Novel compound and organic light-emitting device comprising same

Abstract

The present invention provides a novel compound and an organic light emitting device comprising the same. Specifically, the present invention provides a compound represented by Chemical Formula 1. The compound represented by the above chemical formula 1 can be used as a material of an organic layer of an organic light-emitting device in which an improvement in efficiency, a lower driving voltage, and / or an improvement in lifespan characteristics can be achieved. In particular, the compound represented by the above chemical formula 1 can be used as a material for hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection.

Description

Technical Field

[0001] Cross-references to related applications

[0002] This application claims priority based on Korean Patent Application No. 10-2023-0123269 filed on September 15, 2023, and incorporates all the contents disclosed in the document of the Korean Patent Application as a 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 is continuously required.

[0007] Prior art literature

[0008] Patent Literature

[0009] (Patent Document 0001) Korean Patent Publication No. 10-2000-0051826 Summary of the invention

[0010] Technical issues

[0011] The present invention relates to novel compounds and organic light-emitting devices 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] Any one of R is bonded to L1, and the others are independently hydrogen or deuterium,

[0018] L1 is a single bond, or a substituted or unsubstituted C 6-12 Arylene,

[0019] L2 and L3 are each independently a single bond, or a substituted or unsubstituted C 6-60 Arylene,

[0020] Ar1 and Ar2 are each independently substituted or unsubstituted C 6-60 Aryl, or substituted or unsubstituted C 3-60 Aliphatic cyclic group,

[0021] Dn means n hydrogens are replaced by deuterium.

[0022] n is an integer greater than or equal to 0.

[0023] In addition, the present invention provides an organic light-emitting device, comprising: 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, wherein one or more of the organic layers contains a compound represented by the above chemical formula 1.

[0024] Effects of the Invention

[0025] 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 hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The figure shows 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 .

[0027] 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, a hole transport auxiliary layer 7, a light-emitting layer 3, a hole blocking layer 8, an electron injection and transport layer 9, and a cathode 4.

[0028] Explanation of symbols

[0029] 1: Substrate 2: Anode

[0030] 3: Light-emitting layer 4: Cathode

[0031] 5: Hole injection layer 6: Hole transport layer

[0032] 7: Hole transport auxiliary layer 8: Hole blocking layer

[0033] 9: Electron injection and transport layer DETAILED DESCRIPTION

[0034] In the following, the present invention will be described in more detail to help understanding the present invention.

[0035] In this manual, and "D" represents a bond to other substituents, and "D" represents deuterium.

[0036] 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, the 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 6-20 In 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”.

[0037] 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.

[0038]

[0039] 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.

[0040]

[0041] 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.

[0042]

[0043] 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, or substituted or unsubstituted C 6-20 Specific examples of the silyl group include trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, and phenylsilyl, but are not limited thereto.

[0044] In the present specification, specific examples of the boryl group include trimethylboryl, triethylboryl, tert-butyldimethylboryl, triphenylboryl, and phenylboryl, but are not limited thereto.

[0045] In the present specification, as examples of the halogen group, there are fluorine, chlorine, bromine or iodine.

[0046] 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.

[0047] 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.

[0048] In this specification, the alicyclic group refers to a monovalent substituent derived from a saturated or unsaturated hydrocarbon ring compound containing only carbon as a ring atom and not having aromaticity, and is understood to include all monocyclic or condensed polycyclic compounds. According to one embodiment, the alicyclic group has 3 to 60 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. Examples of such alicyclic groups include monocyclic groups such as cycloalkyl, bridged hydrocarbon groups, spirohydrocarbon groups, substituents derived from hydrogenated derivatives of aromatic hydrocarbon compounds, and the like.

[0049] Specifically, examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, and cyclooctyl, but are not limited thereto.

[0050] Examples of the bridged cyclic hydrocarbon group include, but are not limited to, bicyclo[1.1.0]butyl, bicyclo[2.2.1]heptyl, bicyclo[4.2.0]octa-1,3,5-trienyl, adamantyl, and decalinyl.

[0051] In addition, examples of the spirocyclic hydrocarbon group include spiro[3.4]octyl and spiro[5.5]undecyl, but are not limited to these.

[0052] The substituents derived from hydrogenated derivatives of aromatic hydrocarbon compounds are substituents derived from compounds obtained by hydrogenating some unsaturated bonds of monocyclic or polycyclic aromatic hydrocarbon compounds. Examples of such substituents include, but are not limited to, 1H-indenyl, 2H-indenyl, 4H-indenyl, 2,3-dihydro-1H-indenyl, 1,4-dihydronaphthyl, 1,2,3,4-tetrahydronaphthyl, 6,7,8,9-tetrahydro-5H-benzo[7]annulenyl and 6,7-dihydro-5H-benzocycloheptenyl.

[0053] In the present specification, an aryl group is understood to mean a substituent derived from a monocyclic or condensed polycyclic compound containing only carbon as a ring atom and having aromaticity. The number of carbon atoms is not particularly limited, but preferably the number of carbon atoms is 6 to 60. According to one embodiment, the number of carbon atoms of the above aryl group is 6 to 30. According to one embodiment, the number of carbon atoms of the above aryl group is 6 to 20. Regarding the above aryl group, as a monocyclic aryl group, it can be phenyl, biphenyl, terphenyl, etc., but it is not limited thereto. As the above polycyclic aryl group, it can be naphthyl, anthracenyl, phenanthrenyl, pyrenyl, peryl, yl, fluorenyl, etc., but are not limited to these.

[0054] 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.

[0055] In this specification, a heterocyclic group refers to a monovalent substituent derived from a monocyclic or condensed polycyclic compound containing one or more heteroatoms selected from O, N, Si and S as ring atoms in addition to carbon, and is understood to include all substituents having aromaticity or substituents not having aromaticity. According to one embodiment, the number of carbon atoms in the heterocyclic group is 2 to 60. According to another embodiment, the number of carbon atoms in the heterocyclic group is 2 to 30. According to another embodiment, the number of carbon atoms in the heterocyclic group is 2 to 20. Examples of such heterocyclic groups include heteroaryl groups, substituents derived from hydrogenated derivatives of heteroaromatic compounds, and the like.

[0056] 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.

[0057] The substituent derived from a hydrogenated derivative of a heteroaromatic compound refers to a substituent derived from a compound obtained by hydrogenating a portion of unsaturated bonds of a monocyclic or polycyclic heteroaromatic compound. Examples of such a substituent include, but are not limited to, 1,3-dihydroisobenzofuranyl, 2,3-dihydrobenzofuranyl, 1,3-dihydrobenzo[c]thiophenyl, and 2,3-dihydro[b]thiophenyl.

