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.

Description

Technical Field

[0001] CROSS REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority based on Korean Patent Application No. 10-2023-0108593 filed on August 18, 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] L 1 and L 2 are each independently phenylene or naphthalene diyl,

[0018] The above L 1 and L 2 are each independently unsubstituted or substituted with one or more deuterium,

[0019] Ar 1 is phenyl or naphthyl,

[0020] The above Ar 1 is not substituted, or is substituted with one or more deuterium atoms,

[0021] Among them, L 1 , L 2 and Ar 1 Any one or more of is naphthalenediyl or naphthyl,

[0022] Ar 2 is phenyl, naphthyl, phenylnaphthyl, naphthylphenyl, phenanthryl, or a substituent represented by the following Chemical Formula 2,

[0023] [Chemical formula 2]

[0024]

[0025] In the above chemical formula 2,

[0026] Z 1 To Z 3 Any one of them is phenyl or biphenyl, and the others are independently hydrogen or deuterium, wherein Z 3 Not phenyl,

[0027] R a and R b are each independently hydrogen or deuterium,

[0028] The above Ar 2 is not substituted, or is substituted with one or more deuterium atoms,

[0029] R 1 and R 2 are each independently hydrogen or deuterium,

[0030] a is an integer from 0 to 9,

[0031] b is an integer from 0 to 4,

[0032] Among them, L 1 When it is naphthalene diyl, the following structure is from L1 Excluded:

[0033]

[0034] In the above structure, *1 is the carbon bonded to N, and *2 is the carbon bonded to L. 2 Combined carbon.

[0035] In addition, the present invention provides an organic light-emitting device, which includes: a first electrode, a second electrode arranged opposite to the first electrode, and one or more organic layers arranged between the first electrode and the second electrode, and one or more of the organic layers contains the compound represented by the above chemical formula 1.

[0036] Effects of the Invention

[0037] 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

[0038] 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 .

[0039] 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.

[0040] Explanation of symbols

[0041] 1: Substrate 2: Anode

[0042] 3: Light-emitting layer 4: Cathode

[0043] 5: Hole injection layer 6: Hole transport layer

[0044] 7: Hole transport auxiliary layer 8: Hole blocking layer

[0045] 9: Electron injection and transport layer DETAILED DESCRIPTION

[0046] In the following, the present invention will be described in more detail to help understanding the present invention.

[0047] In this manual, "D" represents a bond to other substituents, and "D" represents deuterium.

[0048] 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 The term "substituted with one or more substituents in an aryl group" may be understood as "substituted with one to the maximum number of replaceable hydrogen atoms" in the present specification. Alternatively, the term "substituted with one or more substituents" may be understood as "substituted with one to five substituents" or "substituted with one or two substituents" in the present specification.

[0049] 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.

[0050]

[0051] 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.

[0052]

[0053] 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.

[0054]

[0055] In this specification, a substituted or unsubstituted silyl group refers to -Si(Z 1 )(Z 2 )(Z 3 ), here, Z 1 , Z 2 and Z 3 Each independently may be 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, Z 1 , Z 2 and Z 3 Each independently may be hydrogen, deuterium, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 1-10 Haloalkyl, substituted or unsubstituted C 1-10 haloalkyl, or substituted or unsubstituted C 6-20 Specific examples of the silyl group include trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, and phenylsilyl, but are not limited thereto.

[0056] In the present specification, specific examples of the boryl group include trimethylboryl, triethylboryl, tert-butyldimethylboryl, triphenylboryl, and phenylboryl, but are not limited thereto.

[0057] In the present specification, as examples of the halogen group, there are fluorine, chlorine, bromine or iodine.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] In addition, examples of the spirocyclic hydrocarbon group include spiro[3.4]octyl and spiro[5.5]undecyl, but are not limited to these.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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 substituents include, but are not limited to, 1,3-dihydroisobenzofuranyl, 2,3-dihydrobenzofuranyl, 1,3-dihydrobenzo[c]thiophenyl, and 2,3-dihydro[b]thiophenyl.

[0070] In the present specification, the aryl group in aralkyl, aralkenyl, alkylaryl, arylamine, and arylsilyl is the same as the examples of the aryl group described above. In the present specification, the alkyl group in aralkyl, alkylaryl, and alkylamine is the same as the examples of the alkyl group described above. In the present specification, the heteroaryl group in heteroarylamine can be applied to the above-mentioned description of the heteroaryl group. In the present specification, the alkenyl group in aralkenyl is the same as the examples of the alkenyl group described above. In the present specification, the arylene group is a divalent group, and the above-mentioned description of the aryl group can be applied. In the present specification, the heteroarylene group is a divalent group, and the above-mentioned description of the heteroaryl group can be applied. In the present specification, the hydrocarbon ring is not a monovalent group, but is formed by combining two substituents, and the above-mentioned description of the aryl group or the cycloalkyl group can be applied. In the present specification, the heterocycle is not a monovalent group, but is formed by combining two substituents, and the above-mentioned description of the heterocyclic group can be applied.

