Organic light emitting device

Abstract

The present invention provides an organic light emitting device.

Description

Technical Field

[0001] Cross-reference with related applications

[0002] This application claims priority based on Korean Patent Application No. 10-2020-0136281 dated October 20, 2020 and Korean Patent Application No. 10-2021-0139315 dated October 19, 2021, the entire contents of which are disclosed in the documents of the Korean patent applications and are incorporated into this specification.

[0003] This invention relates to organic light-emitting devices. Background Technology

[0004] Organic light emission typically refers to the phenomenon of converting electrical energy into light energy using organic materials. Organic light-emitting devices (OLEDs) utilizing organic light emission exhibit wide viewing angles, excellent contrast ratios, fast response times, and superior brightness, driving voltage, and response speed characteristics, thus attracting extensive research.

[0005] Organic light-emitting devices (OLEDs) typically have a structure comprising an anode and a cathode, and an organic layer located between the anode and cathode. To improve the efficiency and stability of OLEDs, the organic layer is often formed by a multilayer structure composed of different materials, such as a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. In such an OLED structure, if a voltage is applied between the two electrodes, holes are injected into the organic layer from the anode, and electrons are injected into the organic layer from the cathode. When the injected holes and electrons meet, an exciton is formed. When this exciton re-enters the ground state, it emits light.

[0006] For organic materials used in organic light-emitting devices as described above, there is a continuous need to develop new materials.

[0007] Existing technical documents

[0008] Patent documents

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

[0010] Technical issues

[0011] This invention relates to organic light-emitting devices.

[0012] Solution to the problem

[0013] The present invention provides the following organic light-emitting device.

[0014] An organic light-emitting device includes: an anode;

[0015] A cathode disposed opposite the aforementioned anode; and

[0016] The light-emitting layer disposed between the anode and the cathode,

[0017] The light-emitting layer comprises a first compound represented by chemical formula 1 and a second compound represented by chemical formula 2.

[0018] [Chemical Formula 1]

[0019]

[0020] In the above chemical formula 1,

[0021] A1 and A2 are each independently a benzene or naphthalene ring fused with an adjacent five-membered ring.

[0022] L represents substituted or unsubstituted C. 6-60 Alpha-aryl

[0023] L1 and L2 are each independently a single bond, or a substituted or unsubstituted C bond. 6-60 Alpha-aryl

[0024] Ar1 and Ar2 are each independently substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms of N, O and S. 2-20 Mixed aromatics,

[0025] R1 and R2 are each independently hydrogen; deuterium; substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms of N, O and S. 2-60 Mixed aromatics,

[0026] When A1 and A2 are each benzene rings, a and b are each independent integers from 0 to 4. When A1 and A2 are each naphthalene rings, a and b are each independent integers from 0 to 6.

[0027] [Chemical Formula 2]

[0028]

[0029] In the above chemical formula 2,

[0030] L' represents substituted or unsubstituted C. 6-60 Alpha-aryl

[0031] L3 and L4 are each independently a single bond, or a substituted or unsubstituted C bond. 6-60 Alpha-aryl

[0032] Ar3 and Ar4 are each independently substituted or unsubstituted C. 6-60 Aryl, substituents represented by chemical formula 2a, substituents represented by chemical formula 2b, or substituents represented by chemical formula 2c, but Ar3 and Ar4 are not fluorene groups.

[0033]

[0034] In the above chemical formulas 2a to 2c,

[0035] X can be independently O, S, or N (Ar).

[0036] Here, Ar is hydrogen, deuterium, or substituted or unsubstituted C. 6-20 Aryl,

[0037] B1 to B3 are each independently a substituted or unsubstituted naphthalene ring fused with an adjacent five-membered ring.

[0038] R is hydrogen, deuterium, or a substituted or unsubstituted C. 6-20 Aryl,

[0039] n is an integer from 0 to 4.

[0040] R3 is either hydrogen or deuterium.

[0041] c is an integer from 0 to 9.

[0042] In this case, when a, b, and c are each 2 or more, the substituents within the parentheses may be the same or different from each other.

[0043] Invention Effects

[0044] The aforementioned organic light-emitting devices contain two host compounds in the light-emitting layer, which can improve efficiency, driving voltage, and / or lifetime characteristics in organic light-emitting devices. Attached Figure Description

[0045] Figure 1 The illustration shows an example of an organic light-emitting device consisting of a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4.

[0046] Figure 2 The illustration shows an example of an organic light-emitting device consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron suppression layer 7, a light-emitting layer 3, a hole blocking layer 8, an electron injection and transport layer 9, and a cathode 4. Detailed Implementation

[0047] The invention will now be described in more detail to aid in understanding.

[0048] In this instruction manual, The symbol indicates a bond that is linked to other substituents; D represents deuterium, and Ph represents phenyl.

[0049] In this specification, the term "substituted or unsubstituted" refers to a group selected from deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thio group. aryl thiols alkylsulfonyl arylsulfonyl Silicyl; boronyl; alkyl; cycloalkyl; alkenyl; aryl; aralkyl; arylenyl; alkylaryl; alkylamino; aralkylamino; heteroarylamino; arylamino; arylphosphinyl; or a substituent formed by connecting two or more substituents of the above-exemplified substituents, whether substituted or unsubstituted. For example, "a substituent formed by connecting two or more substituents" can be biphenyl. That is, biphenyl can be aryl, or it can be interpreted as a substituent formed by connecting two phenyl groups. As an example, the term "substituted or unsubstituted" can be understood as "unsubstituted, or substituted with a substance selected from deuterium, halogen, C 1-10 Alkyl, C 1-10 Alkoxy and C 6-20 The meaning of "substituted by one or more substituents in the aryl group, for example, one to five substituents" is as follows. In addition, in this specification, the term "substituted by one or more substituents" can be understood as, for example, "substituted by one to five substituents" or "substituted by one or two substituents".

[0050] In this specification, the number of carbon atoms in the carbonyl group is not particularly limited, but it is preferred to have 1 to 40 carbon atoms. Specifically, it can be a substituent with the following structures, but is not limited thereto.

[0051]

[0052] In this specification, the oxygen in the ester group can be replaced by a straight-chain, branched, or cyclic alkyl group having 1 to 25 carbon atoms, or an aryl group having 6 to 25 carbon atoms. Specifically, it can be a substituent of the following structural formula, but is not limited thereto.

[0053]

[0054] In this specification, the number of carbon atoms in the imide group is not particularly limited, but it is preferred to have 1 to 25 carbon atoms. Specifically, it can be a substituent with the following structure, but is not limited thereto.

[0055]

[0056] In this specification, silanes specifically include trimethylsilane, triethylsilane, tert-butyldimethylsilane, vinyldimethylsilane, propyldimethylsilane, triphenylsilane, diphenylsilane, phenylsilane, etc., but are not limited to these.

[0057] In this specification, the boron group specifically includes trimethylboryl, triethylboryl, tert-butyldimethylboryl, triphenylboryl, phenylboryl, etc., but is not limited to these.

[0058] Examples of halogen groups in this specification include fluorine, chlorine, bromine, or iodine.

[0059] In this specification, the alkyl group can be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethylbutyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-ethyl-propyl, 1,1-dimethylpropyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-Ethylbutyl, heptyl, n-heptyl, isohexyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2,4,4-trimethyl-1-pentyl, 2,4,4-trimethyl-2-pentyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, etc., but not limited to these.

[0060] In this specification, the alkenyl group can be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to yet another embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples 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, styryl, styryl, etc., but are not limited to these.

[0061] In this specification, the cycloalkyl group is not particularly limited, but is preferably a cycloalkyl group with 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., are used, but are not limited to these.

[0062] In this specification, the aryl group is not particularly limited, but is preferably an aryl group with 6 to 60 carbon atoms, and can be a monocyclic or polycyclic aryl group having aromaticity. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to another embodiment, the aryl group has 6 to 20 carbon atoms. Regarding the aforementioned aryl group, as a monocyclic aryl group, it can be phenyl, biphenyl, terphenyl, etc., but is not limited to these. As the aforementioned polycyclic aryl group, it can be naphthyl, anthraceneyl, phenanthryl, triphenylene, pyrene, perylene, etc. It is based on, but not limited to, the basic level.

[0063] In this specification, a heteroaryl group is a heteroaryl group containing one or more heteroatoms selected from O, N, Si, and S as heteroelements. The number of carbon atoms is not particularly limited, but is preferably 2 to 60. Examples of heteroaryl groups include thienyl, furanyl, pyrroleyl, imidazolyl, and thiazolyl. azole group, Diazolyl, Triazolyl, Pyridyl, Bipyridyl, Pyrimidinyl, Triazinyl, Acridineyl, Pyridazinyl, Quinolinyl, Quinazolinyl, Quinoxalinyl, Phtharazineyl, Pyridopyrimidinyl, Pyridopyrazinyl, Pyrazenopyrazinyl, Isoquinolinyl, Indoleyl, Carbazoleyl, Benzo[] Azolyl, benzimidazolyl, benzothiazolyl, benzocarbazole, benzothiophene, dibenzothiophene, benzofuranyl, phenanthroline, iso The group can be azole, thiadiazole, phenothiazinyl, or dibenzofuranyl, but is not limited to these.

[0064] In this specification, the aryl groups in aralkyl, aryl-alkenyl, alkylaryl, arylamino, and arylsilyl are the same as those exemplified above. In this specification, the alkyl groups in aralkyl, alkylaryl, and alkylamino are the same as those exemplified above. In this specification, the heteroaryl groups in heteroarylamines are subject to the above description of heteroaryl groups. In this specification, the alkenyl groups in aryl-alkenyl are the same as those exemplified above. In this specification, arylene is a divalent group; otherwise, the above description of aryl groups applies. In this specification, heteroarylene is a divalent group; otherwise, the above description of heteroaryl groups applies. In this specification, the hydrocarbon ring is not a monovalent group but is formed by the combination of two substituents; otherwise, the above description of aryl or cycloalkyl groups applies. In this specification, the heterocycle is not a monovalent group but is formed by the combination of two substituents; otherwise, the above description of heteroaryl groups applies.

[0065] On the other hand, an organic light-emitting device according to one embodiment includes: an anode, a cathode disposed opposite to the anode, and a light-emitting layer disposed between the anode and the cathode, wherein the light-emitting layer comprises a first compound represented by the above chemical formula 1 and a second compound represented by the above chemical formula 2.

