Organic light emitting device

Abstract

The present disclosure relates to an organic light emitting device having improved driving voltage, efficiency, and lifespan.

Description

Technical Field

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Korean Patent Application No. 10-2023-0073841 filed on June 8, 2023, in the Korean Intellectual Property Office, and Korean Patent Application No. 10-2024-0074510 filed on June 7, 2024, in the Korean Intellectual Property Office, the disclosures of which are incorporated herein by reference in their entirety.

[0003] The present disclosure relates to organic light emitting devices with improved driving voltage, efficiency, and lifetime. Background Art

[0004] Generally speaking, organic light emitting diodes (OLEDs) are a type of organic light emitting diode (OLED) that converts electrical energy into light energy using organic materials. These devices have been extensively researched due to their wide viewing angles, excellent contrast, fast response time, excellent brightness, driving voltage, and response speed.

[0005] An organic light-emitting device typically has a structure including an anode, a cathode, and an organic material layer interposed between the anode and the cathode. The organic material layer typically has a multilayer structure containing different materials to improve the efficiency and stability of the organic light-emitting device. For example, the organic material layer may be formed from a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of an organic light-emitting device, if a voltage is applied between the two electrodes, holes are injected from the anode into the organic material layer, and electrons are injected from the cathode into the organic material layer. When the injected holes and electrons meet, excitons are formed, and when the excitons fall back to the ground state, light is emitted.

[0006] Among the organic light emitting devices described above, there is a continuous demand for developing organic light emitting devices having improved driving voltage, efficiency, and lifespan.

[0007] [Prior art literature]

[0008] [Patent Document]

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

[0010] Technical issues

[0011] An object of the present disclosure is to provide an organic light emitting device with improved driving voltage, efficiency, and lifetime.

[0012] Technical Solution

[0013] According to the present disclosure, the following organic light-emitting device is provided:

[0014] An organic light-emitting device, comprising:

[0015] an anode, a cathode, and a light-emitting layer between the anode and the cathode,

[0016] The light-emitting layer comprises a compound represented by the following Chemical Formula 1 and a compound represented by the following Chemical Formula 2:

[0017] [Chemical Formula 1]

[0018]

[0019] In Chemical Formula 1,

[0020] Ar1 and Ar2 are each independently substituted or unsubstituted C 6-60 Aryl; or a substituted or unsubstituted C 2-60 heteroaryl,

[0021] L1 is a single bond; or substituted or unsubstituted C 6-60 arylene groups,

[0022] L2 and L3 are each independently a single bond; substituted or unsubstituted C 6-60 Arylene; or a substituted or unsubstituted C containing at least one selected from N, O and S 2-60 Heteroarylene, and

[0023] R1 to R7 are each independently hydrogen or deuterium,

[0024] [Chemical Formula 2]

[0025]

[0026] In Chemical Formula 2,

[0027] Ar'1 is hydrogen; deuterium; substituted or unsubstituted C 6-60 Aryl; or a substituted or unsubstituted C 2-60 heteroaryl,

[0028] Ar'2 and Ar'3 are each independently substituted or unsubstituted C 6-60 Aryl; or a substituted or unsubstituted C 2-60 heteroaryl,

[0029] L'1 to L'3 are each independently a single bond; substituted or unsubstituted C 6-60 Arylene; or a substituted or unsubstituted C containing at least one selected from N, O and S2-60 Heteroarylene,

[0030] L'4 is a single bond or a substituted or unsubstituted C 6-60 arylene groups,

[0031] R'1 is hydrogen or deuterium,

[0032] a is an integer from 1 to 8, and

[0033] - at least one of L'1-Ar'1 and R'1 is deuterium,

[0034] wherein the deuterium substitution rate of the compound represented by Chemical Formula 2 is 50% or greater.

[0035] Beneficial effects

[0036] The organic light emitting device includes the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 in a light emitting layer, thereby improving efficiency, achieving low driving voltage, and / or improving lifespan characteristics in the organic light emitting device. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 An example of an organic light-emitting device including a substrate 1 , an anode 2 , a light-emitting layer 3 , and a cathode 4 is shown.

[0038] Figure 2 An example of an organic light emitting device including a substrate 1 , an anode 2 , a hole injection layer 5 , a hole transport layer 6 , an electron blocking layer 7 , a light emitting layer 3 , a hole blocking layer 8 , an electron injection and transport layer 9 and a cathode 4 is shown. DETAILED DESCRIPTION

[0039] Hereinafter, embodiments of the present disclosure will be described in more detail to help understanding the present invention.

[0040] In this disclosure, the symbol or It refers to a bond to another substituent.

[0041] In the present disclosure, the term "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from the group consisting of 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, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, a silyl group, a boron group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an aralkenyl group, an alkylaryl group, an alkylamino group, an aralkylamino group, a heteroarylamino group, an arylamino group, an arylphosphino group, and a heterocyclic group containing at least one of N, O, and S atoms, or unsubstituted or substituted with a substituent in which two or more substituents are linked together among the substituents exemplified above. For example, a "substituent in which two or more substituents are linked together" may be a biphenyl group. That is, the biphenyl group may be an aryl group, or it may be interpreted as a substituent formed by linking two phenyl groups.

[0042] In the present disclosure, the carbon number of the carbonyl group is not particularly limited, but is preferably 1 to 40. Specifically, the carbonyl group may be a compound having the following structural formula, but is not limited thereto.

[0043]

[0044] In the present disclosure, the ester group may have a structure in which 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 ester group may be a compound having the following structural formula, but is not limited thereto.

[0045]

[0046] In the present disclosure, the carbon number of the imide group is not particularly limited, but is preferably 1 to 25. Specifically, the imide group may be a compound having the following structural formula, but is not limited thereto.

[0047]

[0048] In the present disclosure, the silyl group specifically includes trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl and the like, but is not limited thereto.

[0049] In the present disclosure, the boryl group specifically includes a trimethylboryl group, a triethylboryl group, a tert-butyldimethylboryl group, a triphenylboryl group, and a phenylboryl group, but is not limited thereto.

[0050] In the present disclosure, examples of halogen groups include fluorine, chlorine, bromine, or iodine.

[0051] In the present disclosure, the alkyl group may be linear or branched, and its carbon number is not particularly limited, but is preferably 1 to 40. According to one embodiment, the carbon number of the alkyl group is 1 to 20. According to another embodiment, the carbon number of the alkyl group is 1 to 10. According to another embodiment, the carbon number of 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, 5-methylhexyl and the like, but are not limited thereto.

[0052] In the present disclosure, the alkenyl group may be linear or branched, and its carbon number is not particularly limited, but is preferably 2 to 40. According to one embodiment, the carbon number of the alkenyl group is 2 to 20. According to another embodiment, the carbon number of the alkenyl group is 2 to 10. According to yet another embodiment, the carbon number of the alkenyl group is 2 to 6. Specific examples thereof include 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-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbene, styryl, etc., but are not limited thereto.

[0053] In the present disclosure, the cycloalkyl group is not particularly limited, but its carbon number is preferably 3 to 60. According to one embodiment, the carbon number of the cycloalkyl group is 3 to 30. According to another embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to yet another embodiment, the carbon number of the cycloalkyl group is 3 to 6. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl and the like, but are not limited thereto.

[0054] In the present disclosure, the aryl group is not particularly limited, but its carbon number is preferably 6 to 60, and it 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. As a monocyclic aryl group, the aryl group may be phenyl, biphenyl, terphenyl, etc., but is not limited thereto. Polycyclic aryl groups include naphthyl, anthracenyl, phenanthrenyl, pyrenyl, peryl, fluorenyl, etc., but not limited thereto.

[0055] In the present disclosure, the fluorenyl group may be substituted, and two substituents may be connected to each other to form a spirocyclic structure. In the case where the fluorenyl group is substituted, etc. However, the structure is not limited thereto.

[0056] In the present disclosure, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si and S as a heteroatom, and the carbon number thereof is not particularly limited, but is preferably 2 to 60. Examples of the heterocyclic group include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, Azolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolinyl, indolyl, carbazolyl, benzo[omicron] oxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothiophenyl, dibenzothiophenyl, benzofuranyl, phenanthroline, isothiophene oxazolyl, thiadiazolyl, phenothiazinyl, dibenzofuranyl, etc., but are not limited thereto.

[0057] In the present disclosure, the aryl group in aralkyl, aralkenyl, alkylaryl, and arylamine groups is the same as the example of the aryl group as defined above. In the present disclosure, the alkyl group in aralkyl, alkylaryl, and alkylamine groups is the same as the example of the alkyl group as defined above. In the present disclosure, the heteroaryl group in heteroarylamine groups can be applied to the description of the heterocyclic group as defined above. In the present disclosure, the alkenyl group in aralkenyl groups is the same as the example of the alkenyl group as defined above. In the present disclosure, the description of the aryl group as defined above can be applied, except that the arylene group is a divalent group. In the present disclosure, the description of the heterocyclic group as defined above can be applied, except that the heteroarylene group is a divalent group. In the present disclosure, the description of the aryl group or heterocycloalkyl group as defined above can be applied, except that the hydrocarbon ring is not a monovalent group but is formed by combining two substituents. In the present disclosure, the description of the heterocyclic group as defined above can be applied, except that the heterocyclic ring is not a monovalent group but is formed by combining two substituents.

[0058] In the present disclosure, the term "deuterated or deuterium-substituted" means that at least one of the substitutable hydrogens in a compound, a divalent linking group, or a monovalent substituent is replaced with deuterium.

[0059] In addition, the term "unsubstituted or substituted with deuterium" or "deuterium-substituted or unsubstituted" means "unsubstituted or substituted with deuterium from one to the maximum number of substitutable hydrogen atoms." In one example, considering that the maximum number of hydrogen atoms that can be replaced by deuterium in the phenanthryl structure is 9, the term "unsubstituted or deuterium-substituted phenanthryl" can be understood to mean "phenanthryl that is unsubstituted or substituted with 1 to 9 deuterium atoms."

[0060] Furthermore, the term "deuterated structure" is intended to encompass compounds, divalent linking groups, or monovalent substituents in all structures in which at least one hydrogen is replaced by deuterium. In one example, a deuterated structure of a phenyl group can be understood to refer to monovalent substituents in all structures in which at least one substitutable hydrogen in the phenyl group is replaced by deuterium.

[0061]

[0062] In the present disclosure, the deuterium substitution rate of a compound means the ratio of the number of substituted deuterium atoms to the total number of hydrogen atoms that can be present in the compound (the sum of the number of hydrogen atoms in the compound that can be replaced by deuterium and the number of substituted deuterium atoms), calculated as a percentage. Therefore, when the deuterium substitution rate of a compound is "K%", it means that K% of the hydrogen atoms in the compound that can be replaced by deuterium are replaced by deuterium.

[0063] At this time, the "deuterium substitution rate" or "deuteration degree" can be determined by using MALDI-TOF MS (matrix-assisted laser desorption / ionization time-of-flight mass spectrometry), nuclear magnetic resonance spectroscopy ( 1 H NMR), TLC / MS (thin layer chromatography / mass spectrometry), GC / MS (gas chromatography / mass spectrometry), etc.

[0064] More specifically, when using MALDI-TOF MS, the "deuterium substitution rate" or "degree of deuteration" can be obtained by determining the number of deuterium atoms substituted in a compound through MALDI-TOF MS analysis, and then calculating the ratio of the number of deuterium atoms substituted to the total number of hydrogen atoms that can be present in the compound as a percentage. Therefore, when the deuterium substitution rate of a compound is "K%", it means that K% of the hydrogen atoms in the compound that can be replaced by deuterium are replaced by deuterium.

[0065] Furthermore, when TLC / MS analysis is used, the "deuterium substitution rate" or "deuteration degree" can be obtained by calculating the substitution rate based on the maximum value (max. value) of the distribution formed by the molecular weight at the end of the reaction.

[0066] In addition, when using NMR (1 When analyzing by H NMR), the "deuterium substitution rate" or "deuteration degree" can be determined by 1 The integrated amount of all peaks in H NMR was calculated from the integration ratio.

[0067] Meanwhile, in the present disclosure, “there is no deuterium at a specific position” means that the deuterium substitution rate at the position is 10% or less, and does not mean that the deuterium substitution rate is 0%. In addition, in the present disclosure, “there is deuterium at a specific position” means that the deuterium substitution rate at the position is greater than 1%, and does not mean that the deuterium substitution rate at the position is 100%. In this way, the “deuterium substitution rate at a specific position” can be obtained by analyzing the deuterium substitution rate of the compound that is not deuterated. 1 H NMR spectra of deuterium-substituted compounds 1 The H NMR spectra were compared, and the ratio of the decrease in the integrated amount of the peak at each hydrogen (proton) position was determined and calculated.

[0068] Hereinafter, the present disclosure will be described in detail with respect to each configuration.

[0069] anode and cathode

[0070] Anode and cathode used in this disclosure refer to electrodes used in an organic light emitting device.

[0071] As the anode material, it is generally preferred to use a material with a large work function so that holes can be smoothly injected into the organic material layer. Specific examples of anode materials include: metals such as vanadium, chromium, copper, zinc and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole and polyaniline, etc., but are not limited thereto.

[0072] As the cathode material, a material with a small work function is generally preferred, so that electrons can be easily injected into the organic material layer. Specific examples of cathode materials include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayer structure materials such as LiF / Al or LiO2 / Al; and the like.

[0073] hole injection layer

[0074] If necessary, the organic light-emitting device according to the present disclosure may further include a hole injection layer on the anode.

[0075] The hole injection layer is a layer that injects holes from the electrode, and the hole injection material is preferably a compound that has the ability to transport holes, has an effect of injecting holes into the anode, has an excellent hole injection effect into the light-emitting layer or light-emitting material, prevents excitons generated in the light-emitting layer from migrating to the electron injection layer or electron injection material, and has excellent thin film forming ability. In addition, it is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer.

[0076] Specific examples of the hole injection material include metalloporphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene-based organic materials, anthraquinone, polyaniline and polythiophene-based conductive polymers, etc., but are not limited thereto.

[0077] hole transport layer

[0078] If necessary, the organic light-emitting device according to the present disclosure may include a hole transport layer on the anode (or on the hole injection layer if the hole injection layer exists).

[0079] The hole transport layer is a layer that receives holes from the anode or the hole injection layer and transports the holes to the light emitting layer. The hole transport material is suitably a material having a large hole mobility that can receive holes from the anode or the hole injection layer and transfer the holes to the light emitting layer.

[0080] Specific examples of the hole transport material include arylamine-based organic materials, conductive polymers, block copolymers in which a conjugated portion and a non-conjugated portion exist simultaneously, and the like, but are not limited thereto.

[0081] electron blocking layer

[0082] An electron blocking layer is a layer disposed between a hole transport layer and a light-emitting layer to prevent electrons injected from the cathode from transferring to the hole transport layer and not recombining in the light-emitting layer. It may also be referred to as an electron arresting layer or electron suppressing layer. The electron blocking layer is preferably made of a material with a lower electron affinity than the electron transport layer.

[0083] light-emitting layer

[0084] The light-emitting layer used in the present disclosure is a layer that can emit light in the visible light region by combining holes and electrons transferred from the anode and cathode. Generally, the light-emitting layer contains a host material and a dopant material, and in the present disclosure, contains the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 as the host.

[0085] Preferably, Ar1 and Ar2 can each independently be a substituted or unsubstituted C 6-20Aryl; or a substituted or unsubstituted C 2-20 heteroaryl, and

[0086] More preferably, Ar1 and Ar2 can each independently be phenyl, biphenyl, terphenyl, triphenylsilylphenyl, naphthyl, phenanthryl, dibenzofuranyl, or dibenzothiophenyl, wherein phenyl, biphenyl, terphenyl, triphenylsilylphenyl, naphthyl, phenanthryl, dibenzofuranyl and dibenzothiophenyl can each independently be unsubstituted or substituted with at least one deuterium.

[0087] More preferably, Ar1 and Ar2 may each independently be any one selected from the following compounds, wherein Ar1 and Ar2 may each independently be unsubstituted or substituted with at least one deuterium:

[0088]

[0089] Preferably, L1 can be a single bond; or a substituted or unsubstituted C 6-20 arylene groups,

[0090] More preferably, L1 may be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthalenediyl group, and

[0091] Most preferably, L1 may be a single bond, phenylene or naphthalenediyl, wherein phenylene and naphthalenediyl may each independently be unsubstituted or substituted with at least one deuterium.