[0071] 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.

[0072] In addition, "unsubstituted or substituted with deuterium" or "substituted with deuterium or unsubstituted" means "unsubstituted or substituted with 1 to 9 deuteriums in 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 phenanthrenyl" when considering that the maximum number of hydrogens that can be substituted with deuterium in the phenanthrenyl structure is 9.

[0073] In addition, the meaning of "deuterated structure" refers to compounds, divalent linking groups or monovalent substituents including all structures in which at least one hydrogen is replaced by deuterium. As an example, the deuterated structure of phenyl shown below can be understood as referring to all monovalent substituents in which at least one hydrogen that can be replaced in phenyl is replaced by deuterium.

[0074]

[0075] In addition, the "deuterium substitution rate" or "deuteration degree" of a compound refers to the value calculated as a percentage of the ratio of the number of deuterium substituted in the compound to the total number of hydrogens that can exist (the sum of the number of hydrogens that can be replaced by deuterium in the compound and the number of deuteriums replaced). Therefore, the "deuterium substitution rate" or "deuteration degree" of a compound as "K%" means that K% of the hydrogens that can be replaced by deuterium in the compound are replaced by deuterium.

[0076] 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.

[0077] (Compound)

[0078] The present invention provides a compound represented by the above Chemical Formula 1.

[0079] Preferably, the above Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-3:

[0080] [Chemical formula 1-1]

[0081]

[0082] [Chemical formula 1-2]

[0083]

[0084] [Chemical formula 1-3]

[0085]

[0086] In the above chemical formulas 1-1 to 1-3,

[0087] L 1 , L 2 ,Ar 1 ,Ar 2 , R 1 , R 2 , a and b are the same as defined above.

[0088] Preferably, L 1 and L 2 are phenylene; or

[0089] L 1 and L 2 Any one of them is phenylene, and the other one is naphthalene diyl; or

[0090] L 1 and L 2 All of them are naphthalene diyl.

[0091] For example, L 1 and L 2 Each independently may be any one selected from the following groups and their deuterated structures:

[0092]

[0093] On the other hand, Ar 1 is phenyl or naphthyl, the above Ar 1 Unsubstituted, or substituted with one or more deuterium.

[0094] In addition, in the above chemical formula 1, L 1 , L 2 and Ar 1 Any one or more of is naphthalene diyl or naphthyl. As an example, it can be L 1 and L 2 All are phenylene, Ar 1 is naphthyl; it can also be L 1 and L 2 Any one of them is naphthalene diyl, the other is phenylene, Ar 1 Phenyl; L 1 and L 2 All are naphthalene diyl, Ar 1 It is phenyl.

[0095] Preferably, it can be L 1 and L 2 All are phenylene, Ar 1 is naphthyl; or

[0096] L 1 is phenylene, L 2is naphthalene diyl, Ar 1 is phenyl; or

[0097] L 1 is naphthalene diyl, L 2 is phenylene, Ar 1 It is phenyl.

[0098] In addition, preferably, it can be L 1 is phenylene, L 2 is naphthalene diyl, Ar 1 is naphthyl; or

[0099] L 1 is naphthalene diyl, L 2 is phenylene, Ar 1 is naphthyl; or

[0100] L 1 and L 2 All are naphthalene diyl, Ar 1 It is phenyl.

[0101] Preferably, the substituent -L 1 -L 2 -Ar 1 is any one selected from the following groups and their deuterated structures:

[0102]

[0103]

[0104] On the other hand, Ar 2 is phenyl, naphthyl, phenylnaphthyl, naphthylphenyl, phenanthryl, or a substituent represented by the following Chemical Formula 2:

[0105] [Chemical formula 2]

[0106]

[0107] In the above chemical formula 2,

[0108] Z 1 To Z 3 , R a and R b Same definition as above.

[0109] Preferably, Ar 2 is any one selected from the following groups and their deuterated structures:

[0110]

[0111] In Formula 1, a and b each independently represent R 1 and R2 The number of, a is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, b is 0, 1, 2, 3 or 4.

[0112] In addition, the compound represented by the above Chemical Formula 1 may not contain deuterium, or may contain one or more deuterium.

[0113] 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, 35% or more, 37% 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.

[0114] 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, or 10 or more and 50 or less, 45 or less, 43 or less, 40 or less, 39 or less, 38 or less, 37 or less, 36 or less, 35 or less, 34 or less, 33 or less, 32 or less, 31 or less, or 30 or less deuteriums.

[0115] At this time, when the number of deuterium substitutions in the compound represented by the above chemical formula 1 is desired, it can be represented by the following chemical formula 1D:

[0116] [Chemical formula 1D]

[0117]

[0118] In the above chemical formula 1D,

[0119] Dn means n hydrogens are replaced by deuterium.

[0120] Here, n is an integer greater than 0,

[0121] L 1 ', L 2 '、Ar 1 '、Ar 2 '、R 1 ' and R 2 ' respectively represent L not substituted by deuterium 1 , L 2 ,Ar 1 ,Ar 2 , R 1 and R 2 Substituent.