[0066] The organic light-emitting device according to the present invention contains two compounds with specific structures as host materials in the light-emitting layer, thereby improving the efficiency, driving voltage and / or lifetime characteristics of the organic light-emitting device.

[0067] The present invention will now be described in detail according to its constituent parts.

[0068] Anode and cathode

[0069] As the aforementioned anode material, a material with a high work function is preferred in order to facilitate the injection of holes into the organic layer. Specific examples of the aforementioned anode material include metals such as vanadium, chromium, copper, zinc, and gold, or their alloys; 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; and conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylidene-1,2-dioxo)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited to these.

[0070] As the cathode material described above, a material with a low work function is generally preferred in order to facilitate the injection of electrons into the organic layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or their alloys; multilayer materials such as LiF / Al or LiO2 / Al, etc., but are not limited to these.

[0071] Hole injection layer

[0072] The organic light-emitting device according to the present invention may include a hole injection layer between the anode and the hole transport layer described later, as needed.

[0073] The aforementioned hole injection layer, located on the anode, is a layer for injecting holes from the anode and contains a hole injection material. Preferably, this hole injection material is a compound that possesses the ability to transport holes, the effect of injecting holes from the anode, excellent hole injection performance for the luminescent layer or luminescent material, prevents excitons generated in the luminescent layer from migrating to the electron injection layer or electron injection material, and exhibits excellent thin film formation capability. In particular, it is suitable 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 layer.

[0074] Specific examples of the aforementioned hole-injection materials include metalloporphyrins, oligothiophenes, arylamine-based organic compounds, hexanitrile hexaazabenzophenanthrene-based organic compounds, quinacridone-based organic compounds, perylene-based organic compounds, anthraquinones, and conductive polymers based on polyaniline and polythiophene, but are not limited to these.

[0075] Hole transport layer

[0076] The organic light-emitting device according to the present invention may include a hole transport layer between the anode and the light-emitting layer. The hole transport layer is a layer that receives holes from the anode or a hole injection layer formed on the anode and transports the holes to the light-emitting layer, and contains a hole transport material. The hole transport material is a material capable of receiving holes from the anode or the hole injection layer and transferring them to the light-emitting layer; a material with high hole mobility is suitable. Specific examples include arylamine-based organic compounds, conductive polymers, and block copolymers containing both conjugated and non-conjugated portions, but are not limited to these.

[0077] Electron suppression layer

[0078] The organic light-emitting device according to the present invention may include an electron suppression layer between the hole transport layer and the light-emitting layer as needed. The electron suppression layer refers to a layer formed on the hole transport layer, preferably disposed in contact with the light-emitting layer, which improves the efficiency of the organic light-emitting device by adjusting the hole mobility, preventing excessive electron migration, and thus preventing excessive electron-hole binding. The electron suppression layer contains an electron-blocking material; examples of such electron-blocking materials include arylamine-based organic compounds, but it is not limited to these.

[0079] Emissive layer

[0080] The organic light-emitting device according to the present invention includes a light-emitting layer between the anode and the cathode, wherein the light-emitting layer comprises the first compound and the second compound as host materials. Specifically, the first compound functions as an N-type host material with superior electron transport capability compared to hole transport capability, and the second compound functions as a P-type host material with superior hole transport capability compared to electron transport capability, thereby appropriately maintaining the hole-to-electron ratio within the light-emitting layer. Therefore, excitons emit light uniformly throughout the entire light-emitting layer, thereby simultaneously improving the luminous efficiency and lifetime characteristics of the organic light-emitting device.

[0081] The first compound and the second compound described above will be explained in turn below.

[0082] (First compound)

[0083] The aforementioned first compound is represented by the aforementioned chemical formula 1. Specifically, the aforementioned first compound is a compound in which a triazine group is linked to the N atom of a carbazole-based core via a linking group L, characterized in that the linking group L is an aryl group. In particular, compared with compounds without L, that is, compared with compounds in which a triazine group is linked to the N atom of a carbazole-based core by a single bond, the aforementioned first compound has a further improved electron transport capability, effectively transferring electrons to the dopant material, and thus increasing the electron-hole recombination probability in the luminescent layer.

[0084] According to one embodiment, in the above chemical formula 1,

[0085] A1 and A2 are each independently a benzene ring fused with an adjacent five-membered ring; or

[0086] One of A1 and A2 is a benzene ring fused with an adjacent five-membered ring, and the other is a naphthalene ring fused with an adjacent five-membered ring; or

[0087] A1 and A2 are both independent naphthalene rings fused with adjacent five-membered rings.

[0088] Additionally, in chemical formula 1, 'a' represents the number of R1s, which is an integer from 0 to 6. Specifically, when A1 is a benzene ring, 'a' is 0, 1, 2, 3, or 4; when A1 is a naphthalene ring, 'a' is 0, 1, 2, 3, 4, 5, or 6.

[0089] Additionally, b represents the number of R2 elements, which is an integer from 0 to 6. Specifically, when A2 is a benzene ring, b is 0, 1, 2, 3, or 4; when A2 is a naphthalene ring, b is 0, 1, 2, 3, 4, 5, or 6.

[0090] In this case, a+b can be an integer from 0 to 4. Alternatively, a+b can be 0 or 1.

[0091] More specifically, in the above chemical formula 1, the substituents It can be represented by any one of the following chemical formulas 1a to 1j:

[0092]

[0093] In the above chemical formulas 1a to 1j,

[0094] a' and b' are each an independent integer from 0 to 4.

[0095] a" and b" are each an independent integer from 0 to 6.

[0096] R1 and R2 are defined in the same way as in the above chemical formula 1.

[0097] More specifically, in the above chemical formulas 1a to 1j,

[0098] a', b', a" and b" can each independently be 0, 1 or 2.

[0099] For example, in the above chemical formula 1a, a'+b' is 0 or 1.

[0100] In the above chemical formulas 1b to 1d, a"+b' is 0 or 1.

[0101] In the above chemical formulas 1e to 1j, a"+b" is 0 or 1.

[0102] Therefore, the first compound described above can be represented by any one of the following chemical formulas 1-1 to 1-10:

[0103]

[0104] In the above 1-1 to 1-10,

[0105] a' and b' are each an independent integer from 0 to 4.

[0106] a" and b" are each an independent integer from 0 to 6.

[0107] L, L1, L2, Ar1, Ar2, R1, and R2 are defined in the same way as in the above chemical formula 1.

[0108] More specifically, in 1-1 to 1-10 above,

[0109] a', b', a" and b" can each independently be 0, 1 or 2.

[0110] For example, in the above chemical formula 1-1, a'+b' is 0 or 1.

[0111] In the above chemical formulas 1-2 to 1-4, a"+b' is 0 or 1.

[0112] In the above chemical formulas 1-5 to 1-10, a"+b" is 0 or 1.

[0113] Furthermore, in the above chemical formula 1, L can be an unsubstituted C or a C substituted with one or more deuterium atoms. 6-20 Aryl.

[0114] Specifically, L can be phenylene, biphenyl dimethyl, or naphthylene.

[0115] More specifically, L can be any one of the following groups.

[0116]

[0117] Furthermore, in the above chemical formula 1, L1 and L2 can each independently be single bonds; or C bonds that are unsubstituted or substituted with one or more deuterium atoms. 6-20 Alpha-aryl.

[0118] Specifically, L1 and L2 can each be a single bond, a phenylene group, or a naphthylene group.

[0119] More specifically, L1 and L2 can each be a single bond or selected from any of the following groups.

[0120]

[0121] For example, both L1 and L2 could be single bonds; or

[0122] One of L1 and L2 is a single bond, and the other is a naphthyl group; or

[0123] One of L1 and L2 is a single bond, and the other is a phenylene oxide.

[0124] Furthermore, in the above chemical formula 1, Ar1 and Ar2 do not contain heteroaryl groups with more than 20 carbon atoms, such as monovalent substituents with a spiro(fluorene-xanthine) structure. Using an organic light-emitting device (OLED) with at least one of Ar1 and Ar2 containing a heteroaryl group with more than 20 carbon atoms as the host may result in a significant decrease in efficiency and lifetime compared to an OLED using a compound represented by the above chemical formula 1 as the host.

[0125] Specifically, Ar1 and Ar2 can each independently be C that is either unsubstituted or substituted with one or more deuterium atoms. 6-20 aryl; or C containing one heteroatom of O or S, either unsubstituted or substituted with one or more deuterium atoms. 2-20 Mixed aromatic compounds.

[0126] More specifically, Ar1 and Ar2 can each independently be phenyl, naphthyl, biphenyl, or dibenzofuranyl.

[0127] For example, Ar1 and Ar2 can each independently be...

[0128] Additionally, one of Ar1 and Ar2 can be

[0129] At this point, Ar1 and Ar2 can be the same as or different from each other.

[0130] In addition, R1 and R2 can each be independently C 6-20 aryl; or C containing one heteroatom from N, O, and S. 2-20 Mixed aromatic compounds.

[0131] Specifically, R1 and R2 can each independently be phenyl, dibenzofuranyl, or dibenzothiophene. More specifically, R1 and R2 can each independently be phenyl, naphthyl, or dibenzofuranyl.

[0132] As an example, R1 and R2 can each be independently selected from any of the following groups:

[0133]

[0134] On the other hand, a representative example of the first compound represented by the above chemical formula 1 is shown below:

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178] On the other hand, as an example, the first compound described above can be manufactured by the manufacturing method shown in the following reaction formula 1.

[0179] [Reaction Formula 1]

[0180]

[0181] In the above reaction formula 1, X" is a halogen, preferably bromine or chlorine, and the definitions of other substituents are the same as those described above.

[0182] Specifically, the compound represented by the above chemical formula 1 can be prepared by an amine substitution reaction of starting materials A1 and A2. Such an amine substitution reaction is preferably carried out in the presence of a palladium catalyst and a base, and the reactive groups used in the above amine substitution reaction can be appropriately modified. The method for preparing the compound represented by the above chemical formula 1 can be further specified in the manufacturing examples described later.

[0183] (Second compound)

[0184] The second compound described above is represented by the aforementioned chemical formula 2. Specifically, the second compound is characterized in that it has a 9-phenanthrene group as one of the substituents of the amino group, and the remaining substituents have substituted or unsubstituted C groups. 6-60 aryl or substituted or unsubstituted C-type compounds containing one or more heteroatoms of N, O, and S. 2-15 Heteroaryl groups. In this case, the amino group does not have a fluorene group as a substituent. That is, Ar3 and Ar4 are not fluorene groups.

