Novel compound and organic light-emitting device comprising same

Abstract

The present invention relates to a novel compound having an asymmetric spirobiindan structure and to an organic light-emitting device comprising same. The novel compound of the present invention can be applied to, among organic material layers, particularly an electron transport layer, a hole blocking layer, or a charge generation layer. The novel compound of the present invention is characterized by having an asymmetric chiral structure which has, as a core, spirobiindane in which two indans are bonded in a spiro form, and in which benzene at only one of both sides has one or more extending substituents. This novel compound of the present invention has high thermal stability owing to the high rigidity of spirobiindan, and as a result, the lifespan of the device can be improved.

Description

Novel compound and organic light-emitting device containing the same

[0001] The present invention relates to a novel compound and an organic light-emitting device comprising the same.

[0002] Recently, the technology of organic light emitting devices (OLEDs), one of the flat panel display devices, has been developing rapidly.

[0003] An organic light-emitting device is a device that has an organic thin film layer including a light-emitting layer between an anode and a cathode, and emits light when holes and electrons injected into the light-emitting layer pair up and then disappear.

[0004] Compounds used in organic light-emitting devices require improved performance.

[0005] The purpose of the present invention is to provide a novel compound having an asymmetric spirobindan structure and an organic light-emitting device comprising the same.

[0006] The object of the present invention is achieved by an asymmetric spirobiindane compound represented by the following chemical formula 1 and an organic light-emitting device comprising the same.

[0007]

[0008] In the above chemical formula 1,

[0009] R1 to R4 are each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano group, nitro group, nitrile group, substituted or unsubstituted C1~C30 alkyl group, substituted or unsubstituted C2~C30 alkenyl group, substituted or unsubstituted C1~C30 alkynyl group, substituted or unsubstituted C3~C30 cycloalkyl group, substituted or unsubstituted C2~C30 heterocycloalkyl group, substituted or unsubstituted C1~C30 alkoxy group, substituted or unsubstituted C1~C30 sulfide group, substituted or unsubstituted C6~C30 aryl group, or substituted or unsubstituted C2~C30 heteroaryl group, and adjacent groups may or may not combine with each other to form a ring.

[0010] L is each independently a direct bond, a substituted or unsubstituted C6~C30 arylene group, or a substituted or unsubstituted C2~C30 heteroarylene group,

[0011] Ar is each independently selected from the group consisting of deuterium, halogen, cyano group, nitro group, nitrile group, substituted or unsubstituted C1~C30 alkyl group, substituted or unsubstituted C2~C30 alkenyl group, substituted or unsubstituted C1~C30 alkynyl group, substituted or unsubstituted C3~C30 cycloalkyl group, substituted or unsubstituted C2~C30 heterocycloalkyl group, substituted or unsubstituted C1~C30 alkoxy group, substituted or unsubstituted C1~C30 sulfide group, substituted or unsubstituted C2~C30 amine group, substituted or unsubstituted C6~C30 aryl group, or substituted or unsubstituted C2~C30 heteroaryl group,

[0012] n is an integer from 1 to 4.

[0013] According to the present invention, an asymmetric spirobiindane compound and an organic light-emitting device comprising the same are provided. The novel compound according to the present invention can be applied to an organic layer of an organic light-emitting device, particularly an electron transport layer, a hole blocking layer, or a charge generation layer, thereby enabling the implementation of a device with improved performance.

[0014] In this specification, when a part is said to 'include' a certain component, this does not mean that other components are excluded, but rather that other components may be included, unless otherwise specifically stated.

[0015] In this specification, when it is said that a member is located 'on' another member, this includes not only cases where a member is in contact with another member, but also cases where another member exists between the two members.

[0016] In this specification, examples of substituents are described below, but are not limited thereto.

[0017] As used herein, the term "substitution" refers to the replacement of a hydrogen atom bonded to a carbon atom of a compound with another substituent. The position of substitution is not particularly limited as long as it is a position where substitution is possible, and when substitution is made with two or more substituents, the substituents may be the same or different.

[0018] In this specification, the term 'substituted or unsubstituted' means that it is substituted with one or more substituents selected from the group consisting of deuterium, a halogen group, a cyano group, a nitro group, a nitrile group, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthioxy group, an arylthioxy group, an amine group, a phosphine oxide group, an aryl group, and a heteroaryl group, or is substituted with a substituent in which two or more substituents selected from the above group are connected, or has no substituents, and the selected substituents may or may not form a ring by combining with each other. The substituent in which two or more substituents are connected may be, as an example, a biphenyl group. That is, the biphenyl group corresponds to an aryl group and may also correspond to a substituent in which two phenyl groups are connected.

[0019] In the present specification, the alkyl group may be straight-chain or branched, and specific examples thereof include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 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-ethylpropyl, 1,1-dimethylpropyl, isohexyl, These include, but are not limited to, 2-methylpentyl, 4-methylhexyl, and 5-methylhexyl.

[0020] In the present specification, specific examples of cycloalkyl groups include, but are not limited to, 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.

[0021] In the present specification, the aryl group may be monocyclic or polycyclic. In the case of a monocyclic aryl group, specific examples thereof include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, etc. In the case of a polycyclic aryl group, specific examples thereof include, but are not limited to, a naphthyl group, anthracenyl group, a phenanthrenyl group, a triphenylenyl group, a pyrenyl group, a fluorenyl group, etc.

[0022] In the present specification, a heteroaryl group includes at least one atom other than carbon, i.e., a heteroatom, and specifically may include at least one atom selected from the group consisting of O, N, S, and Se. The heteroaryl group may also be monocyclic or polycyclic. Specific examples include a thiophenyl group, a furanyl group, a pyrrolyl group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a pyridinyl group, a bipyridinyl group, a pyrimidinyl group, a pyrimidinyl group, a pyrazinyl group, a quinolinyl group, a quinazolyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, a pyridopyrazinyl group, a pyrazinopyrazinyl group, a pyridoindolyl group, a benzothienopyrimidyl group, an indenocarbazolyl group, an isoquinolinyl group, an indolyl group, a carbazolyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a benzocarbazolyl group, a benzothiophenyl group, Examples thereof include, but are not limited to, a dibenzothiophenyl group, a benzofuranyl group, a phenanthridinyl group, a phenanthrolinyl group, an isoxazolyl group, a thiadiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group.

[0023] In the present specification, the amine group may be selected from the group consisting of -NH2, an alkylamine group, an N-alkylarylamine group, an arylamine group, an N-arylheteroarylamine group, an N-alkylheteroarylamine group, and a heteroarylamine group.

[0024] In the chemical formula or structural formula in this specification, * or indicates the binding position.

