Novel compound and organic light-emitting device using same

Abstract

The invention provides a novel compound and an organic light-emitting device using the same.

Description

Technical Field

[0001] Cross-references to related applications

[0002] This application claims priority based on Korean Patent Application No. 10-2022-0133501 filed on October 17, 2022 and Korean Patent Application No. 10-2023-0138735 filed on October 17, 2023, and incorporates all the contents disclosed in the documents of the Korean patent applications as part of this specification.

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

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

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

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

[0007] Prior art literature

[0008] Patent Document 1: Korean Patent Publication No. 10-2000-0051826 Summary of the invention

[0009] Technical issues

[0010] The present invention relates to novel compounds and organic light-emitting devices comprising the same.

[0011] Solution to the problem

[0012] The present invention provides a compound represented by the following Chemical Formula 1:

[0013] [Chemical formula 1]

[0014]

[0015] In the above chemical formula 1,

[0016] R 1 , R 2 , R 4 To R 8 and R 10 To R 14 Any one of them and L 1 combined, the rest are each independently hydrogen or deuterium,

[0017] R 3 and R 9 are each independently hydrogen or deuterium,

[0018] L 1 To L 3 are each independently a single bond; substituted or unsubstituted C 6-60 or a substituted or unsubstituted C containing any one or more heteroatoms selected from N, O and S 2-60 Heteroarylene,

[0019] Ar 1 and Ar 2 are each independently substituted or unsubstituted C 6-60 Aryl; or a substituted or unsubstituted C containing any one or more heteroatoms selected from N, O and S 2-60 Heteroaryl,

[0020] However, L is not included 2 and L 3 All are single bonds and Ar 1 and Ar 2 These are all the cases of phenyl.

[0021] In addition, the present invention provides an organic light-emitting device, comprising: a first electrode, a second electrode arranged opposite to the first electrode, and one or more organic layers arranged between the first electrode and the second electrode, wherein one or more of the organic layers contains a compound represented by the above chemical formula 1.

[0022] Effects of the Invention

[0023] 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 a hole transport auxiliary layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1The figure shows an example of an organic light-emitting device composed of a substrate 1 , an anode 2 , an organic layer 3 , and a cathode 4 .

[0025] 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 8, a hole suppression layer 9, an electron transport layer 10, an electron injection layer 11 and a cathode 4.

[0026] Figure 3 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 8, a hole suppression layer 9, an electron injection and transport layer 12, and a cathode 4. DETAILED DESCRIPTION

[0027] In the following, the present invention will be described in more detail to help understanding the present invention.

[0028] The present invention provides a compound represented by the above Chemical Formula 1.

[0029] In this manual, It represents the bond to other substituents.

[0030] In the present specification, the term "substituted or unsubstituted" refers to a group selected from deuterium; a halogen group; a nitrile 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" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may also be interpreted as a substituent formed by connecting two phenyl groups.

[0031] In the present specification, the term "substituted with one or more substituents" can be understood to mean "substituted with from one to the maximum number of substitutable hydrogen atoms".

[0032] 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 group may have the following structure, but is not limited thereto.

[0033]

[0034] 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 group may be a group of the following structure, but is not limited thereto.

[0035]

[0036] 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 group may have the following structure, but is not limited thereto.

[0037]

[0038] In the present specification, specific examples of the silyl group include trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, and phenylsilyl, but are not limited thereto.

[0039] In the present specification, specific examples of the boryl group include trimethylboryl, triethylboryl, tert-butyldimethylboryl, triphenylboryl, and phenylboryl, but are not limited thereto.

[0040] In the present specification, as examples of the halogen group, there are fluorine, chlorine, bromine or iodine.

[0041] 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, the number of carbon atoms in the alkyl group is 1 to 6. 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-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, and 5-methylhexyl, but are not limited thereto.

[0042] 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.

[0043] In the present specification, the cycloalkyl group is not particularly limited, but is preferably a cycloalkyl group having 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, there are cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., but are not limited thereto.

[0044] In the present specification, the aryl group is not particularly limited, but is preferably an aryl group having 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 30. According to one embodiment, the carbon number of the aryl group is 6 to 20. Regarding the aryl group, as a monocyclic aryl group, it may be phenyl, biphenyl, terphenyl, etc., but it is not limited thereto. As the polycyclic aryl group, it may be naphthyl, anthracenyl, phenanthrenyl, pyrenyl, peryl, yl, fluorenyl, etc., but are not limited to these.

[0045] 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.

[0046] In the present specification, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si and S as hetero elements, and the number of carbon atoms is not particularly limited, but preferably the number of carbon atoms is 2 to 60. Examples of the heterocyclic group include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, Azolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzo oxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothiophenyl, dibenzothiophenyl, benzofuranyl, phenanthroline, isothiophene oxazolyl, thiadiazolyl, phenothiazinyl and dibenzofuranyl, but are not limited thereto.

[0047] In the present specification, the aryl group in aralkyl, aralkenyl, alkylaryl, and arylamine is the same as the examples of the aryl group described above. In the present specification, the alkyl group in aralkyl, alkylaryl, and alkylamine is the same as the examples of the alkyl group described above. In the present specification, the heteroaryl group in heteroarylamine can be applied to the above-mentioned description of the heterocyclic 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 heterocyclic group can be applied. In the present specification, the hydrocarbon ring is not a monovalent group, but two substituents are combined, and the above-mentioned description of the aryl group or cycloalkyl group can be applied. In the present specification, the heterocycle is not a monovalent group, but two substituents are combined, and the above-mentioned description of the heterocyclic group can be applied.

[0048] 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.

[0049] In addition, "unsubstituted or substituted with deuterium" or "substituted or unsubstituted with deuterium" means "unsubstituted or substituted with 1 to 9 deuteriums in the substitutable hydrogens". As an example, the term "unsubstituted or substituted with deuterium phenanthrenyl" can be understood to mean "unsubstituted or substituted with 1 to 9 deuteriums in the phenanthrenyl structure" when considering that the maximum number of hydrogens that can be substituted with deuteriums is 9.

[0050] In addition, the meaning of "deuterated structure" refers to a compound, a divalent linking group or a monovalent substituent including all structures in which at least one hydrogen is replaced by deuterium. As an example, the deuterated structure of phenyl shown below can be understood as referring to all structures in which at least one substitutable hydrogen in phenyl is replaced by deuterium and a monovalent substituent.

