specification, the term “substituted with one or more substituents” may be understood as “substituted with 1 to 5 substituents” or “substituted with 1 or 2 substituents”.

[0036] In the present specification, the number of carbon atoms in the carbonyl group is not particularly limited, but preferably the number of carbon atoms is 1 to 40. Specifically, the substituent may be a substituent of the following structure, but the substituent is not limited thereto.

[0037]

[0038] In the present specification, in the ester group, the oxygen of the ester group may be substituted by a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, or an aryl group having 6 to 25 carbon atoms. Specifically, the substituents may be of the following structural formulas, but are not limited thereto.

[0039]

[0040] In the present specification, the number of carbon atoms in the imide group is not particularly limited, but the number of carbon atoms is preferably 1 to 25. Specifically, the substituent may be a substituent of the following structure, but the substituent is not limited thereto.

[0041]

[0042] In the present specification, a substituted or unsubstituted silyl group refers to -Si(Z1)(Z2)(Z3), where Z1, Z2 and Z3 are each independently hydrogen, deuterium, substituted or unsubstituted C 1-60 Alkyl, substituted or unsubstituted C 1-60 Haloalkyl, substituted or unsubstituted C 2-60 Alkenyl, substituted or unsubstituted C 2-60 haloalkenyl, or substituted or unsubstituted C 6-60 According to one embodiment, Z1, Z2 and Z3 can each independently be hydrogen, deuterium, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 1-10 Haloalkyl, substituted or unsubstituted C 1-10 haloalkyl, or substituted or unsubstituted C 6-20Specific examples of the silyl group include trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, and phenylsilyl, but are not limited thereto.

[0043] In the present specification, specific examples of the boryl group include trimethylboryl, triethylboryl, tert-butyldimethylboryl, triphenylboryl, and phenylboryl, but are not limited thereto.

[0044] In the present specification, as examples of the halogen group, there are fluorine, chlorine, bromine or iodine.

[0045] 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 40. According to one embodiment, the number of carbon atoms in the alkyl group is 1 to 20. According to another embodiment, the number of carbon atoms in the alkyl group is 1 to 10. According to another embodiment, specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethylbutyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-ethyl-propyl, 1,1-dimethylpropyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, isohexyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2,4,4-trimethyl-1-pentyl, 2,4,4-trimethyl-2-pentyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl and the like, but are not limited thereto.

[0046] In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the number of carbon atoms of the alkenyl group is 2 to 20. According to another embodiment, the number of carbon atoms of the alkenyl group is 2 to 10. According to another embodiment, the number of carbon atoms of the alkenyl group is 2 to 6. As specific examples, there are vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-(naphthalene-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbene, styryl, etc., but are not limited thereto.

[0047] In the present specification, the cycloalkyl group is not particularly limited, but is preferably a cycloalkyl group having 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, there are 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, etc., but are not limited thereto.

[0048] In the present specification, the aryl group is not particularly limited, but is preferably an aryl group having 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 30. According to one embodiment, the carbon number of the aryl group is 6 to 20. Regarding the aryl group, as a monocyclic aryl group, it may be phenyl, biphenyl, terphenyl, etc., but it is not limited thereto. As the polycyclic aryl group, it may be naphthyl, anthracenyl, phenanthrenyl, pyrenyl, peryl, yl, fluorenyl, etc., but are not limited to these.

[0049] In the present specification, the fluorenyl group may be substituted, and two substituents may be combined with each other to form a spiro structure. etc. However, the present invention is not limited thereto.

[0050] Specifically, the heteroaryl group refers to a substituent derived from a monocyclic or condensed polycyclic compound containing one or more heteroatoms selected from N, O and S as ring atoms in addition to carbon, and refers to a substituent having aromaticity. According to one embodiment, the number of carbon atoms in the heteroaryl group is 2 to 60. According to another embodiment, the number of carbon atoms in the heteroaryl group is 2 to 30. According to another embodiment, the number of carbon atoms in the heteroaryl group is 2 to 20. Examples of the heteroaryl group include thienyl, furanyl, pyrrolyl, imidazolyl, thiazolyl, Azolyl, oxadiazolyl, triazolyl, pyridinyl, bipyridinyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzo oxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothiophenyl, dibenzothiophenyl, benzofuranyl, dibenzofuranyl, phenanthroline, isothiophene Examples of the present invention include, but are not limited to, oxazolyl, thiadiazolyl, and phenothiazinyl.

[0051] In the present specification, the aryl group in aralkyl, aralkenyl, alkylaryl, and arylamine is the same as the examples of the aryl group described above. In the present specification, the alkyl group in aralkyl, alkylaryl, and alkylamine is the same as the examples of the alkyl group described above. In the present specification, the heteroaryl group in heteroarylamine can be applied to the above-mentioned description of the heteroaryl group. In the present specification, the alkenyl group in aralkenyl is the same as the examples of the alkenyl group described above. In the present specification, the arylene group is a divalent group, and the above-mentioned description of the aryl group can be applied. In the present specification, the heteroarylene group is a divalent group, and the above-mentioned description of the heteroaryl group can be applied. In the present specification, the hydrocarbon ring is not a monovalent group, but is formed by combining two substituents, and the above-mentioned description of the aryl group or the cycloalkyl group can be applied. In the present specification, the heteroaryl group is not a monovalent group, but is formed by combining two substituents, and the above-mentioned description of the heteroaryl group can be applied.

[0052] In the present specification, the term "deuterated" or "substituted with deuterium" means that at least one of the replaceable hydrogen atoms in a compound, a divalent linking group or a monovalent substituent is substituted with deuterium.

[0053] In addition, the term "unsubstituted or substituted with deuterium" or "substituted or unsubstituted with deuterium" means "unsubstituted or substituted with 1 to the maximum number of replaceable hydrogen atoms by deuterium". As an example, the term "unsubstituted or substituted with deuterium phenanthrenyl" can be understood to mean "unsubstituted or substituted with 1 to 9 deuterium phenanthrenyl" when considering that the maximum number of hydrogen atoms that can be replaced with deuterium in the phenanthrenyl structure is 9.