[0122] Representative examples of the compound represented by the above Chemical Formula 1 are shown below:

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144] Among the above compounds,

[0145] Dn means that each compound is substituted by n deuteriums.

[0146] n is an integer greater than or equal to 0.

[0147] As an example, n is an integer from 0 to 40, or from 0 to 39, or from 0 to 38, or from 0 to 37.

[0148] 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 similar methods.

[0149] [Reaction 1]

[0150]

[0151] In the above reaction formula 1, L 1 , L 2 ,Ar 1 ,Ar 2 , R 1 , R 2 , a and b are the same as defined in the above Chemical Formula 1, Y is a halogen, preferably, Y is bromine or chlorine.

[0152] The above reaction is an amine substitution reaction, preferably carried out in the presence of a palladium catalyst and a base, and the reactive group used in the above 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.

[0153] (Organic Light Emitting Devices)

[0154] 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.

[0155] 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.

[0156] 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.

[0157] 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, an electron 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.

[0158] In addition, the organic light-emitting device according to the present invention may be an organic light-emitting device having a structure (normal type) in which an anode, one or more organic layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light-emitting device according to the present invention may be an organic light-emitting device having an inverse structure (inverted type) in which a cathode, one or more organic layers, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light-emitting device according to one embodiment of the present invention is shown in FIG. Figure 1 and 2 .

[0159] 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.

[0160] 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.

[0161] 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.

[0162] 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.

[0163] 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.

[0164] 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.

[0165] 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.

[0166] As the above-mentioned anode material, in order to enable holes to be smoothly injected into the organic layer, it is preferred to use a material with a large work function. 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); ZnO:Al or SnO 2 : Combinations of metals such as Sb and oxides; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole and polyaniline, etc., but are not limited to these.

[0167] The cathode material is preferably a material with a small work function in order to facilitate electron injection into the organic layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; LiF / Al or LiO 2 / Al and other multi-layer structure materials, but not limited to these.

[0168] 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.

[0169] 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.

[0170] 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.

[0171] 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 transported from the hole transport layer to the light emitting layer, while excitons are confined in the light emitting layer to prevent light leakage, and the organic light emitting device has an excellent luminous efficiency. Preferably, the compound represented by the above chemical formula 1 can be used as a hole transport auxiliary material.

[0172] The above-mentioned 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. As a specific example, there is 8-hydroxy-quinoline aluminum complex (Alq 3); carbazole compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; benzo Compounds of the oxazole, benzothiazole and benzimidazole series; poly(p-phenylene vinylene) (PPV) series polymers; spiro compounds; polyfluorene, rubrene, etc., but are not limited to these.

[0173] 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.

[0174] 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.

[0175] 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.

[0176] 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 both an electron transport layer and an electron injection layer, and is formed on the light-emitting layer or the hole blocking layer. Such an electron injection and transport material is a material that can well receive electrons from the cathode and transfer them to the light-emitting layer, and a material with a high electron mobility is suitable. As such an electron injection and transport layer material, a compound represented by the above chemical formula 1 can be used. As other examples of electron injection and transport materials, there are Al complexes of 8-hydroxyquinoline, Alq complexes, 3 The invention can be used in combination 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.

[0177] 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 the electron injection and transport material included in the electron transport layer may be the electron injection and transport material. In addition, the electron injection layer is formed on the electron transport layer, and the electron injection material included in the electron injection layer may be LiF, NaCl, CsF, Li 2 O, BaO, fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, Azoles, Oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenyl methane, anthrone, etc. and their derivatives, metal coordination compounds and nitrogen-containing five-membered ring derivatives, etc.

[0178] 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.

[0179] 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.

[0180] 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.

[0181] 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.

[0182] [Example]

[0183] Example 1

[0184]

[0185] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 1 (27.1 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 5 hours, the reaction was completed, 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, and 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 compound 1 (28.4 g).

[0186] (yield 73%, MS: [M+H] + =751)

[0187] Example 2

[0188]

[0189] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 2 (23 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 2 (21 g).

[0190] (yield 60%, MS: [M+H] + =675)

[0191] Example 3

[0192]

[0193] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 3 (20.3 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 3 (25.3 g).

[0194] (yield 78%, MS: [M+H] + =625)

[0195] Example 4

[0196]

[0197] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 4 (27.1 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 4 (30.4 g).

[0198] (yield 78%, MS: [M+H] + =751)

[0199] Example 5

[0200]

[0201] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 5 (27.1 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 5 (29.6 g).

[0202] (yield 76%, MS: [M+H] + =751)

[0203] Example 6

[0204]

[0205] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 6 (23 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 6 (27 g).

[0206] (yield 77%, [M+H] + =675)

[0207] Example 7

[0208]

[0209] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 7 (23 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 7 (22.8 g).

[0210] (yield 65%, MS: [M+H] + =675)

[0211] Example 8

[0212]

[0213] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 8 (27.1 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 8 (28 g).