[0051]

[0052] 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 hydrogen that can exist (the sum of the number of hydrogen that can be substituted with deuterium in the compound and the number of deuterium substituted). Therefore, the "deuterium substitution rate" or "deuteration degree" of a compound as "K%" means that K% of the hydrogen that can be substituted with deuterium in the compound is substituted with deuterium.

[0053] In this case, the above-mentioned "deuterium substitution rate" or "deuteration degree" can be measured by MALDI-TOF MS (Matrix-Assisted Laser Desorption / Ionization Time-of-Flight Mass Spectrometer), nuclear magnetic resonance spectroscopy ( 1 H NMR), TLC / MS (Thin-Layer Chromatography / Mass Spectrometry) or GC / MS (Gas Chromatography / Mass Spectrometry), etc., and are measured according to 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.

[0054] The compound of the above chemical formula 1 satisfies the following conditions: The (Benzo[G]chrysene) core has a structure with an aromatic amine bonded to a specific position, and thus can be used in the organic layer of an organic light-emitting device, especially a hole transport auxiliary layer, thereby exhibiting the characteristics of low voltage, high efficiency and / or long life.

[0055] Specifically, the above Chemical Formula 1 may be represented by any one of the following Chemical Formulas 1-1 to 1-12.

[0056]

[0057] In the above chemical formulas 1-1 to 1-12, R 1 To R 14 , L 1 To L 3 and Ar 1 To Ar 2 Same as defined in Chemical Formula 1.

[0058] Preferably, L 1It is a single bond, a phenylene group which may be substituted by one or more deuterium groups, or a biphenyldiyl group which may be substituted by one or more deuterium groups.

[0059] Preferably, L 2 and L 3 Each is independently a single bond, a phenylene group which may be substituted by one or more deuterium groups, or a naphthalenediyl group which may be substituted by one or more deuterium groups.

[0060] Preferably, Ar 1 and Ar 2 Each of Ar is independently phenyl, biphenyl, terphenyl, naphthyl, (phenyl) naphthyl, phenanthryl, dibenzofuranyl or dibenzothiophenyl. 1 and Ar 2 Each independently may be substituted with one or more deuterium or may be unsubstituted.

[0061] On the other hand, the compound represented by the above chemical formula 1 may have one or more hydrogen atoms substituted with deuterium. 1 Combined R 1 To R 14 At least one of the above chemical formula 1 may be deuterium. 1 To L 3 ,Ar 1 and Ar 2 One or more substituents in may be substituted with deuterium.

[0062] When the compound represented by the above chemical formula 1 contains deuterium, the deuterium substitution rate of the compound may be 1% to 100%. Specifically, the deuterium substitution rate of the above compound may be 4% or more, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, or 40% or more and 100% or less, 97% or less, 95% or less, 90% or less, or 89% or less.

[0063] As an example, the compound may contain no deuterium, or may contain 1 to 50 deuteriums. More specifically, the compound may contain no deuterium, or may contain 1 or more, 3 or more, 5 or more, 8 or more, or 10 or more and 45 or less, 40 or less, 38 or less, 35 or less, or 33 or less deuteriums.

[0064] Representative examples of the compound represented by the above Chemical Formula 1 are shown below:

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095] In the above compounds, Dn refers to the number of deuterium (D) substitutions in each compound described in the brackets, which is different for each compound, and n is an integer greater than 0, and the maximum value of n is the total number of hydrogen atoms in each compound contained in the brackets.

[0096] For example, The total number of hydrogen atoms in the nucleus is 31, so In which n is an integer from 0 to 31, As including unsubstituted by deuterium The term "deuterium" refers to a compound in which 1 to 31 of the hydrogen atoms are replaced by deuterium. On the other hand, when n is 1 or more, the position of deuterium substitution is not limited. For example, means included in Any 13 of the 31 hydrogen atoms in the atom are replaced by deuterium.

[0097] In addition, the present invention provides a method for producing the compound represented by the above Chemical Formula 1.

[0098] As an example, the compound represented by the above Chemical Formula 1 can be prepared by the method shown in the following Reaction Formula 1. The following Reaction Formula 1 illustrates that R 10 With L 1 A method for producing the compound of Chemical Formula 1 in combination with the above-mentioned compound.

[0099] [Reaction formula 1]

[0100]

[0101] In the above reaction formula 1, except for X', the rest are the same as those in chemical formula 1. X' is a halogen, preferably, X' is chlorine or bromine.

[0102] The above reaction formula 1 is an amine substitution reaction, which is preferably carried out in the presence of a palladium catalyst and a base. The reactive group used for the amine substitution reaction can be changed according to the techniques known in the art.

[0103] The above-mentioned production method can be further embodied in the production examples described below.

[0104] 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.

[0105] 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.

[0106] In addition, the organic layer may include a hole injection layer, a hole transport layer or a hole transport auxiliary layer, and the hole injection layer, the hole transport layer or the hole transport auxiliary layer may include the compound represented by Chemical Formula 1.

[0107] 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. Figures 1 to 3 .

[0108] Figure 1 The figure shows an example of an organic light emitting device composed of a substrate 1, an anode 2, an organic 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 organic layer.

[0109] 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 8, a hole suppression layer 9, an electron transport layer 10, an electron injection layer 11, and a cathode 4. As an example, in the structure described above, the compound represented by the above chemical formula 1 may be contained in the hole transport auxiliary layer.

[0110] Figure 3The 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 8, a hole suppression layer 9, an electron injection and transport layer 12, and a cathode 4. As an example, in the structure described above, the compound represented by the above chemical formula 1 may be contained in the hole transport auxiliary layer.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] 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.

[0115] 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.

[0116] 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.

[0117] 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.

[0118] 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.

[0119] 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.

[0120] The hole transport auxiliary layer is located between the hole transport layer and the light emitting layer, and is a layer for adjusting the transfer speed or injection speed of holes. As long as the hole injection barrier is low and the hole mobility is large, there is no particular limitation, and substances known in the technical field can be used without restriction. In one embodiment, the compound represented by the above chemical formula 1 can be used as a hole transport auxiliary layer material. In this case, holes can be smoothly transferred to the light emitting layer, and the stability of the excitons formed in the light emitting layer can be improved, so it is preferred.

[0121] An electron blocking layer may be present between the hole transport auxiliary layer and the light emitting layer. The electron blocking layer inhibits the electrons injected from the cathode from being recombined in the light emitting layer and transferred to the anode side, thereby improving the efficiency of the organic light emitting device. It is preferred to use a substance with a lower electrophilicity than the electron transport layer in the electron blocking layer.