[0025] The novel compound of the present invention is described below.

[0026] The novel compound of the present invention is a compound having an asymmetric spirobiindane structure, and is specifically represented by the following chemical formula 1.

[0027]

[0028] In the above chemical formula 1,

[0029] R1 to R4 are each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano group, nitro group, nitrile group, substituted or unsubstituted C1~C30 alkyl group, substituted or unsubstituted C2~C30 alkenyl group, substituted or unsubstituted C1~C30 alkynyl group, substituted or unsubstituted C3~C30 cycloalkyl group, substituted or unsubstituted C2~C30 heterocycloalkyl group, substituted or unsubstituted C1~C30 alkoxy group, substituted or unsubstituted C1~C30 sulfide group, substituted or unsubstituted C6~C30 aryl group, or substituted or unsubstituted C2~C30 heteroaryl group, and adjacent groups may or may not combine with each other to form a ring.

[0030] L is each independently a direct bond, a substituted or unsubstituted C6~C30 arylene group, or a substituted or unsubstituted C2~C30 heteroarylene group,

[0031] Ar is each independently selected from the group consisting of deuterium, halogen, cyano group, nitro group, nitrile group, substituted or unsubstituted C1~C30 alkyl group, substituted or unsubstituted C2~C30 alkenyl group, substituted or unsubstituted C1~C30 alkynyl group, substituted or unsubstituted C3~C30 cycloalkyl group, substituted or unsubstituted C2~C30 heterocycloalkyl group, substituted or unsubstituted C1~C30 alkoxy group, substituted or unsubstituted C1~C30 sulfide group, substituted or unsubstituted C2~C30 amine group, substituted or unsubstituted C6~C30 aryl group, or substituted or unsubstituted C2~C30 heteroaryl group,

[0032] n is an integer from 1 to 4.

[0033] The novel compound of the present invention is characterized by having a core of spirobiindan, in which two indans are bonded in a spiro form, and an asymmetric chiral structure in which at least one substituent extends to only one of the benzenes. The novel compound of the present invention has high thermal stability due to the high rigidity of spirobiindan, which can ultimately improve the lifespan of the device. In particular, it is characterized by having an asymmetric structure in which the substituent extends to only one benzene, and compared to a structure in which the substituent extends to both benzenes, it has a shallow LUMO energy level, so that electrons can be smoothly transferred to the light-emitting layer, and in addition, since the light-emitting region is located within the light-emitting layer due to the wide energy band gap, it has desirable effects in terms of reducing the driving voltage and increasing the efficiency and lifespan.

[0034] More specifically, the chemical formula 1 may be selected from the following chemical formulas 1-1 to 1-4. In this way, n in chemical formula 1 may be 1. According to one embodiment of the present invention, among chemical formulas 1-1 to 1-4, chemical formula 1-1 or chemical formula 1-2 may be preferable in terms of improving electron transfer characteristics, and chemical formula 1-2 may be the most preferable.

[0035]

[0036]

[0037] In the above chemical formulas 1-1 to 1-4,

[0038] R1 to R4, L and Ar are the same as defined in the above chemical formula 1.

[0039] The above R1 to R4 may specifically be hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C10 aryl group, or a substituted or unsubstituted C2 to C10 heteroaryl group, and more specifically may be hydrogen, deuterium, a methyl group, or a phenyl group, and even more specifically, a methyl group may be preferable in terms of improving the electron transfer characteristics by aligning the stacking "sleeve*" of the molecule in one direction. R1 to R4 may be the same or different from each other.

[0040] Meanwhile, the above Ar is a substituent that is bonded to one benzene of the spirobindan and plays a role in electron transfer, and may have the characteristic of improving electron transfer depending on Ar.

[0041] Ar may be specifically deuterium, a substituted or unsubstituted C1~C30 alkyl group, a substituted or unsubstituted C2~C30 amine group, a substituted or unsubstituted C6~C30 aryl group, or a substituted or unsubstituted C2~C30 heteroaryl group. More specifically, it may be a substituted or unsubstituted C6~C30 aryl group, or a substituted or unsubstituted C2~C30 heteroaryl group. Even more specifically, it may be a substituted or unsubstituted C6~C20 aryl group, or a substituted or unsubstituted C2~C20 heteroaryl group.

[0042] According to one embodiment of the present invention, Ar may be selected from the following structural formulas A-1 to A-5.

[0043]

[0044] In the above structural formulas A-1 to A-5,

[0045] a1 to a5 are each independently N or CR5,

[0046] b1 to b8 are each independently N or CR6, and the binding position is C,

[0047] c1 to c10 are each independently N or CR7, and the binding position is C,

[0048] d1 to d5 are each independently N or CR8, and the binding position is C,

[0049] d6 is O, S, N or NR9, but if it is N, it is a binding site,

[0050] e1 to e8 are each independently N or CR10, and the binding position is C,

[0051] e9 is O, S, N or NR11, but if it is N, it is a binding site,

[0052] At this time, R5 to R11 can each independently be hydrogen, deuterium, a substituted or unsubstituted C1~C30 alkyl group, a substituted or unsubstituted C6~C30 aryl group, or a substituted or unsubstituted C2~C30 heteroaryl group, and more specifically, can be hydrogen, a substituted or unsubstituted C1~C20 alkyl group, a substituted or unsubstituted C6~C20 aryl group, or a substituted or unsubstituted C2~C20 heteroaryl group, and even more specifically, can be hydrogen, a substituted or unsubstituted C6~C15 aryl group, or a substituted or unsubstituted C2~C15 heteroaryl group.

[0053] In the definitions of the above structural formulas A-1 to A-5, the term “bonding position” means the position bonded to the linking group L.

[0054] According to one embodiment of the present invention, it may be preferable that Ar is a nitrogen-containing substituent including one or more nitrogen atoms N. This is because it can exhibit high electron mobility due to the electron-withdrawing property of the nitrogen-containing substituent.

[0055] Therefore, according to one embodiment, in the structural formula A-1, at least one of a1 to a5 may be N, or at least one of R5 may include N. Also, according to one embodiment, in the structural formula A-2, at least one of b1 to b8 may be N, or at least one of R6 may include N. Also, according to one embodiment, in the structural formula A-3, at least one of c1 to c10 may be N, or at least one of R7 may include N. Also, according to one embodiment, in the structural formula A-4, at least one of d1 to d5 may be N, at least one of R8 may include N, or d6 may be N or NR9. Also, according to one embodiment, in the structural formula A-5, at least one of e1 to e8 may be N, at least one of R10 may include N, or e9 may be N or NR11.

