Novel compounds and organic light-emitting devices comprising the same

Abstract

The present invention provides novel compounds and organic light emitting devices comprising the same.

Description

Technical Field

[0001] Cross-reference with related applications

[0002] This application claims priority based on Korean Patent Application No. 10-2021-0166510, dated November 29, 2021, the entire contents of which are disclosed in the document and are incorporated herein by reference.

[0003] This invention relates to novel compounds and organic light-emitting devices containing the same. 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] On the other hand, in recent years, in order to save on process costs, organic light-emitting devices (OLEDs) are being developed that utilize solution processes, especially inkjet processes, to replace existing vapor deposition processes. In the early stages, attempts were made to develop OLEDs by coating all OLED layers using solution processes, but current technology has limitations. Therefore, research is underway on hybrid processes where only HIL, HTL, and EML are coated using solution processes in a normal structural form, while subsequent processes utilize existing vapor deposition processes.

[0008] Therefore, the present invention provides a novel organic light-emitting device material that can be used in organic light-emitting devices and also in solution processing.

[0009] Existing technical documents

[0010] Patent documents

[0011] (Patent Document 0001) Korean Patent Publication No. 10-2000-0051826 Summary of the Invention

[0012] Technical issues

[0013] This invention relates to novel compounds and organic light-emitting devices containing the same.

[0014] Solution to the problem

[0015] This invention provides compounds represented by the following chemical formula 1:

[0016] [Chemical Formula 1]

[0017]

[0018] In the above chemical formula 1,

[0019] One of X1 to X4 is CR, and the rest are independently N, CH or CD.

[0020] Wherein, R is a substituent represented by the following chemical formula 2,

[0021] X5 to X 10 Each can be independently N, CH, or CD.

[0022] However, X1 to X 10 One of them is N,

[0023] [Chemical Formula 2]

[0024]

[0025] In the above chemical formula 2,

[0026] L1 is a direct bond; substituted or unsubstituted C 6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O, and S. 2-60 heteroaryl,

[0027] L2 is a direct bond; substituted or unsubstituted C 6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O, and S. 2-60 heteroaryl,

[0028] L3 is a direct bond; substituted or unsubstituted C 6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O, and S. 2-60 heteroaryl,

[0029] Ar1 represents substituted or unsubstituted C.6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O, and S. 2-60 Mixed aromatics,

[0030] Ar2 is C with or without substitution. 6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O, and S. 2-60 Mixed aromatic compounds.

[0031] Furthermore, the present invention provides an organic light-emitting device, comprising: a first electrode, a second electrode disposed opposite to the first electrode, and an organic layer disposed between the first electrode and the second electrode, wherein the organic layer comprises a compound represented by the aforementioned chemical formula 1. Specifically, the organic layer comprising the aforementioned compound may be a light-emitting layer.

[0032] Invention Effects

[0033] The compounds represented by the above-described chemical formula 1 can be used as materials for the organic layer of organic light-emitting devices, thereby achieving improved efficiency, lower driving voltage, and / or improved lifetime characteristics in organic light-emitting devices. In particular, the compounds represented by the above-described chemical formula 1 can be used as materials for hole injection, hole transport, hole injection and transport, electron suppression, luminescence, electron transport, or electron injection. Attached Figure Description

[0034] 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.

[0035] 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, a light-emitting layer 7, an electron injection and transport layer 8, and a cathode 4. Detailed Implementation

[0036] The invention will now be described in more detail to aid in understanding.

[0037] (Definition of the term)

[0038] In this instruction manual, The symbol indicates a bond that is linked to other substituents; "D" represents deuterium.

[0039] In this specification, the term "substituted or unsubstituted" refers to a group selected from deuterium; halogen group; cyano 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 Silyl; boronyl; alkyl; cycloalkyl; alkenyl; aryl; aralkyl; arylene; alkylaryl; alkylamino; aralkylamino; heteroarylamino; arylamino; arylphosphinyl; or a substituent consisting of one or more heteroaryl groups containing N, O, and S atoms, substituted or unsubstituted, or substituted or unsubstituted by a substituent formed by linking two or more substituents exemplified above. For example, "a substituent formed by linking two or more substituents" can be biphenyl. That is, biphenyl can be aryl, or it can be interpreted as a substituent formed by linking two phenyl groups.

[0040] 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 compound with the following structure, but is not limited thereto.

[0041]

[0042] 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 compound with the following structural formula, but is not limited thereto.

[0043]

[0044] 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 compound with the following structure, but is not limited thereto.

[0045]

[0046] In this specification, silanes specifically include trimethylsilane, triethylsilane, tert-butyldimethylsilane, vinyldimethylsilane, propyldimethylsilane, triphenylsilane, diphenylsilane, phenylsilane, etc., but are not limited to these.

[0047] In this specification, boron groups specifically include trimethylboronyl, triethylboronyl, tert-butyldimethylboronyl, triphenylboronyl, phenylboronyl, etc., but are not limited to these.

[0048] Examples of halogen groups in this specification include fluorine, chlorine, bromine, or iodine.

[0049] 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 yet another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but are not limited to these.

[0050] 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.

[0051] 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.

[0052] 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 aryl or polycyclic aryl. 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, pyrene, perylene, etc. It includes bases, fluorenes, etc., but is not limited to these.

[0053] In this specification, the fluorene group can be substituted, and two substituents can combine with each other to form a spirostructure. When the fluorene group is substituted as described above, it can be used to... Etc. But it is not limited to this.

[0054] In this specification, a heteroaryl group is a heteroaryl group containing one or more of 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 xanthene, thioxanthen, thiophene, furanyl, pyrrole, 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 Azolyl, thiadiazolyl, phenthiazinyl, and dibenzofuranyl groups, but not limited to these.

[0055] 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.

[0056] (compound)

[0057] The present invention provides compounds represented by the above chemical formula 1.

[0058] One of X1 to X4 is CR, and the rest are independently N, CH or CD, where R is a substituent represented by the above chemical formula 2, X5 to X 10 Each is independently N, CH, or CD, but X1 to X 10 One of them is N.

[0059] Specifically, one of X1 to X4 can be CR, another can be N, and the rest can be CH or CD independently, X5 to X 10 Each is independently CH or CD, or one of X1 to X4 is CR, and the rest are independently CH or CD, X5 to X 10 One of them is N, and the rest are independently CH or CD.