[0054] In addition, the meaning of "deuterated structure" refers to compounds, divalent linking groups or monovalent substituents including all structures in which at least one hydrogen is replaced by deuterium. As an example, the deuterated structure of phenyl shown below can be understood as referring to all monovalent substituents in which at least one hydrogen that can be replaced in phenyl is replaced by deuterium.

[0055]

[0056] In addition, the "deuterium substitution rate" or "deuteration degree" of a compound refers to the value calculated as a percentage of the ratio of the number of deuterium substituted in the compound to the total number of hydrogens that can exist (the sum of the number of hydrogens that can be replaced by deuterium in the compound and the number of deuteriums replaced). Therefore, the "deuterium substitution rate" or "deuteration degree" of a compound as "K%" means that K% of the hydrogens that can be replaced by deuterium in the compound are replaced by deuterium.

[0057] In this case, the above-mentioned "deuterium substitution rate" or "deuteration degree" can be measured by MALDI-TOF MS (Matrix-Assisted Laser Desorption / Ionization Time-of-Flight Mass Spectrometer), nuclear magnetic resonance spectroscopy ( 1 H NMR), TLC / MS (Thin-Layer Chromatography / Mass Spectrometry) or GC / MS (Gas Chromatography / Mass Spectrometry), etc., and are measured according to commonly known methods. More specifically, when MALDI-TOF MS is used, the above-mentioned "deuterium substitution rate" or "deuteration degree" can be determined by analyzing the number of deuterium substituted in the compound through MALDI-TOF MS, and then calculating the ratio of the number of deuterium substituted in the compound to the total number of hydrogen that can exist as a percentage.

[0058] (Compound)

[0059] In another aspect, the present invention provides a compound represented by the above Chemical Formula 1.

[0060] Preferably, Ar1 may be a substituted or unsubstituted phenyl group, phenanthryl group, or dibenzofuranyl group, and the above Ar1 may be unsubstituted or substituted with one or more deuterium groups.

[0061] More preferably, Ar1 may be phenyl, phenyl substituted by two phenyl groups, naphthylphenyl, phenanthrenylphenyl, triphenylsilylphenyl, dibenzofuranylphenyl, phenanthrenyl, or dibenzofuranyl, and the above Ar1 may be unsubstituted or substituted by one or more deuterium groups.

[0062] Preferably, Ar2 can be substituted or unsubstituted naphthyl, naphthylphenyl, phenyl substituted by -Si(Q1)(Q2)(Q3), phenanthrenyl, or dibenzofuranyl, and the above Ar2 can be unsubstituted or substituted by one or more deuteriums.

[0063] Wherein, Q1, Q2 and Q3 can be hydrogen, deuterium, methyl, ethyl, phenyl, biphenyl or naphthyl independently of each other. In addition, Q1, Q2 and Q3 can be the same as each other.

[0064] More preferably, Ar2 may be naphthyl, phenylnaphthyl, naphthylphenyl, dibenzofuranylnaphthyl, triphenylsilylphenyl, phenanthryl, or dibenzofuranyl, and the above Ar2 may be unsubstituted or substituted with one or more deuteriums.

[0065] Preferably, Ar1 is a phenyl group, and Ar2 is a naphthyl group substituted with a phenyl group or a phenyl group substituted with a naphthyl group, and the above Ar1 and Ar2 may be unsubstituted or substituted with one or more deuterium groups independently.

[0066] Preferably, L1 and L2 are each independently a single bond or any one selected from the following groups and their deuterated structures:

[0067]

[0068] Preferably, L1 and L2 may be different from each other, or Ar1 and Ar2 may be different from each other.

[0069] Preferably, Ar1 is phenyl, L1 is a single bond, and Ar2 is naphthyl substituted by phenyl or phenyl substituted by naphthyl, L2 is a single bond, and the above Ar1 and Ar2 can each independently be unsubstituted or substituted by one or more deuteriums.

[0070] Preferably, L3 may be a single bond, a 1,2-phenylene group which is unsubstituted or substituted with 1 to 4 deuteriums, or a 1,3-phenylene group which is unsubstituted or substituted with 1 to 4 deuteriums.

[0071] Preferably, each R1 is deuterium and a1 can be 8.

[0072] Preferably, the compound represented by the above Chemical Formula 1 may be substituted with at least 8 deuteriums.

[0073] In addition, the deuterium substitution rate of the above-mentioned compound can be 1% to 100%. Specifically, the deuterium substitution rate of the above-mentioned compound can be 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 75% or more, 80% or more, or 90% or more and 100% or less.

[0074] As an example, the compound may contain 2 to 30 deuteriums. More specifically, the compound may contain 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, or 9 or more and 30 or less, 28 or less, 26 or less, 24 or less, 22 or less, 20 or less, 18 or less, 16 or less, 14 or less, 13 or less, 12 or less, 11 or less, or 10 or less deuteriums.

[0075] At this time, if the total number of deuterium substitutions in the above compound is desired, it can be represented by the following chemical formula 1D:

[0076] [Chemical formula 1D]

[0077]

[0078] In the above chemical formula 1D,

[0079] Dn means that n hydrogen atoms in the compound in brackets are replaced by deuterium.

[0080] Wherein, n is an integer greater than 2,

[0081] L'1, L'2, L'3, Ar'1 and Ar'2 represent L1, L2, L3, Ar1 and Ar2 substituents which are not substituted by deuterium, respectively.

[0082] As an example, in the above chemical formula 1D, n of Dn can be greater than 2, greater than 3, greater than 4, greater than 5, greater than 6, greater than 7, greater than 8, or greater than 9 and less than 30, less than 28, less than 26, less than 24, less than 22, less than 20, less than 18, less than 16, less than 14, less than 13, less than 12, less than 11, or less than 10.

[0083] Representative examples of the compound represented by the above Chemical Formula 1 are shown below:

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104] Among the above compounds,

[0105] Dn means that n hydrogen atoms in the compound in brackets are replaced by deuterium.

[0106] Here, n is an integer greater than or equal to 2.

[0107] More specifically, n may be 2 or more and less than the maximum number of replaceable hydrogen atoms. As an example, n may be 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, or 9 or more and 30 or less, 28 or less, 26 or less, 24 or less, 22 or less, 20 or less, 18 or less, 16 or less, 14 or less, 13 or less, 12 or less, 11 or less, or 10 or less.