[0092] Preferably, L2 and L3 can each independently be a single bond; or a substituted or unsubstituted C 6-20 Arylene; or a substituted or unsubstituted C containing at least one selected from N, O and S 2-20 Heteroarylene,

[0093] More preferably, L2 and L3 may each independently be a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenyldiyl group, or a substituted or unsubstituted naphthalenediyl group, and

[0094] More preferably, L2 and L3 may each independently be a single bond, a phenylene group, a biphenyldiyl group, or a naphthalenediyl group, wherein the phenylene group, the biphenyldiyl group, and the naphthalenediyl group may each independently be unsubstituted or substituted with at least one deuterium group.

[0095] More preferably, L2 and L3 may each independently be a single bond, or be selected from any one of the following compounds, wherein L2 and L3 may each independently be unsubstituted or substituted with at least one deuterium:

[0096]

[0097] Preferably, at least one of Ar1 and Ar2 may be naphthyl, phenylnaphthyl, naphthylphenyl, phenanthryl, fluoranthenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, or benzonaphthothiophenyl, wherein naphthyl, phenylnaphthyl, naphthylphenyl, phenanthryl, fluoranthenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, or benzonaphthothiophenyl may be unsubstituted or substituted with at least one deuterium.

[0098] More preferably, at least one of Ar1 and Ar2 may be naphthyl, phenylnaphthyl, naphthylphenyl, fluoranthenyl, dibenzofuranyl, benzonaphthofuranyl, or benzonaphthothiophenyl, wherein naphthyl, phenylnaphthyl, naphthylphenyl, fluoranthenyl, dibenzofuranyl, benzonaphthofuranyl, or benzonaphthothiophenyl may each independently be unsubstituted or substituted with at least one deuterium.

[0099] Meanwhile, when the deuterium substitution number in a compound is to be expressed, it can be represented by the following Chemical Formula 1D:

[0100] [Chemical Formula 1D]

[0101]

[0102] In Chemical Formula 1D,

[0103] Dn means n hydrogens are replaced by deuterium,

[0104] wherein n is an integer of 13 or greater, and

[0105] Ar1、Ar 2d 、L 1d To L 3d and R 1d to R 7d They respectively mean substituents Ar1, Ar2, L1 to L3 and R1 to R7 which are not substituted with deuterium.

[0106] In one example, in Formula 1D, n of Dn may be 13 or greater, 14 or greater, 15 or greater, 16 or greater, 17 or greater, 18 or greater, or 19 or greater, and 50 or less, 45 or less, 40 or less, 38 or less, 36 or less, 34 or less, 32 or less, 30 or less, 28 or less, 26 or less, 24 or less, 23 or less, 22 or less, 21 or less, or 20 or less.

[0107] Representative examples of the compound represented by Chemical Formula 1 are as follows:

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149] In one example, the compound represented by Chemical Formula 1 can be prepared according to the preparation method shown in the following Reaction Scheme 1, or can be prepared by further performing a deuterium substitution reaction after performing Reaction Scheme 1, and the remaining compounds can also be prepared in a similar manner.

[0150] [Reaction Scheme 1]

[0151]

[0152] In Reaction Scheme 1, Ar1, Ar2, L1 to L3, and R1 to R7 are the same as defined in Chemical Formula 1, and X1 is a halogen, preferably X1 is chlorine or bromine.

[0153] Reaction Scheme 1 is a Suzuki coupling reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactive group used in the Suzuki coupling reaction can be appropriately changed as known in the art. The above-mentioned deuterium substitution reaction is preferably carried out in the presence of D2O, and the reactive group, catalyst, solvent, etc. used in the deuterium substitution reaction can be changed to suit the desired product as known in the art. The preparation method can be described in more detail in the preparation examples described below.

[0154] The compound represented by Chemical Formula 2 has a structure in which at least one of -L'1-Ar'1 and R'1 is deuterium, and thus the phenanthryl group of Chemical Formula 2 is substituted with at least one hydrogen. Herein, "the phenanthryl group is substituted with at least one deuterium" means "at least one of the nine carbon atoms that can be substituted with deuterium in the phenanthryl group of Chemical Formula 2 has deuterium positioned but no hydrogen." More specifically, it means that one carbon atom of each phenanthryl carbon atom contained in the compound represented by Chemical Formula 1 is substituted with deuterium, wherein the deuterium substitution rate of each of the remaining eight carbon atoms is greater than 1%. By replacing the undeuterated carbon atom of the compound with the deuterium atom, the deuterium atom of the compound with the deuterium atom is replaced with the deuterium atom. 1 H NMR spectra of deuterium-substituted compounds 1 By comparing the H NMR spectra, the deuterium substitution rate on each carbon of the phenanthryl group can be calculated.

[0155] Preferably, Chemical Formula 2 may be represented by any one of the following Chemical Formulas 2A to 2I.

[0156] [Chemical Formula 2A]

[0157]

[0158] [Chemical Formula 2B]

[0159]

[0160] [Chemical Formula 2C]

[0161]

[0162] [Chemical Formula 2D]

[0163]

[0164] [Chemical Formula 2E]

[0165]

[0166] [Chemical Formula 2F]

[0167]

[0168] [Chemical formula 2G]

[0169]

[0170] [Chemical formula 2H]

[0171]

[0172] [Chemical Formula 2I]

[0173]

[0174] In Chemical Formulas 2A to 2I,

[0175] D is deuterium,

[0176] a' is an integer from 0 to 7, and

[0177] Ar'1 to Ar'3, L'1 to L'4 and R'1 are as defined in Chemical Formula 2.

[0178] Preferably, Ar'1 can be hydrogen; deuterium; substituted or unsubstituted C 6-20 Aryl; or a substituted or unsubstituted C 2-20 heteroaryl, and

[0179] More preferably, Ar'1 can be hydrogen; deuterium; or substituted or unsubstituted C 6-20 Aryl.

[0180] More preferably, Ar'1 can be hydrogen; deuterium; or phenyl which is unsubstituted or substituted with at least one deuterium group.

[0181] Preferably, Ar'2 and Ar'3 can each independently be a substituted or unsubstituted C 6-20 Aryl; or a substituted or unsubstituted C 2-20 heteroaryl, and

[0182] More preferably, Ar'2 and Ar'3 can each independently be phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, tetrahydronaphthyl, phenanthryl, phenylphenanthryl, triphenylene, dimethylfluorenyl, diphenylfluorenyl, carbazolyl, phenylcarbazolyl, dibenzofuranyl, dibenzothiophenyl, or phenyldibenzofuranyl, wherein phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, tetrahydronaphthyl, phenanthryl, phenylphenanthryl, triphenylene, dimethylfluorenyl, diphenylfluorenyl, carbazolyl, phenylcarbazolyl, dibenzofuranyl, dibenzothiophenyl, and phenyldibenzofuranyl can each independently be unsubstituted or substituted with at least one deuterium or at least one C 1-10 Alkyl substitution.

[0183] Most preferably, Ar'2 and Ar'3 can each independently be phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, tetrahydronaphthyl, phenanthrenyl, phenylphenanthrenyl, triphenylene, dimethylfluorenyl, diphenylfluorenyl, carbazolyl, phenylcarbazolyl, dibenzofuranyl, dibenzothienyl, phenyldibenzofuranyl, tetramethyltetrahydronaphthyl, methylphenyl, isopropylphenyl, tert-butylphenyl, di-tert-butylphenyl, methylbiphenyl, isopropylbiphenyl, tert-butylbiphenyl, dimethylbiphenyl, diisopropylbiphenyl, di-tert-butylbiphenyl, methylterphenyl, isopropylterphenyl, or tert-butylterphenyl , wherein phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, tetrahydronaphthyl, phenanthryl, phenylphenanthryl, triphenylene, dimethylfluorenyl, diphenylfluorenyl, carbazolyl, phenylcarbazolyl, dibenzofuranyl, dibenzothienyl, phenyldibenzofuranyl, tetramethyltetrahydronaphthyl, methylphenyl, isopropylphenyl, tert-butylphenyl, di-tert-butylphenyl, methylbiphenyl, isopropylbiphenyl, tert-butylbiphenyl, dimethylbiphenyl, diisopropylbiphenyl, di-tert-butylbiphenyl, methylterphenyl, isopropylterphenyl and tert-butylterphenyl can each independently be unsubstituted or substituted with at least one deuterium.

[0184] Most preferably, Ar'2 and Ar'3 can each independently be phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, tetrahydronaphthyl, tetramethyltetrahydronaphthyl, phenyl substituted by one or two methyl groups, phenyl substituted by one or two isopropyl groups, phenyl substituted by one or two tert-butyl groups, dibenzofuranyl, or dibenzothienyl, wherein phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, tetrahydronaphthyl, tetramethyltetrahydronaphthyl, phenyl substituted by one or two methyl groups, phenyl substituted by one or two isopropyl groups, phenyl substituted by one or two tert-butyl groups, dibenzofuranyl and dibenzothienyl can each independently be unsubstituted or substituted by at least one deuterium.

[0185] Preferably, L'1 to L'3 are each independently a single bond; substituted or unsubstituted C 6-20 Arylene; or a substituted or unsubstituted C containing at least one selected from N, O and S 2-20 heteroarylene, and

[0186] More preferably, L'1 to L'3 can each independently be a single bond, a phenylene group, a biphenylene group, a naphthylene group, a phenylnaphthylene group, a phenanthrenyl group, a carbazolyl group, a phenylcarbazolyl group, a dibenzofuranyl group, a phenyldibenzofuranyl group, or a dimethylfluorenyl group, wherein the phenylene group, the biphenylene group, the naphthylene group, the phenylnaphthylene group, the phenanthrenyl group, the carbazolyl group, the phenylcarbazolyl group, the dibenzofuranyl group, the phenyldibenzofuranyl group, and the dimethylfluorenyl group can each independently be unsubstituted or substituted with at least one deuterium group.

[0187] Preferably, L'1 may be a single bond, and L'2 and L'3 may each independently be a single bond; substituted or unsubstituted C 6-20 Arylene; or a substituted or unsubstituted C containing at least one selected from N, O and S 2-20 heteroarylene, and

[0188] More preferably, L'1 can be a single bond, and L'2 and L'3 can each independently be a single bond, a phenylene group, a biphenylene group, a naphthylene group, a phenylnaphthylene group, a phenanthrenyl group, a carbazolyl group, a phenylcarbazolyl group, a dibenzofuranyl group, a phenyldibenzofuranyl group, or a dimethylfluorenyl group, wherein the phenylene group, the biphenylene group, the naphthylene group, the phenylnaphthylene group, the phenanthrenyl group, the carbazolyl group, the phenylcarbazolyl group, the dibenzofuranyl group, the phenyldibenzofuranyl group, and the dimethylfluorenyl group can each independently be unsubstituted or substituted with at least one deuterium group.

[0189] Most preferably, L'1 can be a single bond, and L'2 and L'3 can each independently be a single bond, phenylene, biphenylene, naphthylene, or phenylnaphthylene, wherein phenylene, biphenylene, naphthylene and phenylnaphthylene can each independently be unsubstituted or substituted with at least one deuterium.

[0190] Preferably, L'4 can be a single bond or a substituted or unsubstituted C 6-20 arylene groups,

[0191] More preferably, L'4 can be a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted naphthylene group.

[0192] Most preferably, L'4 can be a single bond, phenylene, biphenylene, or naphthylene, wherein phenylene, biphenylene, and naphthylene can each independently be unsubstituted or substituted with at least one deuterium group.

[0193] Preferably, the compound represented by Chemical Formula 2 may be represented by the following Chemical Formula 2-1:

[0194] [Chemical Formula 2-1]

[0195]

[0196] In Chemical Formula 2-1,

[0197] Ar'1 to Ar'3, L'1 to L'3, R'1 and a are as defined in Chemical Formula 2,

[0198] R'2 is hydrogen; deuterium; or substituted or unsubstituted C 6-60 Aryl, and

[0199] b is an integer from 0 to 4.

[0200] Preferably, R'2 is hydrogen; deuterium; or substituted or unsubstituted C 6-20 aryl, and

[0201] More preferably, R'2 can be hydrogen, deuterium, or unsubstituted or deuterium-substituted phenyl.

[0202] The deuterium substitution rate of the compound represented by Chemical Formula 2 may be 50% to 100%. Specifically, the deuterium substitution rate of the compound may be 50% or more, 60% or more, 70% or more, 75% or more, 80% or more, or 90% or more, and 100% or less.

[0203] In one example, the compound represented by Chemical Formula 2 may contain 16 to 50 deuteriums, but is not limited thereto. More specifically, the compound may contain 16 or more, 17 or more, 18 or more, or 19 or more, and 50 or less, 45 or less, 40 or less, 38 or less, 36 or less, 34 or less, 32 or less, 30 or less, 28 or less, 26 or less, 24 or less, 23 or less, 22 or less, 21 or less, or 20 or less deuteriums.

[0204] In this case, when the deuterium substitution number in the compound is to be expressed, it can be represented by the following Chemical Formula 2-D:

[0205] [Chemical Formula 2-D]

[0206]

[0207] In chemical formula 2-D,

[0208] Dn means the total number of deuterium (D) substituted in the entire compound is n,

[0209] R'1 and a are as defined in Chemical Formula 2.

[0210] n is a value including a,

[0211] Ar' 1d to Ar' 3d and L' 1d To L' 4d respectively refer to substituents Ar'1 to Ar'3 and L'1 to L'4 which are not substituted with deuterium, and

[0212] -L' 1d -Ar' 1d At least one of R' and R'1 is deuterium.

[0213] That is, in Chemical Formula 2-D, n is the total number of deuterium substituted in the compound, which is an integer (the deuterium substitution rate of the compound is 50% or more) and is a value including a or a+1, where a or a+1 is the number of deuterium substituted in the phenanthryl group. The compound represented by Chemical Formula 2-D means a compound in which the phenanthryl group is substituted with a or a+1 deuterium atoms and the entire compound is substituted with n deuterium atoms. The reason why the number of deuterium substituted on the phenanthryl group is a or a+1 is because -L' 1d -Ar' 1d It may be deuterium.

[0214] In one example, in Formula 2-D, n of Dn may be 16 or greater, 17 or greater, or 18 or greater, or 19 or greater, and 50 or less, 45 or less, 40 or less, 38 or less, 36 or less, 34 or less, 32 or less, 30 or less, 28 or less, 26 or less, 24 or less, 23 or less, 22 or less, 21 or less, or 20 or less.

[0215] Representative examples of the compound represented by Chemical Formula 2 are as follows:

[0216]

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255] In the above group, D is deuterium, n1 is an integer from 1 to 9, and

[0256] n is the total number of deuterium substituted in the compound,

[0257] wherein the deuterium substitution rate of each of the above compounds is 50% or greater.

[0258] When the compound represented by Chemical Formula 2 is, for example, a compound represented by Chemical Formula 2-D, the compound can be prepared according to the preparation method as shown in the following Reaction Scheme 2, and the remaining compounds can also be prepared in a similar manner.

[0259] [Reaction Scheme 2]

[0260]

[0261] In reaction scheme 2, Dn, Ar' 1d to Ar' 3d and L' 1d To L' 4d As defined in Chemical Formula 2-D, X1' is a halogen, and preferably X1' is chlorine or bromine.

[0262] The compound represented by Chemical Formula 2 in Reaction Scheme 2 can be prepared by subjecting each deuterium-substituted reactant to a Suzuki coupling reaction, and Reaction Scheme 2 is carried out by a deuterium substitution reaction (step 1) followed by a Suzuki coupling reaction (step 2). The deuterium substitution reaction is preferably carried out in the presence of D2O, and the reactive group, catalyst, solvent, etc. for the deuterium substitution reaction can be changed to be suitable for the desired product as known in the art. The Suzuki coupling reaction is preferably carried out in the presence of a palladium catalyst and a base, and the reactive group for the Suzuki coupling reaction can be changed as known in the art. The preparation method can be described in more detail in the preparation example described hereinafter.

[0263] Preferably, the weight ratio of the compound represented by Chemical Formula 1 to the compound represented by Chemical Formula 2 in the light emitting layer is 10:90 to 90:10, more preferably 20:80 to 80:20, and 30:70 to 70:30, or 40:60 to 60:40.