[0056] More specifically, according to an embodiment of the present invention, Ar may be preferably of the structural formula A-1 in terms of electron transfer, and the structural formula A-1 may be specifically any one of the structural formulas A-1-1 to A-1-11 below. According to an embodiment of the present invention, it may be most preferable that Ar is any one selected from among the structural formulas below, particularly phenyl structural formula A-1-1, triazine structural formula A-1-2, pyrimidine structural formulas A-1-3, A-1-5 and A-1-8, and pyridine structural formulas A-1-9 to A-1-11.

[0057]

[0058] In the above structural formulas A-1-1 to A-1-11, R5 has the same definition as in the above structural formula A-1, and o is each independently an integer from 0 to 2, and can be specifically 1 or 2.

[0059] Specifically, R5 may be a substituted or unsubstituted C6~C20 aryl group or a substituted or unsubstituted C2~C20 heteroaryl group, and according to one embodiment, R5 may each independently be a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracene group, a phenanthrene group, a dimethylfluorene group, a diphenylfluorene group, a spirobifluorene group, a quinoline group, an isoquinoline group, a quinazoline group, a quinoxaline group, a phthalazine group, a naphthyridine group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a benzoimidazole group, a benzoxazole group, a benzothiazole group, a benzofuran group, a benzothiophene group, a dibenzofuran group, a dibenzothiophene group, a phenanthroline group, or a combination of one or more thereof. Here, the meaning of one or more combinations may specifically mean two or three or more combinations (bondings) that are the same or different, and may include, for example, a combination of a phenyl group and a pyridine group, a combination of two pyridine groups, a combination of a phenyl group and two pyridine groups, a combination of a phenyl group and a naphthyridine group, a combination of a phenyl group and a phenanthroline group, etc. In this case, the bonding order or bonding position is not particularly limited and may include all bonding orders or bonding positions that can be synthesized.

[0060] Meanwhile, when the above o is 2, it is desirable for the two R5s to have a meta bonding position as in the examples below in terms of electron transfer, and at this time, the R5s may be the same or different from each other.

[0061]

[0062] Meanwhile, as mentioned above, since it is preferable that Ar is a nitrogen-containing substituent containing one or more nitrogen atoms N, in the case of the structural formula A-1-1 above, which is phenyl, it is preferable that o is 1 or more, and at this time, R5 is one or a combination of one or more of the above-mentioned substituents, but it is preferable that it is a substituent that necessarily contains one or more N.

[0063] Meanwhile, the above structural formula A-2 may be a quinoline group, an isoquinoline group, a quinazoline group, a quinoxaline group, a phthalazine group or a naphthyridine group substituted or unsubstituted with one or more substituents R6 according to one embodiment of the present invention.

[0064] Meanwhile, the above structural formula A-3 may be a benzoquinoline group or phenanthroline group substituted or unsubstituted with one or more substituents R7 according to one embodiment of the present invention.

[0065] Meanwhile, the above structural formula A-4 may be a benzimidazole group, benzoxazole group or benzothiazole group substituted or unsubstituted with one or more substituents R8 according to one embodiment of the present invention.

[0066] Meanwhile, the above structural formula A-5 may be a dibenzofuran group, a dibenzothiophene group, a benzofuropyridine or a benzothianopyridine substituted or unsubstituted with one or more substituents R10 according to one embodiment of the present invention.

[0067] At this time, R6 to R10 may be hydrogen, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracene group, a phenanthrene group, a dimethylfluorene group, a diphenylfluorene group, a spirobifluorene group, a quinoline group, an isoquinoline group, a quinazoline group, a quinoxaline group, a phthalazine group, a naphthyridine group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a benzoimidazole group, a benzoxazole group, a benzothiazole group, a benzofuran group, a benzothiophene group, a dibenzofuran group, a dibenzothiophene group, a phenanthroline group, or a combination of one or more of these, but is not particularly limited thereto.

[0068] Meanwhile, the above L may be specifically a direct bond, a C6~C20 arylene group, or a C2~C20 heteroarylene group. More specifically, it may be a direct bond, or a combination of one or two or more of the structural formulae L-1 to L-41 below. Here, the meaning of a combination of two or more may mean a combination (bonding) of two or more identical or different structural formulae, and for example, it may include a combination of two structural formulae L-1, a combination of structural formulae L-1 and L-2, a combination of two structural formulae L-1 and L-4, a combination of structural formulae L-1 and L-32, etc. In this case, the bonding order or bonding position is not particularly limited and may include all bonding orders or bonding positions that can be synthesized.

[0069]

[0070] According to one embodiment of the present invention, the novel compound of the present invention represented by the chemical formula 1 may be selected from compounds 1 to 246 below.

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087] The novel compound of the present invention described so far is characterized by having a core of spirobiindan, in which two indans are bonded in a spiro form, and an asymmetric chiral structure in which at least one substituent extends only to one of the benzenes on both sides. The novel compound of the present invention has high thermal stability due to the high rigidity of spirobiindan, and as a result, has the advantage of improving the lifespan of the device. In particular, due to the asymmetric structure in which the substituent extends only to one benzene, it has the characteristic of having a shallow LUMO energy level compared to a structure in which the substituent extends to both benzenes, so that electrons are smoothly transferred to the light-emitting layer, and since the light-emitting region is located within the light-emitting layer due to the wide energy band gap, there are advantages in terms of reduced driving voltage and increased efficiency and lifespan.

[0088] Meanwhile, the novel compound of the present invention described above can be applied to an organic light-emitting device including a first electrode, a second electrode, and one or more organic layers disposed between the first electrode and the second electrode.

[0089] Below, the organic light-emitting device is described in more detail.

[0090] An organic light-emitting device has an organic layer positioned between first electrodes. The organic layer may be composed of one or more organic layers, and specifically, may be composed of one or more layers selected from known organic layers that constitute a light-emitting portion, such as a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer.

[0091] The hole injection layer (HIL) is a layer that injects holes from an electrode. The hole injection material is preferably a compound that has the ability to transport holes, has an excellent hole injection effect at the anode, an excellent hole injection effect for the light-emitting layer or light-emitting material, prevents the movement of excitons generated in the light-emitting layer to the electron injection layer or electron injection material, and has excellent thin film forming ability.

[0092] The hole transport layer (HTL) is a layer that receives holes from the hole injection layer and transports them to the light-emitting layer. As the hole transport material, a material with high hole mobility is suitable, as it can transport holes from the anode or the hole injection layer and move them to the light-emitting layer.

[0093] The light-emitting material used in the emission layer (EML) is a material that can emit light in the visible light range by transporting holes and electrons from the hole transport layer and the electron transport layer, respectively, and combining them. A material with good quantum efficiency for fluorescence or phosphorescence is preferable. The emission layer may include a host material and a dopant material.