[0060] L1 is a direct bond; substituted or unsubstituted C 6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O, and S. 2-60 Heteroaryl group. Preferably, L1 can be directly bonded or phenylene. When L1 is phenylene, it can be unsubstituted or substituted with one or more deuterium atoms.

[0061] L2 is a direct bond; substituted or unsubstituted C 6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O, and S. 2-60Heteroaryl groups. Preferably, L2 can be directly bonded, phenylene, naphthylene, biphenylene, 9,9-dimethylfluorene, 9,9-diphenylfluorene, or carbazolyl. When L2 is phenylene, naphthylene, biphenylene, 9,9-dimethylfluorene, 9,9-diphenylfluorene, or carbazolyl, it may be unsubstituted or substituted with one or more deuterium groups.

[0062] L3 is a direct bond; substituted or unsubstituted C 6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O, and S. 2-60 Heteroaryl groups. Preferably, L3 can be directly bonded, phenylene, naphthylene, biphenylene, 9,9-dimethylfluorene, or 9,9-diphenylfluorene. When L3 is phenylene, naphthylene, biphenylene, 9,9-dimethylfluorene, or 9,9-diphenylfluorene, it may be unsubstituted or substituted with one or more deuterium groups.

[0063] Ar1 represents substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O, and S. 2-60 Heteroaryl. Ar1 can be phenyl, biphenyl, terphenyl, naphthyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, dibenzofuranyl, dibenzothiopheneyl, 9-phenyl-carbazolyl, 9-naphthyl-carbazolyl, or 9,9'-spirodi[9H-fluorenyl]yl. Ar1 can be unsubstituted or substituted with one or more deuterium groups.

[0064] Ar2 is C with or without substitution. 6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O, and S. 2-60 Heteroaryl. Ar2 can be phenyl, biphenyl, terphenyl, naphthyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, dibenzofuranyl, dibenzothiopheneyl, 9-phenyl-carbazolyl, 9-naphthyl-carbazolyl, or 9,9'-spirodi[9H-fluorenyl]yl. Ar2 can be unsubstituted or substituted with one or more deuterium groups.

[0065] In addition, the compound can be represented by any one of the following chemical formulas 1-1 to 1-4.

[0066] [Chemical Formula 1-1]

[0067]

[0068] In the above chemical formula 1-1,

[0069] X2 to X 10One of them is N, and the rest are independently CH or CD.

[0070] L1 to L3, Ar1 and Ar2 are defined in the same way as in Formula 1.

[0071] [Chemical Formula 1-2]

[0072]

[0073] In the above chemical formulas 1-2,

[0074] X1 and X3 to X 10 One of them is N, and the rest are independently CH or CD.

[0075] L1 to L3, Ar1 and Ar2 are defined in the same way as in Formula 1.

[0076] [Chemical Formulas 1-3]

[0077]

[0078] In the above chemical formulas 1-3,

[0079] X1, X2, and X4 to X 10 One of them is N, and the rest are independently CH or CD. L1 to L3, Ar1 and Ar2 are defined as in chemical formula 1.

[0080] [Chemical Formulas 1-4]

[0081]

[0082] In the above chemical formulas 1-4,

[0083] X1 to X3 and X5 to X 10 One of them is N, and the rest are independently CH or CD. L1 to L3, Ar1 and Ar2 are defined in the same way as in chemical formula 1.

[0084] Representative examples of compounds represented by the above chemical formula 1 are shown below:

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110] In addition, the above compounds may not contain deuterium, or they may contain more than one deuterium.

[0111] On the other hand, as an example, the present invention provides a method for manufacturing the compound represented by the above chemical formula 1, as shown in reaction formulas 1 and 2 below:

[0112] [Reaction Formula 1]

[0113]

[0114] [Reaction 2]

[0115]

[0116] In the above reaction equations 1 and 2, X1 to X 10 The definitions of L1 to L3, and Ar1 and Ar2 are the same as those in chemical formulas 1 and 2, respectively. Furthermore, in reaction formulas 1 and 2, Z is a halogen, preferably chlorine.

[0117] The above-described reaction formula 1 is a reaction that produces chemical formula 1 as the core structure via a Suzuki coupling reaction. Furthermore, reaction formula 2 is also a Suzuki coupling reaction, preferably carried out in the presence of a palladium catalyst. The reactive groups used in the Suzuki coupling reaction can be modified according to techniques known in the art. The above-described manufacturing method can be further specified in the manufacturing and synthesis examples described later.

[0118] (Organic light-emitting devices)

[0119] Furthermore, the present invention provides an organic light-emitting device comprising a compound represented by the above-described chemical formula 1. As an example, the present invention provides an organic light-emitting device comprising: a first electrode, a second electrode disposed opposite to the first electrode, and one or more organic layers disposed between the first electrode and the second electrode, wherein one or more of the organic layers comprises a compound represented by the above-described chemical formula 1.

[0120] The organic layer of the organic light-emitting device of the present invention can be formed as a single layer or as a multilayer structure with two or more organic layers stacked on top of each other. For example, the organic light-emitting device of the present invention can have a structure including a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer as organic layers. However, the structure of the organic light-emitting device is not limited to this and may include fewer organic layers.

[0121] In addition, the aforementioned organic layer may include a hole injection layer, a hole transport layer, or a layer that performs both hole injection and transport simultaneously, and the aforementioned hole injection layer, hole transport layer, or layer that performs both hole injection and transport simultaneously may contain a compound represented by the aforementioned chemical formula 1.

[0122] In addition, the aforementioned organic layer may include a light-emitting layer, which may contain a compound represented by the aforementioned chemical formula 1.

[0123] In addition, the aforementioned organic layer may include a hole-blocking layer, an electron transport layer, an electron injection layer, or a layer that simultaneously performs electron transport and electron injection. The aforementioned hole-blocking layer, electron transport layer, electron injection layer, or layer that simultaneously performs electron transport and electron injection may contain a compound represented by the aforementioned chemical formula 1.

[0124] In addition, the aforementioned organic layer may include a light-emitting layer and an electron injection and transport layer, wherein the electron injection and transport layer may contain a compound represented by the aforementioned chemical formula 1.