[0122] 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.

[0123] 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.

[0124] As dopant materials, there are aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, etc. Specifically, aromatic amine derivatives are aromatic fused ring derivatives having substituted or unsubstituted arylamino groups, and there are pyrene, anthracene, The styrylamine compound is a compound in which at least one arylvinyl group is substituted on a substituted or unsubstituted arylamine, and is substituted or unsubstituted with one or more substituents selected from aryl, silyl, alkyl, cycloalkyl and arylamino. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetramine, etc., but not limited thereto. In addition, as metal complexes, there are iridium complexes, platinum complexes, etc., but not limited thereto.

[0125] The electron transport layer is a layer that receives electrons from the electron injection layer and transports the electrons to the light-emitting layer. The electron transport material is a material that can well receive electrons from the cathode and transfer them to the light-emitting layer. A material with high electron mobility is suitable. As specific examples, there are Al complexes of 8-hydroxyquinoline, Alq 3 The electron transport layer can be used together with any desired cathode material as used in the prior art. In particular, examples of suitable cathode materials are conventional materials with a low work function and accompanied by an aluminum layer or a silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, in each case accompanied by an aluminum layer or a silver layer.

[0126] The electron injection layer is a layer for injecting electrons from the electrode, and preferably uses the following compounds: compounds that have the ability to transport electrons, have the effect of injecting electrons from the cathode, have an excellent electron injection effect on the light-emitting layer or the light-emitting material, prevent the excitons generated in the light-emitting layer from migrating to the hole injection layer, and have excellent thin film forming ability. Specifically, there are fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, Azoles, Examples include, but are not limited to, diazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylene methane, anthrone, and derivatives thereof, metal coordination compounds, and nitrogen-containing five-membered ring derivatives.

[0127] Examples of the metal coordination compounds include, but are not limited to, 8-hydroxyquinoline lithium, bis(8-hydroxyquinoline) zinc, bis(8-hydroxyquinoline) copper, bis(8-hydroxyquinoline) manganese, tris(8-hydroxyquinoline) aluminum, tris(2-methyl-8-hydroxyquinoline) aluminum, tris(8-hydroxyquinoline) gallium, bis(10-hydroxybenzo[h]quinoline) beryllium, bis(10-hydroxybenzo[h]quinoline) zinc, bis(2-methyl-8-quinoline) gallium chloride, bis(2-methyl-8-quinoline)(o-cresol) gallium, bis(2-methyl-8-quinoline)(1-naphthol) aluminum, and bis(2-methyl-8-quinoline)(2-naphthol) gallium.

[0128] The organic light-emitting device according to one embodiment of the present invention may include an electron injection and transport layer that simultaneously functions as an electron transport layer and an electron injection layer instead of the above-mentioned electron transport layer and electron injection layer. As the above-mentioned electron injection and transport layer material, one or more of the above-mentioned electron transport layer and electron injection layer materials can be used.

[0129] 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.

[0130] In addition, the compound represented by the above Chemical Formula 1 may be included in an organic solar cell or an organic transistor in addition to being included in an organic light-emitting device.

[0131] 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.

[0132] [Synthesis example]

[0133] Synthesis example 1

[0134]

[0135] Under nitrogen atmosphere, amine 1 (15 g, 31.4 mmol), substance (sub) 1 (10.3 g, 33 mmol), sodium tert-butoxide (4.5 g, 47.1 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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, 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 15.1 g of compound 1. (Yield 64%, MS: [M+H] + =754)

[0136] Synthesis example 2

[0137]

[0138] Under nitrogen atmosphere, amine 2 (15 g, 37.7 mmol), substance 1 (12.4 g, 39.6 mmol), sodium tert-butoxide (5.4 g, 56.6 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 13.2 g of compound 2. (Yield 52%, MS: [M+H] + =674)

[0139] Synthesis example 3

[0140]

[0141] Under nitrogen atmosphere, amine 3 (15 g, 61.1 mmol), substance 2 (25 g, 64.2 mmol), sodium tert-butoxide (8.8 g, 91.7 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 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 22.6 g of compound 3. (Yield 62%, MS: [M+H] + =598)

[0142] Synthesis example 4

[0143]

[0144] Under nitrogen atmosphere, amine 4 (15 g, 46.7 mmol), substance 3 (15.3 g, 49 mmol), sodium tert-butoxide (6.7 g, 70 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 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 14.8 g of compound 4. (Yield 53%, MS: [M+H] + =598)

[0145] Synthesis example 5

[0146]

[0147] Under nitrogen atmosphere, amine 5 (15 g, 46.7 mmol), substance 4 (22.8 g, 49 mmol), sodium tert-butoxide (6.7 g, 70 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 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 22.7 g of compound 5. (Yield 65%, MS: [M+H] + =750)

[0148] Synthesis example 6

[0149]

[0150] Under nitrogen atmosphere, amine 6 (15 g, 50.8 mmol), substance 5 (20.7 g, 53.3 mmol), sodium tert-butoxide (7.3 g, 76.2 mmol) were added to 300 ml of xylene, 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 20.7 g of compound 6. (Yield 63%, MS: [M+H] + =648)

[0151] Synthesis Example 7

[0152]

[0153] Under nitrogen atmosphere, amine 7 (15 g, 46.7 mmol), substance 5 (19.1 g, 49 mmol), sodium tert-butoxide (6.7 g, 70 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 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 16 g of compound 7. (Yield 51%, MS: [M+H] + =674)

[0154] Synthesis example 8

[0155]

[0156] Under nitrogen atmosphere, amine 8 (15 g, 46.7 mmol), substance 6 (15.3 g, 49 mmol), sodium tert-butoxide (6.7 g, 70 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 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 19 g of compound 8. (Yield 68%, MS: [M+H] + =598)

[0157] Synthesis example 9

[0158]

[0159] Under nitrogen atmosphere, amine 3 (15 g, 61.1 mmol), substance 7 (29.9 g, 64.2 mmol), sodium tert-butoxide (8.8 g, 91.7 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 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 27.6 g of compound 9. (Yield 67%, MS: [M+H] + =674)

[0160] Synthesis example 10

[0161]

[0162] Under nitrogen atmosphere, amine 9 (15 g, 50.8 mmol), substance 8 (20.7 g, 53.3 mmol), sodium tert-butoxide (7.3 g, 76.2 mmol) were added to 300 ml of xylene, 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 21.4 g of compound 10. (Yield 65%, MS: [M+H] + =648)