[0058] In the present specification, the aryl group in aralkyl, aralkenyl, alkylaryl, arylamine, and arylsilyl is the same as the aryl group exemplified above. In the present specification, the alkyl group in aralkyl, alkylaryl, and alkylamine is the same as the alkyl group exemplified above. In the present specification, the heteroaryl group in heteroarylamine can be applied to the above description of heteroaryl. In the present specification, the alkenyl group in aralkenyl is the same as the alkenyl group exemplified above. In the present specification, the arylene group is a divalent group, and the above description of aryl can be applied otherwise. In the present specification, the heteroarylene group is a divalent group, and the above description of heteroaryl can be applied otherwise. In the present specification, the hydrocarbon ring is not a monovalent group, but is formed by combining two substituents, and the above description of aryl or cycloalkyl can be applied otherwise. In the present specification, the heterocycle is not a monovalent group, but is formed by combining two substituents, and the above description of heteroaryl can be applied otherwise.

[0059] In the present specification, "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.

[0060] In addition, "unsubstituted or substituted with deuterium" or "substituted or unsubstituted with deuterium" means "unsubstituted or substituted with 1 to 9 deuteriums in the substitutable hydrogens". As an example, the term "unsubstituted or substituted with deuterium phenanthrenyl" can be understood to mean "unsubstituted or substituted with 1 to 9 deuteriums in the phenanthrenyl structure" when considering that the maximum number of hydrogens that can be substituted with deuteriums is 9.

[0061] 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 structures in which at least one substitutable hydrogen in phenyl is replaced by deuterium and monovalent substituents.

[0062]

[0063] 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 deuteriums substituted in the compound to the total number of hydrogens that can exist (the sum of the number of hydrogens that can be substituted with deuterium in the compound and the number of deuteriums substituted). Therefore, the "deuterium substitution rate" or "deuteration degree" of a compound as "K%" means that K% of the hydrogens that can be substituted with deuterium in the compound are substituted with deuterium.

[0064] At this time, 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 generally 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.

[0065] (Compound)

[0066] The present invention provides a compound represented by the above Chemical Formula 1.

[0067] Preferably, the above Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-10:

[0068]

[0069]

[0070] In the above chemical formulas 1-1 to 1-10,

[0071] L1 to L3, Ar1, Ar2 and Dn are the same as defined above,

[0072] R1 is each independently hydrogen or deuterium.

[0073] Preferably, L1 is a single bond or a phenylene group, and the phenylene group is unsubstituted or substituted with one or more deuterium groups.

[0074] Specifically, L1 is a single bond, or any one selected from the following groups and their deuterated structures:

[0075]

[0076] Preferably, L2 and L3 are each independently a single bond, a phenylene group, a naphthalene diyl group or a biphenyl diyl group, and the phenylene group, the naphthalene diyl group and the biphenyl diyl group are each independently unsubstituted or substituted with one or more deuterium groups.

[0077] On the other hand, Ar1 and Ar2 are each independently substituted or unsubstituted C 6-60 Aryl, or substituted or unsubstituted C 3-60 Specifically, Ar1 and Ar2 are each independently substituted or unsubstituted C 6-20 Aryl, or substituted or unsubstituted C 3-20 Aliphatic cyclic group.

[0078] Preferably, Ar1 and Ar2 are each independently phenyl, biphenyl, terphenyl, naphthyl, naphthylphenyl, phenylnaphthyl, phenanthrenyl, tetrahydronaphthyl, 1,2,3,4-tetrahydro-1,1,4,4-tetramethylnaphthyl or 1,2,3,4-tetrahydro-1,1,4-trimethylnaphthyl, and the above Ar1 and Ar2 are each independently unsubstituted; or are selected from deuterium, substituted or unsubstituted C 1-4 Alkyl, substituted or unsubstituted C 3-10 The aliphatic ring group is substituted with one or more substituents.

[0079] Specifically, Ar1 and Ar2 are each independently phenyl, biphenyl, terphenyl, naphthyl, naphthylphenyl, phenylnaphthyl, phenanthrenyl, tetrahydronaphthyl, 1,2,3,4-tetrahydro-1,1,4,4-tetramethylnaphthyl or 1,2,3,4-tetrahydro-1,1,4-trimethylnaphthyl, and the above Ar1 and Ar2 are each independently unsubstituted; or are substituted by one or more substituents selected from deuterium, methyl substituted or unsubstituted by deuterium, propyl (or isopropyl) substituted or unsubstituted by deuterium, butyl (or tert-butyl) substituted or unsubstituted by deuterium, bicycloheptyl substituted or unsubstituted by deuterium, bicyclooctyl substituted or unsubstituted by deuterium and cyclohexyl substituted or unsubstituted by deuterium.

[0080] More preferably, Ar1 is phenyl, naphthyl, tetrahydronaphthyl, 1,2,3,4-tetrahydro-1,1,4,4-tetramethylnaphthyl or 1,2,3,4-tetrahydro-1,1,4-trimethylnaphthyl,

[0081] Ar2 is phenyl, biphenyl, terphenyl, naphthyl, naphthylphenyl, phenylnaphthyl, phenanthrenyl, tetrahydronaphthyl, 1,2,3,4-tetrahydro-1,1,4,4-tetramethylnaphthyl or 1,2,3,4-tetrahydro-1,1,4-trimethylnaphthyl,

[0082] wherein the phenyl group is unsubstituted; or substituted by one or more substituents selected from the group consisting of deuterium, methyl group substituted or unsubstituted by deuterium, propyl group (or isopropyl group) substituted or unsubstituted by deuterium, butyl group (or tert-butyl group) substituted or unsubstituted by deuterium, bicycloheptyl group substituted or unsubstituted by deuterium, bicyclooctyl group substituted or unsubstituted by deuterium, and cyclohexyl group substituted or unsubstituted by deuterium,

[0083] Ar1 and Ar2 are each independently unsubstituted or substituted with one or more deuterium.

[0084] In addition, the compound represented by the above Chemical Formula 1 may not contain deuterium, or may contain one or more deuterium.

[0085] When the compound represented by the above Chemical Formula 1 contains deuterium, the deuterium substitution rate may be 1% to 100%. Specifically, the deuterium substitution rate of the compound represented by the above Chemical Formula 1 may 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.

[0086] As an example, the first compound may not contain deuterium, or may contain 1 to 50 deuteriums. More specifically, the first compound may not contain deuterium, or may contain 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, 9 or more, 10 or more, 11 or more, 12 or more, 13 or more, 14 or more, or 15 or more and 50 or less, 40 or less, 39 or less, 38 or less, 37 or less, 36 or less, 35 or less, 30 or less, 28 or less, 26 or less, 24 or less, 22 or less, or 20 or less deuteriums.