[0125] Furthermore, the organic light-emitting device according to the present invention can be a structure (normal type) in which an anode, one or more organic layers, and a cathode are sequentially stacked on a substrate. Additionally, the organic light-emitting device according to the present invention can be a reverse structure (inverted type) in which a cathode, one or more organic layers, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light-emitting device according to an embodiment of the present invention is illustrated below. Figure 1 and 2 middle.

[0126] 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.

[0127] 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, a light-emitting layer 7, an electron injection and transport layer 8, and a cathode 4. In the structure described above, the compound represented by the above chemical formula 1 may be included in the light-emitting layer.

[0128] The organic light-emitting device according to the present invention, except that one or more of the organic layers contain a compound represented by the above-described chemical formula 1, can be manufactured using materials and methods known in the art. Furthermore, when the organic light-emitting device comprises a plurality of organic layers, the organic layers can be formed from the same substance or different substances.

[0129] For example, the organic light-emitting device according to the present invention can be manufactured by sequentially stacking an anode, an organic layer, and a cathode on a substrate. This can be achieved by depositing a metal or a conductive metal oxide or alloy thereof onto the substrate using a PVD (physical vapor deposition) method such as sputtering or electron beam evaporation to form an anode, then forming an organic layer comprising a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer on the anode, and finally depositing a material suitable for use as a cathode onto the organic layer. Alternatively, the organic light-emitting device can also be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material onto the substrate.

[0130] Furthermore, the compound represented by the above chemical formula 1 can be used to form an organic layer in the manufacture of organic light-emitting devices not only by vacuum evaporation but also by solution coating. Here, solution coating refers to methods such as spin coating, dip coating, blade coating, inkjet printing, screen printing, spray coating, and roller coating, but is not limited to these.

[0131] In addition to these methods, 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 these methods.

[0132] As an example, the first electrode is the anode and the second electrode is the cathode, or the first electrode is the cathode and the second electrode is the anode.

[0133] 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 materials 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.

[0134] 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 structures such as LiF / Al or LiO2 / Al, etc., but are not limited to these.

[0135] The aforementioned hole injection layer is a layer that injects holes from the electrode. Preferably, the 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 light-emitting layer or light-emitting material, prevents excitons generated in the light-emitting layer from migrating to the electron injection layer or electron injection material, and exhibits excellent thin film formation capability. Preferably, the HOMO (highest occupied molecular orbital) of the hole injection material is between that of the anode material and the HOMO of the surrounding organic layer. Specific examples of hole injection materials include, but are not limited to, metalloporphyrins, oligothiophenes, arylamine-based organic compounds, hexanitrile hexaazabenzophenanthrene-based organic compounds, quinacridone-based organic compounds, perylene-based organic compounds, anthraquinones, and conductive compounds based on polyaniline and polythiophene.

[0136] The aforementioned hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light-emitting layer. The hole transport material is a material capable of receiving holes from the anode or hole injection layer and transferring them to the light-emitting layer; materials with high hole mobility are suitable. Specific examples include aryl amine-based organic compounds, conductive compounds, and block copolymers that simultaneously contain conjugated and non-conjugated portions, but are not limited to these.

[0137] The aforementioned luminescent material is capable of receiving holes and electrons from the hole transport layer and electron transport layer, respectively, and combining them to emit light in the visible light region. Preferably, it is a material with high quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxyquinoline aluminum complex (Alq3); carbazole compounds; diluted styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; and benzo[…]. Compounds of the azole, benzothiazole and benzimidazole series; poly(p-phenylenevinylene) (PPV) polymers; spirocyclic compounds; polyfluorene, fluorene, etc., but not limited to these.

[0138] The aforementioned electron suppression layer is a layer placed between the hole transport layer and the light-emitting layer to prevent electrons injected from the cathode from recombining in the light-emitting layer and transferring to the hole transport layer. It is also called an electron blocking layer. Preferably, the electron suppression layer uses a material with lower electrophilicity compared to the electron transport layer. Preferably, it may contain a compound represented by the above-described chemical formula 1 as the electron suppression layer material.

[0139] The aforementioned luminescent layer may comprise a host material and a dopant material. As the host material, compounds represented by the aforementioned chemical formula 1 can be used. Furthermore, as a host material that can be further used, aromatic fused-ring derivatives or heterocyclic compounds can be used. Specifically, as aromatic fused-ring derivatives, there are anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentane derivatives, phenanthrene compounds, fluoranthene compounds, etc.; as heterocyclic compounds, there are carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, etc. Pyrimidine derivatives, etc., but not limited to these.

[0140] As dopant materials, there are aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, aromatic amine derivatives are aromatic fused-ring derivatives with substituted or unsubstituted aryl amino groups, such as pyrene, anthracene, etc. 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.

[0141] The aforementioned electron transport layer is the layer that receives electrons from the electron injection layer and transports them to the light-emitting layer. The electron transport material is one that can effectively receive electrons from the cathode and transfer them to the light-emitting layer; materials with high electron mobility are suitable. Specific examples include Al complexes of 8-hydroxyquinoline, complexes containing Alq3, organic free radical compounds, hydroxyflavonoid-metal complexes, etc., but are not limited to these. The electron transport layer can be used with any desired cathode material as used in the prior art. In particular, examples of suitable cathode materials are common materials with low work functions and accompanied by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium, and samarium are all accompanied by an aluminum or silver layer.

[0142] The aforementioned electron injection layer is a layer that injects electrons from the electrode. Preferably, compounds are those that possess electron transport capabilities, effectively inject electrons from the cathode, exhibit excellent electron injection performance for the light-emitting layer or light-emitting material, prevent excitons generated in the light-emitting layer from migrating to the hole injection layer, and possess excellent thin-film forming ability. Specifically, these include fluorenone, anthraquinone dimethyl ether, biphenylquinone, thiamethoxam dioxide, etc. azole, Diazoles, triazoles, imidazoles, perylenetetracarboxylic acids, fluorenemethane, anthrones, and their derivatives, metal coordination compounds, and nitrogen-containing five-membered ring derivatives, but not limited to these.

[0143] 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.