[0108] As an example, the compound represented by the above chemical formula 1 can be manufactured by the manufacturing method shown in the following reaction formula 1 when L3 is a single bond, and can be manufactured by the manufacturing method shown in the following reaction formula 2 when L3 is not a single bond. The remaining compounds can also be manufactured by similar methods.

[0109] [Reaction formula 1]

[0110]

[0111] [Reaction 2]

[0112]

[0113] In the above reaction formulas 1 and 2, Ar1, Ar2, L1 to L3, R1 and a1 are the same as those defined in the above chemical formula 1, X1 and X2 are each independently a halogen, preferably, X1 and X2 are each independently chlorine or bromine.

[0114] The above reaction formula 1 is an amine substitution reaction, preferably carried out in the presence of a palladium catalyst and a base, and the reactive group for the amine substitution reaction can be changed according to a technique known in the art. In addition, the above reaction formula 2 is a Suzuki coupling reaction, preferably carried out in the presence of a palladium catalyst and a base, and the reactive group for the Suzuki coupling reaction can be changed according to a technique known in the art. Alternatively, after the amine substitution reaction or the Suzuki coupling reaction of the above reaction formula 1 or 2, a deuterium substitution reaction is performed, so that the compound represented by the chemical formula 1 can be manufactured. The above manufacturing method can be more specifically described in the manufacturing example described later.

[0115] In addition, the present invention provides an organic light-emitting device including the compound represented by the above Chemical Formula 1. As an example, the present invention provides an organic light-emitting device including: a first electrode, a second electrode disposed opposite to the above first electrode, and one or more organic layers disposed between the above first electrode and the above second electrode, wherein one or more of the organic layers includes the compound represented by the above Chemical Formula 1.

[0116] In one embodiment, the organic layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer. In this case, the organic layer including the compound may be a light emitting layer.

[0117] In one embodiment, the organic layer may include a hole injection layer, a hole transport layer, a light emitting layer, and an electron injection and transport layer. In this case, the organic layer including the compound may be a light emitting layer.

[0118] In another embodiment, the organic layer may include a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, and an electron injection and transport layer. In this case, the organic layer containing the compound may be a light emitting layer.

[0119] In another embodiment, the organic layer may include a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, and an electron injection and transport layer. In this case, the organic layer containing the compound may be a light-emitting layer.

[0120] In another embodiment, the organic layer may include a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer. In this case, the organic layer containing the above compound may be a light-emitting layer.

[0121] The organic layer of the organic light-emitting device of the present invention may be formed of a single-layer structure or a multi-layer structure in which two or more organic layers are stacked. For example, the organic light-emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, etc. as organic layers. However, the structure of the organic light-emitting device is not limited thereto and may include a smaller number of organic layers.

[0122] In addition, the organic light-emitting device according to the present invention may be an organic light-emitting device having a structure (normal type) in which an anode, one or more organic layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light-emitting device according to the present invention may be an organic light-emitting device having an inverse structure (inverted type) in which a cathode, one or more organic layers, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light-emitting device according to one embodiment of the present invention is shown in FIG. Figure 1 and Figure 2 .

[0123] Figure 1 An example of an organic light-emitting device composed of a substrate 1 , an anode 2 , a light-emitting layer 3 , and a cathode 4 is shown. Figure 2 The diagram shows an example of an organic light-emitting device composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light-emitting layer 3, a hole blocking layer 8, an electron injection and transport layer 9, and a cathode 4. In the structure described above, the compound represented by the above chemical formula 1 may be contained in the above light-emitting layer.

[0124] The organic light-emitting device according to the present invention can be manufactured using materials and methods known in the art, except that at least one of the organic layers contains the compound represented by the above Chemical Formula 1. In addition, when the organic light-emitting device includes a plurality of organic layers, the organic layers can be formed of the same substance or different substances.

[0125] For example, the organic light-emitting device according to the present invention can be manufactured by sequentially stacking a first electrode, an organic layer, and a second electrode on a substrate. In this case, it can be manufactured as follows: a PVD (physical vapor deposition) method such as sputtering or electron beam evaporation is used to vapor-deposit a metal or a conductive metal oxide or an alloy thereof on a substrate to form an anode, and then an organic layer including a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer is formed on the anode, and then a substance that can be used as a cathode is vapor-deposited on the organic layer. In addition to this method, an organic light-emitting device can also be manufactured by sequentially vapor-depositing a cathode substance, an organic layer, and an anode substance on a substrate.

[0126] In addition, the compound represented by the above chemical formula 1 can be used not only by vacuum evaporation method but also by solution coating method to form an organic layer when manufacturing an organic light-emitting device. Here, the so-called solution coating method refers to spin coating method, dip coating method, blade coating method, inkjet printing method, screen printing method, spray method, roller coating method, etc., but is not limited to these.

[0127] In addition to these methods, an organic light-emitting device can also be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate (WO 2003 / 012890). However, the manufacturing method is not limited to this.

[0128] As an example, the first electrode is an anode and the second electrode is a cathode, or the first electrode is a cathode and the second electrode is an anode.

[0129] As the above-mentioned anode material, in order to enable holes to be smoothly injected into the organic layer, a material with a large work function is preferably used. Specific examples of the above-mentioned anode material include metals such as vanadium, chromium, copper, zinc, gold, or their alloys; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

[0130] In order to facilitate the injection of electrons into the organic layer, the cathode material is preferably a material with a small work function. 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 alloys thereof; multilayer structure materials such as LiF / Al or LiO2 / Al, etc., but are not limited thereto.

[0131] The hole injection layer is a layer for injecting holes from the electrode. As a hole injection material, it is preferably a compound having the ability to transport holes, the effect of injecting holes from the anode, an excellent hole injection effect for the light-emitting layer or the light-emitting material, and a compound having excellent thin film forming ability to prevent the excitons generated in the light-emitting layer from migrating to the electron injection layer or the electron injection material. The HOMO (highest occupied molecular orbital) of the hole injection material is preferably between the work function of the anode material and the HOMO of the surrounding organic layer. As specific examples of hole injection materials, there are metal porphyrins, oligothiophenes, arylamine organics, hexanitrile hexaazatriphenylene organics, quinacridone organics, perylene organics, anthraquinones, polyaniline and polythiophene conductive polymers, but are not limited thereto.