[0214] (yield 72%, MS: [M+H] + =751)

[0215] Example 9

[0216]

[0217] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 9 (28.6 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 9 (28.2 g).

[0218] (yield 70%, MS: [M+H] + =777)

[0219] Example 10

[0220]

[0221] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 10 (27.1 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 10 (26.9 g).

[0222] (yield 69%, MS: [M+H] + =751)

[0223] Embodiment 11

[0224]

[0225] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 11 (20.3 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 11 (23.3 g).

[0226] (yield 72%, MS: [M+H] + =625)

[0227] Example 12

[0228]

[0229] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 12 (23 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 12 (27.3 g).

[0230] (yield 78%, MS: [M+H] + =675)

[0231] Embodiment 13

[0232]

[0233] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 13 (24.4 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 13 (23.3 g).

[0234] (yield 64%, MS: [M+H] + =701)

[0235] Embodiment 14

[0236]

[0237] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 14 (23 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 14 (25.9 g).

[0238] (yield 74%, MS: [M+H] + =675)

[0239] Embodiment 15

[0240]

[0241] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 15 (23 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 15 (27 g).

[0242] (yield 77%, MS: [M+H] + =675)

[0243] Example 16

[0244]

[0245] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 16 (27.1 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 16 (26.5 g).

[0246] (yield 68%, MS: [M+H] + =751)

[0247] Embodiment 17

[0248]

[0249] Under nitrogen atmosphere, sub2 (15 g, 51.9 mmol), amine 17 (27.1 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 17 (25.7 g).

[0250] (yield 66%, MS: [M+H] + =751)

[0251] Embodiment 18

[0252]

[0253] Under nitrogen atmosphere, sub2 (15 g, 51.9 mmol), amine 18 (28.6 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 18 (31 g).

[0254] (yield 77%, MS: [M+H] + =777)

[0255] Embodiment 19

[0256]

[0257] Under nitrogen atmosphere, sub2 (15 g, 51.9 mmol), amine 19 (23 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 19 (26.3 g).

[0258] (yield 75%, MS: [M+H] + =675)

[0259] Embodiment 20

[0260]

[0261] Under nitrogen atmosphere, sub2 (15 g, 51.9 mmol), amine 20 (27.1 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 20 (28 g).

[0262] (yield 72%, MS: [M+H] + =751)

[0263] Embodiment 21

[0264]

[0265] Under nitrogen atmosphere, sub2 (15 g, 51.9 mmol), amine 21 (23 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 21 (28 g).

[0266] (yield 80%, MS: [M+H] + =675)

[0267] Embodiment 22

[0268]

[0269] Under nitrogen atmosphere, sub2 (15 g, 51.9 mmol), amine 22 (20.3 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, 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 compound 22 (25.6 g).

[0270] (yield 79%, MS: [M+H] + =625)

[0271] Embodiment 23

[0272]

[0273] Under nitrogen atmosphere, sub2 (15 g, 51.9 mmol), amine 23 (27.1 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 23 (30.8 g).

[0274] (yield 79%, MS: [M+H] + =751)

[0275] Embodiment 24

[0276]

[0277] Under nitrogen atmosphere, sub2 (15 g, 51.9 mmol), amine 24 (27.1 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 24 (28.4 g).

[0278] (yield 73%, MS: [M+H] + =751)

[0279] Embodiment 25

[0280]

[0281] Under nitrogen atmosphere, sub2 (15 g, 51.9 mmol), amine 25 (27.1 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 25 (29.6 g).

[0282] (yield 76%, MS: [M+H] + =751)

[0283] Embodiment 26

[0284]

[0285] Under nitrogen atmosphere, sub3 (15 g, 51.9 mmol), amine 26 (28.6 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 26 (24.2 g).

[0286] (yield 60%, MS: [M+H] + =777)

[0287] Embodiment 27

[0288]

[0289] Under nitrogen atmosphere, sub3 (15 g, 51.9 mmol), amine 27 (24.4 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 27 (21.8 g).

[0290] (yield 60%, MS: [M+H] + =701)

[0291] Embodiment 28

[0292]

[0293] Under nitrogen atmosphere, sub3 (15 g, 51.9 mmol), amine 28 (24.4 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 28 (22.5 g).

[0294] (yield 62%, MS: [M+H] + =701)

[0295] Embodiment 29

[0296]

[0297] Under nitrogen atmosphere, sub3 (15 g, 51.9 mmol), amine 29 (23 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 29 (22.1 g).

[0298] (yield 63%, MS: [M+H] + =675)

[0299] Embodiment 30

[0300]

[0301] Under nitrogen atmosphere, sub3 (15 g, 51.9 mmol), amine 30 (23 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 30 (26.6 g).

[0302] (yield 76%, MS: [M+H] + =675)

[0303] Embodiment 31

[0304]

[0305] Under nitrogen atmosphere, sub3 (15 g, 51.9 mmol), amine 31 (20.3 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 31 (22 g).