[0094] The electron transport layer (ETL) is a layer that receives electrons from the electron injection layer and transports them to the light-emitting layer. The electron transport material is a material that can easily receive electrons from the cathode and transfer them to the light-emitting layer, and a material with high electron mobility is preferable.

[0095] The electron injection layer (EIL) is a layer that injects electrons from an electrode, has the ability to transport electrons, has an electron injection effect from a cathode, has an excellent electron injection effect for a light-emitting layer or light-emitting material, prevents movement of excitons generated in the light-emitting layer to the hole injection layer, and is preferably a compound having excellent thin-film forming ability.

[0096] The organic layer may further include a hole blocking layer (HBL). The HBL may be positioned between the light-emitting layer and the electron transport layer, and reduces the problem of holes in the hole injection layer invading the electron transport layer.

[0097] Among the organic layers of such organic light-emitting devices, the novel compound of the present invention can be particularly applied to an electron transport layer or a hole blocking layer.

[0098] Meanwhile, the composition of the organic light-emitting device can vary. For example, it can be a tandem structure in which multiple light-emitting layers (or light-emitting units) are provided, and in the case of a tandem structure, a charge generation layer (CGL) can be further included as one of the organic layers in addition to the above-mentioned organic layers. In general, the charge generation layer is composed of multiple layers including an N-type charge generation layer and a P-type charge generation layer, but is not limited thereto and can also be composed of a single layer.

[0099] The novel compound of the present invention can also be applied to a charge generation layer of such a tandem organic light-emitting device, and specifically, can be applied as a host of an N-type charge generation layer.

[0100] An organic light-emitting device in which the novel compound according to the present invention is applied to an electron transport layer, a hole blocking layer, or a charge generation layer can realize low voltage, high efficiency, high brightness, and long life.

[0101] The present invention is described in more detail below through synthetic examples, embodiments, and experimental examples.

[0102] Synthetic example

[0103] Synthesis of intermediate-1

[0104]

[0105] In a 250 mL round-bottomed flask, add 3,3'-(propane-2,2-diyl)diphenol (10.0 g, 43.8 mmol) and methansulfonic acid (37.9 g, 394.2 mmol) and reflux at 60°C for 12 hours. After the reaction was complete, cool to room temperature and quench with water. Extract with dichloromethane and water. The organic layer was dried with MgSO4, concentrated under reduced pressure, and recrystallized with EtOH to obtain intermediate-1 (4.8 g, 35%).

[0106] Synthesis of intermediate-2

[0107]

[0108] Intermediate-1 (4.8 g, 15.6 mmol), trifluoromethanesulfonic anhydride (11.0 g, 38.9 mmol), and pyridine (4.9 g, 62.3 mmol) were added to 60 mL of dichloromethane in a 250 mL round-bottomed flask and stirred at room temperature for 12 hours. After the reaction was completed, the mixture was quenched with an aqueous NaHCO3 solution and extracted with dichloromethane and water. The organic layer was dried over MgSO4, concentrated under reduced pressure, and recrystallized with EtOH to obtain Intermediate-2 (7.9 g, 88%).

[0109] Synthesis of intermediate-3

[0110]

[0111] In a 500 mL round-bottomed flask, intermediate-2 (7.9 g, 13.8 mmol) and 2,4-diphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazine (7.2 g, 16.6 mmol), Pd(pph3)4 (0.8 g, 0.7 mmol), and K2CO3 (5.7 g, 41.4 mmol) were added to 140 mL of 1,4-dioxane and 70 mL of H2O and stirred under reflux for 11 hours. After the reaction was completed, extraction was performed using dichloromethane and water. The organic layer was dried with MgSO4 and concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography to obtain the target compound, intermediate-3 (7.7 g, 76%).

[0112] Synthetic Example 1. Synthesis of Compound 1

[0113]

[0114] In a 250 mL round-bottomed flask, intermediate-6 (7.7 g, 10.5 mmol), Pd(OAc)2 (0.2 g, 1.1 mmol), triphenylphosphine (0.6 g, 2.1 mmol), triethylamine (6.4 g, 63.1 mmol), and formic acid (1.9 g, 42.1 mmol) were added to 110 mL of DMF and heated and stirred at 80 °C for 12 hours. After the reaction was completed, the mixture was extracted using dichloromethane and water. The organic layer was dried with MgSO4 and concentrated under reduced pressure. The resulting filtrate was purified by column chromatography and recrystallized to obtain compound 1 (4.9 g, 80%).

[0115] Synthesis of intermediate-4

[0116]

[0117] In a 1 L round-bottomed flask, dissolve 2-(3-bromophenyl)-4,6-diphenylpyrimidine (20.0 g, 51.6 mmol), bis(pinacolato)diboron (14.4 g, 56.8 mmol), potassium acetate (15.2 g, 14.9 mmol), and Pd(dppf)Cl2 (1.1 g, 1.5 mmol) in 340 mL of 1,4-dioxane, and reflux for 8 hours. After the reaction was completed, cool to room temperature, and the reaction solution was filtered under reduced pressure through Celite to obtain a filtrate. The filtrate was purified by column chromatography to obtain intermediate-4 (18.9 g, 84%).

[0118] Synthesis of intermediate-5

[0119]

[0120] In a 1 L round bottom flask, add intermediate-4 (18.9 g, 43.5 mmol), 1-bromo-4-iodobenzene (10.3 g, 36.5 mmol), tetrakis(triphenylphophine)palladium (2.5 g, 2.2 mmol), and K2CO3 (18.0 g, 130.5 mmol), dissolve 400 mL of 1,4-dioxane, and 200 mL of H2O, and reflux for 8 hours. After the reaction is complete, cool to room temperature and extract using dichloromethane and water. The organic layer was dried over MgSO4, concentrated under reduced pressure, and the obtained filtrate was purified by column chromatography to obtain intermediate-5 (15.3 g, 76%).

[0121] Synthesis of intermediate-6

[0122]

[0123] In a 500 mL round-bottomed flask, intermediate-5 (15.3 g, 33.0 mmol), bis(pinacolato)diboron (9.2 g, 36.3 mmol), potassium acetate (9.7 g, 99.1 mmol), and Pd(dppf)Cl2 (0.7 g, 1.0 mmol) were dissolved in 260 mL of 1,4-dioxane, and stirred under reflux for 8 hours. After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was filtered under reduced pressure through Celite to obtain a filtrate. The filtrate was purified by column chromatography to obtain intermediate-6 (18.9 g, 84%).