[0163] Synthesis example 11

[0164]

[0165] Under nitrogen atmosphere, amine 10 (15 g, 40.4 mmol), substance 9 (13.3 g, 42.4 mmol), sodium tert-butoxide (5.8 g, 60.6 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 15.4 g of compound 11. (Yield 59%, MS: [M+H] + =648)

[0166] Synthesis example 12

[0167]

[0168] Under nitrogen atmosphere, amine 11 (15 g, 40.4 mmol), substance 9 (13.3 g, 42.4 mmol), sodium tert-butoxide (5.8 g, 60.6 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 13.6 g of compound 12. (Yield 52%, MS: [M+H] + =648)

[0169] Synthesis example 13

[0170]

[0171] Under nitrogen atmosphere, amine 12 (15 g, 35.6 mmol), substance 9 (11.7 g, 37.4 mmol), sodium tert-butoxide (5.1 g, 53.4 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 17.4 g of compound 13. (Yield 70%, MS: [M+H] + =698)

[0172] Synthesis example 14

[0173]

[0174] Under nitrogen atmosphere, amine 3 (15 g, 61.1 mmol), substance 10 (25 g, 64.2 mmol), sodium tert-butoxide (8.8 g, 91.7 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 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 23 g of compound 14. (Yield 63%, MS: [M+H] + =598)

[0175] Synthesis Example 15

[0176]

[0177] Under nitrogen atmosphere, amine 4 (15 g, 46.7 mmol), substance 11 (15.3 g, 49 mmol), sodium tert-butoxide (6.7 g, 70 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 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 17.8 g of compound 15. (Yield 64%, MS: [M+H] + =598)

[0178] Synthesis example 16

[0179]

[0180] Under nitrogen atmosphere, amine 13 (15 g, 42.7 mmol), substance 12 (17.4 g, 44.8 mmol), sodium tert-butoxide (6.2 g, 64 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 18.6 g of compound 16. (Yield 62%, MS: [M+H] + =704)

[0181] Synthesis Example 17

[0182]

[0183] Under nitrogen atmosphere, amine 14 (15 g, 61.1 mmol), substance 12 (25 g, 64.2 mmol), sodium tert-butoxide (8.8 g, 91.7 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 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 22.6 g of compound 17. (Yield 62%, MS: [M+H] + =598)

[0184] Synthesis example 18

[0185]

[0186] Under nitrogen atmosphere, amine 15 (15 g, 40.4 mmol), substance 13 (13.3 g, 42.4 mmol), sodium tert-butoxide (5.8 g, 60.6 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 15.9 g of compound 18. (Yield 61%, MS: [M+H] + =648)

[0187] Synthesis example 19

[0188]

[0189] Under nitrogen atmosphere, amine 3 (15 g, 61.1 mmol), substance 14 (29.9 g, 64.2 mmol), sodium tert-butoxide (8.8 g, 91.7 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 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 21 g of compound 19. (Yield 51%, MS: [M+H] + =674)

[0190] Synthesis example 20

[0191]

[0192] Under nitrogen atmosphere, amine 16 (15 g, 57.8 mmol), substance 15 (23.6 g, 60.7 mmol), sodium tert-butoxide (8.3 g, 86.8 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 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 18.4 g of compound 20. (Yield 52%, MS: [M+H] + =612)

[0193] Synthesis Example 21

[0194]

[0195] Under nitrogen atmosphere, amine 9 (15 g, 50.8 mmol), substance 15 (20.7 g, 53.3 mmol), sodium tert-butoxide (7.3 g, 76.2 mmol) were added to 300 ml of xylene, 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 22 g of compound 21. (Yield 67%, MS: [M+H] + =648)

[0196] Synthesis example 22

[0197]

[0198] Under nitrogen atmosphere, amine 10 (15 g, 40.4 mmol), substance 16 (13.3 g, 42.4 mmol), sodium tert-butoxide (5.8 g, 60.6 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 14.1 g of compound 22. (Yield 54%, MS: [M+H] + =648)

[0199] Synthesis example 23

[0200]

[0201] Under nitrogen atmosphere, amine 17 (15 g, 37.7 mmol), substance 16 (12.4 g, 39.6 mmol), sodium tert-butoxide (5.4 g, 56.6 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 17.3 g of compound 23. (Yield 68%, MS: [M+H] + =674)

[0202] Synthesis example 24

[0203]

[0204] Under nitrogen atmosphere, amine 18 (15 g, 46.7 mmol), substance 16 (15.3 g, 49 mmol), sodium tert-butoxide (6.7 g, 70 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 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 19.2 g of compound 24. (Yield 69%, MS: [M+H] + =598)

[0205] Synthesis example 25

[0206]

[0207] Under nitrogen atmosphere, amine 19 (15 g, 37.7 mmol), substance 17 (12.4 g, 39.6 mmol), sodium tert-butoxide (5.4 g, 56.6 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 16.5 g of compound 25. (Yield 65%, MS: [M+H] + =674)

[0208] Synthesis Example 26

[0209]

[0210] Under nitrogen atmosphere, amine 20 (15 g, 37.7 mmol), substance 17 (15.4 g, 39.6 mmol), sodium tert-butoxide (5.4 g, 56.6 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 15.8 g of compound 26. (Yield 62%, MS: [M+H] + =674)

[0211] Synthesis Example 27

[0212]

[0213] Under nitrogen atmosphere, amine 21 (15 g, 42.7 mmol), substance 18 (17.4 g, 44.8 mmol), sodium tert-butoxide (6.2 g, 64 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 15 g of compound 27. (Yield 50%, MS: [M+H] + =704)

[0214] Synthesis example 28

[0215]

[0216] Under nitrogen atmosphere, amine 18 (15 g, 46.7 mmol), substance 19 (15.3 g, 49 mmol), sodium tert-butoxide (6.7 g, 70 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 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 16.4 g of compound 28. (Yield 59%, MS: [M+H] + =598)

[0217] Synthesis Example 29

[0218]

[0219] Under nitrogen atmosphere, amine 5 (15 g, 46.7 mmol), substance 20 (19.1 g, 49 mmol), sodium tert-butoxide (6.7 g, 70 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 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 20.4 g of compound 29. (Yield 65%, MS: [M+H] + =674)

[0220] Synthesis example 30

[0221]