[0306] (yield 68%, MS: [M+H] + =625)

[0307] Embodiment 32

[0308]

[0309] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 32 (20.3 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 32_P1 (22.7 g).

[0310] (yield 70%, MS: [M+H] + =625)

[0311] Compound 32_P1 (10 g, 16 mmol) was added to 1,2,4-trichlorobenzene (1,2,4-trichlor obenzene) (200 ml) and stirred at room temperature. In another container, deuterium oxide (11.6 g, 577.1 mmol) was added to trifluoromethanesulfonic anhydride (27.1 g, 96.2 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 temperature was maintained and stirred after heating to 140°C. 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 Compound 32 (D14, 6.9 g).

[0312] (yield 67%, MS: [M+H] + =639)

[0313] Embodiment 33

[0314]

[0315] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 33 (23 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 33_P1 (23.8 g).

[0316] (yield 68%, MS: [M+H] + =675)

[0317] Compound 33_P1 (10 g, 14.8 mmol) was added to 1,2,4-trichlorobenzene (200 ml) and stirred at room temperature. In another container, heavy water (11.9 g, 593.6 mmol) was added to trifluoromethanesulfonic anhydride (41.9 g, 148.4 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 maintained and stirred after heating to 140°C. 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 compound 33 (D30, 7.1 g).

[0318] (yield 68%, MS: [M+H] + =705)

[0319] Embodiment 34

[0320]

[0321] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 34 (24.4 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 34_P1 (28.7 g).

[0322] (yield 79%, MS: [M+H] + =701)

[0323] Compound 34_P1 (10 g, 14.3 mmol) was added to 1,2,4-trichlorobenzene (200 ml) and stirred at room temperature. In another container, heavy water (11.4 g, 571.5 mmol) was added to trifluoromethanesulfonic anhydride (40.3 g, 142.9 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 compound 34 (D35, 6.6 g).

[0324] (yield 63%, MS: [M+H] + =736)

[0325] Embodiment 35

[0326]

[0327] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 35 (20.3 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 35_P1 (23.3 g).

[0328] (yield 72%, MS: [M+H] + =625)

[0329] Compound 35_P1 (10 g, 16 mmol) was added to 1,2,4-trichlorobenzene (200 ml) and stirred at room temperature. In another container, heavy water (11.6 g, 577.1 mmol) was added to trifluoromethanesulfonic anhydride (27.1 g, 96.2 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 compound 35 (D23, 6.6 g).

[0330] (yield 64%, MS: [M+H] + =648)

[0331] Embodiment 36

[0332]

[0333] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 36 (20.3 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 36_P1 (25.6 g).

[0334] (yield 79%, MS: [M+H] + =625)

[0335] Compound 36_P1 (10 g, 16 mmol) was added to 1,2,4-trichlorobenzene (200 ml) and stirred at room temperature. In another container, heavy water (11.6 g, 577.1 mmol) was added to trifluoromethanesulfonic anhydride (27.1 g, 96.2 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 compound 36 (D16, 5.9 g).

[0336] (yield 58%, MS: [M+H] + =641)

[0337] Embodiment 37

[0338]

[0339] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 37 (27.1 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 37_P1 (28 g).

[0340] (yield 72%, MS: [M+H] + =751)

[0341] Compound 37_P1 (10 g, 13.3 mmol) was added to 1,2,4-trichlorobenzene (200 ml) and stirred at room temperature. In another container, heavy water (9.6 g, 480 mmol) was added to trifluoromethanesulfonic anhydride (22.6 g, 80 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 maintained and stirred after heating to 140°C. 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 compound 37 (D21, 6.4 g).

[0342] (yield 62%, MS: [M+H] + =772)

[0343] Embodiment 38

[0344]

[0345] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 38 (27.1 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 38_P1 (23.8 g).

[0346] (yield 61%, MS: [M+H] + =751)

[0347] Compound 38_P1 (10 g, 13.3 mmol) was added to 1,2,4-trichlorobenzene (200 ml) and stirred at room temperature. In another container, heavy water (10.7 g, 533.4 mmol) was added to trifluoromethanesulfonic anhydride (37.6 g, 133.3 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 maintained and stirred after heating to 140°C. 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 compound 38 (D34, 7.3 g).

[0348] (yield 70%, MS: [M+H] + =785)

[0349] Embodiment 39

[0350]

[0351] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 39 (20.3 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 39_P1 (24.6 g).

[0352] (yield 76%, MS: [M+H] + =625)

[0353] Compound 39_P1 (10 g, 16 mmol) was added to 1,2,4-trichlorobenzene (200 ml) and stirred at room temperature. In another container, heavy water (11.6 g, 577.1 mmol) was added to trifluoromethanesulfonic anhydride (27.1 g, 96.2 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 maintained and stirred after heating to 140°C. 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 compound 39 (D22, 6.8 g).

[0354] (yield 66%, MS: [M+H] + =647)

[0355] Embodiment 40

[0356]

[0357] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 40 (24.4 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 40_P1 (24.4 g).