[0144] On the other hand, in this invention, the "electron injection and transport layer" is a layer that fully utilizes the functions of the aforementioned electron injection layer and electron transport layer. Substances that perform the functions of each layer can be used individually or in combination, but are not limited thereto. Preferably, the substance comprising the compound represented by the aforementioned chemical formula 1 may be used as the electron injection and transport layer.

[0145] 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.

[0146] 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.

[0147] The manufacture of compounds represented by the above chemical formula 1 and organic light-emitting devices containing them is specifically described in the following examples. However, the following examples are for illustrative purposes only and the scope of the invention is not limited thereto.

[0148] Synthetic Example A-1-1: Preparation of Intermediate Compound A-1-1

[0149]

[0150] 3-Bromo-2-chloropyridine (15 g, 77.9 mmol) and (1-(methylthio)naphth-2-yl)boronic acid (17.8 g, 81.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (32.3 g, 233.8 mmol) was dissolved in 100 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol). After reacting for 4 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 13.8 g of compound A-1-1_P1. (Yield 62%, MS: [M+H)) + =286)

[0151] Compound A-1-1_P1 (15 g, 52.5 mmol) and hydrogen peroxide (2.7 g, 78.7 mmol) were added to 300 mL of acetic acid, stirred, and refluxed. After reacting for 3 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved 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 8.1 g of compound A-1-1_P2. (Yield 51%, MS: [M+H)) + =302)

[0152] Compound A-1-1_P2 (15 g, 49.7 mmol) was added to 300 mL of sulfuric acid, stirred, and refluxed. After reacting for 2 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved 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 6.2 g of the intermediate compound A-1-1. (Yield 49%, MS: [M+H]) + =254)

[0153] Synthetic Example A-1-6: Preparation of Intermediate Compound A-1-6

[0154]

[0155] 1-Bromo-2-chlorobenzene (15 g, 78.3 mmol) and (5-(methylthio)isoquinoline-6-yl)boronic acid (18 g, 82.3 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (32.5 g, 235 mmol) was dissolved in 100 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol). After reacting for 4 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 15.4 g of compound A-1-6_P1. (Yield 69%, MS: [M+H)) + =286)

[0156] Compound A-1-6_P1 (15 g, 52.5 mmol) and hydrogen peroxide (2.7 g, 78.7 mmol) were added to 300 mL of acetic acid, stirred, and refluxed. After reacting for 3 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved 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 8.2 g of compound A-1-6_P2. (Yield 52%, MS: [M+H)) + =302)

[0157] Compound A-1-6_P2 (15 g, 49.7 mmol) was added to 300 mL of sulfuric acid, stirred, and refluxed. After reacting for 5 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved 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 5.9 g of the intermediate compound A-1-6. (Yield 47%, MS: [M+H)) + =254)

[0158] Synthetic Example A-2-2: Preparation of Intermediate Compound A-2-2

[0159]

[0160] 4-Bromo-2-chloropyridine (15 g, 77.9 mmol) and (1-(methylthio)naphth-2-yl)boronic acid (17.8 g, 81.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (32.3 g, 233.8 mmol) was dissolved in 100 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol). After reacting for 2 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 13.8 g of compound A-2-2_P1. (Yield 62%, MS: [M+H]) + =286)

[0161] Compound A-2-2_P1 (15 g, 52.5 mmol) and hydrogen peroxide (2.7 g, 78.7 mmol) were added to 300 mL of acetic acid, stirred, and refluxed. After reacting for 4 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved 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 compound A-2-2_P2. (Yield 55%, MS: [M+H)) + =302)

[0162] Compound A-2-2_P2 (15 g, 49.7 mmol) was added to 300 mL of sulfuric acid, stirred, and refluxed. After reacting for 2 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved 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 6.8 g of the intermediate compound A-2-2. (Yield 54%, MS: [M+H]) + =254)

[0163] Synthetic Example A-2-4: Preparation of Intermediate Compound A-2-4

[0164]

[0165] 1-Bromo-3-chlorobenzene (15 g, 78.3 mmol) and (8-(methylthio)quinoline-7-yl)boronic acid (18 g, 82.3 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (32.5 g, 235 mmol) was dissolved in 100 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol). After reacting for 4 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 13.8 g of compound A-2-4_P1. (Yield 62%, MS: [M+H)) + =286)

[0166] Compound A-2-4_P1 (15 g, 52.5 mmol) and hydrogen peroxide (2.7 g, 78.7 mmol) were added to 300 mL of acetic acid, stirred, and refluxed. After reacting for 5 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved 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 9.3 g of compound A-2-4_P2. (Yield 59%, MS: [M+H)) + =302)

[0167] Compound A-2-4_P2 (15 g, 49.7 mmol) was added to 300 mL of sulfuric acid, stirred, and refluxed. After reacting for 2 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved 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 7.2 g of the intermediate compound A-2-4. (Yield 57%, MS: [M+H]) + =254)

[0168] Synthetic Example A-2-7: Preparation of Intermediate Compound A-2-7

[0169]

[0170] 1-Bromo-3-chlorobenzene (15 g, 78.3 mmol) and (5-(methylthio)quinoline-6-yl)boronic acid (18 g, 82.3 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (32.5 g, 235 mmol) was dissolved in 100 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol). After reacting for 3 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 14.3 g of compound A-2-7_P1. (Yield 64%, MS: [M+H)) + =286)

[0171] Compound A-2-7_P1 (15 g, 52.5 mmol) and hydrogen peroxide (2.7 g, 78.7 mmol) were added to 300 mL of acetic acid, stirred, and refluxed. After reacting for 5 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved 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 compound A-2-7_P2. (Yield 58%, MS: [M+H]) + =302)

[0172] Compound A-2-7_P2 (15 g, 49.7 mmol) was added to 300 mL of sulfuric acid, stirred, and refluxed. After reacting for 4 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved 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 5.4 g of the intermediate compound A-2-7. (Yield 43%, MS: [M+H]) + =254)

[0173] Synthetic Example A-3-5: Preparation of Intermediate Compound A-3-5

[0174]

[0175] 1-Bromo-4-chlorobenzene (15 g, 78.3 mmol) and (8-(methylthio)isoquinoline-7-yl)boronic acid (18 g, 82.3 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (32.5 g, 235 mmol) was dissolved in 100 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol). After reacting for 4 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 15.4 g of compound A-3-5_P1. (Yield 69%, MS: [M+H)) + =286)