[0087] Representative examples of the compound represented by the above Chemical Formula 1 are shown below:

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

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[0154]

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[0156]

[0157]

[0158]

[0159]

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[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

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[0174]

[0175]

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[0177]

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[0183]

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[0200]

[0201]

[0202]

[0203]

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[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213] Among the above compounds,

[0214] Dn means that each compound is substituted by n deuteriums.

[0215] n is an integer of 1 or more.

[0216] On the other hand, as an example, the compound represented by the above Chemical Formula 1 can be produced by the production method shown in the following Reaction Formula 1, and the remaining compounds can also be produced by a similar method.

[0217] [Reaction 1]

[0218]

[0219] In the above reaction formula 1, R, L1 to L3, Ar1, Ar2, Dn and n are the same as those defined in the above chemical formula 1, and Y is a halogen, preferably bromine or chlorine.

[0220] The above reaction is an amine substitution reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactive group used for the amine substitution reaction can be changed according to the techniques known in the art. The above production method can be further embodied in the production examples described below.

[0221] (Organic Light Emitting Devices)

[0222] 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, which includes: 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.

[0223] 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 hole transport auxiliary 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.

[0224] In addition, the organic layer may include a light-emitting layer. In this case, the organic layer including the compound represented by Chemical Formula 1 may be the light-emitting layer.

[0225] In another embodiment, the organic layer may include a hole injection layer, a hole transport layer, a hole transport auxiliary layer, a light-emitting layer, a hole blocking layer, and an electron injection and transport layer. In this case, the organic layer containing the above compound may be a light-emitting layer.

[0226] 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 and2 .

[0227] Figure 1 The figure shows 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. In the above structure, the compound represented by the above Chemical Formula 1 may be contained in the above light emitting layer.

[0228] 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, a hole transport auxiliary 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 as described above, the compound represented by the above chemical formula 1 may be contained in the above hole transport auxiliary layer.

[0229] 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.

[0230] 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.

[0231] 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.

[0232] 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.

[0233] 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.

[0234] 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.

[0235] 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.

[0236] 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.

[0237] 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.

[0238] On the other hand, the electron blocking layer refers to 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 contains an electron blocking substance. As an example of such an electron blocking substance, an arylamine-based organic substance can be used, but it is not limited thereto.

[0239] The hole transport auxiliary layer is a layer located between the hole transport layer and the light emitting layer. By including the hole transport auxiliary layer, holes are more smoothly transferred from the hole transport layer to the light emitting layer, and excitons are confined in the light emitting layer to prevent light leakage, which has the effect of making the organic light emitting device have excellent luminous efficiency. Preferably, the compound represented by the above chemical formula 1 can be used as a hole transport auxiliary material.

[0240] 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 Compounds of the oxazole, benzothiazole and benzimidazole series; polymers of the poly(p-phenylene vinylene) (PPV) series; spiro compounds; polyfluorene, rubrene, etc., but are not limited thereto.

[0241] The above-mentioned light-emitting layer may include a host material and a dopant material. The host material includes an aromatic fused ring derivative or a heterocyclic compound. Specifically, as an aromatic fused ring derivative, there are anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., as heterocyclic compounds, there are carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, etc. Pyrimidine derivatives, etc., but are not limited to these.

[0242] 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 a metal complex, there are iridium complexes, platinum complexes, etc., but not limited thereto.

[0243] 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.

[0244] The electron injection and transport layer is a layer that injects electrons from the electrode and transports the received electrons to the light-emitting layer, and acts as an electron transport layer and an electron injection layer at the same time, and is formed on the light-emitting layer or the hole blocking layer. Such an electron injection and transport substance is a substance that can well receive electrons from the cathode and transfer them to the light-emitting layer, and a substance with a large electron mobility is suitable. As such an electron injection and transport layer substance, a compound represented by the above chemical formula 1 can be used. As examples of other electron injection and transport substances, there are Al complexes of 8-hydroxyquinoline, complexes containing Alq3, organic free radical compounds, hydroxyflavone-metal complexes, triazine derivatives, etc., but are not limited to these. Alternatively, it can also be combined with fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, Azoles, Oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylene methane, anthrone and the like, and derivatives thereof, metal coordination compounds, or nitrogen-containing five-membered ring derivatives and the like can be used together, but are not limited thereto.

[0245] The electron injection and transport layer may also be formed as a separate layer such as an electron injection layer and an electron transport layer. In this case, the electron transport layer is formed on the light-emitting layer or the hole blocking layer, and as the electron transport material contained in the electron transport layer, the electron injection and transport material mentioned above can be used. In addition, the electron injection layer is formed on the electron transport layer, and as the electron injection material contained in the electron injection layer, LiF, NaCl, CsF, Li2O, BaO, fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, Azoles, Oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylene methane, anthrone, etc. and their derivatives, metal coordination compounds, or nitrogen-containing five-membered ring derivatives, etc.

[0246] 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-hydroxyquinoline) gallium chloride, bis(2-methyl-8-hydroxyquinoline)(o-cresol) gallium, bis(2-methyl-8-hydroxyquinoline)(1-naphthol) aluminum, and bis(2-methyl-8-hydroxyquinoline)(2-naphthol) gallium.

[0247] 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.

[0248] In addition, the compound according to the present invention may be contained in an organic solar cell or an organic transistor in addition to being contained in an organic light-emitting device.

[0249] 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.

[0250] [Example]

[0251] Example 1

[0252]

[0253] Under nitrogen atmosphere, sub1 (10 g, 28.3 mmol), amine 1 (12.5 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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 16.1 g of compound 1. (Yield 77%, MS: [M+H] + =739)

[0254] Example 2

[0255]

[0256] Under a nitrogen atmosphere, sub1 (10 g, 28.3 mmol), amine 2 (9.6 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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 12.8 g of compound 2. (Yield 71%, MS: [M+H] + =639)

[0257] Example 3

[0258]

[0259] Under a nitrogen atmosphere, sub1 (10 g, 28.3 mmol), amine 3 (10.1 g, 29.8 mmol), and sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 11.2 g of compound 3. (Yield 60%, MS: [M+H] + =657)

[0260] Example 4

[0261]

[0262] Under a nitrogen atmosphere, sub1 (10 g, 28.3 mmol), amine 4 (11.7 g, 29.8 mmol), and sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 14.7 g of compound 4. (Yield 73%, MS: [M+H] + =711)

[0263] Example 5

[0264]

[0265] Under nitrogen atmosphere, sub1 (10 g, 28.3 mmol), amine 5 (8.9 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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 13.6 g of compound 5. (Yield 78%, MS: [M+H] + =617)

[0266] Example 6

[0267]

[0268] Under nitrogen atmosphere, sub2 (10 g, 23.3 mmol), amine 6 (8.5 g, 24.5 mmol), sodium tert-butoxide (2.9 g, 30.3 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. The reaction was terminated after 2 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, 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 13.1 g of compound 6. (Yield 76%, MS: [M+H] + =739)