[0185] In particular, compared with i) compounds having 1-phenanthrene, 2-phenanthrene, 3-phenanthrene, or 4-phenanthrene instead of 9-phenanthrene as one of the substituents of the amino group and ii) compounds having substituted or unsubstituted fluorenyl or carbazole-9-yl as one of the substituents of the amino group, the second compound can effectively transfer holes to the dopant material, thereby increasing the probability of hole-electron recombination in the light-emitting layer together with the first compound, which has excellent electron transport capabilities.

[0186] Additionally, L' can be either unsubstituted or deuterated C.6-20 Alpha-aryl.

[0187] Specifically, L' can be phenylene, biphenyl dimethyl, or naphthylene independently.

[0188] More specifically, L' can be any one of the following groups:

[0189]

[0190] For example, L' can be any one of the following groups:

[0191]

[0192] Furthermore, L3 and L4 can each independently be a single bond, or a C bond that is either unsubstituted or substituted by one or more deuterium atoms. 6-20 Alpha-aryl.

[0193] For example, L3 and L4 can each independently be a single bond, phenylene, biphenyl dimethyl, or naphthylene.

[0194] At this point, L3 and L4 can be the same or different from each other.

[0195] Furthermore, in the above chemical formulas 2a to 2c,

[0196] X can be independently O, S, or N (C) 6-20 Aryl),

[0197] B1 to B3 can each be an independent naphthalene ring fused with an adjacent five-membered ring.

[0198] More specifically, X is independently O, S, or N (phenyl).

[0199] B1 to B3 can each independently be an unsubstituted naphthalene ring fused with an adjacent five-membered ring.

[0200] Additionally, R can be either deuterium or phenyl.

[0201] In this case, n refers to the number of R's. When n is 2 or more, two or more R's are either the same or different from each other. As an example, n can be 0 or 1.

[0202] For example, the substituent represented by the above chemical formula 2a can be any one of the substituents represented by the following chemical formulas 2a-1 to 2a-5:

[0203]

[0204] Furthermore, the substituent represented by the above chemical formula 2b can be any one of the substituents represented by the following chemical formulas 2b-1 to 2b-18:

[0205]

[0206] Furthermore, the substituent represented by the above chemical formula 2c can be any one of the substituents represented by the following chemical formulas 2c-1 to 2c-9:

[0207]

[0208] In the above chemical formulas 2c-1 to 2c-9,

[0209] X is O, S, or N (phenyl).

[0210] In one embodiment, Ar3 and Ar4 can each independently be C3, either unsubstituted or substituted with one or more substituents selected from deuterium, phenyl, and naphthyl. 6-20 Aryl; a substituent represented by any one of the above chemical formulas 2a-1 to 2a-5; a substituent represented by any one of the above chemical formulas 2b-1 to 2b-18; or a substituent represented by any one of the chemical formulas 2c-1 to 2c-9.

[0211] For example, Ar3 and Ar4 can each independently be phenyl, phenylnaphthyl, biphenyl, terphenyl, naphthyl, naphthylphenyl, phenanthrene, phenylenetriene, a substituent represented by any one of the following chemical formulas 2a-1 to 2a-5, or a substituent represented by any one of the following chemical formulas 2b-1 to 2b-4:

[0212]

[0213] Here, the terphenyl group mentioned above is selected from any of the groups shown below:

[0214]

[0215] At this point, Ar3 and Ar4 can be the same as or different from each other.

[0216] Additionally, R3 can be either hydrogen or deuterium, and c refers to the number of R3 molecules, which can be 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9. Specifically, all R3 molecules can be either hydrogen or deuterium. For example, all R3 molecules can be hydrogen.

[0217] On the other hand, representative examples of compounds represented by the above chemical formula 2 are shown below:

[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] On the other hand, as an example, the compound represented by the above chemical formula 2 can be manufactured by the manufacturing method shown in the following reaction formula 2:

[0251] [Reaction 2]

[0252]

[0253] In reaction formula 2 above, X' is a halogen, preferably bromine or chlorine, and the definitions of other substituents are the same as those described above.

[0254] Specifically, the compound represented by the above chemical formula 2 can be prepared by an amine substitution reaction of starting materials A3 and A4. Such an amine substitution reaction is preferably carried out in the presence of a palladium catalyst and a base, and the reactive groups used in the above amine substitution reaction can be appropriately modified. The method for preparing the compound represented by the above chemical formula 2 can be further specified in the manufacturing examples described later.

[0255] Furthermore, the first compound and the second compound may be included in the light-emitting layer in a weight ratio of 1:99 to 99:1. In this case, to suitably maintain the ratio of holes to electrons in the light-emitting layer, it is more preferable to include the first compound and the second compound in a weight ratio of 30:70 to 70:30, 40:60 to 60:40, or 50:50.

[0256] On the other hand, in addition to the two main materials mentioned above, the light-emitting layer may also contain dopant materials. Such dopant materials include aromatic amine derivatives, styrene amine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, aromatic amine derivatives are aromatic fused-ring derivatives having substituted or unsubstituted aryl amino groups, such as pyrene, anthracene, etc., which have aryl amino groups. Diindrone pyrene, etc., styrylamine compounds are compounds in which at least one aryl vinyl group is substituted onto a substituted or unsubstituted arylamine, and is substituted or unsubstituted by one or more substituents selected from aryl, silyl, alkyl, cycloalkyl, and arylamino groups. Specifically, there are styrylamines, styryldiamines, styryltriamines, styryltetraamines, etc., but they are not limited to these. In addition, as metal complexes, there are iridium complexes, platinum complexes, etc., but they are not limited to these.

[0257] More specifically, the compounds shown below can be used as the dopant materials mentioned above, but are not limited to these:

[0258]

[0259]

[0260]

[0261] Cavity barrier

[0262] The organic light-emitting device according to the present invention may include a hole-blocking layer between the light-emitting layer and the electron transport layer (described later) as needed. The hole-blocking layer refers to a layer formed on the light-emitting layer, preferably in contact with it, which improves the probability of hole-electron binding by adjusting electron mobility and preventing excessive hole migration, thereby improving the efficiency of the organic light-emitting device. The hole-blocking layer contains a hole-blocking material; examples of such a hole-blocking material include azine derivatives, triazole derivatives, etc. Compounds containing electron-withdrawing groups, such as diazole derivatives, phenanthrene-rhein derivatives, and phosphine oxide derivatives, are included, but are not limited to these.

[0263] Electron injection and transport layer

[0264] The aforementioned electron injection and transport layer is a layer that injects electrons from the electrode and transports the received electrons to the light-emitting layer, simultaneously functioning as an electron transport layer and an electron injection layer. It is formed on the aforementioned light-emitting layer or the aforementioned hole-blocking layer. Such an electron injection and transport material is suitable because it can effectively receive electrons from the cathode and transfer them to the light-emitting layer, and materials with high electron mobility are preferred. Specific examples of electron injection and transport materials include Al complexes of 8-hydroxyquinoline, complexes containing Alq3, organic free radical compounds, hydroxyflavonoid-metal complexes, triazine derivatives, etc., but are not limited to these. Alternatively, it can be combined with fluorenone, anthraquinone dimethyl ether, biphenylquinone, thiamethoxam dioxide, etc. azole, Diazoles, triazoles, imidazoles, perylenetetracarboxylic acids, fluorenemethane, anthrones, and their derivatives, metal coordination compounds, or nitrogen-containing five-membered ring derivatives may be used together, but are not limited to these.

[0265] The aforementioned electron injection and transport layers can also be formed as separate layers, such as an electron injection layer and an electron transport layer. In this case, the electron transport layer is formed on the aforementioned light-emitting layer or the aforementioned hole-blocking layer, and the aforementioned electron injection and transport materials can be used as the electron transport material contained in the aforementioned electron transport layer. Alternatively, the electron injection layer is formed on the aforementioned electron transport layer, and LiF, NaCl, CsF, Li₂O, BaO, fluorenone, anthraquinone dimethane, biphenylquinone, thiamethoxam dioxide, etc., can be used as the electron injection material contained in the aforementioned electron injection layer. azole, Diazoles, triazoles, imidazoles, perylenetetracarboxylic acid, fluorenemethane, anthrones, and their derivatives, metal coordination compounds, and nitrogen-containing five-membered ring derivatives, etc.

[0266] Examples of the aforementioned metal coordination compounds include lithium 8-hydroxyquinoline, bis(8-hydroxyquinoline)zinc, bis(8-hydroxyquinoline)copper, bis(8-hydroxyquinoline)manganese, tris(8-hydroxyquinoline)aluminum, tris(2-methyl-8-hydroxyquinoline)aluminum, tris(8-hydroxyquinoline)gallium, bis(10-hydroxybenzo[h]quinoline)beryllium, bis(10-hydroxybenzo[h]quinoline)zinc, bis(2-methyl-8-quinoline)gallium chloride, bis(2-methyl-8-quinoline)(o-cresol)gallium, bis(2-methyl-8-quinoline)(1-naphthol)aluminum, and bis(2-methyl-8-quinoline)(2-naphthol)gallium, but are not limited to these.

[0267] Organic light-emitting devices

[0268] The structure of the organic light-emitting device according to the present invention is illustrated in... Figure 1 . Figure 1 The illustration shows an example of an organic light-emitting device consisting of a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4. In the structure described above, the first compound and the second compound may be included in the light-emitting layer.

[0269] Figure 2 The illustration shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron suppression layer 7, a light-emitting layer 3, a hole blocking layer 8, an electron injection and transport layer 9, and a cathode 4. In the structure described above, the first compound and the second compound may be included in the light-emitting layer.

[0270] The organic light-emitting device according to the present invention can be manufactured by sequentially stacking the above-described structures. It can be manufactured as follows: using a PVD (physical vapor deposition) method such as sputtering or electron beam evaporation, a metal or a conductive metal oxide or alloy thereof is deposited on a substrate to form an anode, the aforementioned layers are formed on the anode, and then a material suitable for use as a cathode is deposited on it. Besides this method, an organic light-emitting device can also be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate. Furthermore, not only vacuum evaporation can be used, but solution coating can also be used to form the light-emitting layer from the substrate and the dopant. Here, solution coating refers to methods such as spin coating, dip coating, blade coating, inkjet printing, screen printing, spray coating, and roll coating, but is not limited to these.

[0271] In addition to this method, organic light-emitting devices can also be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate (WO 2003 / 012890). However, the manufacturing method is not limited to this.

[0272] On the other hand, the organic light-emitting device according to the present invention can be a bottom-emission device, a top-emission device, or a bidirectional light-emitting device, and in particular, it can be a bottom-emission device that requires relatively high luminous efficiency.