[0124] Synthesis of intermediate-7

[0125]

[0126] In a 1 L round bottom flask, intermediate-6 (13.1 g, 25.7 mmol), intermediate-2 (14.0 g, 24.4 mmol), tetrakis(triphenylphophine)palladium (1.5 g, 1.3 mmol), and K2CO3 (10.6 g, 77.0 mmol) were added to 250 mL of 1,4-dioxane and 120 mL of H2O and refluxed for 11 hours. After the reaction was complete, cool to room temperature and extract using dichloromethane and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure, and the obtained filtrate was purified by column chromatography to obtain intermediate-7 (14.2 g, 69%).

[0127] Synthetic Example 2. Synthesis of Compound 48

[0128]

[0129] In a 500 mL round-bottomed flask, intermediate-7 (14.2 g, 19.4 mmol), Pd(OAc)2 (0.4 g, 1.9 mmol), triphenylphosphine (1.0 g, 3.9 mmol), triethylamine (11.8 g, 116.4 mmol), and formic acid (3.6 g, 77.6 mmol) were added to 190 mL of DMF and heated and stirred at 80 °C for 12 hours. After the reaction was completed, the mixture was extracted using dichloromethane and water. The organic layer was dried with MgSO4 and concentrated under reduced pressure. The resulting filtrate was purified by column chromatography and recrystallized to obtain compound 48 (10.5 g, 82%).

[0130] Synthesis of intermediate-8

[0131]

[0132] In a 500 mL round-bottomed flask, dissolve 4'-(4-bromophenyl)-2,2':6',2''-terpyridine (10.0 g, 25.8 mmol), bis(pinacolato)diboron (7.2 g, 28.3 mmol), potassium acetate (7.6 g, 77.3 mmol), and Pd(dppf)Cl2 (0.6 g, 0.8 mmol) in 170 mL of 1,4-dioxane, and reflux for 8 hours. After the reaction was completed, cool to room temperature, and the reaction solution was filtered under reduced pressure through Celite to obtain a filtrate. The filtrate was purified by column chromatography to obtain intermediate-8 (8.3 g, 74%).

[0133] Synthesis of intermediate-9

[0134]

[0135] In a 500 mL round-bottomed flask, intermediate-8 (8.3 g, 19.1 mmol), intermediate-2 (10.4 g, 18.1 mmol), tetrakis(triphenylphophine)palladium (1.1 g, 1.0 mmol), and K2CO3 (7.9 g, 57.2 mmol) were added to 190 mL of 1,4-dioxane and 90 mL of H2O, and stirred under reflux for 11 hours. After the reaction was complete, the mixture was cooled to room temperature and extracted with dichloromethane and water. The organic layer was dried over MgSO4, concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography to obtain intermediate-9 (11.1 g, 80%).

[0136] Synthetic Example 3. Synthesis of Compound 143

[0137]

[0138] In a 500 mL round-bottomed flask, intermediate-12 (11.1 g, 15.2 mmol), Pd(OAc)2 (0.3 g, 1.5 mmol), triphenylphosphine (0.8 g, 3.0 mmol), triethylamine (9.2 g, 91.0 mmol), and formic acid (2.8 g, 60.7 mmol) were added to 150 mL of DMF and refluxed at 80 °C for 12 hours. After the reaction was completed, the mixture was extracted using dichloromethane and water. The organic layer was dried with MgSO4, concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography and recrystallized to obtain compound 143 (5.9 g, 67%).

[0139] Synthesis of intermediate-10

[0140]

[0141] In a 250 mL round-bottomed flask, bisphenol A (20.0 g, 87.6 mmol) was added methansulfonic acid (75.8 g, 788.5 mmol) and refluxed at 60°C for 12 hours. After the reaction was complete, cool to room temperature and quench with water. Extract with dichloromethane and water. The organic layer was dried with MgSO4, concentrated under reduced pressure, and recrystallized with EtOH to obtain intermediate-10 (17.3 g, 64%).

[0142] Synthesis of intermediate-11

[0143]

[0144] Intermediate-10 (17.3 g, 56.1 mmol), trifluoromethanesulfonic anhydride (39.6 g, 140.2 mmol), and pyridine (17.7 g, 224.4 mmol) were added to a 250 mL round-bottomed flask and stirred at room temperature for 12 hours in 60 mL of dichloromethane. After the reaction was complete, the mixture was quenched with an aqueous NaHCO3 solution and extracted with dichloromethane and water. The organic layer was dried over MgSO4, concentrated under reduced pressure, and recrystallized with EtOH to obtain intermediate-11 (26.1 g, 81%).

[0145] Synthesis of intermediate-12

[0146]

[0147] In a 500 mL round-bottomed flask, intermediate-11 (10.0 g, 17.5 mmol) and 2,4-diphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazine (8.0 g, 18.3 mmol), Pd(pph3)4 (1.0 g, 0.9 mmol), and K2CO3 (7.2 g, 52.4 mmol) were added to 170 mL of 1,4-dioxane and 85 mL of H2O and stirred under reflux for 11 hours. After the reaction was completed, the mixture was extracted using dichloromethane and water. The organic layer was dried with MgSO4 and concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography to obtain intermediate-12 (8.3 g, 65%).

[0148] Synthetic Example 4. Synthesis of Compound 196

[0149]

[0150] In a 250 mL round-bottomed flask, intermediate-12 (8.3 g, 11.3 mmol), Pd(OAc)2 (0.3 g, 1.1 mmol), triphenylphosphine (0.6 g, 2.3 mmol), triethylamine (6.9 g, 68.0 mmol), and formic acid (2.1 g, 45.4 mmol) were added to 110 mL of DMF and heated and stirred at 80 °C for 12 hours. After the reaction was completed, the mixture was extracted using dichloromethane and water. The organic layer was dried with MgSO4 and concentrated under reduced pressure. The resulting filtrate was purified by column chromatography and recrystallized to obtain compound 196 (5.1 g, 77%).

[0151] Synthesis of intermediate-13

[0152]

[0153] In a 500 mL round-bottomed flask, intermediate-11 (10.0 g, 17.5 mmol) and 2,4-diphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazine (8.0 g, 18.3 mmol), Pd(pph3)4 (1.0 g, 0.9 mmol), and K2CO3 (7.2 g, 52.4 mmol) were added to 170 mL of 1,4-dioxane and 85 mL of H2O and stirred under reflux for 11 hours. After the reaction was completed, the mixture was extracted using dichloromethane and water. The organic layer was dried with MgSO4 and concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography to obtain intermediate-13 (7.9 g, 62%).