[0264] On the other hand, the light-emitting layer may further include a dopant in addition to the host. The dopant material is not particularly limited as long as it is a material used for an organic light-emitting device. As examples, aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, etc. may be mentioned. Specific examples of aromatic amine derivatives include substituted or unsubstituted fused aromatic ring derivatives having an arylamino group, examples of which include pyrene, anthracene, and diindenopyrene. Styrylamine compounds are compounds in which a substituted or unsubstituted arylamine is substituted with at least one arylvinyl group, wherein one or two or more substituents selected from aryl, silyl, alkyl, cycloalkyl, and arylamino groups are substituted or unsubstituted. Specific examples include, but are not limited to, styrylamine, styryldiamine, styryltriamine, and styryltetramine. Furthermore, examples of metal complexes include, but are not limited to, iridium complexes and platinum complexes.

[0265] In one example, the dopant material may be any one or more compounds selected from the following compounds, but is not limited thereto:

[0266]

[0267]

[0268]

[0269]

[0270] hole blocking layer

[0271] A hole-blocking layer is a layer disposed between an electron-transporting layer and an emitting layer to prevent holes injected from the anode from being transferred to the electron-transporting layer and not recombining in the emitting layer. It may also be referred to as a hole-inhibiting layer or a hole-blocking layer. The hole-blocking layer is preferably made of a material with a large ionization energy.

[0272] electron transport layer

[0273] If necessary, the organic light-emitting device according to the present disclosure may include an electron transport layer on the light-emitting layer.

[0274] The electron transport layer is a layer that receives electrons from the cathode or the electron injection layer formed on the cathode and transports the electrons to the light-emitting layer, and inhibits the transfer of holes from the light-emitting layer. The electron transport material is suitably a material that can well receive the injection of electrons from the cathode and transfer the electrons to the light-emitting layer, and has a large electron mobility.

[0275] Specific examples of electron transport materials include, but are not limited to, Al complexes of 8-hydroxyquinoline; complexes containing Alq3; organic free radical compounds; and hydroxyflavone-metal complexes. The electron transport layer can be used with any desired cathode material, as used in conventional techniques. Suitable cathode materials are typically low-work-function materials followed by an aluminum or silver layer. Specific examples include cesium, barium, calcium, ytterbium, and samarium, each followed by an aluminum or silver layer.

[0276] electron injection layer

[0277] If necessary, the organic light-emitting device according to the present disclosure may further include an electron injection layer on the light-emitting layer (or on the electron transport layer if the electron transport layer exists).

[0278] The electron injection layer is a layer that injects electrons from the electrode, and is preferably a compound that has the ability to transport electrons, has the effect of injecting electrons from the cathode, and has an excellent effect of injecting electrons into the light-emitting layer or the light-emitting material, prevents the excitons generated by the light-emitting layer from moving to the hole injection layer, and is also excellent in the ability to form a thin film.

[0279] Specific examples of the electron injection layer include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, Azoles, Oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylmethane, anthrone, etc., and their derivatives; metal complex compounds; nitrogen-containing 5-membered ring derivatives; etc., but not limited thereto.

[0280] Examples of metal complex compounds include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h]quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)(o-cresol)gallium, bis(2-methyl-8-quinolinato)(1-naphthol)aluminum, bis(2-methyl-8-quinolinato)(2-naphthol)gallium, and the like, but are not limited thereto.

[0281] On the other hand, in the present disclosure, the “electron injection and transport layer” is a layer that functions as both an electron injection layer and an electron transport layer, and materials that function as the respective layers may be used alone or in combination, but are not limited thereto.

[0282] organic light-emitting devices

[0283] The structure of the organic light emitting device according to the present disclosure is shown in Figure 1 and Figure 2 middle. Figure 1 An example of an organic light-emitting device including a substrate 1 , an anode 2 , a light-emitting layer 3 , and a cathode 4 is shown. Figure 2 An example of an organic light emitting device including a substrate 1 , an anode 2 , a hole injection layer 5 , a hole transport layer 6 , an electron blocking layer 7 , a light emitting layer 3 , a hole blocking layer 8 , an electron injection and transport layer 9 and a cathode 4 is shown.

[0284] The organic light-emitting device according to the present disclosure can be manufactured by stacking the above-mentioned structures in sequence. In this case, the organic light-emitting device can be manufactured by depositing a metal, a conductive metal oxide or an alloy thereof on a substrate to form an anode by using a PVD (physical vapor deposition) method such as sputtering or electron beam evaporation to form the anode, forming the above-mentioned various layers on the anode, and then depositing a material that can be used as a cathode thereon. In addition to such a method, the organic light-emitting device can also be manufactured by sequentially depositing from the cathode material to the anode material on a substrate in the opposite order of the above-mentioned configuration (WO 2003 / 012890). In addition, the light-emitting layer can be formed by subjecting the host and the dopant to a vacuum deposition method and a solution coating method. In this article, the solution coating method means spin coating, dip coating, blade coating, inkjet printing, screen printing, spraying, roller coating, etc., but is not limited thereto.

[0285] Meanwhile, the organic light emitting device according to the present disclosure may be a bottom-emitting device, a top-emitting device, or a double-sided light emitting device.

[0286] Hereinafter, preferred embodiments are presented to help understand the present disclosure. The following examples are provided only for a better understanding of the present disclosure and are not intended to limit the content of the present disclosure.

[0287] Preparation Example 1-1

[0288]

[0289] Compound Trz1 (15 g, 28.8 mmol) and dibenzo [b, d] furan-1-ylboronic acid (6.4 g, 30.3 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (12 g, 86.5 mmol) was then dissolved in 36 ml of water and added thereto, and the mixture was thoroughly stirred, and then bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2 g of compound 1-1. (Yield: 65%, MS: [M+H] + =652).

[0290] Preparation Example 1-2

[0291]

[0292] Compound Trz2 (15 g, 30.4 mmol) and dibenzo [b, d] furan-1-ylboronic acid (6.8 g, 31.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (12.6 g, 91.1 mmol) was then dissolved in 38 ml of water and added thereto, and the mixture was thoroughly stirred, followed by addition of bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol). After reacting for 5 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14 g of compound 1-2. (Yield: 74%, MS: [M+H] + =626).

[0293] Preparation Examples 1-3

[0294]

[0295] Compound Trz3 (15 g, 33.8 mmol) and dibenzo [b, d] furan-1-ylboronic acid (7.5 g, 35.5 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (14 g, 101.4 mmol) was then dissolved in 42 ml of water and added thereto, and the mixture was thoroughly stirred, followed by addition of bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol). After reacting for 5 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4 g of compound 1-3. (Yield: 69%, MS: [M+H] + =576).

[0296] Preparation Examples 1-4

[0297]

[0298] Compound Trz4 (15 g, 30.4 mmol) and dibenzo [b, d] furan-1-ylboronic acid (6.8 g, 31.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (12.6 g, 91.1 mmol) was then dissolved in 38 ml of water and added thereto, and the mixture was thoroughly stirred, followed by addition of bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol). After reacting for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of compound 1-4. (Yield: 70%, MS: [M+H] + =626).

[0299] Preparation Examples 1-5

[0300]

[0301] Compound Trz5 (15 g, 24.9 mmol) and dibenzo [b, d] furan-1-ylboronic acid (5.5 g, 26.2 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (10.3 g, 74.7 mmol) was then dissolved in 31 ml of water and added thereto, and the mixture was thoroughly stirred, followed by the addition of bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol). After reacting for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.6 g of compound 1-5. (Yield: 69%, MS: [M+H] + =734).

[0302] Preparation Examples 1-6

[0303]

[0304] Compound Trz6 (15 g, 30.2 mmol) and dibenzo [b, d] furan-1-ylboronic acid (6.7 g, 31.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (12.5 g, 90.7 mmol) was then dissolved in 38 ml of water and added thereto, and the mixture was thoroughly stirred, followed by addition of bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol). After reacting for 4 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5 g of compound 1-6. (Yield: 66%, MS: [M+H] + =629).

[0305] Preparation Examples 1-7

[0306]

[0307] Compound Trz7 (15 g, 36.8 mmol) and dibenzo [b, d] furan-1-ylboronic acid (8.2 g, 38.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (15.2 g, 110.3 mmol) was then dissolved in 46 ml of water and added thereto, and the mixture was thoroughly stirred, followed by the addition of bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol). After reacting for 5 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.9 g of compound 1-7. (Yield: 75%, MS: [M+H] + =540).

[0308] Preparation Examples 1-8

[0309]

[0310] Compound Trz8 (15 g, 35.9 mmol) and dibenzo [b, d] furan-1-ylboronic acid (8 g, 37.7 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (14.9 g, 107.7 mmol) was then dissolved in 45 ml of water and added thereto, and the mixture was thoroughly stirred, followed by addition of bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol). After reacting for 5 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8 g of compound 1-8. (Yield: 70%, MS: [M+H] + =550).

[0311] Preparation Examples 1-9

[0312]

[0313] Compound Trz9 (15g, 33.8mmol) and dibenzo[b,d]furan-1-ylboronic acid (7.5g, 35.5mmol) were added to 300ml THF, and the mixture was stirred and refluxed. Potassium carbonate (14g, 101.4mmol) was then dissolved in 42ml water and added thereto, and the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 5 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6g of compound 1-9. (Yield: 70%, MS:[M+H] + =576).

[0314] Preparation Example 1-10

[0315]

[0316] Compound Trz10 (15 g, 35.9 mmol) and dibenzo [b, d] furan-1-ylboronic acid (8 g, 37.7 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (14.9 g, 107.7 mmol) was then dissolved in 45 ml of water and added thereto, and the mixture was thoroughly stirred, followed by addition of bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol). After reacting for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8 g of compound 1-10. (Yield: 70%, MS: [M+H] + =550).

[0317] Preparation Example 1-11

[0318]

[0319] Compound Trz11 (15 g, 30.4 mmol) and dibenzo [b, d] furan-1-ylboronic acid (6.8 g, 31.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (12.6 g, 91.1 mmol) was then dissolved in 38 ml of water and added thereto, and the mixture was thoroughly stirred, followed by the addition of bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol). After reacting for 4 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.7 g of compound 1-11. (Yield: 72%, MS: [M+H] + =626).

[0320] Preparation Example 1-12

[0321]

[0322] Compound Trz12 (15 g, 33.8 mmol) and dibenzo [b, d] furan-1-ylboronic acid (7.5 g, 35.5 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (14 g, 101.4 mmol) was then dissolved in 42 ml of water and added thereto, and the mixture was thoroughly stirred, followed by addition of bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol). After reacting for 5 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2 g of compound 1-12. (Yield: 73%, MS: [M+H] + =576).

[0323] Preparation Example 1-13

[0324]

[0325] Compound Trz13 (15 g, 33.8 mmol) and dibenzo [b, d] furan-1-ylboronic acid (7.5 g, 35.5 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (14 g, 101.4 mmol) was then dissolved in 42 ml of water and added thereto, and the mixture was thoroughly stirred, followed by addition of bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol). After reacting for 4 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4 g of compound 1-13. (Yield: 69%, MS: [M+H] + =576).

[0326] Preparation Example 1-14

[0327]

[0328] Compound Trz14 (15 g, 31.9 mmol) and dibenzo[b,d]furan-1-ylboronic acid (7.1 g, 33.5 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (13.2 g, 95.8 mmol) was then dissolved in 40 ml of water and added thereto, and the mixture was thoroughly stirred, followed by addition of bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol). After reacting for 5 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2 g of compound 1-14. (Yield: 74%, MS:[M+H] + =602).

[0329] Preparation Example 1-15

[0330]

[0331] Compound Trz15 (15 g, 35.4 mmol) and dibenzo[b,d]furan-1-ylboronic acid (7.9 g, 37.2 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (14.7 g, 106.2 mmol) was then dissolved in 44 ml of water and added thereto, and the mixture was thoroughly stirred, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol). After reacting for 4 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3 g of compound 1-15. (Yield: 73%, MS: [M+H] + =556).

[0332] Preparation Example 1-16

[0333]

[0334] Compound Trz16 (15 g, 32.8 mmol) and dibenzo [b, d] furan-1-ylboronic acid (7.3 g, 34.4 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (13.6 g, 98.3 mmol) was then dissolved in 41 ml of water and added thereto, and the mixture was thoroughly stirred, followed by the addition of bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol). After reacting for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3 g of compound 1-16. (Yield: 74%, MS: [M+H] + =590).

[0335] Preparation Example 1-17

[0336]

[0337] Compound Trz17 (15 g, 30 mmol) and dibenzo [b, d] furan-1-ylboronic acid (6.7 g, 31.5 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (12.4 g, 90 mmol) was then dissolved in 37 ml of water and added thereto, and the mixture was thoroughly stirred, followed by the addition of bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol). After reacting for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14 g of compound 1-17. (Yield: 74%, MS: [M+H] + =632).

[0338] Preparation Example 1-18

[0339]

[0340] Compound Trz18 (15 g, 31.6 mmol) and dibenzo[b, d]furan-1-ylboronic acid (7 g, 33.2 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (13.1 g, 94.7 mmol) was then dissolved in 39 ml of water and added thereto, and the mixture was thoroughly stirred, followed by addition of bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol). After reacting for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2 g of compound 1-18. (Yield: 74%, MS:[M+H] + =607).

[0341] Preparation Example 1-19

[0342]

[0343] Compound Trz19 (15 g, 31.9 mmol) and dibenzo[b,d]furan-1-ylboronic acid (7.1 g, 33.5 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (13.2 g, 95.8 mmol) was then dissolved in 40 ml of water and added thereto, and the mixture was thoroughly stirred, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol). After reacting for 5 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.7 g of compound 1-19. (Yield: 66%, MS:[M+H] + =602).

[0344] Preparation Example 1-20

[0345]

[0346] Compound Trz20 (15 g, 34.6 mmol) and dibenzo [b, d] furan-1-ylboronic acid (7.7 g, 36.3 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (14.3 g, 103.7 mmol) was then dissolved in 43 ml of water and added thereto, and the mixture was thoroughly stirred, followed by addition of bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol). After reacting for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.9 g of compound 1-20. (Yield: 71%, MS: [M+H] + =566).

[0347] Preparation Example 1-21

[0348]

[0349] Compound Trz21 (15 g, 33.3 mmol) and dibenzo [b, d] furan-1-ylboronic acid (7.4 g, 35 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (13.8 g, 100 mmol) was then dissolved in 41 ml of water and added thereto, and the mixture was thoroughly stirred, followed by addition of bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol). After reacting for 4 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.9 g of compound 1-21. (Yield: 72%, MS: [M+H] + =582).

[0350] Preparation Example 1-22

[0351]

[0352] Compound Trz22 (15 g, 28.8 mmol) and dibenzo [b, d] furan-1-ylboronic acid (6.4 g, 30.3 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (12 g, 86.5 mmol) was then dissolved in 36 ml of water and added thereto, and the mixture was thoroughly stirred, followed by addition of bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol). After reacting for 4 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of compound 1-22. (Yield: 71%, MS: [M+H] + =652).

[0353] Preparation Example 1-23

[0354]

[0355] Compound Trz23 (15 g, 28.8 mmol) and dibenzo [b, d] furan-1-ylboronic acid (6.4 g, 30.3 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (12 g, 86.5 mmol) was then dissolved in 36 ml of water and added thereto, and the mixture was thoroughly stirred, followed by addition of bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol). After reacting for 5 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.7 g of compound 1-23. (Yield: 73%, MS: [M+H] + =652).

[0356] Preparation Example 1-24

[0357]

[0358] Compound Trz24 (15 g, 28.8 mmol) and dibenzo[b, d]furan-1-ylboronic acid (6.4 g, 30.3 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (12 g, 86.5 mmol) was then dissolved in 36 ml of water and added thereto, and the mixture was thoroughly stirred, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol). After reacting for 4 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.6 g of compound 1-24. (Yield: 67%, MS:[M+H] + =652).

[0359] Preparation Example 1-25

[0360]

[0361] Compound Trz25 (15 g, 30 mmol) and dibenzo [b, d] furan-1-ylboronic acid (6.7 g, 31.5 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (12.4 g, 90 mmol) was then dissolved in 37 ml of water and added thereto, and the mixture was thoroughly stirred, followed by addition of bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol). After reacting for 5 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2 g of compound 1-25. (Yield: 75%, MS: [M+H] + =632).

[0362] Preparation Example 1-26

[0363]

[0364] Compound Trz26 (15 g, 27.5 mmol) and dibenzo [b, d] furan-1-ylboronic acid (6.1 g, 28.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (11.4 g, 82.4 mmol) was then dissolved in 34 ml of water and added thereto, and the mixture was thoroughly stirred, followed by the addition of bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol). After reacting for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14 g of compound 1-26. (Yield: 75%, MS: [M+H] + =678).