[0273] In addition, the compounds according to the present invention can be included not only in organic light-emitting devices, but also in organic solar cells or organic transistors.

[0274] The fabrication of the aforementioned organic light-emitting device is specifically described in the following embodiments. However, the following embodiments are for illustrative purposes only, and the scope of the invention is not limited thereto.

[0275] Synthesis Example 1-1: Preparation of Compound 1-1

[0276]

[0277] Under a nitrogen atmosphere, Trz1 (10 g, 37.4 mmol) and substance (sub) 1-1 (6.1 g, 39.2 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (15.5 g, 112.1 mmol) was dissolved in 46 mL of water and added, stirred thoroughly, followed by tetrakis(triphenylphosphine)palladium(0) (0.4 g, 0.4 mmol). After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 8.1 g of substance 1-1-1. (Yield 63%, MS: [M+H]) + =344)

[0278] Under a nitrogen atmosphere, 10 g (29.1 mmol) of compound 1-1-1, 5.1 g (30.5 mmol) of compound A, and 4.2 g (43.6 mmol) of sodium tert-butoxide were added to 100 mL of xylene, and the mixture was stirred and refluxed. Then, 0.1 g (0.3 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 8.4 g of compound 1-1. (Yield 61%, MS: [M+H]) + =475)

[0279] Synthesis Example 1-2: Preparation of Compound 1-2

[0280]

[0281] Under a nitrogen atmosphere, Trz2 (10 g, 29.1 mmol) and substance 1-2 (4.8 g, 30.5 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (12.1 g, 87.3 mmol) was dissolved in 36 mL of water and added, stirred thoroughly, followed by tetrakis(triphenylphosphine)palladium(0) (0.3 g, 0.3 mmol). After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 8.4 g of substance 1-1-2 (yield 69%, MS: [M+H]+=420).

[0282] Under a nitrogen atmosphere, 10 g (23.8 mmol) of compound 1-1-2, 4.2 g (25 mmol) of compound A, and 3.4 g (35.7 mmol) of sodium tert-butoxide were added to 100 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 8.6 g of compound 1-2. (Yield 66%, MS: [M+H)) + =551)

[0283] Synthetic Examples 1-3: Preparation of Compounds 1-3

[0284]

[0285] Under a nitrogen atmosphere, Trz3 (10 g, 31.5 mmol) and substance 1-2 (5.2 g, 33 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (13 g, 94.4 mmol) dissolved in 39 mL of water was added, and after thorough stirring, tetrakis(triphenylphosphine)palladium(0) (0.4 g, 0.3 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 8.7 g of substance 1-1-3. (Yield 70%, MS: [M+H)) + =394)

[0286] Under a nitrogen atmosphere, 10 g (25.1 mmol) of compound 1-1-3, 4.4 g (26.4 mmol) of compound A, and 3.6 g (37.7 mmol) of sodium tert-butoxide were added to 100 mL of xylene, and the mixture was stirred and refluxed. Then, 0.1 g (0.3 mmol) of bis(tri-tert-butylphosphine)palladium(O) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 6.6 g of compound 1-3. (Yield 50%, MS: [M+H)) + =525)

[0287] Synthetic Examples 1-4: Preparation of Compounds 1-4

[0288]

[0289] Under a nitrogen atmosphere, Trz4 (10 g, 27.9 mmol) and substance 1-1 (4.6 g, 29.3 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (11.6 g, 83.8 mmol) was dissolved in 35 mL of water and added, stirred thoroughly, followed by tetrakis(triphenylphosphine)palladium(0) (0.3 g, 0.3 mmol). After reacting for 8 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 8.8 g of substance 1-1-4. (Yield 73%, MS: [M+H)) + =434)

[0290] Under a nitrogen atmosphere, 10 g (23 mmol) of compound 1-1-4, 4 g (24.2 mmol) of compound A, and 3.3 g (34.6 mmol) of sodium tert-butoxide were added to 100 mL of xylene, and the mixture was stirred and refluxed. Then, 0.1 g (0.2 mmol) of bis(tri-tert-butylphosphine)palladium(O) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 8.1 g of compound 1-4. (Yield 62%, MS: [M+H)) + =565)

[0291] Synthetic Examples 1-5: Preparation of Compounds 1-5

[0292]

[0293] Under a nitrogen atmosphere, Trz5 (10 g, 24.5 mmol) and substance 1-2 (4 g, 25.7 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (10.2 g, 73.6 mmol) was dissolved in 30 mL of water and added, and after thorough stirring, tetrakis(triphenylphosphine)palladium(0) (0.3 g, 0.2 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9.4 g of substance 1-1-5. (Yield 79%, MS: [M+H)) + =484)

[0294] Under a nitrogen atmosphere, compound 1-1-5 (10 g, 20.7 mmol), compound A (3.6 g, 21.7 mmol), and sodium tert-butoxide (3 g, 31 mmol) were added to 100 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 6.5 g of compound 1-5. (Yield 51%, MS: [M+H)) + =615)

[0295] Synthetic Examples 1-6: Preparation of Compounds 1-6

[0296]

[0297] Under a nitrogen atmosphere, Trz6 (10 g, 25.4 mmol) and substance 1-2 (4.2 g, 26.7 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (10.5 g, 76.2 mmol) was dissolved in 32 mL of water and added, and after thorough stirring, tetrakis(triphenylphosphine)palladium(0) (0.3 g, 0.3 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9.5 g of substance 1-1-6. (Yield 80%, MS: [M+H)) +=470)

[0298] Under a nitrogen atmosphere, 10 g (21.3 mmol) of compound 1-1-6, 5.4 g (22.3 mmol) of compound B, and 3.1 g (31.9 mmol) of sodium tert-butoxide were added to 100 mL of xylene, and the mixture was stirred and refluxed. Then, 0.1 g (0.2 mmol) of bis(tri-tert-butylphosphine)palladium(O) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 8.9 g of compound 1-6. (Yield 62%, MS: [M+H)) + =677)

[0299] Synthetic Examples 1-7: Preparation of Compounds 1-7

[0300]

[0301] Under a nitrogen atmosphere, Trz1 (10 g, 37.4 mmol) and substance 1-3 (8.1 g, 39.2 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (15.5 g, 112.1 mmol) was dissolved in 46 mL of water and added, stirred thoroughly, followed by tetrakis(triphenylphosphine)palladium(0) (0.4 g, 0.4 mmol). After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9.5 g of substance 1-1-7. (Yield 65%, MS: [M+H)) + =394)

[0302] Under a nitrogen atmosphere, 10 g (25.1 mmol) of compound 1-1-7, 4.4 g (26.4 mmol) of compound A, and 3.6 g (37.7 mmol) of sodium tert-butoxide were added to 100 mL of xylene, and the mixture was stirred and refluxed. Then, 0.1 g (0.3 mmol) of bis(tri-tert-butylphosphine)palladium(O) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 8.2 g of compound 1-7. (Yield 62%, MS: [M+H)) + =525)

[0303] Synthetic Examples 1-8: Preparation of Compounds 1-8

[0304]

[0305] Under a nitrogen atmosphere, Trz7 (10 g, 25.4 mmol) and substance 1-4 (5.5 g, 26.7 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (10.5 g, 76.2 mmol) was dissolved in 32 mL of water and added, stirred thoroughly, followed by tetrakis(triphenylphosphine)palladium(0) (0.3 g, 0.3 mmol). After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.3 g of substance 1-1-8. (Yield 78%, MS: [M+H)) + =520)

[0306] Under a nitrogen atmosphere, 10 g (19.2 mmol) of compound 1-1-8, 3.4 g (20.2 mmol) of compound A, and 2.8 g (28.8 mmol) of sodium tert-butoxide were added to 100 mL of xylene, and the mixture was stirred and refluxed. Then, 0.1 g (0.2 mmol) of bis(tri-tert-butylphosphine)palladium(O) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 6.9 g of compound 1-8. (Yield 55%, MS: [M+H)) + =651)

[0307] Synthetic Examples 1-9: Preparation of Compounds 1-9

[0308]

[0309] Under a nitrogen atmosphere, Trz6 (10 g, 25.4 mmol) and substance 1-5 (5.5 g, 26.7 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (10.5 g, 76.2 mmol) was dissolved in 32 mL of water and added, stirred thoroughly, followed by tetrakis(triphenylphosphine)palladium(0) (0.3 g, 0.3 mmol). After reacting for 12 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.5 g of substance 1-1-9. (Yield 80%, MS: [M+H)) + =520)

[0310] Under a nitrogen atmosphere, 10 g (19.2 mmol) of compound 1-1-9, 3.4 g (20.2 mmol) of compound A, and 2.8 g (28.8 mmol) of sodium tert-butoxide were added to 100 mL of xylene, and the mixture was stirred and refluxed. Then, 0.1 g (0.2 mmol) of bis(tri-tert-butylphosphine)palladium(O) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.5 g of compound 1-9. (Yield 60%, MS: [M+H)) + =651)

[0311] Synthetic Examples 1-10: Preparation of Compounds 1-10

[0312]

[0313] Under a nitrogen atmosphere, Trz5 (10 g, 24.5 mmol) and substance 1-3 (5.3 g, 25.7 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (10.2 g, 73.6 mmol) was dissolved in 30 mL of water and added, stirred thoroughly, followed by tetrakis(triphenylphosphine)palladium(0) (0.3 g, 0.2 mmol). After reacting for 11 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.2 g of substance 1-1-10. (Yield 78%, MS: [M+H)) + =534)

[0314] Under a nitrogen atmosphere, 10 g (18.7 mmol) of compound 1-1-10, 3.3 g (19.7 mmol) of compound A, and 2.7 g (28.1 mmol) of sodium tert-butoxide were added to 100 mL of xylene, and the mixture was stirred and refluxed. Then, 0.1 g (0.2 mmol) of bis(tri-tert-butylphosphine)palladium(O) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.2 g of compound 1-10. (Yield 58%, MS: [M+H)) + =665)

[0315] Synthetic Example 1-11: Preparation of Compound 1-11

[0316]

[0317] Under a nitrogen atmosphere, Trz1 (10 g, 37.4 mmol) and substance 1-6 (9.1 g, 39.2 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (15.5 g, 112.1 mmol) was dissolved in 46 mL of water and added, stirred thoroughly, followed by tetrakis(triphenylphosphine)palladium(0) (0.4 g, 0.4 mmol). After reacting for 12 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.7 g of substance 1-1-11. (Yield 75%, MS: [M+H]) + =420)