[0358] (yield 67%, MS: [M+H] + =701)

[0359] Compound 40_P1 (10 g, 14.3 mmol) was added to 1,2,4-trichlorobenzene (200 ml) and stirred at room temperature. In another container, heavy water (10.3 g, 514.4 mmol) was added to trifluoromethanesulfonic anhydride (24.2 g, 85.7 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was maintained and stirred after heating to 140°C. 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 compound 40 (D21, 5.7 g).

[0360] (yield 55%, MS: [M+H] + =722)

[0361] Embodiment 41

[0362]

[0363] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 41 (28.6 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 5 hours, the reaction was completed, 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 compound 41_P1 (30.6 g).

[0364] (yield 76%, MS: [M+H] + =777)

[0365] Compound 41_P1 (10 g, 12.9 mmol) was added to 1,2,4-trichlorobenzene (200 ml) and stirred at room temperature. In another container, heavy water (9.3 g, 463.9 mmol) was added to trifluoromethanesulfonic anhydride (21.8 g, 77.3 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 maintained and stirred after heating to 140°C. 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 compound 41 (D24, 6.4 g).

[0366] (yield 62%, MS: [M+H] + =801)

[0367] Embodiment 42

[0368]

[0369] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 42 (20.3 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 42_P1 (25.3 g).

[0370] (yield 78%, MS: [M+H] + =625)

[0371] Compound 42_P1 (10 g, 16 mmol) was added to 1,2,4-trichlorobenzene (200 ml) and stirred at room temperature. In another container, heavy water (12.8 g, 641.2 mmol) was added to trifluoromethanesulfonic anhydride (45.2 g, 160.3 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 maintained and stirred after heating to 140°C. 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 compound 42 (D29, 5.4 g).

[0372] (yield 52%, MS: [M+H] + =654)

[0373] Embodiment 43

[0374]

[0375] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 43 (25.7 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 5 hours, the reaction was completed, 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 compound 43_P1 (25.6 g).

[0376] (yield 68%, MS: [M+H] + =725)

[0377] Compound 43_P1 (10 g, 13.8 mmol) was added to 1,2,4-trichlorobenzene (200 ml) and stirred at room temperature. In another container, heavy water (10 g, 497.3 mmol) was added to trifluoromethanesulfonic anhydride (23.4 g, 82.9 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 maintained and stirred after heating to 140°C. 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 compound 43 (D21, 7 g).

[0378] (yield 68%, MS: [M+H] + =746)

[0379] Embodiment 44

[0380]

[0381] Under nitrogen atmosphere, sub1 (15 g, 51.9 mmol), amine 44 (25.7 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 5 hours, the reaction was completed, 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 compound 44_P1 (29 g).

[0382] (yield 77%, MS: [M+H] + =725)

[0383] Compound 44_P1 (10 g, 13.3 mmol) was added to 1,2,4-trichlorobenzene (200 ml) and stirred at room temperature. In another container, heavy water (10.7 g, 533.4 mmol) was added to trifluoromethanesulfonic anhydride (37.6 g, 133.3 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 maintained and stirred after heating to 140°C. 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 compound 44 (D34, 6.5 g).

[0384] (yield 62%, MS: [M+H] + =785)

[0385] Embodiment 45

[0386]

[0387] Under nitrogen atmosphere, sub2 (15 g, 51.9 mmol), amine 45 (28.6 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After 5 hours, the reaction was completed, 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 compound 45_P1 (25.4 g).

[0388] (yield 63%, MS: [M+H] + =777)

[0389] Compound 45_P1 (10 g, 12.9 mmol) was added to 1,2,4-trichlorobenzene (200 ml) and stirred at room temperature. In another container, heavy water (9.3 g, 463.9 mmol) was added to trifluoromethanesulfonic anhydride (21.8 g, 77.3 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 maintained and stirred after heating to 140°C. 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 compound 45 (D24, 7.2 g).

[0390] (yield 70%, MS: [M+H] + =801)

[0391] Embodiment 46

[0392]

[0393] Under nitrogen atmosphere, sub2 (15 g, 51.9 mmol), amine 46 (28.6 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After 5 hours, the reaction was completed, 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 compound 46_P1 (28.2 g).

[0394] (yield 70%, MS: [M+H] + =777)

[0395] Compound 46_P1 (10 g, 12.9 mmol) was added to 1,2,4-trichlorobenzene (200 ml) and stirred at room temperature. In another container, heavy water (10.3 g, 515.5 mmol) was added to trifluoromethanesulfonic anhydride (36.4 g, 128.9 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 maintained and stirred after heating to 140°C. 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 compound 46 (D36, 5.5 g).

[0396] (yield 53%, MS: [M+H] + =813)

[0397] Embodiment 47

[0398]

[0399] Under nitrogen atmosphere, sub2 (15 g, 51.9 mmol), amine 47 (28.6 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 47_P1 (27.8 g).