[0365] Preparation Example 1-27

[0366]

[0367] Compound Trz27 (15 g, 25 mmol) and dibenzo [b, d] furan-1-ylboronic acid (5.6 g, 26.2 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (10.4 g, 75 mmol) was then dissolved in 31 ml of water and added thereto, and the mixture was thoroughly stirred, followed by addition of bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol). After reacting for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.6 g of compound 1-27. (Yield: 69%, MS: [M+H] + =732).

[0368] Preparation Example 1-28

[0369]

[0370] Compound Trz28 (15 g, 31 mmol) and dibenzo [b, d] furan-1-ylboronic acid (6.9 g, 32.5 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (12.9 g, 93 mmol) was then dissolved in 39 ml of water and added thereto, and the mixture was thoroughly stirred, followed by the addition of bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol). After reacting for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13 g of compound 1-28. (Yield: 68%, MS: [M+H] + =616).

[0371] Preparation Example 1-29

[0372]

[0373] Compound Trz29 (15 g, 31 mmol) and dibenzo [b, d] furan-1-ylboronic acid (6.9 g, 32.5 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (12.9 g, 93 mmol) was then dissolved in 39 ml of water and added thereto, and the mixture was thoroughly stirred, followed by the addition of bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol). After reacting for 4 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of compound 1-29. (Yield: 70%, MS: [M+H] + =616).

[0374] Preparation Example 1-30

[0375]

[0376] Compound Trz30 (15 g, 28.2 mmol) and dibenzo [b, d] furan-1-ylboronic acid (6.3 g, 29.7 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (11.7 g, 84.7 mmol) was then dissolved in 35 ml of water and added thereto, and the mixture was thoroughly stirred, followed by the addition of bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol). After reacting for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of compound 1-30. (Yield: 69%, MS: [M+H] + =663).

[0377] Preparation Example 1-31

[0378]

[0379] Compound Trz31 (15 g, 30.7 mmol) and dibenzo[b, d]furan-1-ylboronic acid (6.8 g, 32.2 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (12.7 g, 92 mmol) was then dissolved in 38 ml of water and added thereto, and the mixture was thoroughly stirred, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol). After reacting for 4 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3 g of compound 1-31. (Yield: 75%, MS: [M+H] + =621).

[0380] Preparation Example 1-32

[0381]

[0382] Compound Trz32 (15 g, 34.6 mmol) and dibenzo [b, d] furan-1-ylboronic acid (7.7 g, 36.3 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (14.3 g, 103.7 mmol) was then dissolved in 43 ml of water and added thereto, and the mixture was thoroughly stirred, followed by addition of bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol). After reacting for 4 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.9 g of compound 1-32. (Yield: 71%, MS: [M+H] + =566).

[0383] Preparation Example 1-33

[0384]

[0385] Trifluoromethanesulfonic anhydride (24g, 85mmol) and deuterium oxide (8.5g, 424.9mmol) were added at 0°C, and the mixture was stirred for 5 hours to prepare a solution. 1-Bromodibenzo[b, d]furan (15g, 60.7mmol) was added to 120mL of 1,2,4-trichlorobenzene, and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly added dropwise to a mixed solution of 1-bromodibenzo[b, d]furan and 1,2,4-trichlorobenzene, and the mixture was stirred while being heated to 140°C, and then the temperature was maintained. After reacting for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.7 g of compound sub1-1-1. (Yield: 38%, MS: [M+H] + =248)

[0386] Compound sub1-1-1 (15 g, 60.5 mmol) and bis(pinacolato)diboron (16.9 g, 66.5 mmol) were added to 300 ml of 1,4-diboron. alkane, and the mixture is stirred under reflux. Then, potassium acetate (8.9 g, 90.7 mmol) is added thereto, the mixture is thoroughly stirred, and then bis(dibenzylideneacetone)palladium (0) (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.6 mmol) are added. After reacting for 6 hours, the reaction mixture is cooled to room temperature, the organic layer is separated using chloroform and water, and then the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated. Anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 13.4 g of compound sub1-1-2. (Yield: 75%, MS: [M+H] + =296)

[0387] Compound sub1-1-2 (15 g, 50.8 mmol) and compound Trz33 (26.4 g, 53.4 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (21.1 g, 152.5 mmol) was then dissolved in 63 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21 g of compound 1-33. (Yield: 66%, MS: [M+H] + =627)

[0388] Preparation Example 1-34

[0389]

[0390] Compound sub1-1-2 (15 g, 50.8 mmol) and compound Trz34 (23.4 g, 53.4 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (21.1 g, 152.5 mmol) was then dissolved in 63 ml of water and added thereto, and the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.4 g of compound 1-34. (Yield: 67%, MS: [M+H] + =572).

[0391] Preparation Example 1-35

[0392]

[0393] Trifluoromethanesulfonic anhydride (48g, 170mmol) and deuterium oxide (17g, 849.9mmol) were added at 0°C, and the mixture was stirred for 5 hours to prepare a solution. 1-Bromodibenzo[b, d]furan (15g, 60.7mmol) was added to 120mL 1,2,4-trichlorobenzene, and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly added dropwise to a mixed solution of 1-bromodibenzo[b, d]furan and 1,2,4-trichlorobenzene, and the mixture was stirred while being heated to 140°C, and then the temperature was maintained. After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6 g of compound sub1-2-1. (Yield: 40%, MS: [M+H] + =249)

[0394] Compound sub1-2-1 (15 g, 60.2 mmol) and bis(pinacolato)diboron (16.8 g, 66.2 mmol) were added to 300 ml of 1,4-diboron. alkane, and the mixture is stirred under reflux. Then, potassium acetate (8.9 g, 90.3 mmol) is added thereto, the mixture is thoroughly stirred, and then bis(dibenzylideneacetone)palladium (0) (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.6 mmol) are added. After reacting for 4 hours, the reaction mixture is cooled to room temperature, the organic layer is separated using chloroform and water, and then the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated. Anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 12.5 g of compound sub1-2-2. (Yield: 70%, MS: [M+H] + =297)

[0395] Compound sub1-2-2 (15 g, 50.6 mmol) and compound Trz35 (28 g, 53.2 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (21 g, 151.9 mmol) was then dissolved in 63 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 4 hours, the reaction mixture was cooled to room temperature, and then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.4 g of compound 1-35. (Yield: 70%, MS: [M+H] + =660)

[0396] Preparation Example 1-36

[0397]

[0398] Compound sub1-2-2 (15 g, 50.6 mmol) and compound Trz36 (27.6 g, 53.2 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (21 g, 151.9 mmol) was then dissolved in 63 ml of water and added thereto, and the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 4 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.5 g of compound 1-36. (Yield: 68%, MS: [M+H] + =654).

[0399] Preparation Example 1-37

[0400]

[0401] Compound sub1-2-2 (15 g, 50.6 mmol) and compound Trz37 (21.9 g, 53.2 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (21 g, 151.9 mmol) was then dissolved in 63 ml of water and added thereto, and the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 4 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.9 g of compound 1-37. (Yield: 65%, MS: [M+H] + =546).

[0402] Preparation Example 1-38

[0403]

[0404] Compound sub1-2-2 (15 g, 50.6 mmol) and compound Trz38 (23.1 g, 53.2 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (21 g, 151.9 mmol) was then dissolved in 63 ml of water and added thereto, and the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19 g of compound 1-38. (Yield: 66%, MS: [M+H] + =568).

[0405] Preparation Example 1-39

[0406]

[0407] Trifluoromethanesulfonic anhydride (71.9 g, 255 mmol) and deuterium oxide (25.5 g, 1274.8 mmol) were added at 0 ° C, and the mixture was stirred for 5 hours to prepare a solution. 1-Bromodibenzo[b, d]furan (15 g, 60.7 mmol) was added to 120 ml of 1,2,4-trichlorobenzene, and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly added dropwise to a mixed solution of 1-bromodibenzo[b, d]furan and 1,2,4-trichlorobenzene, and the mixture was stirred while heating to 140 ° C, and then the temperature was maintained. After reacting for 14 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.3 g of compound sub1-3-1. (Yield: 42%, MS: [M+H] + =250).

[0408] Compound sub1-3-1 (15 g, 60 mmol) and bis(pinacolato)diboron (16.8 g, 66 mmol) were added to 300 ml of 1,4-diboron. oxane, and the mixture is stirred under reflux. Then, potassium acetate (8.8 g, 90 mmol) is added thereto, the mixture is thoroughly stirred, and then bis(dibenzylideneacetone)palladium (0) (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.6 mmol) are added. After reacting for 6 hours, the reaction mixture is cooled to room temperature, the organic layer is separated using chloroform and water, and then the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated. Anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 11.4 g of compound sub1-3-2. (Yield: 64%, MS: [M+H] + =298).

[0409] Compound sub1-3-2 (15 g, 50.5 mmol) and compound Trz18 (25.2 g, 53 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (20.9 g, 151.4 mmol) was then dissolved in 63 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.1 g of compound 1-39. (Yield: 75%, MS: [M+H] + =610).

[0410] Preparation Example 1-40

[0411]

[0412] Compound sub1-3-2 (15 g, 50.5 mmol) and compound Trz39 (22.8 g, 53 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (20.9 g, 151.4 mmol) was then dissolved in 63 ml of water and added thereto, and the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 5 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.5 g of compound 1-40. (Yield: 65%, MS: [M+H] + =565).

[0413] Preparation Example 1-41

[0414]

[0415] Compound sub1-3-2 (15 g, 50.5 mmol) and compound Trz40 (21.1 g, 53 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (20.9 g, 151.4 mmol) was then dissolved in 63 ml of water and added thereto, and the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 5 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.8 g of compound 1-41. (Yield: 66%, MS: [M+H] + =534).

[0416] Preparation Example 1-42

[0417]

[0418] Compound sub1-3-2 (15 g, 50.5 mmol) and compound Trz41 (29.5 g, 53 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (20.9 g, 151.4 mmol) was then dissolved in 63 ml of water and added thereto, and the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 4 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.4 g of compound 1-42. (Yield: 70%, MS: [M+H] + =691).

[0419] Preparation Example 1-43

[0420]

[0421] Trifluoromethanesulfonic anhydride (95.9 g, 340 mmol) and deuterium oxide (34 g, 1699.8 mmol) were added at 0 ° C, and the mixture was stirred for 5 hours to prepare a solution. 1-Bromodibenzo[b, d]furan (15 g, 60.7 mmol) was added to 120 ml of 1,2,4-trichlorobenzene, and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly added dropwise to a mixed solution of 1-bromodibenzo[b, d]furan and 1,2,4-trichlorobenzene, and the mixture was stirred while heating to 140 ° C, and then the temperature was maintained. After reacting for 20 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.6 g of compound sub1-4-1. (Yield: 37%, MS: [M+H] + =251).

[0422] Compound sub1-4-1 (15 g, 59.7 mmol) and bis(pinacolato)diboron (16.7 g, 65.7 mmol) were added to 300 ml of 1,4-diboron. oxane, and the mixture was stirred under reflux. Then, potassium acetate (8.8 g, 89.6 mmol) was added thereto, the mixture was thoroughly stirred, and then bis(dibenzylideneacetone)palladium (0) (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.6 mmol) were added. After reacting for 5 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and then the organic layer was distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated. Anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5 g of compound sub1-4-2. (Yield: 70%, MS: [M+H] + =299).

[0423] Compound sub1-4-2 (15 g, 50.3 mmol) and compound Trz42 (26.1 g, 52.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (20.9 g, 150.9 mmol) was then dissolved in 63 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 4 hours, the reaction mixture was cooled to room temperature, and then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.5 g of compound 1-43. (Yield: 68%, MS: [M+H] + =631).

[0424] Preparation Example 1-44

[0425]

[0426] Compound sub1-4-2 (15 g, 50.3 mmol) and compound Trz43 (24.1 g, 52.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (20.9 g, 150.9 mmol) was then dissolved in 63 ml of water and added thereto, and the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.2 g of compound 1-44. (Yield: 68%, MS: [M+H] + =592).

[0427] Preparation Example 1-45

[0428]

[0429] Compound sub1-4-2 (15 g, 50.3 mmol) and compound Trz44 (28.1 g, 52.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (20.9 g, 150.9 mmol) was then dissolved in 63 ml of water and added thereto, and the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.2 g of compound 1-45. (Yield: 72%, MS: [M+H] + =668).

[0430] Preparation Example 1-46

[0431]

[0432] Trifluoromethanesulfonic anhydride (119.9 g, 424.9 mmol) and deuterium oxide (42.6 g, 2124.7 mmol) were added at 0 ° C, and the mixture was stirred for 5 hours to prepare a solution. 1-Bromodibenzo[b, d]furan (15 g, 60.7 mmol) was added to 120 ml of 1,2,4-trichlorobenzene, and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly added dropwise to a mixed solution of 1-bromodibenzo[b, d]furan and 1,2,4-trichlorobenzene, and the mixture was stirred while heating to 140 ° C, and then the temperature was maintained. After reacting for 24 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.9 g of compound sub1-5-1. (Yield: 39%, MS: [M+H] + =252).

[0433] Compound sub1-5-1 (15 g, 59.5 mmol) and bis(pinacolato)diboron (16.6 g, 65.4 mmol) were added to 300 ml of 1,4-diboron. oxane, and the mixture was stirred under reflux. Then, potassium acetate (8.8 g, 89.2 mmol) was added thereto, the mixture was thoroughly stirred, and then bis(dibenzylideneacetone)palladium (0) (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.6 mmol) were added. After reacting for 4 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and then the organic layer was distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated. Anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2 g of compound sub1-5-2. (Yield: 63%, MS: [M+H] + =300).

[0434] Compound sub1-5-2 (15 g, 50.1 mmol) and compound Trz45 (23.4 g, 52.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (20.8 g, 150.4 mmol) was then dissolved in 62 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 4 hours, the reaction mixture was cooled to room temperature, and then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.1 g of compound 1-46. (Yield: 69%, MS: [M+H] + =581).

[0435] Preparation Example 1-47

[0436]

[0437] Compound sub1-5-2 (15 g, 50.1 mmol) and compound Trz46 (23.6 g, 52.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (20.8 g, 150.4 mmol) was then dissolved in 62 ml of water and added thereto, and the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 5 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.2 g of compound 1-47. (Yield: 69%, MS: [M+H] + =586).

[0438] Preparation Example 1-48

[0439]

[0440] Compound sub1-5-2 (15 g, 50.1 mmol) and compound Trz47 (23.6 g, 52.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (20.8 g, 150.4 mmol) was then dissolved in 62 ml of water and added thereto, and the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 5 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.7 g of compound 1-48. (Yield: 74%, MS: [M+H] + =586).

[0441] Preparation Example 1-49

[0442]

[0443] Compound sub1-5-2 (15 g, 50.1 mmol) and compound Trz48 (27.6 g, 52.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (20.8 g, 150.4 mmol) was then dissolved in 62 ml of water and added thereto, and the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 5 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.5 g of compound 1-49. (Yield: 68%, MS: [M+H] + =662).

[0444] Preparation Example 1-50

[0445]

[0446] Trifluoromethanesulfonic anhydride (167.8 g, 594.9 mmol) and deuterium oxide (59.6 g, 2974.6 mmol) were added at 0 ° C, and the mixture was stirred for 5 hours to prepare a solution. 1-Bromodibenzo[b, d]furan (15 g, 60.7 mmol) was added to 120 ml of 1,2,4-trichlorobenzene, and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly added dropwise to a mixed solution of 1-bromodibenzo[b, d]furan and 1,2,4-trichlorobenzene, and the mixture was stirred while heating to 140 ° C, and then the temperature was maintained. After reacting for 36 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.1 g of compound sub1-6-1. (Yield: 40%, MS: [M+H] + =254).

[0447] Compound sub1-6-1 (15 g, 59 mmol) and bis(pinacolato)diboron (16.5 g, 64.9 mmol) were added to 300 ml of 1,4-diboron. oxane, and the mixture was stirred under reflux. Then, potassium acetate (8.7 g, 88.5 mmol) was added thereto, the mixture was thoroughly stirred, and then bis(dibenzylideneacetone)palladium (0) (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.5 mmol) were added. After reacting for 4 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and then the organic layer was distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated. Anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6 g of compound sub1-6-2. (Yield: 65%, MS: [M+H] + =302).