[0269] Example 7

[0270]

[0271] Under nitrogen atmosphere, sub2 (10 g, 23.3 mmol), amine 7 (8.8 g, 24.5 mmol), sodium tert-butoxide (2.9 g, 30.3 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. The reaction was terminated after 3 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, 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 13.5 g of compound 7. (Yield 77%, MS: [M+H] + =751)

[0272] Example 8

[0273]

[0274] Under nitrogen atmosphere, sub3 (10 g, 28.3 mmol), amine 8 (9.6 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 13 g of compound 8. (Yield 72%, MS: [M+H] +=639)

[0275] Example 9

[0276]

[0277] Under nitrogen atmosphere, sub3 (10 g, 28.3 mmol), amine 9 (12.1 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 15.1 g of compound 9. (Yield 74%, MS: [M+H] + =723)

[0278] Example 10

[0279]

[0280] Under nitrogen atmosphere, sub3 (10 g, 28.3 mmol), amine 10 (10.6 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 13.3 g of compound 10. (Yield 70%, MS: [M+H] + =673)

[0281] Embodiment 11

[0282]

[0283] Under nitrogen atmosphere, sub3 (10 g, 28.3 mmol), amine 11 (11.1 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 10.7 g of compound 11. (Yield 55%, MS: [M+H] + =689)

[0284] Example 12

[0285]

[0286] Under a nitrogen atmosphere, sub3 (10 g, 28.3 mmol), amine 12 (11.8 g, 29.8 mmol), and sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 11.1 g of compound 12. (Yield 55%, MS: [M+H] + =715)

[0287] Embodiment 13

[0288]

[0289] Under nitrogen atmosphere, sub3 (10 g, 28.3 mmol), amine 13 (11.8 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 11.5 g of compound 13. (Yield 57%, MS: [M+H] + =715)

[0290] Embodiment 14

[0291]

[0292] Under nitrogen atmosphere, sub3 (10 g, 28.3 mmol), amine 14 (8.8 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 12 g of compound 14. (Yield 69%, MS: [M+H] + =613)

[0293] Embodiment 15

[0294]

[0295] Under nitrogen atmosphere, sub3 (10 g, 28.3 mmol), amine 15 (8.3 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 12.3 g of compound 15. (Yield 73%, MS: [M+H] + =595)

[0296] Example 16

[0297]

[0298] Under nitrogen atmosphere, sub4 (10 g, 23.3 mmol), amine 16 (7.2 g, 24.5 mmol), sodium tert-butoxide (2.9 g, 30.3 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. The reaction was terminated after 3 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, 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 8.7 g of compound 16. (Yield 54%, MS: [M+H] + =689)

[0299] Embodiment 17

[0300]

[0301] Under nitrogen atmosphere, sub4 (10 g, 23.3 mmol), amine 17 (9.7 g, 24.5 mmol), sodium tert-butoxide (2.9 g, 30.3 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. The reaction was terminated after 2 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, 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 11.6 g of compound 17. (Yield 63%, MS: [M+H] + =791)

[0302] Embodiment 18

[0303]

[0304] Under nitrogen atmosphere, sub4 (10 g, 23.3 mmol), amine 18 (8.5 g, 24.5 mmol), sodium tert-butoxide (2.9 g, 30.3 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. The reaction was terminated after 3 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, 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 12.2 g of compound 18. (Yield 71%, MS: [M+H] + =739)

[0305] Embodiment 19

[0306]

[0307] Under nitrogen atmosphere, sub5 (10 g, 28.3 mmol), amine 19 (9.6 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 14.1 g of compound 19. (Yield 78%, MS: [M+H] + =639)

[0308] Embodiment 20

[0309]

[0310] Under nitrogen atmosphere, sub5 (10 g, 28.3 mmol), amine 20 (8.4 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 12 g of compound 20. (Yield 71%, MS: [M+H] + =599)

[0311] Embodiment 21

[0312]

[0313] Under nitrogen atmosphere, sub5 (10 g, 28.3 mmol), amine 21 (12.9 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 16.2 g of compound 21. (Yield 76%, MS: [M+H] + =751)

[0314] Embodiment 22

[0315]

[0316] Under nitrogen atmosphere, sub5 (10 g, 28.3 mmol), amine 22 (10.1 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 11.2 g of compound 22. (Yield 60%, MS: [M+H] + =657)

[0317] Embodiment 23

[0318]

[0319] Under nitrogen atmosphere, sub5 (10 g, 28.3 mmol), amine 23 (11.1 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 12.9 g of compound 23. (Yield 66%, MS: [M+H] + =689)

[0320] Embodiment 24

[0321]

[0322] Under nitrogen atmosphere, sub5 (10 g, 28.3 mmol), amine 24 (9.6 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 10.3 g of compound 24. (Yield 57%, MS: [M+H] + =639)

[0323] Embodiment 25

[0324]

[0325] Under a nitrogen atmosphere, sub6 (10 g, 23.3 mmol), amine 25 (6 g, 24.5 mmol), and sodium tert-butoxide (2.9 g, 30.3 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. The reaction was terminated after 3 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, 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 9.8 g of compound 25. (Yield 66%, MS: [M+H] + =639)

[0326] Embodiment 26

[0327]

[0328] Under nitrogen atmosphere, sub6 (10 g, 23.3 mmol), amine 26 (8.5 g, 24.5 mmol), sodium tert-butoxide (2.9 g, 30.3 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. The reaction was terminated after 2 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, 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 12.6 g of compound 26. (Yield 73%, MS: [M+H] + =739)

[0329] Embodiment 27

[0330]

[0331] Under nitrogen atmosphere, sub7 (10 g, 28.3 mmol), amine 27 (13.8 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 15 g of compound 27. (Yield 68%, MS: [M+H] + =781)

[0332] Embodiment 28

[0333]

[0334] Under nitrogen atmosphere, sub7 (10 g, 28.3 mmol), amine 28 (9.6 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 11.2 g of compound 28. (Yield 62%, MS: [M+H] + =639)

[0335] Embodiment 29

[0336]

[0337] Under nitrogen atmosphere, sub7 (10 g, 28.3 mmol), amine 29 (10.3 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 9.9 g of compound 29. (Yield 53%, MS: [M+H] + =663)

[0338] Embodiment 30

[0339]

[0340] Under nitrogen atmosphere, sub7 (10 g, 28.3 mmol), amine 30 (11.8 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 11.9 g of compound 30. (Yield 59%, MS: [M+H] + =715)

[0341] Embodiment 31

[0342]

[0343] Under nitrogen atmosphere, sub8 (10 g, 23.3 mmol), amine 31 (7.9 g, 24.5 mmol), sodium tert-butoxide (2.9 g, 30.3 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. The reaction was terminated after 3 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, 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 9.8 g of compound 31. (Yield 59%, MS: [M+H] + =715)