[0400] (yield 69%, MS: [M+H] + =777)

[0401] Compound 47_P1 (10 g, 12.9 mmol) was added to 1,2,4-trichlorobenzene (200 ml) and stirred at room temperature. In another container, heavy water (9.3 g, 463.9 mmol) was added to trifluoromethanesulfonic anhydride (21.8 g, 77.3 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 maintained and stirred after heating to 140°C. 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 compound 47 (D18, 5.8 g).

[0402] (yield 57%, MS: [M+H] + =795)

[0403] Embodiment 48

[0404]

[0405] Under nitrogen atmosphere, sub2 (15 g, 51.9 mmol), amine 48 (24.4 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After 5 hours, the reaction was completed, 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 compound 48_P1 (29.1 g).

[0406] (yield 80%, MS: [M+H] + =701)

[0407] Compound 48_P1 (10 g, 14.3 mmol) was added to 1,2,4-trichlorobenzene (200 ml) and stirred at room temperature. In another container, heavy water (10.3 g, 514.4 mmol) was added to trifluoromethanesulfonic anhydride (24.2 g, 85.7 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140°C, and the temperature was maintained and stirred. After reacting for 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 compound 48 (D20, 5.7 g).

[0408] (yield 55%, MS: [M+H] + =721)

[0409] Embodiment 49

[0410]

[0411] Under nitrogen atmosphere, sub2 (15 g, 51.9 mmol), amine 49 (23 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 49_P1 (23.8 g).

[0412] (yield 68%, MS: [M+H] + =675)

[0413] Compound 49_P1 (10 g, 14.8 mmol) was added to 1,2,4-trichlorobenzene (200 ml) and stirred at room temperature. In another container, heavy water (11.9 g, 593.6 mmol) was added to trifluoromethanesulfonic anhydride (41.9 g, 148.4 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 maintained and stirred after heating to 140°C. 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 compound 49 (D32, 6.6 g).

[0414] (yield 63%, MS: [M+H] + =707)

[0415] Embodiment 50

[0416]

[0417] Under nitrogen atmosphere, sub2 (15 g, 51.9 mmol), amine 50 (27.1 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 50_P1 (27.7 g).

[0418] (yield 71%, MS: [M+H] + =751)

[0419] Compound 50_P1 (10 g, 13.3 mmol) was added to 1,2,4-trichlorobenzene (200 ml) and stirred at room temperature. In another container, heavy water (9.6 g, 480 mmol) was added to trifluoromethanesulfonic anhydride (22.6 g, 80 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 maintained and stirred after heating to 140°C. 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 compound 50 (D24, 6 g).

[0420] (yield 58%, MS: [M+H] + =775)

[0421] Embodiment 51

[0422]

[0423] Under nitrogen atmosphere, sub2 (15 g, 51.9 mmol), amine 51 (20.3 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After 5 hours, the reaction was completed, 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 compound 51_P1 (20.7 g).

[0424] (yield 64%, MS: [M+H] + =625)

[0425] Compound 51_P1 (10 g, 16 mmol) was added to 1,2,4-trichlorobenzene (200 ml) and stirred at room temperature. In another container, heavy water (12.8 g, 641.2 mmol) was added to trifluoromethanesulfonic anhydride (45.2 g, 160.3 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 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 compound 51 (D29, 6.2 g).

[0426] (yield 59%, MS: [M+H] + =654)

[0427] Embodiment 52

[0428]

[0429] Under nitrogen atmosphere, sub2 (15 g, 51.9 mmol), amine 52 (23 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After 5 hours, the reaction was completed, 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 compound 52_P1 (27.7 g).

[0430] (yield 79%, MS: [M+H] + =675)

[0431] Compound 52_P1 (10 g, 14.8 mmol) was added to 1,2,4-trichlorobenzene (200 ml) 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 compound 52 (D20, 7 g).

[0432] (yield 68%, MS: [M+H] + =695)

[0433] Embodiment 53

[0434]

[0435] Under nitrogen atmosphere, sub3 (15 g, 51.9 mmol), amine 53 (28.6 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 53_P1 (25 g).

[0436] (yield 62%, MS: [M+H] + =777)

[0437] Compound 53_P1 (10 g, 12.9 mmol) was added to 1,2,4-trichlorobenzene (200 ml) and stirred at room temperature. In another container, heavy water (10.3 g, 515.5 mmol) was added to trifluoromethanesulfonic anhydride (36.4 g, 128.9 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 compound 53 (D36, 7 g).

[0438] (yield 67%, MS: [M+H] + =813)

[0439] Embodiment 54

[0440]

[0441] Under nitrogen atmosphere, sub3 (15 g, 51.9 mmol), amine 54 (23 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 54_P1 (26.6 g).

[0442] (yield 76%, MS: [M+H] + =675)

[0443] Compound 54_P1 (10 g, 14.8 mmol) was added to 1,2,4-trichlorobenzene (200 ml) 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 compound 54 (D23, 6.8 g).

[0444] (yield 66%, MS: [M+H] + =698)

[0445] Embodiment 55

[0446]

[0447] Under nitrogen atmosphere, sub3 (15 g, 51.9 mmol), amine 55 (27.1 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 55_P1 (23.8 g).