[0448] Compound sub1-6-2 (15 g, 49.8 mmol) and compound Trz49 (22.3 g, 52.3 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (20.6 g, 149.4 mmol) was then dissolved in 62 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 5 hours, the reaction mixture was cooled to room temperature, and then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.3 g of compound 1-50. (Yield: 72%, MS: [M+H] + =566).

[0449] Preparation Example 1-51

[0450]

[0451] Compound sub1-6-2 (15 g, 49.8 mmol) and compound Trz50 (22.5 g, 52.3 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (20.6 g, 149.4 mmol) was then dissolved in 62 ml of water and added thereto, and the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.4 g of compound 1-51. (Yield: 72%, MS: [M+H] + =569).

[0452] Preparation Example 1-52

[0453]

[0454] Compound sub1-6-2 (15 g, 49.8 mmol) and compound Trz51 (27.9 g, 52.3 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (20.6 g, 149.4 mmol) was then dissolved in 62 ml of water and added thereto, and the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.7 g of compound 1-52. (Yield: 74%, MS: [M+H] + =672).

[0455] Preparation Example 1-53

[0456]

[0457] Compound sub1-6-2 (15 g, 49.8 mmol) and compound Trz52 (24.2 g, 52.3 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (20.6 g, 149.4 mmol) was then dissolved in 62 ml of water and added thereto, and the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 5 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.4 g of compound 1-53. (Yield: 75%, MS: [M+H] + =601).

[0458] Preparation Example 1-54

[0459]

[0460] Compound sub1-6-2 (15 g, 49.8 mmol) and compound Trz53 (22.9 g, 52.3 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (20.6 g, 149.4 mmol) was then dissolved in 62 ml of water and added thereto, and the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.7 g of compound 1-54. (Yield: 65%, MS: [M+H] + =577).

[0461] Preparation Example 1-55

[0462]

[0463] Compound Trz45 (15 g, 33.8 mmol) and dibenzo [b, d] furan-1-ylboronic acid (7.5 g, 35.5 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (14 g, 101.4 mmol) was then dissolved in 42 ml of water and added thereto, and the mixture was thoroughly stirred, followed by addition of bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol). After reacting for 4 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound I-55_P1. (Yield: 66%, MS: [M+H] + =576).

[0464] Compound 1-55_P1 (10 g, 17.4 mmol), PtO2 (1.2 g, 5.2 mmol) and D2O (87 ml) were added to an oscillating tube, which was then sealed and heated at 250°C and 600 psi for 12 hours. When the reaction was terminated, chloroform was added thereto, and the reaction solution was transferred to a separatory funnel and extracted. The extract was dried over MgSO4 and concentrated, and the sample was then purified by silica gel column chromatography to prepare 4.1 g of compound 1-55. (Yield: 40%, MS: [M+H] + =598).

[0465] Preparation Example 1-56

[0466]

[0467] Compound 1-3 (10 g, 17.4 mmol), PtO2 (1.2 g, 5.2 mmol) and D2O (87 ml) were added to an oscillating tube, which was then sealed and heated at 250°C and 600 psi for 12 hours. When the reaction was terminated, chloroform was added thereto, and the reaction solution was transferred to a separatory funnel and extracted. The extract was dried over MgSO4 and concentrated, and the sample was then purified by silica gel column chromatography to prepare 4.4 g of compound 1-56. (Yield: 43%, MS: [M+H] + =597).

[0468] Preparation Example 1-57

[0469]

[0470] Compound 1-10 (10 g, 18.2 mmol), PtO 2 (1.2 g, 5.5 mmol) and D 2 O (91 ml) were added to an oscillating tube, which was then sealed and heated at 250° C. and 600 psi for 12 hours. When the reaction was terminated, chloroform was added thereto, and the reaction solution was transferred to a separatory funnel and extracted. The extract was dried over MgSO 4 and concentrated, and the sample was then purified by silica gel column chromatography to prepare 4.1 g of compound 1-57. (Yield: 40%, MS: [M+H] + =570).

[0471] Preparation Example 1-58

[0472]

[0473] Compound 1-13 (10 g, 17.4 mmol), PtO2 (1.2 g, 5.2 mmol) and D2O (87 ml) were added to an oscillating tube, which was then sealed and heated at 250°C and 600 psi for 12 hours. When the reaction was terminated, chloroform was added thereto, and the reaction solution was transferred to a separatory funnel and extracted. The extract was dried over MgSO4 and concentrated, and the sample was then purified by silica gel column chromatography to prepare 4.5 g of compound 1-58. (Yield: 43%, MS: [M+H] + =598).

[0474] Preparation Example 1-59

[0475]

[0476] Compound Trz54 (15 g, 31.9 mmol) and dibenzo [b, d] furan-1-ylboronic acid (7.1 g, 33.5 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (13.2 g, 95.8 mmol) was then dissolved in 40 ml of water and added thereto, and the mixture was thoroughly stirred, followed by the addition of bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol). After reacting for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2 g of compound I-59_P1. (Yield: 74%, MS: [M+H] + =602).

[0477] Compound 1-59_P1 (10 g, 16.6 mmol), PtO2 (1.1 g, 5 mmol) and D2O (83 ml) were added to an oscillating tube, which was then sealed and heated at 250°C and 600 psi for 12 hours. When the reaction was terminated, chloroform was added thereto, and the reaction solution was transferred to a separatory funnel and extracted. The extract was dried over MgSO4 and concentrated, and the sample was then purified by silica gel column chromatography to prepare 4.5 g of compound 1-59. (Yield: 43%, MS: [M+H]) + =626).

[0478] Preparation Example 1-60

[0479]

[0480] Compound Trz55 (15 g, 33.8 mmol) and dibenzo [b, d] furan-1-ylboronic acid (7.5 g, 35.5 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (14 g, 101.4 mmol) was then dissolved in 42 ml of water and added thereto, and the mixture was thoroughly stirred, followed by addition of bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol). After reacting for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2 g of compound 1-60_P1. (Yield: 68%, MS: [M+H] + =576).

[0481] Compound 1-60_P1 (10 g, 17.4 mmol), PtO2 (1.2 g, 5.2 mmol) and D2O (87 ml) were added to an oscillating tube, which was then sealed and heated at 250°C and 600 psi for 12 hours. When the reaction was terminated, chloroform was added thereto, and the reaction solution was transferred to a separatory funnel and extracted. The extract was dried over MgSO4 and concentrated, and the sample was then purified by silica gel column chromatography to prepare 5.2 g of compound 1-60. (Yield: 50%, MS: [M+H] + =595).

[0482] Preparation Example 1-61

[0483]

[0484] Compound 1-28 (10 g, 16.2 mmol), PtO2 (1.1 g, 4.9 mmol) and D2O (81 ml) were added to an oscillating tube, which was then sealed and heated at 250°C and 600 psi for 12 hours. When the reaction was terminated, chloroform was added thereto, and the reaction solution was transferred to a separatory funnel and extracted. The extract was dried over MgSO4 and concentrated, and the sample was then purified by silica gel column chromatography to prepare 5 g of compound 1-61. (Yield: 48%, MS: [M+H] + =638).

[0485] Preparation Example 2-1

[0486]

[0487] Compound amine 1 (10 g, 20.7 mmol) was added to 200 ml of 1,2,4 trichlorobenzene, and the mixture was stirred at room temperature. In another container, deuterium oxide (15 g, 746.9 mmol) was added to trifluoromethanesulfonic anhydride (52.7 g, 186.7 mmol) at 0 ° C, and the mixture was stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was stirred while heating to 140 ° C, and then the temperature was maintained. After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5 g of compound 2-1. (Yield: 48%, MS: [M+H] + =501).

[0488] Compound 2-1 (15g, 30mmol) and phenanthrene-9-ylboronic acid-D4 (7.1g, 31.5mmol) are added to 300ml THF, and the mixture is stirred and refluxed. Then, potassium carbonate (12.4g, 90mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2g, 0.3mmol) is added. After reacting for 3 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 14.7g compound 2-1-D22. (yield: 76%, MS: [M+H] + =647).

[0489] Preparation Example 2-2

[0490]

[0491] Compound amine 2 (10g, 19.7mmol) was added to 200ml of 1,2,4-trichlorobenzene, and the mixture was stirred at room temperature. In another container, deuterium oxide (14.2g, 708.6mmol) was added to trifluoromethanesulfonic anhydride (33.3g, 118.1mmol) at 0°C, and the mixture was stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was stirred while being heated to 140°C, and then the temperature was maintained. After reacting for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.1g of compound 2-2. (yield: 50%, MS: [M+H] + =518).

[0492] Compound 2-2 (15g, 29mmol) and phenanthrene-9-ylboronic acid-D9 (7g, 30.5mmol) are added to 300ml THF, and the mixture is stirred and refluxed. Then, potassium carbonate (12g, 87mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 14.5g compound 2-2-D18. (yield: 75%, MS: [M+H] + =669).

[0493] Preparation Example 2-3

[0494]

[0495] Compound amine 3 (10g, 19.2mmol) is added to 200ml 1,2,4 trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (13.8g, 689.6mmol) is added to trifluoromethanesulfonic anhydride (48.6g, 172.4mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 8 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 5g of compound 2-3. (yield: 48%, MS: [M+H] + =542).

[0496] Compound 2-3 (15g, 27.7mmol) and phenanthrene-9-ylboronic acid-D7 (6.7g, 29.1mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (11.5g, 83.2mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 5 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 11.5g compound 2-3-D26. (yield: 60%, MS: [M+H] + =691).

[0497] Preparation Example 2-4

[0498]

[0499] Compound amine 4 (10g, 16.7mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (12.1g, 601.9mmol) is added to trifluoromethanesulfonic anhydride (42.5g, 150.5mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 8 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.3g compound 2-4. (Yield: 41%, MS: [M+H] + =621).

[0500] Compound 2-4 (15g, 24.2mmol) and phenanthrene-9-ylboronic acid-D6 (5.8g, 25.4mol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10g, 72.6mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.2mmol) is added. After reacting for 4 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 13.9g compound 2-4-D28. (yield: 75%, MS: [M+H] + =769).

[0501] Preparation Example 2-5

[0502]

[0503] Compound amine 5 (10g, 18.8mmol) was added to 200ml of 1,2,4-trichlorobenzene, and the mixture was stirred at room temperature. In another container, deuterium oxide (13.6g, 676.6mmol) was added to trifluoromethanesulfonic anhydride (63.6g, 225.5mmol) at 0°C, and the mixture was stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was stirred while being heated to 140°C, and then the temperature was maintained. After reacting for 15 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.2g of compound 2-5. (yield: 50%, MS: [M+H] + =559).

[0504] Compound 2-5 (15g, 26.9mmol) and phenanthrene-9-ylboronic acid-D9 (6.5g, 28.2mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (11.1g, 80.6mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 14.1g compound 2-5-D35. (yield: 74%, MS: [M+H] + =710).

[0505] Preparation Example 2-6

[0506]

[0507] Compound amine 6 (10g, 17.1mmol) is added to 200ml 1,2,4 trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (12.3g, 616.3mmol) is added to trifluoromethanesulfonic anhydride (43.5g, 154.1mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 8 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.7g compound 2-6. (yield: 45%, MS: [M+H] + =609).

[0508] Compound 2-6 (15g, 24.7mmol) and phenanthrene-9-ylboronic acid-D2 (5.8g, 25.9mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.2g, 74mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.2mmol) is added. After reacting for 3 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 13.9g compound 2-6-D26. (yield: 75%, MS: [M+H] + =753).

[0509] Preparation Example 2-7

[0510]

[0511] Compound amine 7 (10g, 17.1mmol) is added to 200ml 1,2,4 trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (12.3g, 616.3mmol) is added to trifluoromethanesulfonic anhydride (58g, 205.4mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 15 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.8g of compound 2-7. (yield: 46%, MS: [M+H] + =615).

[0512] Compound 2-7 (15g, 24.4mmol) and phenanthrene-9-ylboronic acid-D9 (5.9g, 25.6mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.1g, 73.3mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.2mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 11.4g compound 2-7-D39. (yield: 61%, MS: [M+H] + =766).

[0513] Preparation Example 2-8

[0514]

[0515] Compound amine 8 (10g, 18.4mmol) was added to 200ml of 1,2,4-trichlorobenzene, and the mixture was stirred at room temperature. In another container, deuterium oxide (13.3g, 661.5mmol) was added to trifluoromethanesulfonic anhydride (31.1g, 110.3mmol) at 0°C, and the mixture was stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was stirred while being heated to 140°C, and then the temperature was maintained. After reacting for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 4.8g of compound 2-8. (yield: 47%, MS: [M+H] + =563).

[0516] Compound 2-8 (15g, 26.8mmol) and phenanthrene-9-ylboronic acid-D6 (6.4g, 28.1mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (11.1g, 80.3mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 5 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 13.1g compound 2-8-D25. (yield: 69%, MS: [M+H] + =711).

[0517] Preparation Example 2-9

[0518]

[0519] Compound amine 9 (10g, 19.4mmol) is added to 200ml 1,2,4 trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (14g, 697.5mmol) is added to trifluoromethanesulfonic anhydride (32.8g, 116.2mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.4g compound 2-9. (yield: 43%, MS: [M+H] + =534).

[0520] Compound 2-9 (15g, 28.3mmol) and phenanthrene-9-ylboronic acid-D5 (6.7g, 29.7mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (11.7g, 84.9mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 3 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 15.3g compound 2-9-D23. (yield: 80%, MS: [M+H] + =681).

[0521] Preparation Example 2-10

[0522]

[0523] Compound amine 10 (10g, 17.9mmol) was added to 200ml of 1,2,4-trichlorobenzene, and the mixture was stirred at room temperature. In another container, deuterium oxide (12.9g, 645mmol) was added to trifluoromethanesulfonic anhydride (45.5g, 161.3mmol) at 0°C, and the mixture was stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was stirred while being heated to 140°C, and then the temperature was maintained. After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 4.4g of compound 2-10. (yield: 42%, MS: [M+H] + =580).

[0524] Compound 2-10 (15g, 25.9mmol) and phenanthrene-9-ylboronic acid-D8 (6.3g, 27.2mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.7g, 77.7mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 12.6g compound 2-10-D29. (yield: 67%, MS: [M+H] + =730).

[0525] Preparation Example 2-11

[0526]

[0527] Compound amine 11 (10g, 16.4mmol) was added to 200ml of 1,2,4-trichlorobenzene, and the mixture was stirred at room temperature. In another container, deuterium oxide (11.9g, 591.9mmol) was added to trifluoromethanesulfonic anhydride (27.8g, 98.7mmol) at 0°C, and the mixture was stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was stirred while being heated to 140°C, and then the temperature was maintained. After reacting for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 4.9g of compound 2-11. (yield: 48%, MS: [M+H] + =623).

[0528] Compound 2-11 (15g, 24.1mmol) and phenanthrene-9-ylboronic acid-D7 (5.8g, 25.3mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10g, 72.3mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.2mmol) is added. After reacting for 4 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 11.5g compound 2-11-D21. (yield: 62%, MS: [M+H] + =772).

[0529] Preparation Example 2-12

[0530]

[0531] Compound amine 12 (10g, 17.9mmol) was added to 200ml of 1,2,4-trichlorobenzene, and the mixture was stirred at room temperature. In another container, deuterium oxide (12.9g, 645mmol) was added to trifluoromethanesulfonic anhydride (45.5g, 161.3mmol) at 0°C, and the mixture was stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was stirred while being heated to 140°C, and then the temperature was maintained. After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.1g of compound 2-12. (Yield: 49%, MS: [M+H] + =581).

[0532] Compound 2-12 (15g, 25.9mmol) and phenanthrene-9-ylboronic acid-D5 (6.2g, 27.1mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.7g, 77.6mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 4 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 11.5g compound 2-12-D27. (yield: 61%, MS: [M+H] + =728).

[0533] Preparation Example 2-13

[0534]

[0535] Compound amine 13 (10g, 18.8mmol) was added to 200ml of 1,2,4-trichlorobenzene, and the mixture was stirred at room temperature. In another container, deuterium oxide (13.6g, 676.6mmol) was added to trifluoromethanesulfonic anhydride (47.7g, 169.1mmol) at 0°C, and the mixture was stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was stirred while being heated to 140°C, and then the temperature was maintained. After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.1g of compound 2-13. (Yield: 49%, MS: [M+H] + =553).

[0536] Compound 2-13 (15g, 27.2mmol) and phenanthrene-9-ylboronic acid-D9 (6.6g, 28.5mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (11.3g, 81.5mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 3 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 15.1g compound 2-13-D29. (yield: 79%, MS: [M+H] + =704).