[0318] Under a nitrogen atmosphere, 10 g (23.8 mmol) of compound 1-1-11, 4.2 g (25 mmol) of compound A, and 3.4 g (35.7 mmol) of sodium tert-butoxide were added to 100 mL of xylene, and the mixture was stirred and refluxed. Then, 0.1 g (0.2 mmol) of bis(tri-tert-butylphosphine)palladium(O) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.6 g of compound 1-11. (Yield 58%, MS: [M+H)) + =551)

[0319] Synthetic Examples 1-12: Preparation of Compounds 1-12

[0320]

[0321] Under a nitrogen atmosphere, Trz3 (10 g, 31.5 mmol) and substance 1-7 (7.7 g, 33 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (13 g, 94.4 mmol) dissolved in 39 mL of water was added, and after thorough stirring, tetrakis(triphenylphosphine)palladium(0) (0.4 g, 0.3 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.6 g of substance 1-1-12. (Yield 72%, MS: [M+H)) + =470)

[0322] Under a nitrogen atmosphere, 10 g (21.3 mmol) of compound 1-1-12, 3.7 g (22.3 mmol) of compound A, and 3.1 g (31.9 mmol) of sodium tert-butoxide were added to 100 mL of xylene, and the mixture was stirred and refluxed. Then, 0.1 g (0.2 mmol) of bis(tri-tert-butylphosphine)palladium(O) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 6.9 g of compound 1-12. (Yield 54%, MS: [M+H)) + =601)

[0323] Synthetic Examples 1-13: Preparation of Compound 1-13

[0324]

[0325] Under a nitrogen atmosphere, Trz4 (10 g, 27.9 mmol) and substance 1-8 (6.8 g, 29.3 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (11.6 g, 83.8 mmol) was dissolved in 35 mL of water and added, stirred thoroughly, followed by tetrakis(triphenylphosphine)palladium(0) (0.3 g, 0.3 mmol). After reacting for 12 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 8.5 g of substance 1-1-13. (Yield 60%, MS: [M+H)) + =510)

[0326] Under a nitrogen atmosphere, 10 g (20 mmol) of compound 1-1-13, 3.5 g (21 mmol) of compound A, and 2.9 g (29.9 mmol) of sodium tert-butoxide were added to 100 mL of xylene, and the mixture was stirred and refluxed. Then, 0.1 g (0.2 mmol) of bis(tri-tert-butylphosphine)palladium(O) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.4 g of compound 1-13. (Yield 58%, MS: [M+H]) + =641)

[0327] Synthetic Examples 1-14: Preparation of Compounds 1-14

[0328]

[0329] Under a nitrogen atmosphere, Trz6 (10 g, 25.4 mmol) and substance 1-9 (6.2 g, 26.7 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (10.5 g, 76.2 mmol) was dissolved in 32 mL of water and added, stirred thoroughly, followed by tetrakis(triphenylphosphine)palladium(0) (0.3 g, 0.3 mmol). After reacting for 8 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9.4 g of substance 1-1-14. (Yield 68%, MS: [M+H)) + =546)

[0330] Under a nitrogen atmosphere, 10 g (18.3 mmol) of compound 1-1-14, 3.2 g (19.2 mmol) of compound A, and 2.6 g (27.5 mmol) of sodium tert-butoxide were added to 100 mL of xylene, and the mixture was stirred and refluxed. Then, 0.1 g (0.2 mmol) of bis(tri-tert-butylphosphine)palladium(O) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 6.7 g of compound 1-14. (Yield 54%, MS: [M+H)) + =677)

[0331] Synthetic Examples 1-15: Preparation of Compounds 1-15

[0332]

[0333] Under a nitrogen atmosphere, Trz7 (10 g, 25.4 mmol) and substance 1-9 (6.2 g, 26.7 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (10.5 g, 76.2 mmol) was dissolved in 32 mL of water and added, stirred thoroughly, followed by tetrakis(triphenylphosphine)palladium(0) (0.3 g, 0.3 mmol). After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9.8 g of substance 1-1-15. (Yield 71%, MS: [M+H)) + =546)

[0334] Under a nitrogen atmosphere, 10 g (18.3 mmol) of compound 1-1-15, 4.7 g (19.2 mmol) of compound B, and 2.6 g (27.5 mmol) of sodium tert-butoxide were added to 100 mL of xylene, and the mixture was stirred and refluxed. Then, 0.1 g (0.2 mmol) of bis(tri-tert-butylphosphine)palladium(O) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.2 g of compound 1-15. (Yield 52%, MS: [M+H]) + =753)

[0335] Synthetic Examples 1-16: Preparation of Compounds 1-16

[0336]

[0337] Under a nitrogen atmosphere, Trz8 (10 g, 25.4 mmol) and substance 1-2 (4.2 g, 26.7 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (10.5 g, 76.2 mmol) was dissolved in 32 mL of water and added, stirred thoroughly, followed by tetrakis(triphenylphosphine)palladium(0) (0.3 g, 0.3 mmol). After reacting for 12 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 8.9 g of substance 1-1-16. (Yield 75%, MS: [M+H)) + =470)

[0338] Under a nitrogen atmosphere, 10 g (21.3 mmol) of compound 1-1-16, 4.9 g (22.3 mmol) of compound C, and 3.1 g (31.9 mmol) of sodium tert-butoxide were added to 100 mL of xylene, and the mixture was stirred and refluxed. Then, 0.1 g (0.2 mmol) of bis(tri-tert-butylphosphine)palladium(O) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 9.3 g of compound 1-16. (Yield 67%, MS: [M+H)) + =651)

[0339] Synthetic Examples 1-17: Preparation of Compound 1-17

[0340]

[0341] Under a nitrogen atmosphere, 10 g (21.3 mmol) of compound 1-1-6, 4.9 g (22.3 mmol) of compound D, and 3.1 g (31.9 mmol) of sodium tert-butoxide were added to 100 mL of xylene, and the mixture was stirred and refluxed. Then, 0.1 g (0.2 mmol) of bis(tri-tert-butylphosphine)palladium(O) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.5 g of compound 1-17. (Yield 54%, MS: [M+H))+ =651)

[0342] Synthetic Examples 1-18: Preparation of Compounds 1-18

[0343]

[0344] Under a nitrogen atmosphere, Trz5 (10 g, 24.5 mmol) and substance 1-1 (4 g, 25.7 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (10.2 g, 73.6 mmol) was dissolved in 30 mL of water and added, stirred thoroughly, followed by tetrakis(triphenylphosphine)palladium(0) (0.3 g, 0.2 mmol). After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9.2 g of substance 1-1-17. (Yield 78%, MS: [M+H)) + =484)

[0345] Under a nitrogen atmosphere, compound 1-1-17 (10 g, 20.7 mmol), compound E (4.7 g, 21.7 mmol), and sodium tert-butoxide (3 g, 31 mmol) were added to 100 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.5 g of compound 1-18. (Yield 55%, MS: [M+H)) + =665)

[0346] Synthetic Examples 1-19: Preparation of Compounds 1-19

[0347]

[0348] Under a nitrogen atmosphere, Trz7 (10 g, 25.4 mmol) and substance 1-10 (6.2 g, 26.7 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (10.5 g, 76.2 mmol) was dissolved in 32 mL of water and added, stirred thoroughly, followed by tetrakis(triphenylphosphine)palladium(0) (0.3 g, 0.3 mmol). After reacting for 11 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 8.3 g of substance 1-1-18. (Yield 60%, MS: [M+H)) + =546)

[0349] Under a nitrogen atmosphere, 10 g (18.3 mmol) of compound 1-1-18, 4.2 g (19.2 mmol) of compound C, and 2.6 g (27.5 mmol) of sodium tert-butoxide were added to 100 mL of xylene, and the mixture was stirred and refluxed. Then, 0.1 g (0.2 mmol) of bis(tri-tert-butylphosphine)palladium(O) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.7 g of compound 1-19. (Yield 58%, MS: [M+H)) + =727)

[0350] Synthetic Examples 1-20: Preparation of Compounds 1-20

[0351]

[0352] Under a nitrogen atmosphere, Trz5 (10 g, 24.5 mmol) and substance 1-5 (5.3 g, 25.7 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (10.2 g, 73.6 mmol) was dissolved in 30 mL of water and added, and after thorough stirring, tetrakis(triphenylphosphine)palladium(0) (0.3 g, 0.2 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 8.6 g of substance 1-1-19. (Yield 66%, MS: [M+H)) + =534)

[0353] Under a nitrogen atmosphere, 10 g (18.7 mmol) of compound 1-1-19, 4.3 g (19.7 mmol) of compound D, and 2.7 g (28.1 mmol) of sodium tert-butoxide were added to 100 mL of xylene, and the mixture was stirred and refluxed. Then, 0.1 g (0.2 mmol) of bis(tri-tert-butylphosphine)palladium(O) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.9 g of compound 1-20. (Yield 59%, MS: [M+H)) + =715)

[0354] Synthetic Example 1-21: Preparation of Compound 1-21

[0355]

[0356] Under a nitrogen atmosphere, Trz8 (10 g, 25.4 mmol) and substance 1-3 (5.5 g, 26.7 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (10.5 g, 76.2 mmol) was dissolved in 32 mL of water and added, stirred thoroughly, followed by tetrakis(triphenylphosphine)palladium(0) (0.3 g, 0.3 mmol). After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9.6 g of substance 1-1-20. (Yield 73%, MS: [M+H)) + =520)

[0357] Under a nitrogen atmosphere, 10 g (19.2 mmol) of compound 1-1-20, 4.4 g (20.2 mmol) of compound E, and 2.8 g (28.8 mmol) of sodium tert-butoxide were added to 100 mL of xylene, and the mixture was stirred and refluxed. Then, 0.1 g (0.2 mmol) of bis(tri-tert-butylphosphine)palladium(O) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 8.1 g of compound 1-21. (Yield 60%, MS: [M+H)) + =701)

[0358] Synthetic Examples 1-22: Preparation of Compounds 1-22

[0359]

[0360] Under a nitrogen atmosphere, Trz1 (10 g, 37.4 mmol) and substance 1-11 (6.1 g, 39.2 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (15.5 g, 112.1 mmol) was dissolved in 46 mL of water and added, stirred thoroughly, followed by tetrakis(triphenylphosphine)palladium(0) (0.4 g, 0.4 mmol). After reacting for 8 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 7.8 g of substance 1-1-21. (Yield 61%, MS: [M+H)) + =344)