[0448] (yield 61%, MS: [M+H] + =751)

[0449] Compound 55_P1 (10 g, 13.3 mmol) was added to 1,2,4-trichlorobenzene (200 ml) and stirred at room temperature. In another container, heavy water (9.6 g, 480 mmol) was added to trifluoromethanesulfonic anhydride (22.6 g, 80 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 compound 55 (D21, 6.3 g).

[0450] (yield 61%, MS: [M+H] + =772)

[0451] Embodiment 56

[0452]

[0453] Under nitrogen atmosphere, sub3 (15 g, 51.9 mmol), amine 56 (20.3 g, 54.5 mmol), sodium tert-butoxide (7.5 g, 77.9 mmol) were added to xylene (300 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. The reaction was completed after 5 hours, cooled to room temperature, and the solvent was removed by decompression. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 56_P1 (21.1 g).

[0454] (yield 65%, MS: [M+H] + =625)

[0455] Compound 56_P1 (10 g, 16 mmol) was added to 1,2,4-trichlorobenzene (200 ml) and stirred at room temperature. In another container, heavy water (12.8 g, 641.2 mmol) was added to trifluoromethanesulfonic anhydride (45.2 g, 160.3 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 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 compound 56 (D29, 5.3 g).

[0456] (yield 51%, MS: [M+H] + =654)

[0457] [Experimental example]

[0458] Experimental Example 1

[0459] ITO (Indium Tin Oxide) 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.

[0460] 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 Example 1 was Next, as a light-emitting layer, the compounds represented by the following chemical formulas BH-1 and BD-1 were deposited at a weight ratio of 25:1 and 1:1. Vacuum evaporation is performed on the film to a thickness of .

[0461] Next, as a hole blocking layer, a compound represented by the following chemical formula HB-1 was prepared in the following manner: Next, as a layer for simultaneous electron injection and electron transport, 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 injection and transport layer, 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.

[0462]

[0463] Experimental Examples 2 to 56

[0464] 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.

[0465] Comparative Examples 1 to 8

[0466] 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. Compounds C-1 to C-8 in Table 1 below are as follows.

[0467]

[0468] The organic light-emitting devices manufactured in Experimental Examples 1 to 56 and Comparative Examples 1 to 8 were subjected to a 15 mA / cm 2 The voltage and efficiency were measured when the current was 1.0 0.05 ...

[0469]

Table 1

[0470]

[0471]

[0472] 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. 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, L1 and L2 are each independently phenylene or naphthalene diyl, The L1 and L2 are each independently unsubstituted or substituted with one or more deuteriums, Ar1 is phenyl or naphthyl, The Ar1 is unsubstituted or substituted with one or more deuteriums, in, Any one or more of L1, L2 and Ar1 is naphthalenediyl or naphthyl, Ar2 is phenyl, naphthyl, phenylnaphthyl, naphthylphenyl, phenanthryl, or a substituent represented by the following chemical formula 2, [Chemical formula 2] In the chemical formula 2, Any one of Z1 to Z3 is phenyl or biphenyl, and the others are each independently hydrogen or deuterium, wherein Z3 is not phenyl, R a and R b are each independently hydrogen or deuterium, The Ar2 is unsubstituted or substituted with one or more deuteriums, R1 and R2 are each independently hydrogen or deuterium, a is an integer from 0 to 9, b is an integer from 0 to 4, When L1 is naphthalene diyl, the following structures are excluded from L1: In the above structure, *1 is the carbon bonded to N, and *2 is the carbon bonded to L2.

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 1-3: [Chemical formula 1-1] [Chemical formula 1-2] [Chemical formula 1-3] In the chemical formulas 1-1 to 1-3, L1, L2, Ar1, Ar2, R1, R2, a and b are the same as defined in claim 1.

3. The compound according to claim 1, wherein L1 and L2 are both phenylene; or Either one of L1 and L2 is phenylene, and the other one is naphthalene diyl; or L1 and L2 are both naphthalene diyl.

4. The compound according to claim 1, wherein L1 and L2 are both phenylene, and Ar1 is naphthyl; or L1 is phenylene, L2 is naphthalene diyl, and Ar1 is phenyl; or L1 is naphthalenediyl, L2 is phenylene, and Ar1 is phenyl.

5. The compound according to claim 1, wherein L1 is phenylene, L2 is naphthalenediyl, and Ar1 is naphthyl; or L1 is naphthalenediyl, L2 is phenylene, and Ar1 is naphthyl; or L1 and L2 are both naphthalene diyl, and Ar1 is phenyl.

6. The compound according to claim 1, wherein The substituent -L1-L2-Ar1 is any one selected from the following groups and their deuterated structures:

7. The compound according to claim 1, wherein Ar2 is any one selected from the following groups and their deuterated structures:

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 greater than or equal to 0.

9. An organic light emitting device, wherein: include: 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 light-emitting layer.

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