[0176] Compound A-3-5_P1 (15 g, 52.5 mmol) and hydrogen peroxide (2.7 g, 78.7 mmol) were added to 300 mL of acetic acid, stirred, and refluxed. After reacting for 4 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved 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 g of compound A-3-5_P2. (Yield 57%, MS: [M+H)) + =302)

[0177] Compound A-3-5_P2 (15 g, 49.7 mmol) was added to 300 mL of sulfuric acid, stirred, and refluxed. After reacting for 2 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved 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 5.9 g of the intermediate compound A-3-5. (Yield 47%, MS: [M+H)) + =254)

[0178] Synthetic Example A-3-9: Preparation of Intermediate Compound A-3-9

[0179]

[0180] 1-Bromo-4-chlorobenzene (15 g, 78.3 mmol) and (4-(methylthio)isoquinoline-3-yl)boronic acid (18 g, 82.3 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (32.5 g, 235 mmol) was dissolved in 100 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol). After reacting for 5 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 13.4 g of compound A-3-9_P1. (Yield 60%, MS: [M+H)) + =286)

[0181] Compound A-3-9_P1 (15 g, 52.5 mmol) and hydrogen peroxide (2.7 g, 78.7 mmol) were added to 300 mL of acetic acid, stirred, and refluxed. After reacting for 3 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved 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 8.1 g of compound A-3-9_P2. (Yield 51%, MS: [M+H]) + =302)

[0182] Compound A-3-9_P2 (15 g, 49.7 mmol) was added to 300 mL of sulfuric acid, stirred, and refluxed. After reacting for 5 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved 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 5 g of the intermediate compound A-3-9. (Yield 40%, MS: [M+H)) + =254)

[0183] Synthetic Example A-4-3: Preparation of Intermediate Compound A-4-3

[0184]

[0185] 4-Bromo-2-chloropyridine (15 g, 77.9 mmol) and (1-(methylthio)naphth-2-yl)boronic acid (17.8 g, 81.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (32.3 g, 233.8 mmol) was dissolved in 100 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol). After reacting for 3 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 15.6 g of compound A-4-3_P1. (Yield 70%, MS: [M+H)) + =286)

[0186] Compound A-4-3_P1 (15 g, 52.5 mmol) and hydrogen peroxide (2.7 g, 78.7 mmol) were added to 300 mL of acetic acid, stirred, and refluxed. After reacting for 4 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved 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 g of compound A-4-3_P2. (Yield 57%, MS: [M+H)) + =302)

[0187] Compound A-4-3_P2 (15 g, 49.7 mmol) was added to 300 mL of sulfuric acid, stirred, and refluxed. After reacting for 5 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved 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 5.7 g of the intermediate compound A-4-3. (Yield 45%, MS: [M+H]) + =254)

[0188] Synthetic Example A-4-8: Preparation of Intermediate Compound A-4-8

[0189]

[0190] 1-Bromo-3-chlorobenzene (15 g, 78.3 mmol) and (5-(methylthio)quinoline-6-yl)boronic acid (18 g, 82.3 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (32.5 g, 235 mmol) was dissolved in 100 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol). After reacting for 2 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 13.8 g of compound A-4-8_P1. (Yield 62%, MS: [M+H)) + =286)

[0191] Compound A-4-8_P1 (15 g, 52.5 mmol) and hydrogen peroxide (2.7 g, 78.7 mmol) were added to 300 mL of acetic acid, stirred, and refluxed. After reacting for 5 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved 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 8.2 g of compound A-4-8_P2. (Yield 52%, MS: [M+H)) + =302)

[0192] Compound A-4-8_P2 (15 g, 49.7 mmol) was added to 300 mL of sulfuric acid, stirred, and refluxed. After reacting for 5 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved 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 7 g of the intermediate compound A-4-8. (Yield 56%, MS: [M+H]) + =254)

[0193] Synthesis example 1

[0194]

[0195] Under a nitrogen atmosphere, intermediate compound A-1-1 (15 g, 55.6 mmol), amine 1 (19.6 g, 58.4 mmol), and potassium phosphate (35.4 g, 166.8 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. 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 19.3 g of compound 1. (Yield 61%, MS: [M+H)) + =569)

[0196] Synthesis example 2

[0197]

[0198] Under a nitrogen atmosphere, intermediate compound A-1-1 (15 g, 55.6 mmol), amine 2 (20.4 g, 58.4 mmol), and potassium phosphate (35.4 g, 166.8 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 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 23.6 g of compound 2. (Yield 73%, MS: [M+H)) + =583)

[0199] Synthesis example 3

[0200]

[0201] First, in Synthesis Example A-1-1, 3-bromo-4-chloropyridine was used instead of 3-bromo-2-chloropyridine as the starting material. Otherwise, intermediate compound A-1-3 was prepared using the same method as in Synthesis Example A-1-1.

[0202] Then, under a nitrogen atmosphere, intermediate compound A-1-3 (15 g, 55.6 mmol), amine 3 (20.4 g, 58.4 mmol), and potassium phosphate (35.4 g, 166.8 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 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, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 23.3 g of compound 3. (Yield 72%, MS: [M+H)) + =583)

[0203] Synthesis example 4

[0204]

[0205] Under a nitrogen atmosphere, intermediate compound A-1-6 (15 g, 55.6 mmol), amine 4 (19.6 g, 58.4 mmol), and potassium phosphate (35.4 g, 166.8 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. 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 20.2 g of compound 4. (Yield 64%, MS: [M+H)) + =569)

[0206] Synthesis example 5

[0207]

[0208] First, in Synthesis Example A-1-6, (5-(methylthio)quinoline-6-yl)boronic acid was used instead of (5-(methylthio)isoquinoline-6-yl)boronic acid as the starting material. Otherwise, intermediate compound A-1-7 was prepared using the same method as in Synthesis Example A-1-6.