[0154] Synthetic Example 5. Synthesis of Compound 198

[0155]

[0156] In a 250 mL round-bottomed flask, intermediate-13 (7.9 g, 10.8 mmol), Pd(OAc)2 (0.2 g, 1.1 mmol), triphenylphosphine (0.6 g, 2.2 mmol), triethylamine (6.6 g, 65.0 mmol), and formic acid (2.0 g, 43.2 mmol) were added to 110 mL of DMF and heated and stirred at 80 °C for 12 hours. After the reaction was completed, the mixture was extracted using dichloromethane and water. The organic layer was dried with MgSO4, concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography and recrystallized to obtain compound 198 (5.1 g, 76%).

[0157] Synthesis of intermediate-14

[0158]

[0159] In a 1 L round bottom flask, 2-bromo-4,6-diphenyl-1,3,5-triazine (20.0 g, 64.1 mmol), (4-bromonaphthalen-1-yl)boronic acid (16.9 g, 67.3 mmol), tetrakis(triphenylphophine)palladium (3.7 g, 3.2 mmol), and K2CO3 (26.6 g, 192.2 mmol) were added to 320 mL of 1,4-dioxane and 160 mL of H2O, and stirred under reflux for 11 hours. After the reaction was complete, cool to room temperature and extract using dichloromethane and water. The organic layer was dried over MgSO4, concentrated under reduced pressure, and the obtained filtrate was purified by column chromatography to obtain intermediate-14 (16.8 g, 60%).

[0160] Synthesis of intermediate-15

[0161]

[0162] In a 500 mL round-bottomed flask, intermediate-14 (16.8 g, 38.3 mmol), bis(pinacolato)diboron (10.7 g, 42.2 mmol), potassium acetate (11.3 g, 115.0 mmol), and Pd(dppf)Cl2 (0.8 g, 1.1 mmol) were dissolved in 290 mL of 1,4-dioxane and stirred under reflux for 8 hours. After the reaction was completed, it was cooled to room temperature and the reaction solution was filtered under reduced pressure through Celite to obtain a filtrate. This filtrate was purified by column chromatography to obtain intermediate-15 (12.6 g, 68%).

[0163] Synthesis of intermediate-16

[0164]

[0165] In a 500 mL round-bottomed flask, intermediate-15 (12.6 g, 26.0 mmol), intermediate-11 (14.1 g, 24.7 mmol), Pd(pph3)4 (1.5 g, 1.3 mmol), and K2CO3 (10.8 g, 77.9 mmol) were added to 130 mL of 1,4-dioxane and 65 mL of H2O, and stirred under reflux for 11 hours. After the reaction was completed, the mixture was extracted using dichloromethane and water. The organic layer was dried with MgSO4, concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography to obtain intermediate-16 (14.3 g, 70%).

[0166] Synthetic Example 6. Synthesis of Compound 201

[0167]

[0168] In a 500 mL round-bottomed flask, intermediate-16 (14.3 g, 18.3 mmol), Pd(OAc)2 (0.4 g, 1.8 mmol), triphenylphosphine (1.0 g, 3.7 mmol), triethylamine (11.1 g, 109.7 mmol), and formic acid (3.4 g, 73.2 mmol) were added to 180 mL of DMF and heated and stirred at 80 °C for 12 hours. After the reaction was completed, the mixture was extracted using dichloromethane and water. The organic layer was dried with MgSO4 and concentrated under reduced pressure. The resulting filtrate was purified by column chromatography and recrystallized to obtain compound 201 (7.9 g, 68%).

[0169] Synthesis of intermediate-17

[0170]

[0171] In a 1 L round bottom flask, 1,3-dibromo-5-chlorobenzene (20.0 g, 74.0 mmol), pyridin-3-ylboronic acid (19.1 g, 155.4 mmol), Pd(pph3)4 (4.3 g, 3.7 mmol), and K2CO3 (30.7 g, 221.9 mmol) were added to 370 mL of 1,4-dioxane and 185 mL of H2O, and stirred under reflux for 11 hours. After the reaction was completed, the mixture was extracted using dichloromethane and water. The organic layer was dried with MgSO4, concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography to obtain intermediate-17 (12.6 g, 64%).

[0172] Synthesis of intermediate-18

[0173]

[0174] In a 500 mL round-bottomed flask, intermediate-17 (12.6 g, 47.2 mmol), bis(pinacolato)diboron (13.2 g, 52.0 mmol), potassium acetate (13.9 g, 141.7 mmol), and Pd(dppf)Cl2 (1.0 g, 1.4 mmol) were dissolved in 210 mL of 1,4-dioxane, and stirred under reflux for 8 hours. After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was filtered under reduced pressure through Celite to obtain a filtrate. The filtrate was purified by column chromatography to obtain intermediate-18 (12.1 g, 71%).

[0175] Synthesis of intermediate-19

[0176]

[0177] In a 1 L round bottom flask, intermediate-18 (22.1 g, 33.8 mmol), 1,3-dibromo-5-chlorobenzene (4.4 g, 16.2 mmol), Pd(pph3)4 (2.0 g, 1.7 mmol), and K2CO3 (14.0 g, 101.3 mmol) were added to 170 mL of 1,4-dioxane and 85 mL of H2O, and stirred under reflux for 11 hours. After the reaction was completed, the mixture was extracted using dichloromethane and water. The organic layer was dried with MgSO4 and concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography to obtain intermediate-19 (10.1 g, 52%).

[0178] Synthesis of intermediate-20

[0179]

[0180] Intermediate-19 (10.1 g, 17.6 mmol), bis(pinacolato)diboron (4.9 g, 19.4 mmol), potassium acetate (5.2 g, 52.9 mmol), and Pd(dppf)Cl2 (0.4 g, 0.5 mmol) were dissolved in 170 mL of 1,4-dioxane in a 500 mL round-bottomed flask and stirred under reflux for 8 hours. After the reaction was completed, the mixture was cooled to room temperature and the reaction solution was filtered under reduced pressure through Celite to obtain a filtrate. The filtrate was purified by column chromatography to obtain intermediate-20 (8.0 g, 68%).

[0181] Synthesis of intermediate-21

[0182]

[0183] In a 500 mL round-bottomed flask, intermediate-20 (8.0 g, 12.0 mmol), intermediate-11 (6.6 g, 11.4 mmol), Pd(pph3)4 (0.7 g, 0.6 mmol), and K2CO3 (5.0 g, 36.1 mmol) were added to 120 mL of 1,4-dioxane and 60 mL of H2O, and stirred under reflux for 11 hours. After the reaction was completed, the mixture was extracted using dichloromethane and water. The organic layer was dried with MgSO4, concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography to obtain intermediate-21 (6.3 g, 54%).