[0132] The hole transport layer is a layer that receives holes from the hole injection layer and transfers the holes to the light-emitting layer. The hole transport material is a material that can receive holes from the anode or the hole injection layer and transfer them to the light-emitting layer. Materials with high hole mobility are suitable. Specific examples include arylamine organic substances, conductive polymers, and block copolymers having both conjugated and non-conjugated parts, but are not limited thereto.

[0133] The electron blocking layer is a layer formed on the hole transport layer, preferably in contact with the light-emitting layer, and improves the efficiency of the organic light-emitting device by adjusting the hole mobility and preventing the excessive migration of electrons to increase the probability of hole-electron bonding. The electron blocking layer includes an electron blocking substance, and examples of such an electron blocking substance include arylamine organic substances, but are not limited thereto.

[0134] The luminescent material is a material 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 material with high quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq3); carbazole compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; benzo azole, benzothiazole and benzimidazole compounds; poly(p-phenylene vinylene) (PPV) polymers; spiro compounds; polyfluorene, rubrene, etc., but are not limited to these.

[0135] The above-mentioned light-emitting layer may include a host material and a dopant material. The host material may use a compound represented by the above-mentioned chemical formula 1, an aromatic condensed ring derivative, or a heterocyclic compound. Specifically, as the aromatic condensed ring derivative, there are anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., as the heterocyclic compound, there are carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, etc. Pyrimidine derivatives, etc., but are not limited to these.

[0136] As dopant materials, there are aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, etc. Specifically, aromatic amine derivatives are aromatic fused ring derivatives having substituted or unsubstituted arylamino groups, and there are pyrene, anthracene, The styrylamine compound is a compound in which at least one arylvinyl group is substituted on a substituted or unsubstituted arylamine, and is substituted or unsubstituted with one or more substituents selected from aryl, silyl, alkyl, cycloalkyl and arylamino. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetramine, etc., but not limited thereto. In addition, as metal complexes, there are iridium complexes, platinum complexes, etc., but not limited thereto.

[0137] As an example, the dopant material may be any one or more compounds selected from the following compounds, but is not limited thereto:

[0138]

[0139]

[0140] The hole blocking layer is a layer formed on the light-emitting layer, preferably in contact with the light-emitting layer, which improves the efficiency of the organic light-emitting device by adjusting the electron mobility and preventing the excessive migration of holes to increase the probability of hole-electron bonding. The hole blocking layer contains a hole blocking substance. Examples of such a hole blocking substance include azine derivatives containing triazine, triazole derivatives, Compounds into which an electron-withdrawing group is introduced include, but are not limited to, oxadiazole derivatives, phenanthroline derivatives, phosphine oxide derivatives, and the like.

[0141] The electron transport layer is a layer that receives electrons from the electron injection layer and transfers the electrons to the light-emitting layer. The electron transport material is a material that can well receive electrons from the cathode and transfer them to the light-emitting layer. The material with high electron mobility is suitable. As a specific example, there are compounds represented by the above chemical formula 1, Al complexes of 8-hydroxyquinoline, complexes containing Alq3, organic free radical compounds, hydroxyflavone-metal complexes, etc., but are not limited to this. 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 common materials with low work function and accompanied by an aluminum layer or a silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, in each case accompanied by an aluminum layer or a silver layer.

[0142] The electron injection layer is a layer for injecting 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 on the light-emitting layer or the light-emitting material, prevents the excitons generated in the light-emitting layer from migrating to the hole injection layer, and has excellent thin film forming ability. Specifically, there are fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, Azoles, Examples include, but are not limited to, diazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylene methane, anthrone, and derivatives thereof, metal coordination compounds, and nitrogen-containing five-membered ring derivatives.

[0143] Examples of the metal coordination compounds include, but are not limited to, 8-hydroxyquinoline lithium, bis(8-hydroxyquinoline) zinc, bis(8-hydroxyquinoline) copper, bis(8-hydroxyquinoline) manganese, tris(8-hydroxyquinoline) aluminum, tris(2-methyl-8-hydroxyquinoline) aluminum, tris(8-hydroxyquinoline) gallium, 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, and bis(2-methyl-8-quinoline)(2-naphthol) gallium.

[0144] On the other hand, in the present invention, the "electron injection and transport layer" is a layer that functions as both the electron injection layer and the electron transport layer, and substances that function as the above layers may be used alone or in combination, but are not limited thereto.

[0145] The organic light-emitting device according to the present invention may be a bottom emission device, a top emission device, or a bidirectional light-emitting device, and in particular, may be a bottom emission device requiring relatively high light-emitting efficiency.

[0146] In addition, the compound represented by the above Chemical Formula 1 may be included in an organic solar cell or an organic transistor in addition to an organic light emitting device.

[0147] The preparation of the compound represented by the above Chemical Formula 1 and the organic light-emitting device including the same is specifically described in the following examples. However, the following examples are used to illustrate the present invention, and the scope of the present invention is not limited thereto.

[0148] Production Example 1

[0149]

[0150] Compound substance (sub) 1 (15 g, 40.6 mmol) and compound Trz1 (18.9 g, 42.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in 100 ml of water and added. After sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 3 hours, it was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved in chloroform again, washed with water twice, and then the organic layer was separated. Anhydrous magnesium sulfate was added, and the mixture was filtered after stirring. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 17.2 g of compound 1_P1. (Yield 65%, MS: [M+H] + =651)

[0151] Compound 1_P1 (10 g, 15.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (11.1 g, 553.6 mmol) was added to trifluoromethanesulfonic anhydride (26 g, 92.3 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140°C and stirred while maintaining the temperature. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. The organic layer was separated after washing with water twice, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.1 g of compound 1. (Yield 70%, MS: [M+H] + =664)

[0152] Production Example 2

[0153]

[0154] Compound 1 (15 g, 40.6 mmol) and compound Trz2 (18.9 g, 42.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in 100 ml of water and added. After sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved in chloroform again, washed with water twice, and the organic layer was separated. Anhydrous magnesium sulfate was added, and the mixture was filtered after stirring. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 18.2 g of compound 2_P1. (Yield 69%, MS: [M+H] + =651)