[0222] Under nitrogen atmosphere, amine 22 (15 g, 54.5 mmol), substance 20 (22.2 g, 57.2 mmol), sodium tert-butoxide (7.9 g, 81.7 mmol) were added to 300 ml of xylene, 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 21.9 g of compound 30. (Yield 64%, MS: [M+H] + =628)

[0223] Synthesis Example 31

[0224]

[0225] Under nitrogen atmosphere, amine 4 (15 g, 46.7 mmol), substance 21 (15.3 g, 49 mmol), sodium tert-butoxide (6.7 g, 70 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 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 17.3 g of compound 31. (Yield 62%, MS: [M+H] + =598)

[0226] Synthesis example 32

[0227]

[0228] Under nitrogen atmosphere, amine 23 (15 g, 41 mmol), substance 21 (13.5 g, 43.1 mmol), sodium tert-butoxide (5.9 g, 61.6 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 16.3 g of compound 32. (Yield 62%, MS: [M+H] + =642)

[0229] Synthesis example 33

[0230]

[0231] Under nitrogen atmosphere, amine 24 (15 g, 43.4 mmol), substance 21 (14.3 g, 45.6 mmol), sodium tert-butoxide (6.3 g, 65.1 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 18.3 g of compound 33. (Yield 68%, MS: [M+H] + =622)

[0232] Synthesis example 34

[0233]

[0234] Under nitrogen atmosphere, amine 25 (15 g, 37.7 mmol), substance 22 (15.4 g, 39.6 mmol), sodium tert-butoxide (5.4 g, 56.6 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 18.7 g of compound 34. (Yield 66%, MS: [M+H] + =750)

[0235] Synthesis Example 35

[0236]

[0237] Under nitrogen atmosphere, amine 3 (15 g, 61.1 mmol), substance 23 (20.1 g, 64.2 mmol), sodium tert-butoxide (8.8 g, 91.7 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 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 22.3 g of compound 35. (Yield 70%, MS: [M+H] + =522)

[0238] Synthesis Example 36

[0239]

[0240] Under nitrogen atmosphere, amine 26 (15 g, 40.4 mmol), substance 23 (13.3 g, 42.4 mmol), sodium tert-butoxide (5.8 g, 60.6 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 18.3 g of compound 36. (Yield 70%, MS: [M+H] + =648)

[0241] Synthesis Example 37

[0242]

[0243] Under nitrogen atmosphere, amine 27 (15 g, 43.4 mmol), substance 24 (17.7 g, 45.6 mmol), sodium tert-butoxide (6.3 g, 65.1 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 20.6 g of compound 37. (Yield 68%, MS: [M+H] + =698)

[0244] Synthesis example 38

[0245]

[0246] Under nitrogen atmosphere, amine 28 (15 g, 46.7 mmol), substance 1 (15.3 g, 49 mmol), sodium tert-butoxide (6.7 g, 70 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 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 14.2 g of compound 38_P1. (Yield 51%, MS: [M+H] + =598)

[0247] Compound 38_P1 (10 g, 16.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (8.4 g, 418.6 mmol) was added to trifluoromethanesulfonic anhydride (23.6 g, 83.7 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 raised to 140 degrees, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous 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 5.6 g of compound 38. (Yield 55%, MS: [M+H] + =610)

[0248] Synthesis Example 39

[0249]

[0250] Under nitrogen atmosphere, amine 29 (15 g, 43.4 mmol), substance 1 (14.3 g, 45.6 mmol), sodium tert-butoxide (6.3 g, 65.1 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 15.6 g of compound 39_P1. (Yield 58%, MS: [M+H] + =622)

[0251] Compound 39_P1 (10 g, 16.1 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (8.1 g, 402.4 mmol) was added to trifluoromethanesulfonic anhydride (22.7 g, 80.5 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140 degrees, and the temperature was maintained and stirred. After reacting for 4 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.8 g of compound 39. (Yield 66%, MS: [M+H] + =637)

[0252] Synthesis Example 40

[0253]

[0254] Under nitrogen atmosphere, amine 16 (15 g, 57.8 mmol), substance 5 (23.6 g, 60.7 mmol), sodium tert-butoxide (8.3 g, 86.8 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 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 22.6 g of compound 40_P1. (Yield 64%, MS: [M+H] + =612)

[0255] Compound 40_P1 (10 g, 16.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (8.2 g, 409 mmol) was added to trifluoromethanesulfonic anhydride (23.1 g, 81.8 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 degrees. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.8 g of compound 40. (Yield 67%, MS: [M+H] + =624)

[0256] Synthesis Example 41

[0257]

[0258] Under nitrogen atmosphere, amine 30 (15 g, 40.4 mmol), substance 3 (13.3 g, 42.4 mmol), sodium tert-butoxide (5.8 g, 60.6 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 13.9 g of compound 41_P1. (Yield 53%, MS: [M+H] + =648)

[0259] Compound 41_P1 (10 g, 15.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (7.7 g, 386.2 mmol) was added to trifluoromethanesulfonic anhydride (21.8 g, 77.2 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 degrees. After reacting for 4 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.6 g of compound 41. (Yield 55, MS: [M+H] + =661)

[0260] Synthesis Example 42

[0261]

[0262] Under nitrogen atmosphere, amine 31 (15 g, 36.5 mmol), substance 3 (12 g, 38.3 mmol), sodium tert-butoxide (5.3 g, 54.7 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 13.4 g of compound 42_P1. (Yield 56%, MS: [M+H] + =688)

[0263] Compound 42_P1 (10 g, 14.6 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (7.3 g, 363.8 mmol) was added to trifluoromethanesulfonic anhydride (20.5 g, 72.8 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 degrees, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.3 g of compound 42. (Yield 62%, MS: [M+H] + =703)

[0264] Synthesis Example 43

[0265]

[0266] Under nitrogen atmosphere, amine 32 (15 g, 37.7 mmol), substance 8 (15.4 g, 39.6 mmol), sodium tert-butoxide (5.4 g, 56.6 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. The reaction was completed after 10 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 17.5 g of compound 43_P1. (Yield 62%, MS: [M+H] + =750)

[0267] Compound 43_P1 (10 g, 13.3 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (6.7 g, 333.6 mmol) was added to trifluoromethanesulfonic anhydride (18.8 g, 66.7 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 degrees. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.1 g of compound 43. (Yield 60%, MS: [M+H] + =766)

[0268] Synthesis Example 44

[0269]