[0209] Then, intermediate compound A-1-7 (15 g, 55.6 mmol) and amine 5 (29.5 g, 58.4 mmol) were added to 300 mL of THF, stirred, and refluxed. Potassium carbonate (23.1 g, 166.8 mmol) was then dissolved in 100 mL of water and added, stirred thoroughly, followed by bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol). After reacting for 4 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 24.7 g of compound 5. (Yield 64%, MS: [M+H)) + =694)

[0210] Synthesis example 6

[0211]

[0212] First, in Synthesis Example A-1-6, (5-(methylthio)isoquinoline-3-yl)boronic acid was used instead of (5-(methylthio)isoquinoline-6-yl)boronic acid as the starting material. Otherwise, intermediate compound A-1-9 was prepared using the same method as in Synthesis Example A-1-6.

[0213] Then, intermediate compound A-1-9 (15 g, 55.6 mmol) and amine 6 (26.5 g, 58.4 mmol) were added to 300 mL of THF, stirred, and refluxed. Potassium carbonate (23.1 g, 166.8 mmol) was then dissolved in 100 mL of water and added, stirred thoroughly, followed by bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol). After reacting for 4 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 22.2 g of compound 6. (Yield 62%, MS: [M+H)) + =644)

[0214] Synthesis Example 7

[0215]

[0216] Intermediate compound A-2-2 (15 g, 55.6 mmol) and amine 7 (25.8 g, 58.4 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (23.1 g, 166.8 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 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 26.6 g of compound 7. (Yield 76%, MS: [M+H]) + =631)

[0217] Synthesis example 8

[0218]

[0219] First, in Synthesis Example A-2-2, 3-bromo-5-chloropyridine was used instead of 4-bromo-2-chloropyridine as the starting material. Otherwise, intermediate compound A-2-3 was prepared using the same method as in Synthesis Example A-2-2.

[0220] Then, under a nitrogen atmosphere, intermediate compound A-2-3 (15 g, 55.6 mmol), amine 8 (20.5 g, 58.4 mmol), and potassium phosphate (35.4 g, 166.8 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 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, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 23.4 g of compound 8. (Yield 72%, MS: [M+H)) + =585)

[0221] Synthesis example 9

[0222]

[0223] Intermediate compound A-2-4 (15 g, 55.6 mmol) and amine 9 (27.5 g, 58.4 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (23.1 g, 166.8 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 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 29.4 g of compound 9. (Yield 80%, MS: [M+H)) + =661)

[0224] Synthesis example 10

[0225]

[0226] First, in Synthesis Example A-2-7, (4-(methylthio)quinoline-3-yl)boronic acid was used instead of (5-(methylthio)quinoline-6-yl)boronic acid as the starting material. Otherwise, intermediate compound A-2-8 was prepared using the same method as in Synthesis Example A-2-7.

[0227] Then, intermediate compound A-2-8 (15 g, 55.6 mmol) and amine 10 (23.1 g, 58.4 mmol) were added to 300 mL of THF, stirred, and refluxed. Potassium carbonate (23.1 g, 166.8 mmol) was then dissolved in 100 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol). After reacting for 3 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 26 g of compound 10. (Yield 80%, MS: [M+H)) + =585)

[0228] Synthesis example 11

[0229]

[0230] First, in Synthesis Example A-2-7, (4-(methylthio)isoquinoline-3-yl)boronic acid was used instead of (5-(methylthio)quinoline-6-yl)boronic acid as the starting material. Otherwise, intermediate compound A-2-9 was prepared using the same method as in Synthesis Example A-2-7.

[0231] Then, under a nitrogen atmosphere, intermediate compound A-2-9 (15 g, 55.6 mmol), amine 3 (20.4 g, 58.4 mmol), and potassium phosphate (35.4 g, 166.8 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 4 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, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 20.1 g of compound 11. (Yield 62%, MS: [M+H)) + =583)

[0232] Synthesis example 12

[0233]

[0234] First, in Synthesis Example A-2-2, 2-bromo-5-chloropyridine was used instead of 4-bromo-2-chloropyridine as the starting material. Otherwise, intermediate compound A-3-1 was prepared using the same method as in Synthesis Example A-2-2.

[0235] Then, intermediate compound A-3-1 (15 g, 55.6 mmol) and amine 11 (26.6 g, 58.4 mmol) were added to 300 mL of THF, stirred, and refluxed. Potassium carbonate (23.1 g, 166.8 mmol) was then dissolved in 100 mL of water and added, stirred thoroughly, followed by bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol). After reacting for 5 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 25.4 g of compound 12. (Yield 71%, MS: [M+H)) + =645)

[0236] Synthesis example 13

[0237]

[0238] First, in Synthesis Example A-2-2, 5-bromo-2-chloropyridine was used instead of 4-bromo-2-chloropyridine as the starting material. Otherwise, intermediate compound A-3-2 was prepared using the same method as in Synthesis Example A-2-2.

[0239] Then, intermediate compound A-3-2 (15 g, 55.6 mmol) and amine 12 (26.6 g, 58.4 mmol) were added to 300 mL of THF, stirred, and refluxed. Potassium carbonate (23.1 g, 166.8 mmol) was then dissolved in 100 mL of water and added, stirred thoroughly, followed by bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol). After reacting for 4 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 21.5 g of compound 13. (Yield 60%, MS: [M+H)) + =645)

[0240] Synthesis example 14

[0241]

[0242] First, in Synthesis Example A-2-2, 5-bromo-2-chloropyridine was used instead of 4-bromo-2-chloropyridine as the starting material. Otherwise, intermediate compound A-3-2 was prepared using the same method as in Synthesis Example A-2-2.

[0243] Then, under a nitrogen atmosphere, intermediate compound A-3-2 (15 g, 55.6 mmol), amine 13 (21.7 g, 58.4 mmol), and potassium phosphate (35.4 g, 166.8 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 4 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, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 21.2 g of compound 14. (Yield 63%, MS: [M+H)) + =605)

[0244] Synthesis Example 15

[0245]

[0246] First, in Synthesis Example A-2-2, 2-bromo-6-chloropyridine was used instead of 4-bromo-2-chloropyridine as the starting material. Otherwise, intermediate compound A-3-3 was prepared using the same method as in Synthesis Example A-2-2.