[0155] Compound 2_P1 (10 g, 15.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (11.1 g, 553.6 mmol) was added to trifluoromethanesulfonic anhydride (26 g, 92.3 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.2 g of compound 2. (Yield 61%, MS: [M+H] + =661)

[0156] Production Example 3

[0157]

[0158] Compound 1 (15 g, 40.6 mmol) and compound Trz3 (20 g, 42.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in 100 ml of water and added. After sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved in chloroform again, washed with water twice, and the organic layer was separated. Anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 19.2 g of compound 3_P1. (Yield 70%, MS: [M+H] + =677)

[0159] Compound 3_P1 (10 g, 14.8 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (10.7 g, 532.3 mmol) was added to trifluoromethanesulfonic anhydride (25 g, 88.7 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.3 g of compound 3. (Yield 62%, MS: [M+H] + =690)

[0160] Production Example 4

[0161]

[0162] Compound 1 (15 g, 40.6 mmol) and compound Trz4 (17.4 g, 42.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in 100 ml of water and added. After sufficient stirring, bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After reacting for 2 hours, it was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved in chloroform again, washed with water twice, and then the organic layer was separated. Anhydrous magnesium sulfate was added, and the mixture was filtered after stirring. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 20 g of compound 4_P1. (Yield 80%, MS: [M+H] + =615)

[0163] Compound 4_P1 (10 g, 16.3 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (11.7 g, 586.1 mmol) was added to trifluoromethanesulfonic anhydride (27.6 g, 97.7 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.5 g of compound 4. (Yield 64%, MS: [M+H] + =626)

[0164] Production Example 5

[0165]

[0166] Compound 1 (15 g, 40.6 mmol) and compound Trz5 (20 g, 42.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in 100 ml of water and added. After sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved in chloroform again, washed with water twice, and the organic layer was separated. Anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 19.8 g of compound 5_P1. (Yield 72%, MS: [M+H] + =677)

[0167] Compound 5_P1 (10 g, 14.8 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (10.7 g, 532.3 mmol) was added to trifluoromethanesulfonic anhydride (25 g, 88.7 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.2 g of compound 5. (Yield 51%, MS: [M+H] + =690)

[0168] Production Example 6

[0169]

[0170] Compound 1 (15 g, 40.6 mmol) and compound Trz6 (17.5 g, 42.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in 100 ml of water and added. After sufficient stirring, bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved in chloroform again, the organic layer was separated after washing with water twice, anhydrous magnesium sulfate was added, the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 17.2 g of compound 6_P1. (Yield 65%, MS: [M+H] + =651)

[0171] Compound 6_P1 (10 g, 15.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (11.1 g, 553.6 mmol) was added to trifluoromethanesulfonic anhydride (26 g, 92.3 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.7 g of compound 6. (Yield 65%, MS: [M+H] + =667)

[0172] Production Example 7

[0173]

[0174] Compound 1 (15 g, 40.6 mmol) and compound Trz7 (22.4 g, 42.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in 100 ml of water and added. After sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved in chloroform again, the organic layer was separated after washing with water twice, anhydrous magnesium sulfate was added, the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 20.8 g of compound 7_P1. (Yield 70%, MS: [M+H] + =733)

[0175] Compound 7_P1 (10 g, 13.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (9.8 g, 491.6 mmol) was added to trifluoromethanesulfonic anhydride (23.1 g, 81.9 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.7 g of compound 7. (Yield 56%, MS: [M+H] + =745)

[0176] Production Example 8

[0177]

[0178] Compound 2 (15 g, 40.6 mmol) and compound Trz4 (17.4 g, 42.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in 100 ml of water and added. After sufficient stirring, bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved in chloroform again, washed with water twice, and the organic layer was separated. Anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 17.2 g of compound 8_P1. (Yield 69%, MS: [M+H] + =615)

[0179] Compound 8_P1 (10 g, 16.3 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (11.7 g, 586.1 mmol) was added to trifluoromethanesulfonic anhydride (27.6 g, 97.7 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.2 g of compound 8. (Yield 70%, MS: [M+H] + =629)

[0180] Production Example 9

[0181]

[0182] Compound 2 (15 g, 40.6 mmol) and compound Trz8 (15.3 g, 42.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in 100 ml of water and added. After sufficient stirring, bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved in chloroform again, washed with water twice, and the organic layer was separated. Anhydrous magnesium sulfate was added, and the mixture was filtered after stirring. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 17.4 g of compound 9_P1. (Yield 76%, MS: [M+H] + =565)

[0183] Compound 9_P1 (10 g, 17.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (12.8 g, 638.1 mmol) was added to trifluoromethanesulfonic anhydride (30 g, 106.3 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.6 g of compound 9. (Yield 65%, MS: [M+H] + =577)

[0184] Production Example 10

[0185]

[0186] Compound 2 (15 g, 40.6 mmol) and compound Trz9 (17.8 g, 42.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in 100 ml of water and added. After sufficient stirring, bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved in chloroform again, washed with water twice, and the organic layer was separated. Anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 19.3 g of compound 10_P1. (Yield 76%, MS: [M+H] + =625)

[0187] Compound 10_P1 (10 g, 16 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (11.6 g, 576.7 mmol) was added to trifluoromethanesulfonic anhydride (27.1 g, 96.1 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.2 g of compound 10. (Yield 61%, MS: [M+H] + =640)

[0188] Production Example 11

[0189]

[0190] Compound 2 (15 g, 40.6 mmol) and compound Trz10 (16.8 g, 42.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in 100 ml of water and added. After sufficient stirring, bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved in chloroform again, washed with water twice, and the organic layer was separated. Anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 16.8 g of compound 11_P1. (Yield 69%, MS: [M+H] + =601)

[0191] Compound 11_P1 (10 g, 16.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (12 g, 599.8 mmol) was added to trifluoromethanesulfonic anhydride (28.2 g, 100 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7 g of compound 11. (Yield 69%, MS: [M+H] + =614)

[0192] Production Example 12

[0193]