[0270] Under nitrogen atmosphere, amine 33 (15 g, 44.7 mmol), substance 9 (14.7 g, 47 mmol), sodium tert-butoxide (6.4 g, 67.1 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. The reaction was completed after 10 hours, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water twice, the organic layer was separated, filtered after treatment with anhydrous magnesium sulfate, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.2 g of compound 44_P1. (Yield 52%, MS: [M+H] + =612)

[0271] Compound 44_P1 (10 g, 16.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (8.2 g, 409 mmol) was added to trifluoromethanesulfonic anhydride (23.1 g, 81.8 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 degrees, and the temperature was maintained and stirred. After reacting for 4 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.2 g of compound 44. (Yield 51%, MS: [M+H] + =625)

[0272] Synthesis Example 45

[0273]

[0274] Under nitrogen atmosphere, amine 2 (15 g, 37.7 mmol), substance 9 (12.4 g, 39.6 mmol), sodium tert-butoxide (5.4 g, 56.6 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 16.3 g of compound 45_P1. (Yield 64%, MS: [M+H] + =674)

[0275] Compound 45_P1 (10 g, 14.9 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (7.4 g, 371.3 mmol) was added to trifluoromethanesulfonic anhydride (21 g, 74.3 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 degrees, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.9 g of compound 45. (Yield 68%, MS: [M+H] + =685)

[0276] Synthesis Example 46

[0277]

[0278] Under nitrogen atmosphere, amine 34 (15 g, 37.7 mmol), substance 11 (12.4 g, 39.6 mmol), sodium tert-butoxide (5.4 g, 56.6 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 15.5 g of compound 46_P1. (Yield 61%, MS: [M+H] + =674)

[0279] Compound 46_P1 (10 g, 14.9 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (7.4 g, 371.3 mmol) was added to trifluoromethanesulfonic anhydride (21 g, 74.3 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 degrees, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.7 g of compound 46. (Yield 66%, MS: [M+H] + =686)

[0280] Synthesis Example 47

[0281]

[0282] Under nitrogen atmosphere, amine 35 (15 g, 43.4 mmol), substance 11 (14.3 g, 45.6 mmol), sodium tert-butoxide (6.3 g, 65.1 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 18.1 g of compound 47_P1. (Yield 67%, MS: [M+H] + =622)

[0283] Compound 47_P1 (10 g, 16.1 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (8.1 g, 402.4 mmol) was added to trifluoromethanesulfonic anhydride (22.7 g, 80.5 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140 degrees, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.1 g of compound 47. (Yield 50%, MS: [M+H] + =636)

[0284] Synthesis Example 48

[0285]

[0286] Under nitrogen atmosphere, amine 36 (15 g, 42.7 mmol), substance 13 (14 g, 44.8 mmol), sodium tert-butoxide (6.2 g, 64 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 16.9 g of compound 48_P1. (Yield 63%, MS: [M+H] + =629)

[0287] Compound 48_P1 (10 g, 15.9 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (8 g, 398.2 mmol) was added to trifluoromethanesulfonic anhydride (22.5 g, 79.6 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was maintained and stirred after heating to 140 degrees. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7 g of compound 48. (Yield 69%, MS: [M+H]+ =642)

[0288] Synthesis Example 49

[0289]

[0290] Under nitrogen atmosphere, amine 37 (15 g, 37.7 mmol), substance 13 (12.7 g, 39.6 mmol), sodium tert-butoxide (5.4 g, 56.6 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 12.7 g of compound 49_P1. (Yield 50%, MS: [M+H] + =674)

[0291] Compound 49_P1 (10 g, 14.9 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (7.4 g, 371.3 mmol) was added to trifluoromethanesulfonic anhydride (21 g, 74.3 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 degrees, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.4 g of compound 49. (Yield 53%, MS: [M+H] + =686)

[0292] Synthesis Example 50

[0293]

[0294] Under nitrogen atmosphere, amine 38 (15 g, 43.4 mmol), substance 16 (14.3 g, 45.6 mmol), sodium tert-butoxide (6.3 g, 65.1 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 18.6 g of compound 50_P1. (Yield 69%, MS: [M+H] + =622)

[0295] Compound 50_P1 (10 g, 16.1 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (8.1 g, 402.4 mmol) was added to trifluoromethanesulfonic anhydride (22.7 g, 80.5 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140 degrees, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.3 g of compound 50. (Yield 52%, MS: [M+H] + =636)

[0296] Synthesis Example 51

[0297]

[0298] Under nitrogen atmosphere, amine 39 (15 g, 35.6 mmol), substance 17 (11.7 g, 37.4 mmol), sodium tert-butoxide (5.1 g, 53.4 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 12.7 g of compound 51_P1. (Yield 51%, MS: [M+H] + =698)

[0299] Compound 51_P1 (10 g, 14.3 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (7.2 g, 358.5 mmol) was added to trifluoromethanesulfonic anhydride (20.2 g, 71.7 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 degrees, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.8 g of compound 51. (Yield 66%, MS: [M+H] + =714)

[0300] Synthesis example 52

[0301]

[0302] Under nitrogen atmosphere, amine 40 (15 g, 40.4 mmol), substance 19 (13.3 g, 42.4 mmol), sodium tert-butoxide (5.8 g, 60.6 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 13.1 g of compound 52_P1. (Yield 50%, MS: [M+H] + =648)

[0303] Compound 52_P1 (10 g, 15.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (7.7 g, 386.2 mmol) was added to trifluoromethanesulfonic anhydride (21.8 g, 77.2 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 degrees, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.8 g of compound 52. (Yield 57%, MS: [M+H] + =662)

[0304] Synthesis example 53

[0305]

[0306] Under nitrogen atmosphere, amine 41 (15 g, 40.4 mmol), substance 21 (13.3 g, 42.4 mmol), sodium tert-butoxide (5.8 g, 60.6 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 18 g of compound 53_P1. (Yield 69%, MS: [M+H] + =648)

[0307] Compound 53_P1 (10 g, 15.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (7.7 g, 386.2 mmol) was added to trifluoromethanesulfonic anhydride (21.8 g, 77.2 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 degrees, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7 g of compound 53. (Yield 69%, MS: [M+H] + =660)

[0308] Synthesis example 54

[0309]

[0310] Under nitrogen atmosphere, amine 42 (15 g, 43.4 mmol), substance 21 (14.7 g, 45.6 mmol), sodium tert-butoxide (6.3 g, 65.1 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 18.9 g of compound 54_P1. (Yield 70%, MS: [M+H] + =622)