[0361] Under a nitrogen atmosphere, 10 g (29.1 mmol) of compound 1-1-21, 8.2 g (30.5 mmol) of compound F, and 4.2 g (43.6 mmol) of sodium tert-butoxide were added to 100 mL of xylene, and the mixture was stirred and refluxed. Then, 0.1 g (0.3 mmol) of bis(tri-tert-butylphosphine)palladium(O) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 11.4 g of compound 1-22. (Yield 68%, MS: [M+H)) + =575)

[0362] Synthetic Example 1-23: Preparation of Compound 1-23

[0363]

[0364] Under a nitrogen atmosphere, 10 g (21.3 mmol) of compound 1-1-16, 6 g (22.3 mmol) of compound G, and 3.1 g (31.9 mmol) of sodium tert-butoxide were added to 100 mL of xylene, and the mixture was stirred and refluxed. Then, 0.1 g (0.2 mmol) of bis(tri-tert-butylphosphine)palladium(O) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 8 g of compound 1-23. (Yield 54%, MS: [M+H))+ =701)

[0365] Synthetic Examples 1-24: Preparation of Compounds 1-24

[0366]

[0367] Under a nitrogen atmosphere, Trz3 (10 g, 31.5 mmol) and substance 1-3 (6.8 g, 33 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (13 g, 94.4 mmol) dissolved in 39 mL of water was added, and after thorough stirring, tetrakis(triphenylphosphine)palladium(0) (0.4 g, 0.3 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.6 g of substance 1-1-22. (Yield 76%, MS: [M+H)) + =444)

[0368] Under a nitrogen atmosphere, 10 g (22.5 mmol) of compound 1-1-22, 6.3 g (23.7 mmol) of compound H, and 3.2 g (33.8 mmol) of sodium tert-butoxide were added to 100 mL of xylene, and the mixture was stirred and refluxed. Then, 0.1 g (0.2 mmol) of bis(tri-tert-butylphosphine)palladium(O) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 10.2 g of compound 1-24. (Yield 67%, MS: [M+H]) + =675)

[0369] Synthetic Examples 1-25: Preparation of Compounds 1-25

[0370]

[0371] Under a nitrogen atmosphere, Trz2 (10 g, 29.1 mmol) and substance 1-12 (7.1 g, 30.5 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (12.1 g, 87.3 mmol) was dissolved in 36 mL of water and added, and after thorough stirring, tetrakis(triphenylphosphine)palladium(0) (0.3 g, 0.3 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.4 g of substance 1-1-23. (Yield 79%, MS: [M+H)) + =496)

[0372] Under a nitrogen atmosphere, 10 g (20.2 mmol) of compound 1-1-23, 5.7 g (21.2 mmol) of compound G, and 2.9 g (30.2 mmol) of sodium tert-butoxide were added to 100 mL of xylene, and the mixture was stirred and refluxed. Then, 0.1 g (0.2 mmol) of bis(tri-tert-butylphosphine)palladium(O) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 8.5 g of compound 1-25. (Yield 58%, MS: [M+H]) + =727)

[0373] Synthetic Examples 1-26: Preparation of Compounds 1-26

[0374]

[0375] Under a nitrogen atmosphere, Trz5 (10 g, 24.5 mmol) and substance 1-8 (6 g, 25.7 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (10.2 g, 73.6 mmol) was dissolved in 30 mL of water and added, stirred thoroughly, followed by tetrakis(triphenylphosphine)palladium(0) (0.3 g, 0.2 mmol). After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11 g of substance 1-1-24. (Yield 80%, MS: [M+H)) + =560)

[0376] Under a nitrogen atmosphere, 10 g (17.9 mmol) of compound 1-1-24, 5 g (18.7 mmol) of compound F, and 2.6 g (26.8 mmol) of sodium tert-butoxide were added to 100 mL of xylene, and the mixture was stirred and refluxed. Then, 0.1 g (0.2 mmol) of bis(tri-tert-butylphosphine)palladium(O) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 8.3 g of compound 1-26. (Yield 59%, MS: [M+H]) + =791)

[0377] Synthesis Example 2-1: Preparation of Compound 2-1

[0378]

[0379] Under a nitrogen atmosphere, substances 2-1 (10 g, 38.9 mmol) and 2-2 (6.7 g, 42.8 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (16.1 g, 116.7 mmol) was dissolved in 48 mL of water and added to the solution. After thorough stirring, tetrakis(triphenylphosphine)palladium(0) (0.4 g, 0.4 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 8.9 g of substance 2-1-1. (Yield 79%, MS: [M+H)) + =289)

[0380] Under a nitrogen atmosphere, 10 g (34.6 mmol) of compound 2-1-1, 14.5 g (36.4 mmol) of amine 1, and 8.3 g (86.6 mmol) of sodium tert-butoxide were added to 300 mL of xylene, and the mixture was stirred and refluxed. Then, 0.5 g (1 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 13.9 g of compound 2-1. (Yield 62%, MS: [M+H)) + =650)

[0381] Synthesis Example 2-2: Preparation of Compound 2-2

[0382]

[0383] Under a nitrogen atmosphere, 10 g (34.6 mmol) of compound 2-1-1, 14.5 g (36.4 mmol) of amine 2, and 8.3 g (86.6 mmol) of sodium tert-butoxide were added to 300 mL of xylene, and the mixture was stirred and refluxed. Then, 0.5 g (1 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 13.9 g of compound 2-2. (Yield 62%, MS: [M+H)) + =650)

[0384] Synthetic Example 2-3: Preparation of Compound 2-3

[0385]

[0386] Under a nitrogen atmosphere, 10 g (34.6 mmol) of compound 2-1-1, 11.7 g (36.4 mmol) of amine 3, and 8.3 g (86.6 mmol) of sodium tert-butoxide were added to 300 mL of xylene, and the mixture was stirred and refluxed. Then, 0.5 g (1 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 13.1 g of compound 2-3. (Yield 66%, MS: [M+H)) + =574)

[0387] Synthetic Example 2-4: Preparation of Compound 2-4

[0388]

[0389] Under a nitrogen atmosphere, 10 g (34.6 mmol) of compound 2-1-1, 14.5 g (36.4 mmol) of amine 4, and 8.3 g (86.6 mmol) of sodium tert-butoxide were added to 300 mL of xylene, and the mixture was stirred and refluxed. Then, 0.5 g (1 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 13.5 g of compound 2-4. (Yield 60%, MS: [M+H)) + =650)

[0390] Synthetic Example 2-5: Preparation of Compound 2-5

[0391]

[0392] Under a nitrogen atmosphere, 10 g (34.6 mmol) of compound 2-1-1, 16.3 g (36.4 mmol) of amine 5, and 8.3 g (86.6 mmol) of sodium tert-butoxide were added to 300 mL of xylene, and the mixture was stirred and refluxed. Then, 0.5 g (1 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 13.6 g of compound 2-5. (Yield 56%, MS: [M+H)) + =700)

[0393] Synthetic Example 2-6: Preparation of Compound 2-6

[0394]

[0395] Under a nitrogen atmosphere, 10 g (34.6 mmol) of compound 2-1-1, 14.5 g (36.4 mmol) of amine 6, and 8.3 g (86.6 mmol) of sodium tert-butoxide were added to 300 mL of xylene, and the mixture was stirred and refluxed. Then, 0.5 g (1 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 11.9 g of compound 2-6. (Yield 53%, MS: [M+H)) + =650)

[0396] Synthetic Example 2-7: Preparation of Compound 2-7

[0397]

[0398] Under a nitrogen atmosphere, 10 g (34.6 mmol) of compound 2-1-1, 14.5 g (36.4 mmol) of amine 7, and 8.3 g (86.6 mmol) of sodium tert-butoxide were added to 300 mL of xylene, and the mixture was stirred and refluxed. Then, 0.5 g (1 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.8 g of compound 2-7. (Yield 57%, MS: [M+H)) + =650)

[0399] Synthetic Example 2-8: Preparation of Compound 2-8

[0400]

[0401] Under a nitrogen atmosphere, 10 g (34.6 mmol) of compound 2-1-1, 14.4 g (36.4 mmol) of amine 8, and 8.3 g (86.6 mmol) of sodium tert-butoxide were added to 300 mL of xylene, and the mixture was stirred and refluxed. Then, 0.5 g (1 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 14.8 g of compound 2-8. (Yield 66%, MS: [M+H)) + =648)

[0402] Synthesis Example 2-9: Preparation of Compound 2-9

[0403]

[0404] Under a nitrogen atmosphere, 10 g (34.6 mmol) of compound 2-1-1, amine 9 (12.6 g, 36.4 mmol), and sodium tert-butoxide (8.3 g, 86.6 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, 0.5 g (1 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 13.4 g of compound 2-9. (Yield 65%, MS: [M+H)) + =598)

[0405] Synthetic Example 2-10: Preparation of Compound 2-10

[0406]

[0407] Under a nitrogen atmosphere, substances 2-1 (10 g, 38.9 mmol) and 2-3 (6.7 g, 42.8 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (16.1 g, 116.7 mmol) was dissolved in 48 mL of water and added to the solution. After thorough stirring, tetrakis(triphenylphosphine)palladium(0) (0.4 g, 0.4 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9 g of substance 2-1-2. (Yield 80%, MS: [M+H)) + =289)

[0408] Under a nitrogen atmosphere, 10 g (34.6 mmol) of compound 2-1-2, 10 g (36.4 mmol) of amine 10, and 8.3 g (86.6 mmol) of sodium tert-butoxide were added to 300 mL of xylene, and the mixture was stirred and refluxed. Then, 0.5 g (1 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 13.7 g of compound 2-10. (Yield 61%, MS: [M+H)) + =648)

[0409] Synthetic Example 2-11: Preparation of Compound 2-11

[0410]

[0411] Under a nitrogen atmosphere, amine 11 (10 g, 59.1 mmol), substance 2-1-1 (35.8 g, 124.1 mmol), and sodium tert-butoxide (19.9 g, 206.8 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.9 g, 1.8 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 27.1 g of compound 2-11. (Yield 68%, MS: [M+H)) + =674)

[0412] Synthetic Example 2-12: Preparation of Compound 2-12

[0413]

[0414] Under a nitrogen atmosphere, amine 12 (10 g, 40.8 mmol), substance 2-1-1 (24.7 g, 85.6 mmol), and sodium tert-butoxide (13.7 g, 142.7 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 17.7 g of compound 2-12. (Yield 58%, MS: [M+H)) + =750)