[0344] Embodiment 32

[0345]

[0346] Under nitrogen atmosphere, sub9 (10 g, 28.3 mmol), amine 32 (9.2 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 13.4 g of compound 32. (Yield 76%, MS: [M+H] + =625)

[0347] Embodiment 33

[0348]

[0349] Under nitrogen atmosphere, sub9 (10 g, 28.3 mmol), amine 33 (9.9 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 13.6 g of compound 33. (Yield 74%, MS: [M+H] + =651)

[0350] Embodiment 34

[0351]

[0352] Under nitrogen atmosphere, sub9 (10 g, 28.3 mmol), amine 34 (11.1 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 11.5 g of compound 34. (Yield 59%, MS: [M+H] + =689)

[0353] Embodiment 35

[0354]

[0355] Under nitrogen atmosphere, sub10 (10 g, 23.3 mmol), amine 35 (8.5 g, 24.5 mmol), sodium tert-butoxide (2.9 g, 30.3 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. The reaction was terminated after 3 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, 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 13.4 g of compound 35. (Yield 78%, MS: [M+H] + =739)

[0356] Embodiment 36

[0357]

[0358] Under nitrogen atmosphere, sub10 (10 g, 23.3 mmol), amine 36 (9.5 g, 24.5 mmol), sodium tert-butoxide (2.9 g, 30.3 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. The reaction was terminated after 2 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, 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 9.1 g of compound 36. (Yield 50%, MS: [M+H] + =783)

[0359] Embodiment 37

[0360]

[0361] Under nitrogen atmosphere, sub11 (10 g, 28.3 mmol), amine 37 (10.3 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 11.6 g of compound 37. (Yield 62%, MS: [M+H] + =663)

[0362] Embodiment 38

[0363]

[0364] Under nitrogen atmosphere, sub11 (10 g, 28.3 mmol), amine 38 (8.8 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 9.2 g of compound 38. (Yield 53%, MS: [M+H] + =613)

[0365] Embodiment 39

[0366]

[0367] Under a nitrogen atmosphere, sub11 (10 g, 28.3 mmol), amine 39 (11.6 g, 29.8 mmol), and sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 13.2 g of compound 39. (Yield 66%, MS: [M+H] + =707)

[0368] Embodiment 40

[0369]

[0370] Under nitrogen atmosphere, sub12 (10 g, 28.3 mmol), amine 40 (10.7 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 9.6 g of compound 40. (Yield 50%, MS: [M+H] + =677)

[0371] Embodiment 41

[0372]

[0373] Under a nitrogen atmosphere, sub13 (10 g, 23.3 mmol), amine 41 (7.9 g, 24.5 mmol), and sodium tert-butoxide (2.9 g, 30.3 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. The reaction was terminated after 2 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, 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 9.7 g of compound 41. (Yield 58%, MS: [M+H] + =715)

[0374] Embodiment 42

[0375]

[0376] Under a nitrogen atmosphere, sub13 (10 g, 23.3 mmol), amine 42 (7.2 g, 24.5 mmol), and sodium tert-butoxide (2.9 g, 30.3 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. The reaction was terminated after 2 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, 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 8.3 g of compound 42. (Yield 52%, MS: [M+H] + =689)

[0377] Embodiment 43

[0378]

[0379] Under a nitrogen atmosphere, sub14 (10 g, 28.3 mmol), amine 43 (9.6 g, 29.8 mmol), and sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 13.2 g of compound 43. (Yield 73%, MS: [M+H] + =639)

[0380] Embodiment 44

[0381]

[0382] Under nitrogen atmosphere, sub14 (10 g, 28.3 mmol), amine 44 (11.1 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 14.2 g of compound 44. (Yield 73%, MS: [M+H] + =689)

[0383] Embodiment 45

[0384]

[0385] Under a nitrogen atmosphere, sub14 (10 g, 28.3 mmol), amine 45 (8.4 g, 29.8 mmol), and sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 11.5 g of compound 45. (Yield 68%, MS: [M+H] + =599)

[0386] Embodiment 46

[0387]

[0388] Under a nitrogen atmosphere, sub1 (10 g, 28.3 mmol), amine 46 (11.1 g, 29.8 mmol), and sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 12.5 g of compound 46-P1. (Yield 64%, MS: [M+H] + =689)

[0389] Compound 46-P1 (10 g, 14.5 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (10.5 g, 523.4 mmol) was added to trifluoromethanesulfonic anhydride (24.6 g, 87.2 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 5 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 solution of potassium carbonate. 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 6.4 g of compound 46D15. (Yield 63%, MS: [M+H] + =704)

[0390] Embodiment 47

[0391]

[0392] Under a nitrogen atmosphere, sub1 (10 g, 28.3 mmol), amine 47 (10.6 g, 29.8 mmol), and sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 10.1 g of compound 47-P1. (Yield 53%, MS: [M+H] + =675)

[0393] Compound 47-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, 534.2 mmol) was added to trifluoromethanesulfonic anhydride (25.1 g, 89 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 5 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 47D21. (Yield 60%, MS: [M+H] + =696)

[0394] Embodiment 48

[0395]

[0396] Under a nitrogen atmosphere, sub1 (10 g, 28.3 mmol), amine 48 (8.9 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 10.1 g of compound 48-P1. (Yield 58%, MS: [M+H] + =617)

[0397] Compound 48-P1 (10 g, 16.2 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (13 g, 649.6 mmol) was added to trifluoromethanesulfonic anhydride (45.8 g, 162.4 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, 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 48D25. (Yield 61%, MS: [M+H] + =642)

[0398] Embodiment 49

[0399]

[0400] Under a nitrogen atmosphere, sub1 (10 g, 28.3 mmol), amine 49 (12.5 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 10.5 g of compound 49-P1. (Yield 50%, MS: [M+H] + =739)

[0401] Compound 49-P1 (10 g, 13.6 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (9.8 g, 487.9 mmol) was added to trifluoromethanesulfonic anhydride (22.9 g, 81.3 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 5 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 6.7 g of compound 49D19. (Yield 65%, MS: [M+H] + =758)

[0402] Embodiment 50

[0403]

[0404] Under nitrogen atmosphere, sub3 (10 g, 28.3 mmol), amine 50 (10.1 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 14.5 g of compound 50-P1. (Yield 78%, MS: [M+H] + =657)

[0405] Compound 50-P1 (10 g, 15.2 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (11 g, 548.9 mmol) was added to trifluoromethanesulfonic anhydride (25.8 g, 91.5 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 5 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 7.1 g of compound 50D16. (Yield 69%, MS: [M+H] + =673)

[0406] Embodiment 51

[0407]