[0537] Preparation Example 2-14

[0538]

[0539] Compound amine 14 (10g, 17.1mmol) was added to 200ml of 1,2,4-trichlorobenzene, and the mixture was stirred at room temperature. In another container, deuterium oxide (12.3g, 616.3mmol) was added to trifluoromethanesulfonic anhydride (43.5g, 154.1mmol) at 0°C, and the mixture was stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was stirred while being heated to 140°C, and then the temperature was maintained. After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 4.5g of compound 2-14. (yield: 43%, MS: [M+H] + =608).

[0540] Compound 2-14 (15g, 24.7mmol) and phenanthrene-9-ylboronic acid-D7 (5.9g, 25.9mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.2g, 74.1mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.2mmol) is added. After reacting for 3 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 12g compound 2-14-D30. (yield: 64%, MS: [M+H] + =757).

[0541] Preparation Example 2-15

[0542]

[0543] Compound amine 15 (10g, 16.7mmol) was added to 200ml of 1,2,4-trichlorobenzene, and the mixture was stirred at room temperature. In another container, deuterium oxide (12.1g, 601.9mmol) was added to trifluoromethanesulfonic anhydride (28.3g, 100.3mmol) at 0°C, and the mixture was stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was stirred while being heated to 140°C, and then the temperature was maintained. After reacting for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 4.4g of compound 2-15. (yield: 43%, MS: [M+H] + =614).

[0544] Compound 2-15 (15g, 24.5mmol) and phenanthrene-9-ylboronic acid-D4 (5.8g, 25.7mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.1g, 73.4mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.2mmol) is added. After reacting for 3 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 13.7g compound 2-15-D19. (yield: 74%, MS: [M+H] + =760).

[0545] Preparation Example 2-16

[0546]

[0547] Compound amine 16 (10g, 16.1mmol) was added to 200ml of 1,2,4-trichlorobenzene, and the mixture was stirred at room temperature. In another container, deuterium oxide (11.6g, 580.4mmol) was added to trifluoromethanesulfonic anhydride (27.3g, 96.7mmol) at 0°C, and the mixture was stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was stirred while being heated to 140°C, and then the temperature was maintained. After reacting for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5g of compound 2-16. (Yield: 49%, MS: [M+H] + =639).

[0548] Compound 2-16 (15g, 23.5mmol) and phenanthrene-9-ylboronic acid-D8 (5.7g, 24.7mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (9.8g, 70.6mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.2mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 11.5g compound 2-16-D27. (yield: 62%, MS: [M+H] + =789).

[0549] Preparation Example 2-17

[0550]

[0551] Compound amine 17 (10g, 18.4mmol) was added to 200ml of 1,2,4-trichlorobenzene, and the mixture was stirred at room temperature. In another container, deuterium oxide (13.3g, 664mmol) was added to trifluoromethanesulfonic anhydride (46.8g, 166mmol) at 0°C, and the mixture was stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was stirred while being heated to 140°C, and then the temperature was maintained. After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.1g of compound 2-17. (Yield: 49%, MS: [M+H] + =570).

[0552] Compound 2-17 (15g, 26.4mmol) and phenanthren-9-ylboronic acid-D1 (6.2g, 27.7mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.9g, 79.1mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 3 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 14.1g compound 2-17-D28. (yield: 75%, MS: [M+H] + =713).

[0553] Preparation Example 2-18

[0554]

[0555] Compound amine 18 (10g, 23.2mmol) was added to 200ml 1,2,4 trichlorobenzene, and the mixture was stirred at room temperature. In another container, deuterium oxide (16.7g, 833.4mmol) was added to trifluoromethanesulfonic anhydride (58.8g, 208.4mmol) at 0°C, and the mixture was stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was stirred while being heated to 140°C, and then the temperature was maintained. After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 4.3g of compound 2-18. (Yield: 41%, MS: [M+H] + =449).

[0556] Compound 2-18 (15g, 33.5mmol) and phenanthrene-9-ylboronic acid-D8 (8.1g, 35.2mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (13.9g, 100.5mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2g, 0.3mmol) is added. After reacting for 4 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 15.8g compound 2-18-D24. (yield: 79%, MS: [M+H] + =599).

[0557] Preparation Example 2-19

[0558]

[0559] Compound amine 19 (10g, 17.9mmol) was added to 200ml of 1,2,4-trichlorobenzene, and the mixture was stirred at room temperature. In another container, deuterium oxide (12.9g, 645mmol) was added to trifluoromethanesulfonic anhydride (45.5g, 161.3mmol) at 0°C, and the mixture was stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was stirred while being heated to 140°C, and then the temperature was maintained. After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 4.3g of compound 2-19. (Yield: 41%, MS: [M+H] + =581).

[0560] Compound 2-19 (15g, 25.9mmol) and phenanthrene-9-ylboronic acid-D4 (6.1g, 27.1mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.7g, 77.6mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 12.2g compound 2-19-D26. (yield: 65%, MS: [M+H] + =727).

[0561] Preparation Example 2-20

[0562]

[0563] Compound amine 20 (10g, 17.9mmol) is added to 200ml 1,2,4 trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (12.9g, 645mmol) is added to trifluoromethanesulfonic anhydride (30.3g, 107.5mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.9g compound 2-20. (yield: 48%, MS: [M+H] + =572).

[0564] Compound 2-20 (15g, 26.3mmol) and phenanthrene-9-ylboronic acid-D9 (6.4g, 27.6mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.9g, 78.8mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 13.7g compound 2-20-D22. (yield: 72%, MS: [M+H] + =723).

[0565] Preparation Example 2-21

[0566]

[0567] Compound amine 21 (10g, 17.9mmol) was added to 200ml of 1,2,4-trichlorobenzene, and the mixture was stirred at room temperature. In another container, deuterium oxide (12.9g, 645mmol) was added to trifluoromethanesulfonic anhydride (60.7g, 215mmol) at 0°C, and the mixture was stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was stirred while being heated to 140°C, and then the temperature was maintained. After reacting for 15 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.3g of compound 2-21. (yield: 50%, MS: [M+H] + =587).

[0568] Compound 2-21 (15g, 25.6mmol) and phenanthren-9-ylboronic acid-D9 (6.2g, 26.9mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.6g, 76.8mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 4 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 13.2g compound 2-21-D37. (yield: 70%, MS: [M+H] + =738).

[0569] Preparation Example 2-22

[0570]

[0571] Compound amine 22 (10g, 17.1mmol) is added to 200ml 1,2,4 trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (12.3g, 616.3mmol) is added to trifluoromethanesulfonic anhydride (29g, 102.7mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.2g compound 2-22. (Yield: 41%, MS: [M+H] + =600).

[0572] Compound 2-22 (15g, 25mmol) and phenanthrene-9-ylboronic acid-D5 (6g, 26.3mmol) are added to 300ml THF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.4g, 75.1mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 5 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 13.3g compound 2-22-D20. (yield: 71%, MS: [M+H] + =747).

[0573] Preparation Example 2-23

[0574]

[0575] Compound amine 23 (10g, 16.7mmol) was added to 200ml of 1,2,4-trichlorobenzene, and the mixture was stirred at room temperature. In another container, deuterium oxide (12.1g, 601.9mmol) was added to trifluoromethanesulfonic anhydride (28.3g, 100.3mmol) at 0°C, and the mixture was stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was stirred while being heated to 140°C, and then the temperature was maintained. After reacting for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.1g of compound 2-23. (yield: 50%, MS: [M+H] + =613).

[0576] Compound 2-23 (15g, 24.5mmol) and phenanthrene-9-ylboronic acid-D7 (5.9g, 25.7mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.2g, 73.5mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.2mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 12.5g compound 2-23-D21. (yield: 67%, MS: [M+H] + =762).

[0577] Preparation Example 2-24

[0578]

[0579] Compound amine 24 (10g, 17.1mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (12.3g, 616.3mmol) is added to trifluoromethanesulfonic anhydride (43.5g, 154.1mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 8 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 5g of compound 2-24. (yield: 48%, MS: [M+H] + =604).

[0580] Compound 2-24 (15g, 24.9mmol) and phenanthrene-9-ylboronic acid-D3 (5.9g, 26.1mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.3g, 74.6mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.2mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 12.3g compound 2-24-D22. (yield: 66%, MS: [M+H] + =749).

[0581] Preparation Example 2-25

[0582]

[0583] Compound amine 25 (10g, 16.2mmol) is added to 200ml 1,2,4 trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (11.7g, 582.3mmol) is added to trifluoromethanesulfonic anhydride (27.4g, 97mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 5g of compound 2-25. (Yield: 49%, MS: [M+H] + =637).

[0584] Compound 2-25 (15g, 23.6mmol) and phenanthrene-9-ylboronic acid-D9 (5.7g, 24.8mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (9.8g, 70.7mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.2mmol) is added. After reacting for 5 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 12.1g compound 2-25-D27. (yield: 65%, MS: [M+H] + =788).

[0585] Preparation Example 2-26

[0586]

[0587] Compound amine 26 (10g, 18.4mmol) is added to 200ml 1,2,4 trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (13.3g, 661.5mmol) is added to trifluoromethanesulfonic anhydride (31.1g, 110.3mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.4g compound 2-26. (yield: 43%, MS: [M+H] + =563).

[0588] Compound 2-26 (15g, 26.7mmol) and phenanthrene-9-ylboronic acid-D7 (6.4g, 28mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (11.1g, 80mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 4 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 12g compound 2-26-D25. (yield: 63%, MS: [M+H] + =712).

[0589] Preparation Example 2-27

[0590]

[0591] Compound amine 27 (10g, 19.7mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (14.2g, 708.6mmol) is added to trifluoromethanesulfonic anhydride (50g, 177.1mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 8 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 5g of compound 2-27. (yield: 48%, MS: [M+H] + =529).

[0592] Compound 2-27 (15g, 28.4mmol) and phenanthrene-9-ylboronic acid-D8 (6.9g, 29.8mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (11.8g, 85.2mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 5 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 12.1g compound 2-27-D28. (yield: 63%, MS: [M+H] + =679).

[0593] Preparation Example 2-28

[0594]

[0595] Compound amine 28 (10g, 19.7mmol) was added to 200ml of 1,2,4-trichlorobenzene, and the mixture was stirred at room temperature. In another container, deuterium oxide (14.2g, 708.6mmol) was added to trifluoromethanesulfonic anhydride (66.6g, 236.2mmol) at 0°C, and the mixture was stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was stirred while being heated to 140°C, and then the temperature was maintained. After reacting for 15 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.2g of compound 2-28. (Yield: 49%, MS: [M+H] + =535).

[0596] Compound 2-28 (15g, 28.1mmol) and phenanthrene-9-ylboronic acid-D9 (6.8g, 29.5mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (11.6g, 84.3mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 5 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 12.5g compound 2-28-D35. (yield: 65%, MS: [M+H] + =686).

[0597] Preparation Example 2-29

[0598]

[0599] Compound amine 29 (10g, 17.9mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (12.9g, 645mmol) is added to trifluoromethanesulfonic anhydride (30.3g, 107.5mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.2g of compound 2-29. (Yield: 41%, MS: [M+H] + =573).

[0600] Compound 2-29 (15g, 26.2mmol) and phenanthrene-9-ylboronic acid-D9 (6.4g, 27.5mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.9g, 78.7mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 3 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 11.4g compound 2-29-D23. (yield: 60%, MS: [M+H] + =724).

[0601] Preparation Example 2-30

[0602]

[0603] Compound amine 30 (10g, 16.4mmol) is added to 200ml 1,2,4 trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (11.9g, 591.9mmol) is added to trifluoromethanesulfonic anhydride (41.8g, 148mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 8 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 5.2g compound 2-30. (yield: 50%, MS: [M+H] + =628).

[0604] Compound 2-30 (15g, 23.9mmol) and phenanthrene-9-ylboronic acid-D3 (5.7g, 25.1mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (9.9g, 71.7mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.2mmol) is added. After reacting for 4 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 11.3g compound 2-30-D22. (yield: 61%, MS: [M+H] + =773).

[0605] Preparation Example 2-31

[0606]

[0607] Compound amine 31 (10g, 17.1mmol) was added to 200ml of 1,2,4-trichlorobenzene, and the mixture was stirred at room temperature. In another container, deuterium oxide (12.3g, 616.3mmol) was added to trifluoromethanesulfonic anhydride (43.5g, 154.1mmol) at 0°C, and the mixture was stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was stirred while being heated to 140°C, and then the temperature was maintained. After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 4.8g of compound 2-31. (yield: 46%, MS: [M+H] + =607).

[0608] Compound 2-31 (15g, 24.7mmol) and phenanthrene-9-ylboronic acid-D9 (6g, 26mmol) are added to 300ml THF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.3g, 74.2mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.2mmol) is added. After reacting for 3 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 14.6g compound 2-31-D31. (yield: 78%, MS: [M+H] + =758).

[0609] Preparation Example 2-32

[0610]

[0611] Compound amine 32 (10g, 18.8mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (13.6g, 676.6mmol) is added to trifluoromethanesulfonic anhydride (47.7g, 169.1mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 8 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.3g of compound 2-32. (yield: 42%, MS: [M+H] + =552).

[0612] Compound 2-32 (15g, 27.2mmol) and phenanthrene-9-ylboronic acid-D5 (6.5g, 28.6mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (11.3g, 81.7mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 13.5g compound 2-32-D24. (yield: 71%, MS: [M+H] + =699).

[0613] Preparation Example 2-33

[0614]

[0615] Compound amine 33 (10g, 18.6mmol) is added to 200ml 1,2,4 trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (13.4g, 669mmol) is added to trifluoromethanesulfonic anhydride (31.5g, 111.5mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.5g of compound 2-33. (yield: 44%, MS: [M+H] + =551).

[0616] Compound 2-33 (15g, 27.3mmol) and phenanthren-9-ylboronic acid-D7 (6.6g, 28.6mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (11.3g, 81.8mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 14.3g compound 2-33-D19. (yield: 75%, MS: [M+H] + =700).

[0617] Preparation Example 2-34

[0618]

[0619] Compound amine 34 (10g, 16.3mmol) was added to 200ml of 1,2,4-trichlorobenzene, and the mixture was stirred at room temperature. In another container, deuterium oxide (11.7g, 586.1mmol) was added to trifluoromethanesulfonic anhydride (41.3g, 146.5mmol) at 0°C, and the mixture was stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was stirred while being heated to 140°C, and then the temperature was maintained. After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 4.5g of compound 2-34. (yield: 44%, MS: [M+H] + =635).

[0620] Compound 2-34 (15g, 23.7mmol) and phenanthrene-9-ylboronic acid-D3 (5.6g, 24.8mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (9.8g, 71mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.2mmol) is added. After reacting for 3 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 12.7g compound 2-34-D23. (yield: 69%, MS: [M+H] + =780).

[0621] Preparation Example 2-35

[0622]

[0623] Compound amine 35 (10g, 17.8mmol) was added to 200ml 1,2,4 trichlorobenzene, and the mixture was stirred at room temperature. In another container, deuterium oxide (12.8g, 640.4mmol) was added to trifluoromethanesulfonic anhydride (45.2g, 160.1mmol) at 0°C, and the mixture was stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was stirred while being heated to 140°C, and then the temperature was maintained. After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 4.7g of compound 2-35. (yield: 46%, MS: [M+H] + =581).

[0624] Compound 2-35 (15g, 25.9mmol) and phenanthrene-9-ylboronic acid-D7 (6.2g, 27.1mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.7g, 77.6mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 11.3g compound 2-35-D25. (yield: 60%, MS: [M+H] + =730).

[0625] Preparation Example 2-36

[0626]

[0627] Compound amine 36 (10g, 21.7mmol) is added to 200ml 1,2,4 trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (15.7g, 782.6mmol) is added to trifluoromethanesulfonic anhydride (36.8g, 130.4mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.1g compound 2-36. (yield: 40%, MS: [M+H] + =472).

[0628] Compound 2-36 (15g, 31.8mmol) and phenanthrene-9-ylboronic acid-D9 (7.7g, 33.4mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (13.2g, 95.5mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2g, 0.3mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 12.5g compound 2-36-D20. (yield: 63%, MS: [M+H] + =623).

[0629] Preparation Example 2-37

[0630]

[0631] Compound amine 37 (10g, 19.7mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (14.2g, 708.6mmol) is added to trifluoromethanesulfonic anhydride (50g, 177.1mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 8 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 5g of compound 2-37. (yield: 48%, MS: [M+H] + =527).