[0184] Synthetic Example 7. Synthesis of Compound 242

[0185]

[0186] In a 250 mL round-bottomed flask, intermediate-21 (6.3 g, 6.6 mmol), Pd(OAc)2 (0.2 g, 0.7 mmol), triphenylphosphine (0.3 g, 1.3 mmol), triethylamine (4.0 g, 39.3 mmol), and formic acid (1.2 g, 26.2 mmol) were added to 70 mL of DMF and heated and stirred at 80 °C for 12 hours. After the reaction was completed, the mixture was extracted using dichloromethane and water. The organic layer was dried with MgSO4, concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography and recrystallized to obtain compound 242 (3.9 g, 73%).

[0187] Synthesis of intermediate-22

[0188]

[0189] In a 1 L round bottom flask, 2-bromopyrimidine (20.0 g, 125.8 mmol), (4-bromophenyl)boronic acid (26.5 g, 132.1 mmol), Pd(pph3)4 (7.2, 6.3 mmol), and K2CO3 (52.2 g, 377.4 mmol) were added to 400 mL of 1,4-dioxane and 200 mL of H2O, and stirred under reflux for 11 hours. After the reaction was completed, the mixture was extracted using dichloromethane and water. The organic layer was dried with MgSO4, concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography to obtain intermediate-22 (15.9 g, 54%).

[0190] Synthesis of intermediate-23

[0191]

[0192] In a 500 mL round-bottomed flask, intermediate-22 (15.9 g, 67.6 mmol), bis(pinacolato)diboron (18.9 g, 74.4 mmol), potassium acetate (19.9 g, 202.9 mmol), and Pd(dppf)Cl2 (1.5 g, 2.0 mmol) were dissolved in 270 mL of 1,4-dioxane, and stirred under reflux for 8 hours. After the reaction was completed, it was cooled to room temperature, and the reaction solution was filtered under reduced pressure through Celite to obtain a filtrate. This filtrate was purified by column chromatography to obtain intermediate-23 (16.4 g, 86%).

[0193] Synthesis of intermediate-24

[0194]

[0195] In a 1 L round bottom flask, intermediate-24 (16.4 g, 33.8 mmol), 1,3-dibromo-5-chlorobenzene (7.5 g, 27.9 mmol), Pd(pph3)4 (3.4 g, 2.9 mmol), and K2CO3 (24.1 g, 174.4 mmol) were added to 290 mL of 1,4-dioxane and 145 mL of H2O, and stirred under reflux for 11 hours. After the reaction was completed, the mixture was extracted using dichloromethane and water. The organic layer was dried with MgSO4, concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography to obtain intermediate-24 (12.7 g, 52%).

[0196] Synthesis of intermediate-25

[0197]

[0198] In a 500 mL round-bottomed flask, intermediate-24 (12.7 g, 30.2 mmol), bis(pinacolato)diboron (8.4 g, 33.2 mmol), potassium acetate (8.9 g, 90.5 mmol), and Pd(dppf)Cl2 (0.7 g, 0.9 mmol) were dissolved in 220 mL of 1,4-dioxane, and stirred under reflux for 8 hours. After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was filtered under reduced pressure through Celite to obtain a filtrate. The filtrate was purified by column chromatography to obtain intermediate-25 (11.1 g, 72%).

[0199] Synthesis of intermediate-26

[0200]

[0201] In a 500 mL round-bottomed flask, intermediate-25 (11.1 g, 21.7 mmol), intermediate-11 (11.8 g, 20.6 mmol), Pd(pph3)4 (1.3 g, 1.1 mmol), and K2CO3 (9.0 g, 65.0 mmol) were added to 200 mL of 1,4-dioxane and 100 mL of H2O, and stirred under reflux for 11 hours. After the reaction was completed, the mixture was extracted using dichloromethane and water. The organic layer was dried with MgSO4, concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography to obtain intermediate-26 (11.5 g, 65%).

[0202] Synthetic Example 8. Synthesis of Compound 243

[0203]

[0204] In a 250 mL round-bottomed flask, intermediate-26 (11.5 g, 14.2 mmol), Pd(OAc)2 (0.3 g, 1.4 mmol), triphenylphosphine (0.7 g, 2.8 mmol), triethylamine (8.6 g, 85.3 mmol), and formic acid (2.6 g, 56.9 mmol) were added to 140 mL of DMF and heated and stirred at 80 °C for 12 hours. After the reaction was completed, the mixture was extracted using dichloromethane and water. The organic layer was dried with MgSO4, concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography and recrystallized to obtain compound 243 (7.2 g, 77%).

[0205] Synthesis of intermediate-27

[0206]

[0207] In a 1 L round-bottomed flask, 2-bromo-1H-benzo[d]imidazole (31.9 g, 161.8 mmol) and sodium tert-butoxide (15.6 g, 161.8 mmol) were added to 600 mL of toluene, and stirred for 30 minutes. Iodobenzene (30 g, 147.1 mmol) was added dropwise, and the mixture was stirred at 50°C for 1 hour. A solution of bis(dibenzylideneacetone)palladium(0) (0.9 g, 1.5 mmol) dissolved in tri-tert-butylphosphine (0.7 g, 3.7 mmol) was added to the reaction solution, and the mixture was stirred under reflux for 6 hours. After confirming the completion of the reaction, the mixture was cooled to room temperature, and the reaction solution was filtered under reduced pressure through Celite to obtain a filtrate. Intermediate-27 (23.9 g, 6%) was obtained by purification using column chromatography.

[0208] Synthesis of intermediate-28

[0209]

[0210] In a 1 L round-bottomed flask, intermediate-27 (23.9 g, 87.5 mmol), bis(pinacolato)diboron (24.4 g, 96.3 mmol), potassium acetate (25.8 g, 262.5 mmol), and Pd(dppf)Cl2 (1.9 g, 2.6 mmol) were dissolved in 400 mL of 1,4-dioxane, and stirred under reflux for 8 hours. After the reaction was completed, it was cooled to room temperature, and the reaction solution was filtered under reduced pressure through Celite to obtain a filtrate. This filtrate was purified by column chromatography to obtain intermediate-28 (20.1 g, 72%).

[0211] Synthesis of intermediate-29

[0212]

[0213] In a 1 L round bottom flask, intermediate-28 (20.1 g, 62.8 mmol), 1,3-dibromo-5-chlorobenzene (8.2 g, 30.1 mmol), Pd(pph3)4 (3.6 g, 3.1 mmol), and K2CO3 (26.0 g, 188.3 mmol) were added to 320 mL of 1,4-dioxane and 160 mL of H2O, and stirred under reflux for 11 hours. After the reaction was completed, the mixture was extracted using dichloromethane and water. The organic layer was dried with MgSO4, concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography to obtain intermediate-29 (19.2 g, 62%).