[0311] Compound 54_P1 (10 g, 16.1 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (8.1 g, 402.4 mmol) was added to trifluoromethanesulfonic anhydride (22.7 g, 80.5 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140 degrees, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.2 g of compound 54. (Yield 70%, MS: [M+H] + =636)

[0312] Synthesis example 55

[0313]

[0314] Under nitrogen atmosphere, amine 43 (15 g, 46.7 mmol), substance 23 (15.3 g, 49 mmol), sodium tert-butoxide (6.7 g, 70 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 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 17.8 g of compound 55_P1. (Yield 64%, MS: [M+H] + =598)

[0315] Compound 55_P1 (10 g, 16.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (8.4 g, 418.6 mmol) was added to trifluoromethanesulfonic anhydride (23.6 g, 83.7 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 degrees, and the temperature was maintained and stirred. After reacting for 3 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.5 g of compound 55. (Yield 64%, MS: [M+H] + =610)

[0316] Synthesis example 56

[0317]

[0318] Under nitrogen atmosphere, amine 9 (15 g, 50.8 mmol), substance 1 (16.7 g, 53.3 mmol), sodium tert-butoxide (7.3 g, 76.2 mmol) were added to 300 ml of xylene, 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 17.1 g of compound 56_P1. (Yield 59%, MS: [M+H] + =572)

[0319] Compound 56_P1 (10 g, 17.5 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (12.6 g, 630.2 mmol) was added to trifluoromethanesulfonic anhydride (44.5 g, 157.6 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140 degrees, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.1 g of compound 56. (Yield 59%, MS: [M+H] + =593)

[0320] Synthesis Example 57

[0321]

[0322] Under nitrogen atmosphere, amine 27 (15 g, 43.4 mmol), substance 3 (14.3 g, 45.6 mmol), sodium tert-butoxide (6.3 g, 65.1 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 13.5 g of compound 57_P1. (Yield 50%, MS: [M+H] + =622)

[0323] Compound 57_P1 (10 g, 16.1 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (11.6 g, 579.5 mmol) was added to trifluoromethanesulfonic anhydride (40.9 g, 144.9 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 degrees, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.4 g of compound 57. (Yield 61%, MS: [M+H] + =650)

[0324] Synthesis example 58

[0325]

[0326] Under nitrogen atmosphere, amine 44 (15 g, 37.7 mmol), substance 6 (12.4 g, 39.6 mmol), sodium tert-butoxide (5.4 g, 56.6 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 15.2 g of compound 58_P1. (Yield 60%, MS: [M+H] + =674)

[0327] Compound 58_P1 (10 g, 14.9 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (10.7 g, 534.7 mmol) was added to trifluoromethanesulfonic anhydride (37.7 g, 133.7 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 degrees, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.9 g of compound 58. (Yield 66%, MS: [M+H] + =704)

[0328] Synthesis Example 59

[0329]

[0330] Under nitrogen atmosphere, amine 45 (15 g, 57.8 mmol), substance 10 (23.6 g, 60.7 mmol), sodium tert-butoxide (8.3 g, 86.8 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 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 23.3 g of compound 59_P1. (Yield 66%, MS: [M+H] + =612)

[0331] Compound 59_P1 (10 g, 16.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (11.8 g, 589 mmol) was added to trifluoromethanesulfonic anhydride (41.5 g, 147.2 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 degrees, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.9 g of compound 59. (Yield 66%, MS: [M+H] + =637)

[0332] Synthesis Example 60

[0333]

[0334] Under a nitrogen atmosphere, amine 46 (15 g, 42.9 mmol), substance 11 (14.1 g, 45.1 mmol), and sodium tert-butoxide (6.2 g, 64.4 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 13.4 g of compound 60_P1. (Yield 50%, MS: [M+H] + =626)

[0335] Compound 60_P1 (10 g, 16 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (11.5 g, 575.8 mmol) was added to trifluoromethanesulfonic anhydride (40.6 g, 144 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 degrees, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6 g of compound 60. (Yield 58%, MS: [M+H] + =651)

[0336] Synthesis Example 61

[0337]

[0338] Under nitrogen atmosphere, amine 24 (15 g, 43.4 mmol), substance 13 (14.3 g, 45.6 mmol), sodium tert-butoxide (6.3 g, 65.1 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 16.5 g of compound 61_P1. (Yield 61%, MS: [M+H] + =622)

[0339] Compound 61_P1 (10 g, 16.1 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (11.6 g, 579.5 mmol) was added to trifluoromethanesulfonic anhydride (40.9 g, 144.9 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 degrees, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.8 g of compound 61. (Yield 65%, MS: [M+H] + =648)

[0340] Synthesis example 62

[0341]

[0342] Under nitrogen atmosphere, amine 47 (15 g, 50.8 mmol), substance 25 (20.7 g, 53.3 mmol), sodium tert-butoxide (7.3 g, 76.2 mmol) were added to 300 ml of xylene, 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 21.4 g of compound 62_P1. (Yield 65%, MS: [M+H] + =648)

[0343] Compound 62_P1 (10 g, 15.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (11.1 g, 556.2 mmol) was added to trifluoromethanesulfonic anhydride (39.2 g, 139 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 degrees, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.2 g of compound 62. (Yield 69%, MS: [M+H] + =677)

[0344] Synthesis example 63

[0345]

[0346] Under nitrogen atmosphere, amine 48 (15 g, 40.4 mmol), substance 17 (13.3 g, 42.4 mmol), sodium tert-butoxide (5.8 g, 60.6 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 17 g of compound 63_P1. (Yield 65%, MS: [M+H] + =648)

[0347] Compound 63_P1 (10 g, 15.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (11.1 g, 556.2 mmol) was added to trifluoromethanesulfonic anhydride (39.2 g, 139 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 degrees, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.1 g of compound 63. (Yield 58%, MS: [M+H] + =676)

[0348] Synthesis example 64

[0349]

[0350] Under nitrogen atmosphere, amine 6 (15 g, 50.8 mmol), substance 20 (20.7 g, 53.3 mmol), sodium tert-butoxide (7.3 g, 76.2 mmol) were added to 300 ml of xylene, 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 17.4 g of compound 64_P1. (Yield 53%, MS: [M+H] + =648)