[0194] Under nitrogen atmosphere, 9H-carbazole (15 g, 89.7 mmol), compound Trz11 (41.8 g, 94.2 mmol), potassium phosphate (57.1 g, 269.1 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.5 g, 0.9 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 25.8 g of compound 12_P1. (Yield 50%, MS: [M+H] + =575)

[0195] Compound 12_P1 (10 g, 17.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (12.6 g, 626.9 mmol) was added to trifluoromethanesulfonic anhydride (29.5 g, 104.5 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.5 g of compound 12. (Yield 64%, MS: [M+H] + =588)

[0196] Production Example 13

[0197]

[0198] Under nitrogen atmosphere, 9H-carbazole (15 g, 89.7 mmol), compound Trz12 (46.5 g, 94.2 mmol), potassium phosphate (57.1 g, 269.1 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 37.5 g of compound 13_P1. (Yield 67%, MS: [M+H] + =625)

[0199] Compound 13_P1 (10 g, 16 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (11.6 g, 576.7 mmol) was added to trifluoromethanesulfonic anhydride (27.1 g, 96.1 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.3 g of compound 13. (Yield 61%, MS: [M+H] + =641)

[0200] Production Example 14

[0201]

[0202] Under nitrogen atmosphere, 9H-carbazole (15 g, 89.7 mmol), compound Trz13 (65.2 g, 94.2 mmol), potassium phosphate (57.1 g, 269.1 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 42 g of compound 14_P1. (Yield 57%, MS: [M+H] + =823)

[0203] Compound 14_P1 (10 g, 12.2 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (8.8 g, 437.8 mmol) was added to trifluoromethanesulfonic anhydride (20.6 g, 73 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.9 g of compound 14. (Yield 58%, MS: [M+H] + =841)

[0204] Production Example 15

[0205]

[0206] Under nitrogen atmosphere, 9H-carbazole (15 g, 89.7 mmol), compound Trz14 (65.2 g, 94.2 mmol), potassium phosphate (57.1 g, 269.1 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 39.1 g of compound 15_P1. (Yield 53%, MS: [M+H] + =823)

[0207] Compound 15_P1 (10 g, 12.2 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (8.8 g, 437.8 mmol) was added to trifluoromethanesulfonic anhydride (20.6 g, 73 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.4 g of compound 15. (Yield 63%, MS: [M+H] + =840)

[0208] Production Example 16

[0209]

[0210] Under nitrogen atmosphere, 9H-carbazole (15 g, 89.7 mmol), compound Trz15 (45.6 g, 94.2 mmol), potassium phosphate (57.1 g, 269.1 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 35.8 g of compound 16_P1. (Yield 65%, MS: [M+H] + =615)

[0211] Compound 16_P1 (10 g, 16.3 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (11.7 g, 586.1 mmol) was added to trifluoromethanesulfonic anhydride (27.6 g, 97.7 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.4 g of compound 16. (Yield 53%, MS: [M+H] + =627)

[0212] Production Example 17

[0213]

[0214] Compound 1 (15 g, 40.6 mmol) and compound Trz16 (17.8 g, 42.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in 100 ml of water and added. After sufficient stirring, bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After reacting for 4 hours, it was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved in chloroform again, washed with water twice, and then the organic layer was separated. Anhydrous magnesium sulfate was added, and the mixture was filtered after stirring. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 18.3 g of compound 17_P1. (Yield 72%, MS: [M+H] + =625)

[0215] Compound 17_P1 (10 g, 16 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (11.6 g, 576.7 mmol) was added to trifluoromethanesulfonic anhydride (40.7 g, 144.2 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.3 g of compound 17. (Yield 61%, MS: [M+H] + =648)

[0216] Production Example 18

[0217]

[0218] Compound 1 (15 g, 40.6 mmol) and compound Trz17 (16.8 g, 42.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in 100 ml of water and added. After sufficient stirring, bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved in chloroform again, washed with water twice, and the organic layer was separated. Anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 17.6 g of compound 18_P1. (Yield 72%, MS: [M+H] + =601)

[0219] Compound 18_P1 (10 g, 16.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (12 g, 599.8 mmol) was added to trifluoromethanesulfonic anhydride (42.3 g, 149.9 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.4 g of compound 18. (Yield 52%, MS: [M+H] + =624)

[0220] Production Example 19

[0221]

[0222] Compound 1 (15 g, 40.6 mmol) and compound Trz18 (20 g, 42.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in 100 ml of water and added. After sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved in chloroform again, washed with water twice, and the organic layer was separated. Anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 19.2 g of compound 19_P1. (Yield 70%, MS: [M+H] + =677)

[0223] Compound 19_P1 (10 g, 14.8 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (10.7 g, 532.3 mmol) was added to trifluoromethanesulfonic anhydride (37.5 g, 133.1 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.8 g of compound 19. (Yield 66%, MS: [M+H] + =698)

[0224] Production Example 20

[0225]

[0226] Compound 1 (15 g, 40.6 mmol) and compound Trz19 (22.4 g, 42.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in 100 ml of water and added. After sufficient stirring, bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After reacting for 2 hours, it was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved in chloroform again, washed with water twice, and then the organic layer was separated. Anhydrous magnesium sulfate was added, and the mixture was filtered after stirring. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 21.1 g of compound 20_P1. (Yield 71%, MS: [M+H] + =733)

[0227] Compound 20_P1 (10 g, 13.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (9.8 g, 491.6 mmol) was added to trifluoromethanesulfonic anhydride (34.7 g, 122.9 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. The organic layer was separated after washing with water twice, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6 g of compound 20. (Yield 58%, MS: [M+H] + =762)

[0228] Production Example 21

[0229]

[0230] Compound 1 (15 g, 40.6 mmol) and compound Trz20 (20.6 g, 42.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in 100 ml of water and added. After sufficient stirring, bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved in chloroform again, washed with water twice, and the organic layer was separated. Anhydrous magnesium sulfate was added, and the mixture was filtered after stirring. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 20.7 g of compound 21_P1. (Yield 74%, MS: [M+H] + =691)

[0231] Compound 21_P1 (10 g, 14.5 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (10.4 g, 521.6 mmol) was added to trifluoromethanesulfonic anhydride (36.8 g, 130.4 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.1 g of compound 21. (Yield 68%, MS: [M+H] + =717)

[0232] Production Example 22

[0233]