[0408] Under nitrogen atmosphere, sub3 (10 g, 28.3 mmol), amine 51 (10.3 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 12.4 g of compound 51-P1. (Yield 66%, MS: [M+H] + =663)

[0409] Compound 51-P1 (10 g, 15.1 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (12.1 g, 604.4 mmol) was added to trifluoromethanesulfonic anhydride (42.6 g, 151.1 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, 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 51D25. (yield 64%, MS: [M+H] + =688)

[0410] Embodiment 52

[0411]

[0412] Under nitrogen atmosphere, sub3 (10 g, 28.3 mmol), amine 52 (11.6 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 12.6 g of compound 52-P1. (Yield 63%, MS: [M+H] + =707)

[0413] Compound 52-P1 (10 g, 14.2 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (10.2 g, 509.9 mmol) was added to trifluoromethanesulfonic anhydride (24 g, 85 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 5 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 7.5 g of compound 52D19. (Yield 73%, MS: [M+H] + =726)

[0414] Embodiment 53

[0415]

[0416] Under nitrogen atmosphere, sub3 (10 g, 28.3 mmol), amine 53 (12.5 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 16.5 g of compound 53-P1. (Yield 79%, MS: [M+H] + =739)

[0417] Compound 53-P1 (10 g, 13.6 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (10.9 g, 542.1 mmol) was added to trifluoromethanesulfonic anhydride (38.2 g, 135.5 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, 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 6.4 g of compound 53D31. (yield 61%, MS: [M+H] + =770)

[0418] Embodiment 54

[0419]

[0420] Under nitrogen atmosphere, sub3 (10 g, 28.3 mmol), amine 54 (9.6 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 11.2 g of compound 54-P1. (Yield 62%, MS: [M+H] + =639)

[0421] Compound 54-P1 (10 g, 15.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (11.3 g, 564.5 mmol) was added to trifluoromethanesulfonic anhydride (26.5 g, 94.1 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 5 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 54D20. (Yield 68%, MS: [M+H] + =659)

[0422] Embodiment 55

[0423]

[0424] Under nitrogen atmosphere, sub3 (10 g, 28.3 mmol), amine 55 (10.5 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 10.3 g of compound 55-P1. (Yield 54%, MS: [M+H] + =671)

[0425] Compound 55-P1 (10 g, 14.9 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (10.8 g, 537.4 mmol) was added to trifluoromethanesulfonic anhydride (25.3 g, 89.6 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 5 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 55D17. (Yield 63%, MS: [M+H] + =688)

[0426] Embodiment 56

[0427]

[0428] Under nitrogen atmosphere, sub4 (10 g, 23.3 mmol), amine 56 (7.9 g, 24.5 mmol), sodium tert-butoxide (2.9 g, 30.3 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. The reaction was terminated after 3 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, 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 11.3 g of compound 56-P1. (Yield 68%, MS: [M+H] + =715)

[0429] Compound 56-P1 (10 g, 14 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (10.1 g, 504.3 mmol) was added to trifluoromethanesulfonic anhydride (23.7 g, 84 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 5 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 56D19. (Yield 68%, MS: [M+H] + =734)

[0430] Embodiment 57

[0431]

[0432] Under nitrogen atmosphere, sub4 (10 g, 23.3 mmol), amine 57 (7.9 g, 24.5 mmol), sodium tert-butoxide (2.9 g, 30.3 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. The reaction was terminated after 3 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, 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 13.1 g of compound 57-P1. (Yield 79%, MS: [M+H] + =715)

[0433] Compound 57-P1 (10 g, 14 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (11.2 g, 560.3 mmol) was added to trifluoromethanesulfonic anhydride (39.5 g, 140.1 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, 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 57D30. (Yield 67%, MS: [M+H] + =745)

[0434] Embodiment 58

[0435]

[0436] Under nitrogen atmosphere, sub4 (10 g, 23.3 mmol), amine 58 (8.5 g, 24.5 mmol), sodium tert-butoxide (2.9 g, 30.3 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. The reaction was terminated after 2 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, 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 11.7 g of compound 58-P1. (Yield 68%, MS: [M+H] + =739)

[0437] Compound 58-P1 (10 g, 13.6 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (9.8 g, 487.9 mmol) was added to trifluoromethanesulfonic anhydride (22.9 g, 81.3 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 5 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 6.9 g of compound 58D17. (Yield 67%, MS: [M+H] + =756)

[0438] Embodiment 59

[0439]

[0440] Under nitrogen atmosphere, sub5 (10 g, 28.3 mmol), amine 59 (8.8 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 13.7 g of compound 59-P1. (Yield 79%, MS: [M+H] + =613)

[0441] Compound 59-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 (13.1 g, 653.9 mmol) was added to trifluoromethanesulfonic anhydride (46.1 g, 163.5 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, 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 6.8 g of compound 59D27. (yield 65%, MS: [M+H] + =640)

[0442] Embodiment 60

[0443]

[0444] Under nitrogen atmosphere, sub5 (10 g, 28.3 mmol), amine 60 (11.2 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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 11.8 g of compound 60-P1. (Yield 60%, MS: [M+H] + =695)

[0445] Compound 60-P1 (10 g, 14.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (10.4 g, 518.8 mmol) was added to trifluoromethanesulfonic anhydride (24.4 g, 86.5 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 5 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 60D17. (Yield 61%, MS: [M+H] + =712)

[0446] Embodiment 61

[0447]

[0448] Under nitrogen atmosphere, sub5 (10 g, 28.3 mmol), amine 61 (10.1 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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 12.8 g of compound 61-P1. (Yield 69%, MS: [M+H] + =657)

[0449] Compound 61-P1 (10 g, 15.2 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (11 g, 548.9 mmol) was added to trifluoromethanesulfonic anhydride (25.8 g, 91.5 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 5 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 61D15. (Yield 68%, MS: [M+H] + =672)

[0450] Embodiment 62

[0451]

[0452] Under nitrogen atmosphere, sub5 (10 g, 28.3 mmol), amine 62 (11.6 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 15 g of compound 62-P1. (Yield 75%, MS: [M+H] + =707)

[0453] Compound 62-P1 (10 g, 14.2 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (11.3 g, 566.6 mmol) was added to trifluoromethanesulfonic anhydride (40 g, 141.6 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, 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 7.8 g of compound 62D34. (Yield 74%, MS: [M+H] + =741)

[0454] Embodiment 63

[0455]

[0456] Under nitrogen atmosphere, sub6 (10 g, 23.3 mmol), amine 63 (7.9 g, 24.5 mmol), sodium tert-butoxide (2.9 g, 30.3 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. The reaction was terminated after 3 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, 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 12.3 g of compound 63-P1. (Yield 74%, MS: [M+H] + =715)