[0415] Synthetic Example 2-13: Preparation of Compound 2-13

[0416]

[0417] Under a nitrogen atmosphere, amine 13 (10 g, 51.7 mmol), substance 2-1-2 (31.4 g, 108.7 mmol), and sodium tert-butoxide (17.4 g, 181.1 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.8 g, 1.6 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 23.5 g of compound 2-13. (Yield 65%, MS: [M+H)) + =698)

[0418] Synthetic Example 2-14: Preparation of Compound 2-14

[0419]

[0420] Under a nitrogen atmosphere, substances 2-1 (10 g, 38.9 mmol) and 2-4 (9.9 g, 42.8 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (16.1 g, 116.7 mmol) was dissolved in 48 mL of water and added to the solution. After thorough stirring, tetrakis(triphenylphosphine)palladium(0) (0.4 g, 0.4 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.9 g of substance 2-1-3. (Yield 77%, MS: [M+H)) + =365)

[0421] Under a nitrogen atmosphere, amine 14 (10 g, 45.6 mmol), substance 2-1-3 (34.9 g, 95.8 mmol), and sodium tert-butoxide (15.3 g, 159.6 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.7 g, 1.4 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 22 g of compound 2-14. (Yield 55%, MS: [M+H)) + =876)

[0422] Synthetic Example 2-15: Preparation of Compound 2-15

[0423]

[0424] Under a nitrogen atmosphere, 10 g (34.6 mmol) of compound 2-1-1, 12.2 g (36.4 mmol) of amine 15, and 8.3 g (86.6 mmol) of sodium tert-butoxide were added to 300 mL of xylene, and the mixture was stirred and refluxed. Then, 0.5 g (1 mmol) of bis(tri-tert-butylphosphine)palladium(O) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 11.8 g of compound 2-15. (Yield 58%, MS: [M+H)) + =588)

[0425] Synthetic Example 2-16: Preparation of Compound 2-16

[0426]

[0427] Under a nitrogen atmosphere, 10 g (34.6 mmol) of compound 2-1-1, 15 g (36.4 mmol) of amine 16, and 8.3 g (86.6 mmol) of sodium tert-butoxide were added to 300 mL of xylene, and the mixture was stirred and refluxed. Then, 0.5 g (1 mmol) of bis(tri-tert-butylphosphine)palladium(O) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 14.7 g of compound 2-16. (Yield 64%, MS: [M+H)) + =664)

[0428] Synthetic Example 2-17: Preparation of Compound 2-17

[0429]

[0430] Under a nitrogen atmosphere, 10 g (34.6 mmol) of compound 2-1-1, 14 g (36.4 mmol) of amine 17, and 8.3 g (86.6 mmol) of sodium tert-butoxide were added to 300 mL of xylene, and the mixture was stirred and refluxed. Then, 0.5 g (1 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 11.7 g of compound 2-17. (Yield 53%, MS: [M+H)) + =638)

[0431] Synthetic Example 2-18: Preparation of Compound 2-18

[0432]

[0433] Under a nitrogen atmosphere, 10 g (34.6 mmol) of compound 2-1-1, 12.8 g (36.4 mmol) of amine 18, and 8.3 g (86.6 mmol) of sodium tert-butoxide were added to 300 mL of xylene, stirred, and refluxed. Then, 0.5 g (1 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 14.4 g of compound 2-18. (Yield 69%, MS: [M+H)) + =604)

[0434] Synthetic Example 2-19: Preparation of Compound 2-19

[0435]

[0436] Under a nitrogen atmosphere, 10 g (34.6 mmol) of compound 2-1-1, 14.6 g (36.4 mmol) of amine 19, and 8.3 g (86.6 mmol) of sodium tert-butoxide were added to 300 mL of xylene, and the mixture was stirred and refluxed. Then, 0.5 g (1 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 13.3 g of compound 2-19. (Yield 59%, MS: [M+H)) +=654)

[0437] Synthesis Example 2-20: Preparation of Compound 2-20

[0438]

[0439] Under a nitrogen atmosphere, 10 g (34.6 mmol) of compound 2-1-1, 12.8 g (36.4 mmol) of amine 20, and 8.3 g (86.6 mmol) of sodium tert-butoxide were added to 300 mL of xylene, and the mixture was stirred and refluxed. Then, 0.5 g (1 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.1 g of compound 2-20. (Yield 58%, MS: [M+H)) + =604)

[0440] Synthetic Example 2-21: Preparation of Compound 2-21

[0441]

[0442] Under a nitrogen atmosphere, 10 g (34.6 mmol) of compound 2-1-1, 15.4 g (36.4 mmol) of amine 21, and 8.3 g (86.6 mmol) of sodium tert-butoxide were added to 300 mL of xylene, and the mixture was stirred and refluxed. Then, 0.5 g (1 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 14.8 g of compound 2-21. (Yield 63%, MS: [M+H)) + =677)

[0443] Synthetic Example 2-22: Preparation of Compound 2-22

[0444]

[0445] Under a nitrogen atmosphere, 10 g (34.6 mmol) of compound 2-1-1, 15.4 g (36.4 mmol) of amine 22, and 8.3 g (86.6 mmol) of sodium tert-butoxide were added to 300 mL of xylene, and the mixture was stirred and refluxed. Then, 0.5 g (1 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 16.2 g of compound 2-22. (Yield 69%, MS: [M+H)) + =677)

[0446] Synthetic Example 2-23: Preparation of Compound 2-23

[0447]

[0448] Under a nitrogen atmosphere, 10 g (34.6 mmol) of compound 2-1-2, 15.8 g (36.4 mmol) of amine 23, and 8.3 g (86.6 mmol) of sodium tert-butoxide were added to 300 mL of xylene, and the mixture was stirred and refluxed. Then, 0.5 g (1 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 13.6 g of compound 2-23. (Yield 57%, MS: [M+H)) + =688)

[0449] Synthetic Example 2-24: Preparation of Compound 2-24

[0450]

[0451] Under a nitrogen atmosphere, 10 g (34.6 mmol) of compound 2-1-2, 13.1 g (36.4 mmol) of amine 24, and 8.3 g (86.6 mmol) of sodium tert-butoxide were added to 300 mL of xylene, and the mixture was stirred and refluxed. Then, 0.5 g (1 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 14.2 g of compound 2-24. (Yield 67%, MS: [M+H))+ =612)

[0452] Synthetic Example 2-25: Preparation of Compound 2-25

[0453]

[0454] Under a nitrogen atmosphere, amine 25 (10 g, 38.6 mmol), substance 2-1-1 (23.4 g, 81 mmol), and sodium tert-butoxide (13 g, 135 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 15.6 g of compound 2-25. (Yield 53%, MS: [M+H)) + =764)

[0455] Synthetic Example 2-26: Preparation of Compound 2-26

[0456]

[0457] Under a nitrogen atmosphere, 10 g (34.6 mmol) of compound 2-1-1, 14 g (36.4 mmol) of amine 26, and 8.3 g (86.6 mmol) of sodium tert-butoxide were added to 300 mL of xylene, and the mixture was stirred and refluxed. Then, 0.5 g (1 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 11.9 g of compound 2-26. (Yield 54%, MS: [M+H)) + =638)

[0458] Synthetic Example 2-27: Preparation of Compound 2-27

[0459]

[0460] Under a nitrogen atmosphere, 10 g (34.6 mmol) of compound 2-1-1, 17.3 g (36.4 mmol) of amine 27, and 8.3 g (86.6 mmol) of sodium tert-butoxide were added to 300 mL of xylene, and the mixture was stirred and refluxed. Then, 0.5 g (1 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 14.6 g of compound 2-27. (Yield 58%, MS: [M+H)) + =727)

[0461] Synthetic Example 2-28: Preparation of Compound 2-28

[0462]

[0463] Under a nitrogen atmosphere, 10 g (34.6 mmol) of compound 2-1-2, 14 g (36.4 mmol) of amine 28, and 8.3 g (86.6 mmol) of sodium tert-butoxide were added to 300 mL of xylene, and the mixture was stirred and refluxed. Then, 0.5 g (1 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 11.9 g of compound 2-28. (Yield 54%, MS: [M+H)) + =638)

[0464] Synthetic Example 2-29: Preparation of Compound 2-29

[0465]

[0466] Under a nitrogen atmosphere, substances 2-1 (10 g, 38.9 mmol) and 2-5 (8.8 g, 42.8 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (16.1 g, 116.7 mmol) was dissolved in 48 mL of water and added to the solution. After thorough stirring, tetrakis(triphenylphosphine)palladium(0) (0.4 g, 0.4 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 8.8 g of substance 2-1-4. (Yield 67%, MS: [M+H)) + =339)

[0467] Under a nitrogen atmosphere, 10 g (29.5 mmol) of compound 2-1-4, 11.9 g (31 mmol) of amine 26, and 7.1 g (73.8 mmol) of sodium tert-butoxide were added to 300 mL of xylene, and the mixture was stirred and refluxed. Then, 0.5 g (0.9 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.8 g of compound 2-29. (Yield 63%, MS: [M+H]) + =688)

[0468] Synthetic Example 2-30: Preparation of Compound 2-30

[0469]

[0470] Under a nitrogen atmosphere, 10 g (29.5 mmol) of compound 2-1-4, 14.2 g (31 mmol) of amine 29, and 7.1 g (73.8 mmol) of sodium tert-butoxide were added to 300 mL of xylene, and the mixture was stirred and refluxed. Then, 0.5 g (0.9 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.4 g of compound 2-30. (Yield 55%, MS: [M+H)) + =762)

[0471] Comparative Example 1: Fabrication of Organic Light-Emitting Devices

[0472] ITO (indium tin oxide) is used as A glass substrate coated with a thin film of ITO was immersed in distilled water containing detergent and washed using ultrasound. The detergent used was from Fischer Co., and the distilled water was filtered twice using a filter manufactured by Millipore Co. After washing the ITO for 30 minutes, the process was repeated twice with distilled water for 10 minutes of ultrasonic washing. Following the distilled water washing, the substrate was ultrasonically washed with a solvent of isopropanol, acetone, and methanol, dried, and then transferred to a plasma cleaner. Additionally, the substrate was cleaned with oxygen plasma for 5 minutes before being transferred to a vacuum evaporation machine.

[0473] On the prepared ITO transparent electrode, as a hole injection layer, the following HI-1 compound is applied... The thickness is formed by p-doping the A-1 compound at a concentration of 1.5%. The HT-1 compound is then vacuum-deposited onto the hole-implanted layer to form a film thickness. The hole transport layer. Next, on the aforementioned hole transport layer, at a film thickness of... An electron suppression layer is formed by vacuum evaporation of the following EB-1 compound.