[0351] Compound 64_P1 (10 g, 15.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (11.1 g, 556.2 mmol) was added to trifluoromethanesulfonic anhydride (39.2 g, 139 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 degrees, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.1 g of compound 64. (Yield 68%, MS: [M+H] + =676)

[0352] Synthesis Example 65

[0353]

[0354] Under nitrogen atmosphere, amine 49 (15 g, 40.4 mmol), substance 22 (16.5 g, 42.4 mmol), sodium tert-butoxide (5.8 g, 60.6 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 16.6 g of compound 65_P1. (Yield 57%, MS: [M+H] + =724)

[0355] Compound 65_P1 (10 g, 13.8 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (10 g, 497.7 mmol) was added to trifluoromethanesulfonic anhydride (35.1 g, 124.4 mmol) at 0°C and stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and heavy water was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was raised to 140 degrees, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.6 g of compound 65. (Yield 63%, MS: [M+H] + =757)

[0356] Synthesis example 66

[0357]

[0358] Under nitrogen atmosphere, amine 33 (15 g, 44.7 mmol), substance 23 (14.7 g, 47 mmol), sodium tert-butoxide (6.4 g, 67.1 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 16.9 g of compound 66_P1. (Yield 62%, MS: [M+H] + =612)

[0359] Compound 66_P1 (10 g, 16.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, heavy water (11.8 g, 589 mmol) was added to trifluoromethanesulfonic anhydride (41.5 g, 147.2 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 degrees, and the temperature was maintained and stirred. After reacting for 10 hours, the mixture was cooled to room temperature and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.5 g of compound 66. (Yield 62%, MS: [M+H] + =638)

[0360] [Example]

[0361] Example 1-1

[0362] 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.

[0363] 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 prepared in the above-mentioned synthesis example 1 was prepared with Next, as a light-emitting layer, a compound represented by the following chemical formula BH-1 and a compound represented by BD-1 were added at a weight ratio of 25:1 and a thickness of Next, as a hole suppression layer, a compound represented by the following chemical formula HB-1 was deposited in an amount of Next, as an electron injection and transport layer, 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.

[0364]

[0365] In the above process, the evaporation rate of organic matter is maintained / second, the cathode lithium fluoride maintains / second evaporation speed, aluminum maintains The evaporation speed is 2x10 / s. During evaporation, the vacuum degree is maintained at 2x10 -7 ~5ⅹ10 -6 A support is provided to produce an organic light-emitting device.

[0366] Example 1-2 to Example 1-66

[0367] Organic light-emitting devices of Examples 1-2 to 1-66 were manufactured by the same method as in Example 1-1, except that the compounds described in the following Table 1 were used instead of Compound 1.

[0368] Comparative Examples 1-1 to 1-11

[0369] Organic light-emitting devices of Comparative Examples 1-1 to 1-11 were manufactured by the same method as Example 1-1, except that the compounds listed in Table 1 were used instead of Compound 1. Compounds C-1 to C-11 used in each Comparative Example are shown below.

[0370]

[0371] Experimental example

[0372] The organic light-emitting devices manufactured in Examples 1-1 to 1-66 and Comparative Examples 1-1 to 1-11 were subjected to a 15 mA / cm 2 The voltage and efficiency were measured when the current was 1.0 0.05 ...

[0373] [Table 1]

[0374]

[0375]

[0376]

[0377] With reference to Table 1, it can be confirmed that the organic light-emitting devices of Examples 1-1 to 1-66 using the compound represented by the above Chemical Formula 1 as a hole transport auxiliary layer material of the blue light-emitting layer have low driving voltages, significantly improved efficiency and lifespans compared to Comparative Examples 1-1 to 1-11. In particular, it can be confirmed that when the compound represented by Chemical Formula 1 substituted with deuterium is used, the lifespan characteristics of the organic light-emitting device are further improved. It is judged that the devices of the above Examples show excellent characteristics in driving voltage, efficiency and lifespan because the compound represented by Chemical Formula 1 contributes to the stability of the excitons formed in the light-emitting layer.

[0378] [Explanation of symbols]

[0379] 1: Substrate 2: Anode

[0380] 3: Organic layer 4: Cathode

[0381] 5: Hole injection layer 6: Hole transport layer

[0382] 7: Hole transport auxiliary layer 8: Light-emitting layer

[0383] 9: Hole suppression layer 10: Electron transport layer

[0384] 11: Electron injection layer 12: Electron injection and transport layer.

Claims

1. A compound represented by the following chemical formula 1: [Chemical formula 1] In the chemical formula 1, R1, R2, R4 to R8 and R 10 To R 14 Any one of is combined with L1, and the others are independently hydrogen or deuterium, R3 and R9 are each independently hydrogen or deuterium, L1 to L3 are each independently a single bond; substituted or unsubstituted C 6-60 or a substituted or unsubstituted C containing any one or more heteroatoms selected from N, O and S 2-60 Heteroarylene, Ar1 and Ar2 are each independently substituted or unsubstituted C 6-60 Aryl; or a substituted or unsubstituted C containing any one or more heteroatoms selected from N, O and S 2-60 Heteroaryl, However, the case where both L2 and L3 are single bonds and both Ar1 and Ar2 are phenyl groups is excluded.

2. The compound according to claim 1, wherein L1 is a single bond, a phenylene group which may be substituted by one or more deuterium groups, or a biphenyldiyl group which may be substituted by one or more deuterium groups.

3. The compound according to claim 1, wherein L2 and L3 are each independently a single bond, a phenylene group which may be substituted by one or more deuterium groups, or a naphthalenediyl group which may be substituted by one or more deuterium groups.

4. The compound according to claim 1, wherein Ar1 and Ar2 are each independently phenyl, biphenyl, terphenyl, naphthyl, (phenyl)naphthyl, phenanthryl, dibenzofuranyl or dibenzothiophenyl, The Ar1 and Ar2 are each independently substituted with one or more deuterium or are unsubstituted.

5. 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 above compounds, Dn refers to the number of deuterium (D) substitutions in each compound described in the brackets, which is different for each compound, and n is an integer greater than 0, and the maximum value of n is the total number of hydrogen atoms in each compound contained in the brackets.

6. An organic light-emitting device, comprising: A first electrode, a second electrode disposed opposite to the first electrode, and one or more organic layers disposed between the first electrode and the second electrode, wherein one or more of the organic layers comprises the compound according to any one of claims 1 to 5.

7. The organic light emitting device according to claim 6, wherein: The organic layer containing the compound is a hole transport auxiliary layer.

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