[0247] Then, under a nitrogen atmosphere, intermediate compound A-3-3 (15 g, 55.6 mmol), amine 14 (19.6 g, 58.4 mmol), and potassium phosphate (35.4 g, 166.8 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 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, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 21.5 g of compound 15. (Yield 68%, MS: [M+H)) + =569)

[0248] Synthesis Example 16

[0249]

[0250] First, in Synthesis Example A-2-2, 2-bromo-6-chloropyridine was used instead of 4-bromo-2-chloropyridine as the starting material. Otherwise, intermediate compound A-3-3 was prepared using the same method as in Synthesis Example A-2-2.

[0251] Then, under a nitrogen atmosphere, intermediate compound A-3-3 (15 g, 55.6 mmol), amine 15 (14.3 g, 58.4 mmol), and potassium phosphate (35.4 g, 166.8 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 4 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, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 19.4 g of compound 16. (Yield 73%, MS: [M+H)) + =479)

[0252] Synthesis Example 17

[0253]

[0254] First, in Synthesis Example A-3-5, (8-(methylthio)quinoline-7-yl)boronic acid was used instead of (8-(methylthio)isoquinoline-7-yl)boronic acid as the starting material. Otherwise, intermediate compound A-3-4 was prepared using the same method as in Synthesis Example A-3-5.

[0255] Then, under a nitrogen atmosphere, intermediate compound A-3-4 (15 g, 55.6 mmol), amine 16 (28.2 g, 58.4 mmol), and potassium phosphate (35.4 g, 166.8 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 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, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 27.9 g of compound 17. (Yield 70%, MS: [M+H)) + =717)

[0256] Synthesis Example 18

[0257]

[0258] First, in Synthesis Example A-3-9, (4-(methylthio)quinoline-3-yl)boronic acid was used instead of (4-(methylthio)isoquinoline-3-yl)boronic acid as the starting material. Otherwise, intermediate compound A-3-8 was prepared using the same method as in Synthesis Example A-3-9.

[0259] Then, under a nitrogen atmosphere, intermediate compound A-3-8 (15 g, 55.6 mmol), amine 17 (28.2 g, 58.4 mmol), and potassium phosphate (35.4 g, 166.8 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 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, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 25.5 g of compound 18. (Yield 64%, MS: [M+H)) + =717)

[0260] Synthesis example 19

[0261]

[0262] First, in Synthesis Example A-4-3, 2-bromo-4-chloropyridine was used instead of 4-bromo-2-chloropyridine as the starting material. Otherwise, intermediate compound A-4-1 was prepared using the same method as in Synthesis Example A-4-3.

[0263] Then, under a nitrogen atmosphere, intermediate compound A-4-1 (15 g, 55.6 mmol), amine 14 (19.6 g, 58.4 mmol), and potassium phosphate (35.4 g, 166.8 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 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, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 22.7 g of compound 19. (Yield 72%, MS: [M+H)) + =569)

[0264] Synthesis example 20

[0265]

[0266] First, in Synthesis Example A-4-3, 2-bromo-4-chloropyridine was used instead of 4-bromo-2-chloropyridine as the starting material. Otherwise, intermediate compound A-4-1 was prepared using the same method as in Synthesis Example A-4-3.

[0267] Then, under a nitrogen atmosphere, intermediate compound A-4-1 (15 g, 55.6 mmol), amine 18 (21.3 g, 58.4 mmol), and potassium phosphate (35.4 g, 166.8 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 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 20.6 g of compound 20. (Yield 62%, MS: [M+H)) + =599)

[0268] Synthesis Example 21

[0269]

[0270] First, in Synthesis Example A-4-3, 2-bromo-4-chloropyridine was used instead of 4-bromo-2-chloropyridine as the starting material. Otherwise, intermediate compound A-4-1 was prepared using the same method as in Synthesis Example A-4-3.

[0271] Then, under a nitrogen atmosphere, intermediate compound A-4-1 (15 g, 55.6 mmol), amine 19 (28.4 g, 58.4 mmol), and potassium phosphate (35.4 g, 166.8 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. 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 29.2 g of compound 21. (Yield 73%, MS: [M+H)) + =719)

[0272] Synthesis example 22

[0273]

[0274] First, in Synthesis Example A-4-3, 3-bromo-5-chloropyridine was used instead of 4-bromo-2-chloropyridine as the starting material. Otherwise, intermediate compound A-4-2 was prepared using the same method as in Synthesis Example A-4-3.

[0275] Then, under a nitrogen atmosphere, intermediate compound A-4-2 (15 g, 55.6 mmol), amine 20 (21.1 g, 58.4 mmol), and potassium phosphate (35.4 g, 166.8 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. 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, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 24.8 g of compound 22. (Yield 75%, MS: [M+H)) + =595)

[0276] Synthesis example 23

[0277]

[0278] First, in Synthesis Example A-4-3, 3-bromo-5-chloropyridine was used instead of 4-bromo-2-chloropyridine as the starting material. Otherwise, intermediate compound A-4-2 was prepared using the same method as in Synthesis Example A-4-3.

[0279] Then, under a nitrogen atmosphere, intermediate compound A-4-2 (15 g, 55.6 mmol), amine 21 (17.2 g, 58.4 mmol), and potassium phosphate (35.4 g, 166.8 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. 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 20 g of compound 23. (Yield 68%, MS: [M+H)) + =529)

[0280] Synthesis example 24

[0281]

[0282] First, in Synthesis Example A-4-3, 3-bromo-5-chloropyridine was used instead of 4-bromo-2-chloropyridine as the starting material. Otherwise, intermediate compound A-4-2 was prepared using the same method as in Synthesis Example A-4-3.

[0283] Then, under a nitrogen atmosphere, intermediate compound A-4-2 (15 g, 55.6 mmol), amine 22 (32.8 g, 58.4 mmol), and potassium phosphate (35.4 g, 166.8 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 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, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 29.2 g of compound 24. (Yield 66%, MS: [M+H)) + =795)

[0284] Synthesis example 25

[0285]

[0286] Under a nitrogen atmosphere, intermediate compound A-4-8 (15 g, 55.6 mmol), amine 23 (18.8 g, 58.4 mmol), and potassium phosphate (35.4 g, 166.8 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 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 18.8 g of compound 25. (Yield 61%, MS: [M+H)) + =555)

[0287] Comparative Example 1

[0288] ITO (indium tin oxide) is used in... 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.