[0457] Compound 63-P1 (10 g, 14 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (10.1 g, 504.3 mmol) was added to trifluoromethanesulfonic anhydride (23.7 g, 84 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 5 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 63D19. (Yield 60%, MS: [M+H] + =734)

[0458] Embodiment 64

[0459]

[0460] Under nitrogen atmosphere, sub7 (10 g, 28.3 mmol), amine 64 (11.1 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 12.1 g of compound 64-P1. (Yield 62%, MS: [M+H] + =689)

[0461] Compound 64-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 (10.5 g, 523.4 mmol) was added to trifluoromethanesulfonic anhydride (24.6 g, 87.2 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 5 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 7.7 g of compound 64D17. (Yield 75%, MS: [M+H] + =706)

[0462] Embodiment 65

[0463]

[0464] Under nitrogen atmosphere, sub7 (10 g, 28.3 mmol), amine 65 (10.6 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 10.5 g of compound 65-P1. (Yield 55%, MS: [M+H] + =673)

[0465] Compound 65-P1 (10 g, 14.9 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (10.7 g, 535.8 mmol) was added to trifluoromethanesulfonic anhydride (25.2 g, 89.3 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 5 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 65D15. (Yield 65%, MS: [M+H] + =688)

[0466] Embodiment 66

[0467]

[0468] Under nitrogen atmosphere, sub8 (10 g, 23.3 mmol), amine 66 (9 g, 24.5 mmol), sodium tert-butoxide (2.9 g, 30.3 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. The reaction was terminated after 3 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, 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 12.1 g of compound 66-P1. (Yield 68%, MS: [M+H] + =763)

[0469] Compound 66-P1 (10 g, 13.1 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (10.5 g, 525 mmol) was added to trifluoromethanesulfonic anhydride (37 g, 131.2 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 7.5 g of compound 66D32. (Yield 72%, MS: [M+H] + =795)

[0470] Embodiment 67

[0471]

[0472] Under nitrogen atmosphere, sub9 (10 g, 28.3 mmol), amine 67 (11.1 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 12.1 g of compound 67-P1. (Yield 62%, MS: [M+H] + =689)

[0473] Compound 67-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 (10.5 g, 523.4 mmol) was added to trifluoromethanesulfonic anhydride (24.6 g, 87.2 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 5 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 7.1 g of compound 67D20. (Yield 69%, MS: [M+H] + =709)

[0474] Embodiment 68

[0475]

[0476] Under nitrogen atmosphere, sub9 (10 g, 28.3 mmol), amine 68 (10.3 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 12.8 g of compound 68-P1. (Yield 68%, MS: [M+H] + =663)

[0477] Compound 68-P1 (10 g, 15.1 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (12.1 g, 604.3 mmol) was added to trifluoromethanesulfonic anhydride (42.6 g, 151.1 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, 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 7.7 g of compound 68D33. (yield 73%, MS: [M+H] + =696)

[0478] Embodiment 69

[0479]

[0480] Under nitrogen atmosphere, sub10 (10 g, 23.3 mmol), amine 69 (7.9 g, 24.5 mmol), sodium tert-butoxide (2.9 g, 30.3 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. The reaction was terminated after 3 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, 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 9.3 g of compound 69-P1. (Yield 56%, MS: [M+H] + =715)

[0481] Compound 69-P1 (10 g, 14 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (10.1 g, 504.3 mmol) was added to trifluoromethanesulfonic anhydride (23.7 g, 84 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 5 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 69D20. (Yield 61%, MS: [M+H] + =735)

[0482] Embodiment 70

[0483]

[0484] Under a nitrogen atmosphere, sub11 (10 g, 28.3 mmol), amine 70 (9.9 g, 29.8 mmol), and sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 11.4 g of compound 70-P1. (Yield 62%, MS: [M+H] + =651)

[0485] Compound 70-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 (12.3 g, 615.53 mmol) was added to trifluoromethanesulfonic anhydride (43.4 g, 153.9 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, 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 6.8 g of compound 70D32. (yield 65%, MS: [M+H] + =683)

[0486] Embodiment 71

[0487]

[0488] Under nitrogen atmosphere, sub15 (10 g, 23.3 mmol), amine 71 (8.5 g, 24.5 mmol), sodium tert-butoxide (2.9 g, 30.3 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. The reaction was terminated after 2 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 13.6 g of compound 71-P1. (Yield 79%, MS: [M+H] + =739)

[0489] Compound 71-P1 (10 g, 13.6 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (9.8 g, 487.9 mmol) was added to trifluoromethanesulfonic anhydride (22.9 g, 81.3 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 5 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 7.6 g of compound 71D16. (Yield 74%, MS: [M+H] + =755)

[0490] Embodiment 72

[0491]

[0492] Under nitrogen atmosphere, sub12 (10 g, 28.3 mmol), amine 72 (7.3 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 9.7 g of compound 72-P1. (Yield 61%, MS: [M+H] + =563)

[0493] Compound 72-P1 (10 g, 17.8 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (14.3 g, 712.1 mmol) was added to trifluoromethanesulfonic anhydride (50.2 g, 178 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 72D22. (Yield 61%, MS: [M+H] + =585)

[0494] Embodiment 73

[0495]

[0496] Under a nitrogen atmosphere, sub12 (10 g, 28.3 mmol), amine 73 (12.5 g, 29.8 mmol), and sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 13 g of compound 73-P1. (Yield 62%, MS: [M+H] + =739)

[0497] Compound 73-P1 (10 g, 13.6 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (9.8 g, 487.91 mmol) was added to trifluoromethanesulfonic anhydride (22.9 g, 81.3 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 5 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 7.3 g of compound 73D19. (Yield 71%, MS: [M+H] + =758)

[0498] Embodiment 74

[0499]

[0500] Under nitrogen atmosphere, sub14 (10 g, 28.3 mmol), amine 74 (11.8 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 15.6 g of compound 74-P1. (Yield 77%, MS: [M+H] + =715)

[0501] Compound 74-P1 (10 g, 14 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (11.2 g, 560.2 mmol) was added to trifluoromethanesulfonic anhydride (39.5 g, 140.1 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, 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 7.5 g of compound 74D30. (Yield 72%, MS: [M+H] + =745)

[0502] Embodiment 75

[0503]

[0504] Under nitrogen atmosphere, sub14 (10 g, 28.3 mmol), amine 75 (11.1 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 14.6 g of compound 75-P1. (Yield 75%, MS: [M+H] + =689)

[0505] Compound 75-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 (10.5 g, 523.4 mmol) was added to trifluoromethanesulfonic anhydride (24.6 g, 87.2 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 5 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 75D17. (Yield 64%, MS: [M+H] + =706)

[0506] Embodiment 76

[0507]