[0632] Compound 2-37 (15g, 28.5mmol) and phenanthrene-9-ylboronic acid-D9 (6.9g, 29.9mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (11.8g, 85.4mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 14.2g compound 2-37-D28. (yield: 74%, MS: [M+H] + =678).

[0633] Preparation Example 2-38

[0634]

[0635] Compound amine 38 (10g, 17.9mmol) is added to 200ml 1,2,4 trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (12.9g, 642.7mmol) is added to trifluoromethanesulfonic anhydride (30.2g, 107.1mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 5g of compound 2-38. (Yield: 49%, MS: [M+H] + =575).

[0636] Compound 2-38 (15g, 26.1mmol) and phenanthren-9-ylboronic acid-D6 (6.3g, 27.4mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.8g, 78.4mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 4 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 12.4g compound 2-38-D20. (yield: 66%, MS: [M+H] + =721).

[0637] Preparation Example 2-39

[0638]

[0639] Compound amine 39 (10g, 16.4mmol) is added to 200ml 1,2,4 trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (11.9g, 591.9mmol) is added to trifluoromethanesulfonic anhydride (41.8g, 148mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 8 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.9g compound 2-39. (yield: 48%, MS: [M+H] + =628).

[0640] Compound 2-39 (15g, 23.9mmol) and phenanthrene-9-ylboronic acid-D2 (5.6g, 25.1mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (9.9g, 71.7mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.2mmol) is added. After reacting for 4 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 12.2g compound 39-D21. (yield: 66%, MS: [M+H] + =772).

[0641] Preparation Example 2-40

[0642]

[0643] Compound amine 40 (10g, 17.9mmol) is added to 200ml 1,2,4 trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (12.9g, 645mmol) is added to trifluoromethanesulfonic anhydride (30.3g, 107.5mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 5g of compound 2-40. (Yield: 49%, MS: [M+H] + =574).

[0644] Compound 2-40 (15g, 26.2mmol) and phenanthrene-9-ylboronic acid-D5 (6.2g, 27.5mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.9g, 78.5mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 5 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 12.4g compound 2-40-D20. (yield: 66%, MS: [M+H] + =721).

[0645] Preparation Example 2-41

[0646]

[0647] Compound amine 41 (10g, 17.1mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (12.3g, 616.3mmol) is added to trifluoromethanesulfonic anhydride (29g, 102.7mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.1g of compound 2-41. (yield: 40%, MS: [M+H] + =597).

[0648] Compound 2-41 (15g, 25.2mmol) and phenanthrene-9-ylboronic acid-D9 (6.1g, 26.4mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.4g, 75.5mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 13.9g compound 2-41-D21. (yield: 74%, MS: [M+H] + =748).

[0649] Preparation Example 2-42

[0650]

[0651] Compound amine 42 (10g, 17.9mmol) was added to 200ml of 1,2,4-trichlorobenzene, and the mixture was stirred at room temperature. In another container, deuterium oxide (12.9g, 645mmol) was added to trifluoromethanesulfonic anhydride (60.7g, 215mmol) at 0°C, and the mixture was stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was stirred while being heated to 140°C, and then the temperature was maintained. After reacting for 15 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 4.6g of compound 2-42. (yield: 44%, MS: [M+H] + =587).

[0652] Compound 2-42 (15g, 25.6mmol) and phenanthrene-9-ylboronic acid-D9 (6.2g, 26.9mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.6g, 76.8mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 13.6g compound 2-42-D37. (yield: 72%, MS: [M+H] + =738).

[0653] Preparation Example 2-43

[0654]

[0655] Compound amine 43 (10g, 17.1mmol) is added to 200ml 1,2,4 trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (12.3g, 616.3mmol) is added to trifluoromethanesulfonic anhydride (29g, 102.7mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.2g compound 2-43. (Yield: 41%, MS: [M+H] + =600).

[0656] Compound 2-43 (15g, 25mmol) and phenanthrene-9-ylboronic acid-D6 (6g, 26.3mmol) are added to 300ml THF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.4g, 75.1mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 5 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 13.5g compound 2-43-D21. (yield: 72%, MS: [M+H] + =748).

[0657] Preparation Example 2-44

[0658]

[0659] Compound amine 44 (10g, 17.1mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (12.3g, 616.3mmol) is added to trifluoromethanesulfonic anhydride (29g, 102.7mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.6g of compound 2-44. (yield: 45%, MS: [M+H] + =598).

[0660] Compound 2-44 (15g, 25.1mmol) and phenanthren-9-ylboronic acid-D8 (6.1g, 26.4mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.4g, 75.4mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 5 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 14.3g compound 2-44-D21. (yield: 76%, MS: [M+H] + =748).

[0661] Preparation Example 2-45

[0662]

[0663] Compound amine 45 (10g, 16.7mmol) is added to 200ml 1,2,4 trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (12.1g, 601.9mmol) is added to trifluoromethanesulfonic anhydride (42.5g, 150.5mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 8 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 5.1g compound 2-45. (Yield: 49%, MS: [M+H] + =621).

[0664] Compound 2-45 (15g, 24.2mmol) and phenanthrene-9-ylboronic acid-D2 (5.7g, 25.4mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10g, 72.6mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.2mmol) is added. After reacting for 3 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 12.2g compound 2-45-D24. (yield: 66%, MS: [M+H] + =765).

[0665] Preparation Example 2-46

[0666]

[0667] Compound amine 46 (10g, 18.6mmol) is added to 200ml 1,2,4 trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (13.4g, 669mmol) is added to trifluoromethanesulfonic anhydride (31.5g, 111.5mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 5g of compound 2-46. (Yield: 49%, MS: [M+H] + =549).

[0668] Compound 2-46 (15g, 27.4mmol) and phenanthrene-9-ylboronic acid-D9 (6.6g, 28.7mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (11.3g, 82.1mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 3 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 14g compound 2-46-D19. (yield: 73%, MS: [M+H] + =700).

[0669] Preparation Example 2-47

[0670]

[0671] Compound amine 47 (10g, 18.7mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (13.4g, 671.5mmol) is added to trifluoromethanesulfonic anhydride (31.6g, 111.9mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.3g of compound 2-47. (yield: 42%, MS: [M+H] + =552).

[0672] Compound 2-47 (15g, 27.2mmol) and phenanthren-9-ylboronic acid-D6 (6.5g, 28.6mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (11.3g, 81.7mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 3 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 14.3g compound 2-47-D21. (yield: 75%, MS: [M+H] + =700).

[0673] Preparation Example 2-48

[0674]

[0675] Compound amine 48 (10g, 20.6mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (14.8g, 740.6mmol) is added to trifluoromethanesulfonic anhydride (52.2g, 185.2mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 8 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.4g of compound 2-48. (yield: 42%, MS: [M+H] + =505).

[0676] Compound 2-48 (15g, 29.8mmol) and phenanthrene-9-ylboronic acid-D2 (7g, 31.2mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (12.3g, 89.3mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2g, 0.3mmol) is added. After reacting for 3 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 11.6g compound 2-48-D20. (yield: 60%, MS: [M+H] + =649).

[0677] Preparation Example 2-49

[0678]

[0679] Compound amine 49 (10g, 19.7mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (14.2g, 708.6mmol) is added to trifluoromethanesulfonic anhydride (33.3g, 118.1mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.2g of compound 2-49. (Yield: 41%, MS: [M+H] + =520).

[0680] Compound 2-49 (15g, 28.9mmol) and phenanthrene-9-ylboronic acid-D9 (7g, 30.3mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (12g, 86.7mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 4 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 13.2g compound 2-49-D20. (yield: 68%, MS: [M+H] + =671).

[0681] Preparation Example 2-50

[0682]

[0683] Compound amine 50 (10g, 17.9mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (12.9g, 645mmol) is added to trifluoromethanesulfonic anhydride (45.5g, 161.3mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 8 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 5.2g of compound 2-50. (yield: 50%, MS: [M+H] + =578).

[0684] Compound 2-50 (15g, 26mmol) and phenanthrene-9-ylboronic acid-D1 (6.1g, 27.3mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.8g, 78mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 4 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 15g compound 2-50-D20. (yield: 80%, MS: [M+H] + =721).

[0685] Preparation Example 2-51

[0686]

[0687] Compound amine 51 (10g, 19.7mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (14.2g, 708.6mmol) is added to trifluoromethanesulfonic anhydride (33.3g, 118.1mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.5g of compound 2-51. (yield: 44%, MS: [M+H] + =521).

[0688] Compound 2-51 (15g, 28.8mmol) and phenanthren-9-ylboronic acid-D9 (7g, 30.3mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (12g, 86.5mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 5 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 15.5g of compound 2-51-D21. (Yield: 80%, MS: [M+H] + =672).

[0689] Preparation Example 2-52

[0690]

[0691] Compound amine 52 (10g, 17.9mmol) was added to 200ml of 1,2,4-trichlorobenzene, and the mixture was stirred at room temperature. In another container, deuterium oxide (12.9g, 645mmol) was added to trifluoromethanesulfonic anhydride (60.7g, 215mmol) at 0°C, and the mixture was stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was stirred while being heated to 140°C, and then the temperature was maintained. After reacting for 15 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was then neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.3g of compound 2-52. (yield: 50%, MS: [M+H] + =587).

[0692] Compound 2-52 (15g, 25.6mmol) and phenanthrene-9-ylboronic acid-D9 (6.2g, 26.9mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.6g, 76.8mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 4 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 14.9g compound 2-52-D37. (yield: 79%, MS: [M+H] + =738).

[0693] Preparation Example 2-53

[0694]

[0695] Compound amine 53 (10g, 18.8mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (13.6g, 676.6mmol) is added to trifluoromethanesulfonic anhydride (31.8g, 112.8mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.8g of compound 2-53. (yield: 47%, MS: [M+H] + =545).

[0696] Compound 2-53 (15g, 27.6mmol) and phenanthren-9-ylboronic acid-D7 (6.6g, 28.9mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (11.4g, 82.7mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 14.1g compound 2-53-D19. (yield: 74%, MS: [M+H] + =694).

[0697] Preparation Example 2-54

[0698]

[0699] Compound amine 54 (10g, 18.4mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (13.3g, 664mmol) is added to trifluoromethanesulfonic anhydride (31.2g, 110.7mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.9g compound 2-54. (yield: 48%, MS: [M+H] + =559).

[0700] Compound 2-54 (15g, 26.9mmol) and phenanthren-9-ylboronic acid-D9 (6.5g, 28.2mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (11.1g, 80.6mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 5 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 14.1g compound 2-54-D25. (yield: 74%, MS: [M+H] + =710).

[0701] Preparation Example 2-55

[0702]

[0703] Compound amine 55 (10g, 18.6mmol) is added to 200ml 1,2,4 trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (13.4g, 669mmol) is added to trifluoromethanesulfonic anhydride (47.2g, 167.3mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 8 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.9g compound 2-55. (yield: 47%, MS: [M+H] + =559).

[0704] Compound 2-55 (15g, 26.9mmol) and phenanthrene-9-ylboronic acid-D3 (6.4g, 28.2mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (11.1g, 80.6mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 11.3g compound 2-55-D23. (yield: 60%, MS: [M+H] + =704).

[0705] Preparation Example 2-56

[0706]

[0707] Compound amine 56 (10g, 17.9mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (12.9g, 645mmol) is added to trifluoromethanesulfonic anhydride (30.3g, 107.5mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.1g of compound 2-56. (yield: 40%, MS: [M+H] + =571).

[0708] Compound 2-56 (15g, 26.3mmol) and phenanthren-9-ylboronic acid-D9 (6.4g, 27.6mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.9g, 78.9mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 5 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 11.4g compound 2-56-D21. (yield: 60%, MS: [M+H] + =722).

[0709] Preparation Example 2-57

[0710]

[0711] Compound amine 57 (10g, 17.9mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (12.9g, 645mmol) is added to trifluoromethanesulfonic anhydride (45.5g, 161.3mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 8 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.6g of compound 2-57. (yield: 44%, MS: [M+H] + =579).

[0712] Compound 2-57 (15g, 25.9mmol) and phenanthrene-9-ylboronic acid-D9 (6.3g, 27.2mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.8g, 77.8mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 11.7g compound 2-57-D29. (yield: 62%, MS: [M+H] + =730).

[0713] Preparation Example 2-58

[0714]

[0715] Compound amine 58 (10g, 16.4mmol) is added to 200ml 1,2,4 trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (11.9g, 591.9mmol) is added to trifluoromethanesulfonic anhydride (41.8g, 148mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 8 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.1g compound 2-58. (yield: 40%, MS: [M+H] + =631).

[0716] Compound 2-58 (15g, 23.8mmol) and phenanthrene-9-ylboronic acid-D5 (5.7g, 25mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (9.9g, 71.4mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.2mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 14.2g compound 2-58-D27. (yield: 77%, MS: [M+H] + =778).

[0717] Preparation Example 2-59

[0718]

[0719] Compound amine 59 (10g, 17.9mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (12.9g, 645mmol) is added to trifluoromethanesulfonic anhydride (45.5g, 161.3mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 8 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.3g of compound 2-59. (Yield: 41%, MS: [M+H] + =582).

[0720] Compound 2-59 (15 g, 25.8 mmol) and phenanthrene-9-ylboronic acid-D1 (6 g, 27.1 mmol) are added to 300 ml of THF, and the mixture is stirred and refluxed. Potassium carbonate (10.7 g, 77.4 mmol) is then dissolved in 100 ml of water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.3 mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 11.2 g of compound 2-59-D24. (Yield: 60%, MS: [M+H] + =725).

[0721] Preparation Example 2-60

[0722]

[0723] Compound amine 60 (10g, 17.9mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (12.9g, 645mmol) is added to trifluoromethanesulfonic anhydride (30.3g, 107.5mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.7g of compound 2-60. (yield: 46%, MS: [M+H] + =572).

[0724] Compound 2-60 (15g, 26.3mmol) and phenanthrene-9-ylboronic acid-D7 (6.3g, 27.6mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.9g, 78.8mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 3 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 14.2g compound 2-60-D20. (yield: 75%, MS: [M+H] + =721).

[0725] Preparation Example 2-61

[0726]

[0727] Compound amine 61 (10g, 17.1mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (12.3g, 616.3mmol) is added to trifluoromethanesulfonic anhydride (43.5g, 154.1mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 8 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.2g of compound 2-61. (Yield: 41%, MS: [M+H] + =605).

[0728] Compound 2-61 (15g, 24.8mmol) and phenanthrene-9-ylboronic acid-D5 (5.9g, 26.1mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.3g, 74.5mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.2mmol) is added. After reacting for 5 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 11.6g compound 2-61-D25. (yield: 62%, MS: [M+H] + =752).

[0729] Preparation Example 2-62

[0730]

[0731] Compound amine 62 (10g, 16.7mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (12.1g, 601.9mmol) is added to trifluoromethanesulfonic anhydride (42.5g, 150.5mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 8 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.6g of compound 2-62. (yield: 45%, MS: [M+H] + =617).

[0732] Compound 2-62 (15g, 24.3mmol) and phenanthrene-9-ylboronic acid-D3 (5.8g, 25.6mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.1g, 73mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.2mmol) is added. After reacting for 3 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 13.2g compound 2-62-D21. (yield: 71%, MS: [M+H] + =762).

[0733] Preparation Example 2-63

[0734]

[0735] Compound amine 63 (10g, 19.2mmol) is added to 200ml 1,2,4 trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (13.8g, 689.5mmol) is added to trifluoromethanesulfonic anhydride (48.6g, 172.4mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 8 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.8g of compound 2-63. (yield: 46%, MS: [M+H] + =545).

[0736] Compound 2-63 (15g, 27.6mmol) and phenanthrene-9-ylboronic acid-D8 (6.7g, 28.9mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (11.4g, 82.7mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 3 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 13.2g compound 2-63-D30. (yield: 69%, MS: [M+H] + =695).

[0737] Preparation Example 2-64

[0738]

[0739] Compound amine 64 (10g, 19.7mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (14.2g, 708.6mmol) is added to trifluoromethanesulfonic anhydride (33.3g, 118.1mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.8g of compound 2-64. (yield: 47%, MS: [M+H] + =520).

[0740] Compound 2-64 (15g, 28.9mmol) and phenanthrene-9-ylboronic acid-D9 (7g, 30.3mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (12g, 86.7mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 14.1g compound 2-64-D20. (yield: 73%, MS: [M+H] + =671).