[0289] 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 following A-1 compound at a concentration of 1.5%. The following 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 blocking layer is formed by vacuum evaporation of the following EB-1 compound. Next, the following RH-1 compound and the following Dp-39 compound are vacuum evaporated onto the above EB-1 evaporated film at a weight ratio of 98:2, thereby forming... A red luminescent layer of a certain thickness. On the aforementioned luminescent layer, a film thickness of... 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.

[0290] 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.

[0291]

[0292] Comparative Examples 2 to 6

[0293] The following compounds RH-2 to RH-6 were used instead of RH-1 as the host material for the red emitting layer, and the procedure was otherwise performed in the same manner as in Comparative Example 1, and the device performance was measured.

[0294]

[0295] Examples 1 to 25

[0296] Compounds 1 to 25, which were synthesized by the synthesis example, were used instead of the compound of Comparative Example 1 as the host material of the red light-emitting layer. Otherwise, the same method as that of Comparative Example 1 was used, and the device performance was measured.

[0297] For organic light-emitting devices manufactured using various compounds as red host materials, as described in Comparative Examples 1 to 6 and Examples 1 to 25 above, the driving voltage, current efficiency, and lifetime were measured, and the results are shown in Table 1 below.

[0298] [Table 1]

[0299]

[0300]

[0301] Referring to Table 1 above, it can be seen that the organic light-emitting device of the embodiment using the compound represented by the above chemical formula 1 as the host material of the light-emitting layer shows a lower driving voltage and improved efficiency and lifetime characteristics compared with the organic light-emitting device of the comparative example using a compound with a different structure.

[0302] [Symbol Explanation]

[0303] 1: Substrate 2: Anode

[0304] 3: Light-emitting layer 4: Cathode

[0305] 5: Hole injection layer; 6: Hole transport layer

[0306] 7: Light-emitting layer; 8: Electron injection and transport layer.

Claims

1. A compound represented by the following chemical formula 1: [Chemical Formula 1] In the chemical formula 1, One of X1 to X4 is CR, another is N, and the rest are independently CH or CD, X5 to X 10 Each independently can be CH or CD, or One of X1 to X4 is CR, and the rest are independently CH or CD, X5 to X 10 One of them is N, and the rest are independently CH or CD. in, R is a substituent represented by the following chemical formula 2. [Chemical Formula 2] In the chemical formula 2, L1 is a direct bond; substituted or unsubstituted C 6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O, and S. 2-60 heteroaryl, L2 is a direct bond; substituted or unsubstituted C 6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O, and S. 2-60 heteroaryl, L3 is a direct bond; substituted or unsubstituted C 6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O, and S. 2-60 heteroaryl, Ar1 represents substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O, and S. 2-60 Mixed aromatics, Ar2 is C with or without substitution. 6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O, and S. 2-60 Mixed aromatics, "Substituted or unsubstituted" means substituted by one or more substituents selected from deuterium, halogen groups, cyano, alkyl and aryl; or substituted by a substituent formed by two or more of the substituents linked together; or unsubstituted.

2. The compound according to claim 1, wherein, L1 is either directly bonded or phenylene. When L1 is phenylene, it is either unsubstituted or substituted with one or more deuterium atoms.

3. The compound according to claim 1, wherein, L2 can be directly bonded, phenylene, naphthylene, biphenylene, 9,9-dimethyl-fluorene, 9,9-diphenyl-fluorene, or carbazolyl. When L2 is phenylene, naphthylene, biphenylene, 9,9-dimethylfluorene, 9,9-diphenylfluorene, or carbazolyl, it is either unsubstituted or substituted with one or more deuterium groups.

4. The compound according to claim 1, wherein, L3 can be directly bonded, phenylene, naphthylene, biphenylene, 9,9-dimethyl-fluorene, or 9,9-diphenyl-fluorene. When L3 is phenylene, naphthylene, biphenylene, 9,9-dimethylfluorene, or 9,9-diphenylfluorene, it is either unsubstituted or substituted with one or more deuterium atoms.

5. The compound according to claim 1, wherein, Ar1 is phenyl, biphenyl, terphenyl, naphthyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, dibenzofuranyl, dibenzothiophenyl, 9-phenyl-carbazolyl, 9-naphthyl-carbazolyl, or 9,9'-spirobis[9H-fluorenyl]yl. Ar1 was either not substituted or was substituted by more than one deuterium.

6. The compound according to claim 1, wherein, Ar2 is phenyl, biphenyl, terphenyl, naphthyl, 9,9-dimethyl-fluorenyl, 9,9-diphenyl-fluorenyl, dibenzofuranyl, dibenzothiophenyl, 9-phenyl-carbazoleyl, or 9,9'-spirobis[9H-fluorenyl]yl. Ar2 is either not substituted or is substituted by more than one deuterium.

7. The compound according to claim 1, wherein, The compound is represented by any one of the following chemical formulas 1-1 to 1-4: [Chemical Formula 1-1] In the chemical formula 1-1, X2 to X 10 One of them is N, and the rest are independently CH or CD. L1 to L3, Ar1 and Ar2 are the same as defined in claim 1. [Chemical Formula 1-2] In the chemical formulas 1-2, X1 and X3 to X 10 One of them is N, and the rest are independently CH or CD. L1 to L3, Ar1 and Ar2 are the same as defined in claim 1. [Chemical Formulas 1-3] In the chemical formulas 1-3, X1, X2, and X4 to X 10 One of them is N, and the rest are independently CH or CD. L1 to L3, Ar1 and Ar2 are the same as defined in claim 1. [Chemical Formulas 1-4] In the chemical formulas 1-4, X1 to X3 and X5 to X 10 One of them is N, and the rest are independently CH or CD. L1 to L3, Ar1 and Ar2 are the same as defined in claim 1.

8. The compound according to claim 1, wherein, The compound represented by the chemical formula 1 is selected from any one of the following: 。 9. An organic light-emitting device, wherein, include: A first electrode, a second electrode disposed opposite to the first electrode, and an organic layer disposed between the first electrode and the second electrode, the organic layer comprising a compound according to any one of claims 1 to 8.

10. The organic light-emitting device according to claim 9, wherein, The organic layer containing the compound is a light-emitting layer.

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