[0234] Compound 2 (15 g, 40.6 mmol) and compound Trz21 (20 g, 42.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in 100 ml of water and added. After sufficient stirring, bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved in chloroform again, washed with water twice, and the organic layer was separated. Anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 20.3 g of compound 22_P1. (Yield 74%, MS: [M+H] + =677)

[0235] Compound 22_P1 (10 g, 14.8 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (10.7 g, 532.3 mmol) was added to trifluoromethanesulfonic anhydride (37.5 g, 133.1 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.8 g of compound 22. (Yield 56%, MS: [M+H] + =702)

[0236] Production Example 23

[0237]

[0238] Compound 2 (15 g, 40.6 mmol) and compound Trz17 (16.8 g, 42.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in 100 ml of water and added. After sufficient stirring, bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved in chloroform again, washed with water twice, and the organic layer was separated. Anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 18.3 g of compound 23_P1. (Yield 75%, MS: [M+H] + =601)

[0239] Compound 23_P1 (10 g, 16.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (12 g, 599.8 mmol) was added to trifluoromethanesulfonic anhydride (42.3 g, 149.9 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.9 g of compound 23. (Yield 66%, MS: [M+H] + =624)

[0240] Production Example 24

[0241]

[0242] Compound 2 (15 g, 40.6 mmol) and compound Trz22 (20 g, 42.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in 100 ml of water and added. After sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved in chloroform again, washed with water twice, and the organic layer was separated. Anhydrous magnesium sulfate was added, and the mixture was filtered after stirring. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 21.2 g of compound 24_P1. (Yield 77%, MS: [M+H] + =677)

[0243] Compound 24_P1 (10 g, 14.8 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (10.7 g, 532.3 mmol) was added to trifluoromethanesulfonic anhydride (37.5 g, 133.1 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.2 g of compound 24. (Yield 60%, MS: [M+H] + =703)

[0244] Production Example 25

[0245]

[0246] Under nitrogen atmosphere, 9H-carbazole (15 g, 89.7 mmol), compound Trz6 (41.8 g, 94.2 mmol), potassium phosphate (57.1 g, 269.1 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 30.9 g of compound 25_P1. (Yield 60%, MS: [M+H] + =575)

[0247] Compound 25_P1 (10 g, 17.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (12.6 g, 626.9 mmol) was added to trifluoromethanesulfonic anhydride (44.2 g, 156.7 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.4 g of compound 25. (Yield 62%, MS: [M+H] + =598)

[0248] Production Example 26

[0249]

[0250] Under nitrogen atmosphere, 9H-carbazole (15 g, 89.7 mmol), compound Trz17 (37.1 g, 94.2 mmol), potassium phosphate (57.1 g, 269.1 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 26.8 g of compound 26_P1. (Yield 57%, MS: [M+H] + =525)

[0251] Compound 26_P1 (10 g, 19.1 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (13.8 g, 686.8 mmol) was added to trifluoromethanesulfonic anhydride (48.4 g, 171.7 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.8 g of compound 26. (Yield 56%, MS: [M+H] + =545)

[0252] Production Example 27

[0253]

[0254] Under nitrogen atmosphere, 9H-carbazole (15 g, 89.7 mmol), compound Trz23 (65.2 g, 94.2 mmol), potassium phosphate (57.1 g, 269.1 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 49.4 g of compound 27_P1. (Yield 67%, MS: [M+H] + =823)

[0255] Compound 27_P1 (10 g, 12.2 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (8.8 g, 437.8 mmol) was added to trifluoromethanesulfonic anhydride (30.9 g, 109.5 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.3 g of compound 27. (Yield 70%, MS: [M+H] + =857)

[0256] Production Example 28

[0257]

[0258] Under nitrogen atmosphere, 9H-carbazole (15 g, 89.7 mmol), compound Trz24 (58 g, 94.2 mmol), potassium phosphate (57.1 g, 269.1 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 43.5 g of compound 28_P1. (Yield 65%, MS: [M+H] + =747)

[0259] Compound 28_P1 (10 g, 13.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (9.7 g, 482.4 mmol) was added to trifluoromethanesulfonic anhydride (34 g, 120.6 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.1 g of compound 28. (Yield 68%, MS: [M+H] + =778)

[0260] Production Example 29

[0261]

[0262] Under nitrogen atmosphere, 9H-carbazole (15 g, 89.7 mmol), compound Trz25 (58 g, 94.2 mmol), potassium phosphate (57.1 g, 269.1 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 38.8 g of compound 29_P1. (Yield 58%, MS: [M+H] + =747)

[0263] Compound 29_P1 (10 g, 13.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (9.7 g, 482.4 mmol) was added to trifluoromethanesulfonic anhydride (34 g, 120.6 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.4 g of compound 29. (Yield 52%, MS: [M+H] + =777)

[0264] Production Example 30

[0265]

[0266] Under nitrogen atmosphere, 9H-carbazole (15 g, 89.7 mmol), compound Trz26 (65.2 g, 94.2 mmol), potassium phosphate (57.1 g, 269.1 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 51.6 g of compound 30_P1. (Yield 70%, MS: [M+H] + =823)

[0267] Compound 30_P1 (10 g, 12.2 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (8.8 g, 437.8 mmol) was added to trifluoromethanesulfonic anhydride (30.9 g, 109.5 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.3 g of compound 30. (Yield 51%, MS: [M+H] + =854)

[0268] Example 1

[0269] ITO (indium tin oxide) is used The glass substrate coated with a film of a thickness of 10000 mm was placed in distilled water dissolved with a detergent and washed with ultrasonic waves. At this time, the detergent used a product of Fischer Co., and the distilled water used distilled water filtered twice by a filter manufactured by Millipore Co. After ITO was washed for 30 minutes, ultrasonic washing was repeated twice with distilled water for 10 minutes. After the distilled water washing was completed, ultrasonic washing was carried out with a solvent of isopropanol, acetone, and methanol and dried, and then transported to a plasma cleaning machine. In addition, after the above-mentioned substrate was cleaned for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

[0270] On the ITO transparent electrode prepared in this way, the following compound HI-1 was added as a hole injection layer. The following compound HT-1 was vacuum-deposited on the hole injection layer to form a film with a thickness of Next, on the hole transport layer, a layer with a film thickness of The following compound EB-1 was vacuum-deposited to form an electron blocking layer. Next, the above-produced compound 1 as a main component and the following compound Dp-7 as a dopant were vacuum-deposited at a weight ratio of 98:2 on the above-produced EB-1 vapor-deposited film to form an electron blocking layer. On the above-mentioned luminescent layer, the film thickness is The following compound HB-1 was vacuum-deposited to form a hole blocking layer. Next, the following ET-1 compound and the following LiQ compound were vacuum-deposited at a weight ratio of 2:1 on the hole blocking layer to form a hole blocking layer. On the electron injection and transport layer, lithium fluoride (LiF) is sequentially added with The thickness of the aluminum A cathode is formed by evaporation with a thickness of .