[0474] Next, on the EB-1 vapor-deposited film described above, the host material, namely compound 1-1 manufactured in synthesis example 1-1, and the dopant material, namely compound Dp-7, are vacuum-deposited at a weight ratio of 98:2 to form... A thick red luminescent layer.

[0475] On the aforementioned light-emitting layer, with film thickness A hole-blocking layer was formed by vacuum evaporation of the HB-1 compound described below. Next, the ET-1 compound and the LiQ compound described below were vacuum evaporated onto the hole-blocking layer in a 2:1 weight ratio, thereby achieving... The thickness forms an electron injection and transport layer. On this electron injection and transport layer, lithium fluoride (LiF) is sequentially applied... The thickness, using aluminum The cathode is formed by vapor deposition of a certain thickness.

[0476]

[0477] During the above process, the evaporation rate of organic matter is maintained. / second, lithium fluoride at the cathode maintains Evaporation rate of / second, aluminum maintains A vapor deposition rate of / second is achieved, while maintaining a vacuum level of 2×10⁻⁶ during vapor deposition. -7 ~5×10 -6 This led to the creation of organic light-emitting devices.

[0478] Comparative Examples 2 to 15

[0479] In the organic light-emitting device of Comparative Example 1, the compound listed in Table 1 below was used instead of compound 1-1, and the organic light-emitting device was otherwise manufactured by the same method as in Comparative Example 1.

[0480] Examples 1 to 104

[0481] In the organic light-emitting device of Comparative Example 1, the compound represented by the above chemical formula 1, which is the first main body as listed in Tables 2 to 4, and the compound represented by the above chemical formula 2, which is the second main body, were co-deposited in a weight ratio of 1:1 to replace compound 1-1. Otherwise, the organic light-emitting device was manufactured by the same method as that of Comparative Example 1.

[0482] Here, the structures of the compounds used in Examples and Comparative Examples 2 to 15 are summarized as follows.

[0483]

[0484]

[0485]

[0486]

[0487]

[0488]

[0489] Comparative Examples 16 to 47

[0490] In the organic light-emitting device of Comparative Example 1, the first and second host compounds listed in Table 5 below were co-deposited in a 1:1 weight ratio instead of compound 1-1. Otherwise, the organic light-emitting device was manufactured by the same method as in Comparative Example 1. Here, the structures of comparative compounds RH1 to RH8 are shown below.

[0491]

[0492] Experiment Example 1: Device Characteristic Evaluation

[0493] When an electric current was applied to the organic light-emitting devices fabricated in Examples 1 to 104 and Comparative Examples 1 to 47, the voltage, efficiency, and lifetime (10 mA / cm²) were measured. 2 The results are shown in Tables 1 to 5 below. Here, lifetime T95 refers to the time required for the brightness to decrease from the initial brightness (5000 nits) to 95%.

[0494] [Table 1]

[0495] Comparative Example 1 Compound 1-1 18.2 183 red Comparative Example 2 Compounds 1-2 19.4 162 red Comparative Example 3 Compounds 1-3 19.2 161 red Comparative Example 4 Compounds 1-5 19.5 198 red Comparative Example 5 Compounds 1-7 18.7 169 red Comparative Example 6 Compounds 1-9 19.8 194 red Comparative Example 7 Compounds 1-10 18.9 182 red Comparative Example 8 Compounds 1-11 18.7 164 red Comparative Example 9 Compounds 1-13 18.8 166 red Comparative Example 10 Compounds 1-15 17.2 161 red Comparative Example 11 Compounds 1-17 18.4 179 red Comparative Example 12 Compounds 1-19 17.5 152 red Comparative Example 13 Compounds 1-20 18.7 164 red Comparative Example 14 Compounds 1-21 18.1 162 red Comparative Example 15 Compounds 1-25 18.6 153 red

[0496] [Table 2]

[0497]

[0498]

[0499] [Table 3]

[0500]

[0501]

[0502] [Table 4]

[0503]

[0504] [Table 5]

[0505]

[0506]

[0507] As shown in Tables 1 to 5 above, the organic light-emitting devices of the embodiments that use both the first compound represented by Chemical Formula 1 and the second compound represented by Chemical Formula 2 as the host material of the light-emitting layer exhibit superior driving voltage, luminous efficiency, and lifetime characteristics compared to the organic light-emitting devices of the comparative examples that use only one of the compounds represented by Chemical Formulas 1 and 2, or neither of them.

[0508] In particular, compared with the devices of Comparative Examples 32 to 47, which used comparative compounds RH5 to RH8 as the first host and the compound represented by Chemical Formula 2 as the second host, and the devices of Comparative Examples 16 to 31, which used the compound represented by Chemical Formula 1 as the first host and the comparative compounds RH1 to RH4 as the second host, the devices according to the embodiments all showed improved driving voltage, efficiency, and lifetime characteristics. This confirms that when the combination of the first compound represented by Chemical Formula 1 and the second compound represented by Chemical Formula 2 is used as a common host, energy transfer to the red dopant within the red emitting layer is effectively achieved. It can be determined that this is because the first compound has high stability for electrons and holes, and furthermore, it is determined that due to the simultaneous use of the second compound, while the amount of holes increases, a more stable balance between electrons and holes is maintained within the red emitting layer.

[0509] Therefore, it can be confirmed that using both the first and second compounds described above as the main materials of an organic light-emitting device can improve the driving voltage, luminous efficiency, and lifetime characteristics of the organic light-emitting device. Considering that the luminous efficiency and lifetime characteristics of organic light-emitting devices typically have a trade-off relationship, it is evident that the organic light-emitting device employing the combination of compounds of the present invention exhibits significantly improved device characteristics compared to the comparative example device.

[0510] [Symbol Explanation]

[0511] 1: Substrate 2: Anode

[0512] 3: Light-emitting layer 4: Cathode

[0513] 5: Hole injection layer; 6: Hole transport layer

[0514] 7: Electron suppression layer; 8: Hole blocking layer

[0515] 9: Electron injection and transport layer.

Claims

1. An organic light-emitting device, comprising: anode; A cathode is disposed opposite the anode; as well as A light-emitting layer disposed between the anode and the cathode. The light-emitting layer comprises a first compound represented by the following chemical formula 1 and a second compound represented by the following chemical formula 2: Chemical Formula 1 In the chemical formula 1, A1 and A2 are each independently a benzene or naphthalene ring fused with an adjacent five-membered ring. L represents substituted or unsubstituted C. 6-60 Alpha-aryl L1 and L2 are each independently a single bond, or a substituted or unsubstituted C bond. 6-60 Alpha-aryl Ar1 and Ar2 are each independently substituted or unsubstituted phenyl, biphenyl, naphthyl, or dibenzofuranyl. R1 and R2 are each independently hydrogen; deuterium; substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms of N, O and S. 2-60 Mixed aromatics, When A1 and A2 are each benzene rings, a and b are each independent integers from 0 to 4. When A1 and A2 are each naphthalene rings, a and b are each independent integers from 0 to 6. Chemical formula 2 In the chemical formula 2, L' represents substituted or unsubstituted C. 6-60 Alpha-aryl L3 and L4 are each independently a single bond, or a substituted or unsubstituted C bond. 6-60 Alpha-aryl Ar3 and Ar4 are each independently substituted or unsubstituted C. 6-60 Aryl, substituents represented by chemical formula 2a, substituents represented by chemical formula 2b, or substituents represented by chemical formula 2c, but Ar3 and Ar4 are not fluorene groups. In the chemical formulas 2a to 2c, X can be independently O, S, or N (Ar). Wherein, Ar is hydrogen, deuterium, or substituted or unsubstituted C. 6-20 Aryl, B1 to B3 are each independently a substituted or unsubstituted naphthalene ring fused with an adjacent five-membered ring. R is hydrogen, deuterium, or a substituted or unsubstituted C. 6-20 Aryl, n is an integer from 0 to 4. R3 is either hydrogen or deuterium. c is an integer from 0 to 9. When a, b, and c are each 2 or more, the substituents in the parentheses may be the same or different from each other.

2. The organic light-emitting device according to claim 1, wherein, The first compound is represented by any one of the following chemical formulas 1-1 to 1-10: In the chemical formulas 1-1 to 1-10, a' and b' are each an independent integer from 0 to 4. a" and b" are each an independent integer from 0 to 6. L, L1, L2, Ar1, Ar2, R1, and R2 are the same as defined in claim 1.

3. The organic light-emitting device according to claim 1, wherein, L represents phenylene, biphenyl dimethyl, or naphthylene.

4. The organic light-emitting device according to claim 1, wherein, L1 and L2 are each independently a single bond, a phenylene group, or a naphthylene group.

5. The organic light-emitting device according to claim 1, wherein, Ar1 and Ar2 are each independently phenyl, biphenyl, naphthyl, or dibenzofuranyl.

6. The organic light-emitting device according to claim 1, wherein, R1 and R2 are each independently phenyl, naphthyl, or dibenzofuranyl.

7. The organic light-emitting device according to claim 1, wherein, a+b is 0 or 1.

8. The organic light-emitting device according to claim 1, wherein, The first compound is selected from any one of the following compounds: 。 9. The organic light-emitting device according to claim 1, wherein, L' is phenylene, biphenyl dimethyl, or naphthylene.

10. The organic light-emitting device according to claim 9, wherein, L' is selected from any of the following: 。 11. The organic light-emitting device according to claim 1, wherein, L3 and L4 are each independently a single bond, phenylene, biphenyl dimethyl, or naphthylene.

12. The organic light-emitting device according to claim 1, wherein, In the chemical formulas 2a to 2c, X can be O, S, or N (phenyl) independently. B1 to B3 are each an unsubstituted naphthalene ring fused with an adjacent five-membered ring.

13. The organic light-emitting device according to claim 1, wherein, Ar3 and Ar4 are each independently a phenyl, phenylnaphthyl, biphenyl, terphenyl, naphthyl, naphthylphenyl, phenanthrene, phenylenetriene, a substituent represented by any one of the following chemical formulas 2a-1 to 2a-5, or a substituent represented by any one of the following chemical formulas 2b-1 to 2b-4: 。 14. The organic light-emitting device according to claim 1, wherein, R3 is hydrogen.

15. The organic light-emitting device according to claim 1, wherein, The second compound is selected from any one of the following compounds: 。

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