[0741] Preparation Example 2-65

[0742]

[0743] Compound amine 65 (10g, 16.4mmol) is added to 200ml 1,2,4 trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (11.9g, 591.9mmol) is added to trifluoromethanesulfonic anhydride (41.8g, 148mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 8 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.4g compound 2-65. (yield: 42%, MS: [M+H] + =634).

[0744] Compound 2-65 (15g, 23.7mmol) and phenanthrene-9-ylboronic acid-D3 (5.6g, 24.9mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (9.8g, 71.1mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.2mmol) is added. After reacting for 3 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 14.6g compound 2-65-D28. (yield: 79%, MS: [M+H] + =779).

[0745] Preparation Example 2-66

[0746]

[0747] Compound amine 66 (10g, 17.9mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (12.9g, 645mmol) is added to trifluoromethanesulfonic anhydride (60.7g, 215mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 15 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.5g of compound 2-66. (yield: 43%, MS: [M+H] + =587).

[0748] Compound 2-66 (15g, 25.6mmol) and phenanthrene-9-ylboronic acid-D9 (6.2g, 26.9mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.6g, 76.8mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 13.2g compound 2-66-D37. (yield: 70%, MS: [M+H] + =738).

[0749] Preparation Example 2-67

[0750]

[0751] Compound amine 67 (10g, 17.1mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (12.3g, 616.3mmol) is added to trifluoromethanesulfonic anhydride (43.5g, 154.1mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 8 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.7g of compound 2-67. (yield: 45%, MS: [M+H] + =608).

[0752] Compound 2-67 (15g, 24.7mmol) and phenanthrene-9-ylboronic acid-D6 (5.9g, 25.9mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (10.2g, 74.1mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.2mmol) is added. After reacting for 4 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 12.9g compound 2-67-D29. (yield: 69%, MS: [M+H] + =756).

[0753] Preparation Example 2-68

[0754]

[0755] Compound amine 68 (10g, 18.8mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (13.6g, 676.6mmol) is added to trifluoromethanesulfonic anhydride (47.7g, 169.1mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 8 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.5g of compound 2-68. (yield: 43%, MS: [M+H] + =553).

[0756] Compound 2-68 (15g, 27.2mmol) and phenanthrene-9-ylboronic acid-D9 (6.6g, 28.5mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (11.3g, 81.5mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 5 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 13.2g compound 2-68-D29. (yield: 69%, MS: [M+H] + =704).

[0757] Preparation Example 2-69

[0758]

[0759] Compound amine 69 (10g, 16.3mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (11.7g, 586.1mmol) is added to trifluoromethanesulfonic anhydride (41.3g, 146.5mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 8 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.3g of compound 2-69. (yield: 42%, MS: [M+H] + =636).

[0760] Compound 2-69 (15g, 23.6mmol) and phenanthrene-9-ylboronic acid-D2 (5.6g, 24.8mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (9.8g, 70.8mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.2mmol) is added. After reacting for 5 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 12g compound 2-69-D23. (yield: 65%, MS: [M+H] + =780).

[0761] Preparation Example 2-70

[0762]

[0763] Compound amine 70 (10g, 19.2mmol) is added to 200ml 1,2,4 trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (13.8g, 689.6mmol) is added to trifluoromethanesulfonic anhydride (48.6g, 172.4mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 8 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.1g of compound 2-70. (yield: 40%, MS: [M+H] + =541).

[0764] Compound 2-70 (15g, 27.7mmol) and phenanthrene-9-ylboronic acid-D5 (6.6g, 29.1mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (11.5g, 83mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 4 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 14.1g compound 2-70-D25. (yield: 74%, MS: [M+H] + =690).

[0765] Preparation Example 2-71

[0766]

[0767] Compound 71 (10g, 16.1mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (11.6g, 580.4mmol) is added to trifluoromethanesulfonic anhydride (27.3g, 96.7mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.8g of compound 2-71. (yield: 47%, MS: [M+H] + =640).

[0768] Compound 2-71 (15g, 23.5mmol) and phenanthrene-9-ylboronic acid-D7 (5.6g, 24.6mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (9.7g, 70.4mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.2mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 14.2g compound 2-71-D26. (yield: 77%, MS: [M+H] + =789).

[0769] Preparation Example 2-72

[0770]

[0771] Compound 72 (10g, 19.7mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (14.2g, 708.6mmol) is added to trifluoromethanesulfonic anhydride (33.3g, 118.1mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 4.2g of compound 2-72. (Yield: 41%, MS: [M+H] + =523).

[0772] Compound 2-72 (15g, 28.7mmol) and phenanthrene-9-ylboronic acid-D9 (7g, 30.2mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (11.9g, 86.2mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 2 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 14.9g compound 2-72-D23. (yield: 77%, MS: [M+H] + =674).

[0773] Preparation Example 2-73

[0774]

[0775] Compound 73 (20g, 37.6mmol) is added to 200ml 1,2,4-trichlorobenzene, and the mixture is stirred at room temperature. In another container, deuterium oxide (14.2g, 708.6mmol) is added to trifluoromethanesulfonic anhydride (66.6g, 236.2mmol) at 0°C, and the mixture is stirred for 10 hours to prepare a solution. Then, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture is stirred while being heated to 140°C, and then the temperature is maintained. After reacting for 4 hours, the reaction mixture is cooled to room temperature, and the organic layer and the aqueous layer are separated. Then, the organic layer is neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 10.8g of compound 2-73. (yield: 53%, MS: [M+H] + =544).

[0776] Compound 2-73 (15g, 27.6mmol) and phenanthrene-9-ylboronic acid-D9 (7g, 29.0mmol) are added to 300mlTHF, and the mixture is stirred and refluxed. Then, potassium carbonate (12g, 86.5mmol) is dissolved in 100ml water and added thereto, and the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1g, 0.3mmol) is added. After reacting for 3 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 9.6g of compound 2-73-D21. (Yield: 75%, MS: [M+H] + =674).

[0777] Example 1

[0778] It is coated with a thickness of The ITO (indium tin oxide) of the present invention is put into the distilled water that is dissolved with wherein detergent as the glass substrate of film, and carry out ultrasonic cleaning.Use the product manufactured by Fischer Co. as detergent, and as distilled water, use the distilled water that utilizes the filter manufactured by Millipore Co. to filter twice.After ITO was cleaned 30 minutes, distilled water was used to repeat twice ultrasonic cleaning 10 minutes.After completing with distilled water cleaning, with isopropyl alcohol, acetone and methanol solvent, substrate was carried out ultrasonic cleaning, it was dried, and then transferred to plasma cleaner.In addition, oxygen plasma was used to clean substrate 5 minutes, and then it was transferred to vacuum deposition machine.

[0779] On the thus prepared ITO transparent electrode, the following compound HI-1 was formed to The hole injection layer was prepared by vacuum depositing the following compound HT-1 on the hole injection layer to form a layer with a thickness of Then, the following compounds EB-1 to EB-2 were vacuum deposited on the hole transport layer. Then, the following compound 1-1 as the first host, the following compound 2-1-D22 as the second host, and the following compound Dp-7 as the dopant were vacuum deposited on the EB-1 deposited layer at a weight ratio of 49:49:2 to form a layer with a thickness of The following compounds HB-1 to HB-2 were vacuum deposited on the luminescent layer. Then, the following compound ET-1 and the following compound LiQ were vacuum deposited on the hole blocking layer at a weight ratio of 2:1 to form a layer with a thickness of The electron injection and transport layer is sequentially deposited with lithium fluoride (LiF) and aluminum to a thickness of 100 Å and 100 Å, respectively. and Thus, a cathode is formed.

[0780]

[0781] During the above process, the vacuum deposition rate of the organic material is kept at to The deposition rates of lithium fluoride and aluminum at the cathode were kept at and And the vacuum degree during deposition is maintained at 2*10 -7 Up to 5*10 -6 support, thereby manufacturing an organic light-emitting device.

[0782] Examples 2 to 245

[0783] An organic light-emitting device was manufactured in the same manner as in Example 1, except that, as shown in Tables 1 to 6 below, the compound represented by Chemical Formula 1 as the first host and the compound represented by Chemical Formula 2 as the second host were co-deposited at a ratio of 1:1 and used instead of Compound 1 in the organic light-emitting device of Example 1.

[0784] Comparative Examples 1 to 60

[0785] An organic light-emitting device was manufactured in the same manner as in Example 1, except that, as shown in Tables 7 and 8 below, comparative compounds A-1 to A-12 as the first host and the compound represented by Chemical Formula 2 as the second host were co-deposited at a ratio of 1:1 and used instead of Compound 1 in the organic light-emitting device of Example 1. Compounds A-1 to A-12 shown in Tables 7 and 8 below are as follows.

[0786]

[0787] Comparative Examples 61 to 268

[0788] An organic light-emitting device was manufactured in the same manner as in Example 1, except that, as shown in Tables 9 to 14 below, a compound represented by Chemical Formula 1 as a first host and a comparative compound shown in Tables 9 to 14 below as a second host were co-deposited at a ratio of 1:1 and used instead of Compound 1 in the organic light-emitting device of Example 1. The second host compounds shown in Tables 9 to 14 below are as follows.

[0789]

[0790]

[0791]

[0792] Experimental example

[0793] The voltage and efficiency (based on 15 mA / cm 2 ), and the results are shown in the following Tables 1 to 14. The lifespan T95 was measured based on 6000 nits, and T95 means the time required for the lifespan to decrease to 95% of the initial lifespan.

[0794] [Table 1]

[0795]

[0796] [Table 2]

[0797]

[0798] [Table 3]

[0799]

[0800] [Table 4]

[0801]

[0802] [Table 5]

[0803]

[0804] [Table 6]

[0805]

[0806] [Table 7]

[0807]

[0808] [Table 8]

[0809]

[0810] [Table 9]

[0811]

[0812] [Table 10]

[0813]

[0814] [Table 11]

[0815]

[0816] [Table 12]

[0817]

[0818] [Table 13]

[0819]

[0820] [Table 14]

[0821]

[0822] When current was applied to the organic light-emitting devices manufactured in Examples 1 to 245 and Comparative Examples 1 to 268, the results shown in Tables 1 to 14 were obtained. The red organic light-emitting device of Example 1 uses materials that have been widely used in the past and has a structure using compound EB-1 as an electron blocking layer and Dp-7 as a dopant in the red light-emitting layer. As shown in Tables 7 to 8, when the comparative example compounds A-1 to A-12 and the compound of Chemical Formula 2 of the present disclosure are co-deposited and used as a red light-emitting layer, the results show an overall increase in driving voltage and a decrease in efficiency and lifespan compared to the combination of the present disclosure. In addition, as shown in Tables 9 to 14, even when the comparative compound and the compound of Chemical Formula 1 of the present disclosure are co-deposited and used as a red light-emitting layer, the results show an increase in driving voltage and a decrease in efficiency and lifespan.

[0823] From the above results, it can be determined that when the compound represented by Chemical Formula 1 as the first host of the present disclosure and the compound represented by Chemical Formula 2 as the second host of the present disclosure are used in combination, energy transfer to the red dopant in the red light-emitting layer is excellently achieved, thereby achieving a more stable balance in the light-emitting layer than the combination in the comparative example, and combining electrons and holes to effectively form excitons and significantly improve efficiency and lifespan. In addition, it is inferred that deuterium substitution for the compound of the present disclosure contributes to molecular stability and further improved lifespan characteristics. In summary, when the compound represented by Chemical Formula 1 of the present disclosure and the compound represented by Chemical Formula 2 are combined, co-deposited and used as the host of the red light-emitting layer, the driving voltage, luminous efficiency and lifespan characteristics of the organic light-emitting device can be improved.

[0824] [Explanation of Reference Numerals]

[0825] 1: substrate 2: anode

[0826] 3: Light-emitting layer 4: Cathode

[0827] 5: Hole injection layer 6: Hole transport layer

[0828] 7: Electron blocking layer 8: Hole blocking layer

[0829] 9: Electron injection and transport layer

Claims

1. An organic light-emitting device, comprising: anode; cathode; and a light-emitting layer between the anode and the cathode, The light-emitting layer comprises a compound represented by the following Chemical Formula 1 and a compound represented by the following Chemical Formula 2: [Chemical Formula 1] In Chemical Formula 1, Ar1 and Ar2 are each independently substituted or unsubstituted C 6-60 Aryl; or a substituted or unsubstituted C 2-60 heteroaryl, L1 is a single bond; or substituted or unsubstituted C 6-60 arylene groups, L2 and L3 are each independently a single bond; substituted or unsubstituted C 6-60 Arylene; or a substituted or unsubstituted C containing at least one selected from N, O and S 2-60 Heteroarylene, and R1 to R7 are each independently hydrogen or deuterium, [Chemical Formula 2] In Chemical Formula 2, Ar'1 is hydrogen; deuterium; substituted or unsubstituted C 6-60 Aryl; or a substituted or unsubstituted C 2-60 heteroaryl, Ar'2 and Ar'3 are each independently substituted or unsubstituted C 6-60 Aryl; or a substituted or unsubstituted C 2-60 heteroaryl, L'1 to L'3 are each independently a single bond; substituted or unsubstituted C 6-60 Arylene; or a substituted or unsubstituted C containing at least one selected from N, O and S 2-60 Heteroarylene, L'4 is a single bond or a substituted or unsubstituted C 6-60 arylene groups, R'1 is hydrogen or deuterium, a is an integer from 1 to 8, and - at least one of L'1-Ar'1 and R'1 is deuterium, wherein the deuterium substitution rate of the compound represented by Chemical Formula 2 is 50% or greater.

2. The organic light-emitting device according to claim 1, wherein: Ar1 and Ar2 are each independently phenyl, biphenyl, terphenyl, triphenylsilylphenyl, naphthyl, phenanthrenyl, dibenzofuranyl, or dibenzothiophenyl, wherein the phenyl, biphenyl, terphenyl, triphenylsilylphenyl, naphthyl, phenanthrenyl, dibenzofuranyl, and dibenzothienyl groups are each independently unsubstituted or substituted with at least one deuterium group.

3. The organic light emitting device according to claim 1, wherein: L1 is a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthalenediyl group.

4. The organic light emitting device according to claim 1, wherein: L2 and L3 are each independently a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenyldiyl group, or a substituted or unsubstituted naphthalenediyl group.

5. The organic light emitting device according to claim 1, wherein: The compound represented by Chemical Formula 1 is any one selected from the following compounds:

6. The organic light emitting device according to claim 1, wherein: Ar'1 is hydrogen, deuterium, or phenyl which is unsubstituted or substituted with at least one deuterium group.

7. The organic light emitting device according to claim 1, wherein: Ar'2 and Ar'3 are each independently phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, tetrahydronaphthyl, phenanthrenyl, phenylphenanthrenyl, triphenylene, dimethylfluorenyl, diphenylfluorenyl, carbazolyl, phenylcarbazolyl, dibenzofuranyl, dibenzothiophenyl, or phenyldibenzofuranyl, wherein the phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, tetrahydronaphthyl, phenanthrenyl, phenylphenanthrenyl, triphenylene, dimethylfluorenyl, diphenylfluorenyl, carbazolyl, phenylcarbazolyl, dibenzofuranyl, dibenzothienyl and phenyldibenzofuranyl are each independently unsubstituted or substituted with at least one deuterium or at least one C 1-10 Alkyl substitution.

8. The organic light emitting device according to claim 1, wherein: L'1 to L'3 are each independently a single bond, a phenylene group, a biphenylene group, a naphthylene group, a phenylnaphthylene group, a phenanthrenyl group, a carbazolylene group, a phenylcarbazolylene group, a dibenzofuranyl group, a phenyldibenzofuranyl group, or a dimethylfluorenyl group, wherein the phenylene, biphenylene, naphthylene, phenylnaphthylene, phenanthrenylene, carbazolylene, phenylcarbazolylene, dibenzofuranylene, phenyldibenzofuranylene and dimethylfluorenylene are each independently unsubstituted or substituted with at least one deuterium.

9. The organic light emitting device according to claim 1, wherein: L'4 is a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted naphthylene group.

10. The organic light emitting device according to claim 1, wherein: The compound represented by Chemical Formula 2 is any one selected from the group consisting of the following compounds, In the following groups, D is deuterium, n1 is an integer from 1 to 9, n is the total number of deuterium substituted in the compound, and The deuterium substitution rate of each compound in the following groups is 50% or greater: 。

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