[0508] Under nitrogen atmosphere, sub14 (10 g, 28.3 mmol), amine 76 (11.1 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 2 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, 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 12.5 g of compound 76-P1. (Yield 64%, MS: [M+H] + =689)

[0509] Compound 76-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 (10.5 g, 523.4 mmol) was added to trifluoromethanesulfonic anhydride (24.6 g, 87.2 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 5 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 6.4 g of compound 76D19. (Yield 62%, MS: [M+H] + =708)

[0510] Embodiment 77

[0511]

[0512] Under nitrogen atmosphere, sub14 (10 g, 28.3 mmol), amine 77 (9.6 g, 29.8 mmol), sodium tert-butoxide (3.5 g, 36.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. The reaction was terminated after 3 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, 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 11.1 g of compound 77-P1. (Yield 55%, MS: [M+H] + =715)

[0513] Compound 77-P1 (10 g, 14 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (11.2 g, 560.3 mmol) was added to trifluoromethanesulfonic anhydride (39.5 g, 140.1 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, 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 77D31. (Yield 67%, MS: [M+H] + =746)

[0514] [Experimental example]

[0515] Experimental Example 1

[0516] 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.

[0517] On the ITO transparent electrode prepared in this way, as a hole injection layer, the following HI-1 compound was added in the form of The following A-1 compound was p-doped at a concentration of 1.5%. On the hole injection layer, the following HT-1 compound was vacuum-deposited to form a film with a thickness of Next, as a hole transport auxiliary layer, the compound 1 of the present invention is Thermal vacuum evaporation is performed on the film to a thickness of .

[0518] Next, as a light-emitting layer, the compounds represented by the following chemical formulas BH-1 and BD-1 were mixed at a weight ratio of 25:1 and 1:1. Next, as a hole blocking layer, a compound represented by the following chemical formula HB-1 was deposited in an amount of Next, as a layer for simultaneously performing electron transport and electron injection, a compound represented by the following chemical formula ET-1 and a compound represented by the following LiQ were added at a weight ratio of 1:1 and at a weight ratio of On the electron transport and electron injection layers, lithium fluoride (LiF) is deposited in the form of The thickness of the aluminum A cathode is formed by evaporation with a thickness of , thereby manufacturing an organic light-emitting device.

[0519]

[0520] Experimental Examples 2 to 77

[0521] An organic light-emitting device was manufactured by the same method as in Experimental Example 1 except that the compounds described in Table 1 below were used instead of Compound 1.

[0522] Comparative Examples 1 to 6

[0523] An organic light-emitting device was manufactured by the same method as in Experimental Example 1, except that the comparative example compounds described in the following Table 1 were used instead of Compound 1. Compounds C-1 to C-6 in the following Table 1 are shown below.

[0524]

[0525] The organic light-emitting devices manufactured in Experimental Examples 1 to 77 and Comparative Examples 1 to 6 were subjected to a 15 mA / cm 2 The voltage and efficiency were measured when the current was 1.0 0.05 ...

[0526]

Table 1

[0527]

[0528]

[0529]

[0530] As can be confirmed in the above Table 1, it can be confirmed that the organic light-emitting device using the compound of the present invention shows improved effects in terms of driving voltage, efficiency and life compared with the organic light-emitting device using the comparative example compound, and it can be confirmed that the life characteristics of the deuterium-substituted compound are further increased. It is believed that this is because the compound of the present invention contributes to the stability of excitons formed in the light-emitting layer of the organic light-emitting device.

Claims

1. A compound represented by the following chemical formula 1: [Chemical formula 1] In the chemical formula 1, Any one of R is bonded to L1, and the others are independently hydrogen or deuterium, L1 is a single bond, or a substituted or unsubstituted C 6-12 Arylene, L2 and L3 are each independently a single bond, or a substituted or unsubstituted C 6-60 Arylene, Ar1 and Ar2 are each independently substituted or unsubstituted C 6-60 Aryl, or substituted or unsubstituted C 3-60 Aliphatic cyclic group, Dn means n hydrogens are replaced by deuterium. n is an integer greater than or equal to 0.

2. The compound according to claim 1, wherein The chemical formula 1 is represented by any one of the following chemical formulas 1-1 to 1-10: In the chemical formulas 1-1 to 1-10, L1 to L3, Ar1, Ar2 and Dn are the same as defined in claim 1, R1 is each independently hydrogen or deuterium.

3. The compound according to claim 1, wherein L1 is a single bond or a phenylene group, The phenylene group is unsubstituted or substituted with one or more deuteriums.

4. The compound according to claim 1, wherein L1 is a single bond, or is selected from the following groups and any one of their deuterated structures:

5. The compound according to claim 1, wherein L2 and L3 are each independently a single bond, a phenylene group, a naphthalene diyl group or a biphenyl diyl group, The phenylene group, naphthalenediyl group and biphenyldiyl group are each independently unsubstituted or substituted with one or more deuterium groups.

6. The compound according to claim 1, wherein Ar1 and Ar2 are each independently phenyl, biphenyl, terphenyl, naphthyl, naphthylphenyl, phenylnaphthyl, phenanthrenyl, tetrahydronaphthyl, 1,2,3,4-tetrahydro-1,1,4,4-tetramethylnaphthyl or 1,2,3,4-tetrahydro-1,1,4-trimethylnaphthyl, The Ar1 and Ar2 are each independently unsubstituted; or are selected from deuterium, substituted or unsubstituted C 1-4 Alkyl, substituted or unsubstituted C 3-10 The aliphatic ring group is substituted with one or more substituents.

7. The compound according to claim 1, wherein Ar1 is phenyl, naphthyl, tetrahydronaphthyl, 1,2,3,4-tetrahydro-1,1,4,4-tetramethylnaphthyl or 1,2,3,4-tetrahydro-1,1,4-trimethylnaphthyl, Ar2 is phenyl, biphenyl, terphenyl, naphthyl, naphthylphenyl, phenylnaphthyl, phenanthrenyl, tetrahydronaphthyl, 1,2,3,4-tetrahydro-1,1,4,4-tetramethylnaphthyl or 1,2,3,4-tetrahydro-1,1,4-trimethylnaphthyl, wherein the phenyl group is unsubstituted; or substituted by one or more substituents selected from the group consisting of deuterium, methyl group substituted or unsubstituted by deuterium, propyl group (or isopropyl group) substituted or unsubstituted by deuterium, butyl group (or tert-butyl group) substituted or unsubstituted by deuterium, bicycloheptyl group substituted or unsubstituted by deuterium, bicyclooctyl group substituted or unsubstituted by deuterium, and cyclohexyl group substituted or unsubstituted by deuterium, Ar1 and Ar2 are each independently unsubstituted or substituted with one or more deuterium.

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 each compound is substituted by n deuteriums. n is an integer of 1 or more.

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 containing the compound is a hole transport auxiliary layer.

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