[0271]

[0272] In the above process, the evaporation rate of organic matter is maintained Lithium fluoride at the cathode maintains Aluminum maintenance The evaporation speed is 2*10 -7 ~5*10 -6 A support is provided to manufacture an organic light-emitting device.

[0273] Example 2 to Example 30

[0274] An organic light-emitting device was manufactured by the same method as in Example 1, except that each compound listed in Table 1 was used as a host.

[0275] Comparative Examples 1 to 12

[0276] The organic light-emitting device of Example 1 was manufactured by the same method as in Example 1 except that each compound described in Table 2 was used as a host. The structures of compounds B-1 to B-12 in Table 2 are shown below.

[0277]

[0278] Experimental example

[0279] When current was applied to the organic light-emitting devices manufactured in Examples 1 to 30 and Comparative Examples 1 to 12, the voltage and efficiency (15 mA / cm 2 The results are shown in the following Tables 1 and 2. The lifespan T95 refers to the time required for the luminance to decrease from the initial luminance (6000 nits) to 95%.

[0280] [Table 1]

[0281]

[0282] [Table 2]

[0283]

[0284] When current was applied to the organic light emitting devices manufactured by Examples 1 to 30 and Comparative Examples 1 to 12, the results shown in Tables 1 and 2 were obtained.

[0285] When the compound of the present invention is used as a red light-emitting layer, as shown in Table 1, it can be confirmed that the driving voltage is reduced, the efficiency and life are increased compared with the comparative example of Table 2, and in addition, it can be confirmed that the life characteristics of the compound substituted by deuterium are further increased. When analogized by such results, the reason for the improvement of driving voltage and the improvement of efficiency and life is that when the compound of the present invention is used as a main body, compared with the comparative example compound, the energy transfer of the red dopant in the red light-emitting layer is well formed. It can be inferred from this that, compared with the comparative example compound, the compound of the present invention forms a more stable balance in the light-emitting layer, and electrons and holes combine to form excitons, thereby improving efficiency and life.

[0286] In summary, when the compound of the present invention is used as a host of a red light-emitting layer, the driving voltage, luminous efficiency and lifespan characteristics of an organic light-emitting device can be improved.

[0287] [Explanation of symbols]

[0288] 1: Substrate 2: Anode

[0289] 3: Light-emitting layer 4: Cathode

[0290] 5: Hole injection layer 6: Hole transport layer

[0291] 7: Electron blocking layer 8: Hole blocking layer

[0292] 9: Electron injection and transport layer.

Claims

1. A compound represented by the following chemical formula 1: [Chemical formula 1] In the chemical formula 1, Ar1 is phenyl, dibenzofuranyl, dibenzothiophenyl, Ar1 is substituted or unsubstituted, Ar2 is naphthyl, naphthylphenyl, phenyl substituted by -Si(Q1)(Q2)(Q3), dibenzofuranyl, dibenzothiophenyl, Ar2 is substituted or unsubstituted, in, Q1, Q2 and Q3 are each independently hydrogen, deuterium, C 1-10 Alkyl or C 6-20 Aryl, L1 and L2 are each independently a single bond, a phenylene group, a biphenyl diyl group or a naphthalene diyl group, wherein the phenylene group, the biphenyl diyl group and the naphthalene diyl group are each independently unsubstituted or substituted with one or more deuterium groups, However, L1-Ar1 and L2-Ar2 are different from each other. L3 is a single bond, R1 to R3 are each independently hydrogen or deuterium, a1 is an integer from 1 to 8, a2 and a3 are each independently an integer from 1 to 4, The compound represented by the Chemical Formula 1 is substituted with at least 2 deuteriums.

2. The compound according to claim 1, wherein Ar1 is phenyl, phenyl substituted by two phenyl groups, naphthylphenyl, phenanthrenylphenyl, triphenylsilylphenyl, dibenzofuranylphenyl, phenanthrenyl or dibenzofuranyl, The Ar1 is unsubstituted or substituted with one or more deuterium.

3. The compound according to claim 1, wherein Ar2 is naphthyl, phenylnaphthyl, naphthylphenyl, dibenzofuranylnaphthyl, triphenylsilylphenyl, phenanthryl or dibenzofuranyl, The Ar2 is unsubstituted or substituted with one or more deuterium.

4. The compound according to claim 1, wherein Ar1 is phenyl, Ar2 is naphthyl substituted by phenyl or phenyl substituted by naphthyl, The Ar1 and Ar2 are each independently unsubstituted or substituted with one or more deuterium.

5. The compound according to claim 1, wherein L1 and L2 are different from each other, or Ar1 and Ar2 are different from each other.

6. The compound according to claim 1, wherein R1 is deuterium, a1 is 8.

7. The compound according to claim 1, wherein The compound represented by the Chemical Formula 1 is substituted with at least 8 deuteriums.

8. The compound according to claim 1, wherein The compound represented by the chemical formula 1 is any one selected from the following compounds: In the compound, Dn means that n hydrogen atoms in the compound in brackets are replaced by deuterium. Here, n is an integer greater than or equal to 2.

9. An organic light emitting device, comprising: A first electrode, a second electrode disposed opposite to the first electrode, and one or more organic layers disposed between the first electrode and the second electrode, wherein one or more of the organic layers comprises the compound according to any one of claims 1 to 8.

10. The organic light emitting device according to claim 9, wherein: The organic layer is a light-emitting layer, an electron transport layer, or an electron injection and transport layer.

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