[0214] Synthesis of intermediate-30

[0215]

[0216] In a 1 L round-bottomed flask, intermediate-29 (19.2 g, 38.6 mmol), bis(pinacolato)diboron (10.8 g, 42.5 mmol), potassium acetate (11.4 g, 115.9 mmol), and Pd(dppf)Cl2 (0.8 g, 1.2 mmol) were dissolved in 320 mL of 1,4-dioxane and stirred under reflux for 8 hours. After the reaction was completed, it was cooled to room temperature and the reaction solution was filtered under reduced pressure through Celite to obtain a filtrate. This filtrate was purified by column chromatography to obtain intermediate-30 (15.7 g, 69%).

[0217] Synthesis of intermediate-31

[0218]

[0219] In a 500 mL round-bottomed flask, intermediate-30 (10.0 g, 17.0 mmol), intermediate-11 (9.2 g, 16.1 mmol), Pd(pph3)4 (1.0 g, 0.8 mmol), and K2CO3 (7.0 g, 51.0 mmol) were added to 170 mL of 1,4-dioxane and 85 mL of H2O, and stirred under reflux for 11 hours. After the reaction was completed, the mixture was extracted using dichloromethane and water. The organic layer was dried with MgSO4, concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography to obtain intermediate-31 (10.1 g, 67%).

[0220] Synthetic Example 9. Synthesis of Compound 244

[0221]

[0222] In a 250 mL round-bottomed flask, intermediate-31 (10.1 g, 11.4 mmol), Pd(OAc)2 (0.3 g, 1.1 mmol), triphenylphosphine (0.6 g, 2.3 mmol), triethylamine (6.9 g, 68.5 mmol), and formic acid (2.1 g, 45.6 mmol) were added to 110 mL of DMF and heated and stirred at 80 °C for 12 hours. After the reaction was completed, the mixture was extracted using dichloromethane and water. The organic layer was dried with MgSO4, concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography and recrystallized to obtain compound 244 (6.3 g, 75%).

[0223] Synthesis of intermediate-32

[0224]

[0225] In a 1 L round bottom flask, 2-bromo-4,6-diphenylpyrimidine (20.0 g, 64.3 mmol), (4-bromonaphthalen-1-yl)boronic acid (17.7 g, 70.7 mmol), Pd(pph3)4 (3.7 g, 3.2 mmol), and K2CO3 (26.6 g, 192.8 mmol) were added to 320 mL of 1,4-dioxane and 160 mL of H2O, and stirred under reflux for 11 hours. After the reaction was completed, the mixture was extracted using dichloromethane and water. The organic layer was dried with MgSO4, concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography to obtain intermediate-32 (14.6 g, 52%).

[0226] Synthesis of intermediate-33

[0227]

[0228] Intermediate-32 (14.6 g, 33.4 mmol), bis(pinacolato)diboron (9.3 g, 36.7 mmol), potassium acetate (9.8 g, 100.2 mmol), and Pd(dppf)Cl2 (0.7 g, 1.0 mmol) were dissolved in 250 mL of 1,4-dioxane in a 1 L round-bottomed flask and stirred under reflux for 8 hours. After the reaction was completed, the mixture was cooled to room temperature and the reaction solution was filtered under reduced pressure through Celite to obtain a filtrate. The filtrate was purified by column chromatography to obtain intermediate-33 (13.1 g, 81%).

[0229] Synthesis of intermediate-34

[0230]

[0231] In a 1 L round bottom flask, intermediate-33 (13.1 g, 27.0 mmol), intermediate-11 (14.7 g, 25.7 mmol), tetrakis(triphenylphophine)palladium (1.6 g, 1.4 mmol), and K2CO3 (11.2 g, 81.1 mmol) were added to 270 mL of 1,4-dioxane and 135 mL of H2O and refluxed for 11 hours. After the reaction was complete, the mixture was cooled to room temperature and extracted with dichloromethane and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography to obtain intermediate-34 (11.6 g, 55%).

[0232] Synthetic Example 10. Synthesis of Compound 245

[0233]

[0234] In a 250 mL round-bottomed flask, intermediate-34 (11.6 g, 14.9 mmol), Pd(OAc)2 (0.3 g, 1.5 mmol), triphenylphosphine (0.8 g, 3.0 mmol), triethylamine (9.0 g, 89.1 mmol), and formic acid (2.7 g, 59.4 mmol) were added to 150 mL of DMF and heated and stirred at 80 °C for 12 hours. After the reaction was completed, the mixture was extracted using dichloromethane and water. The organic layer was dried with MgSO4, concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography and recrystallized to obtain compound 245 (5.9 g, 63%).

[0235] Synthesis of intermediate-35

[0236]

[0237] In a 1 L round bottom flask, 2-bromo-4,6-diphenylpyrimidine (20.0 g, 64.3 mmol), (3-bromophenyl)boronic acid (14.2 g, 70.7 mmol), Pd(pph3)4 (3.7 g, 3.2 mmol), and K2CO3 (26.6 g, 192.8 mmol) were added to 320 mL of 1,4-dioxane and 160 mL of H2O, and stirred under reflux for 11 hours. After the reaction was completed, the mixture was extracted using dichloromethane and water. The organic layer was dried with MgSO4, concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography to obtain intermediate-35 (12.9 g, 51%).

[0238] Synthesis of intermediate-36

[0239]

[0240] Intermediate-35 (12.9 g, 33.3 mmol), bis(pinacolato)diboron (9.3 g, 36.6 mmol), potassium acetate (9.8 g, 99.9 mmol), and Pd(dppf)Cl2 (0.7 g, 1.0 mmol) were dissolved in 250 mL of 1,4-dioxane in a 1 L round-bottomed flask and stirred under reflux for 8 hours. After the reaction was completed, the mixture was cooled to room temperature and the reaction solution was filtered under reduced pressure through Celite to obtain a filtrate. The filtrate was purified by column chromatography to obtain intermediate-36 (10.1 g, 70%).

[0241] Synthesis of intermediate-37

[0242]

[0243] In a 1 L round bottom flask, intermediate-36 (10.1 g, 23.3 mmol), intermediate-11 (12.7 g, 22.1 mmol), tetrakis(triphenylphophine)palladium (1.3 g, 1.2 mmol), and K2CO3 (9.6 g, 69.8 mmol) were added to 230 mL of 1,4-dioxane and 110 mL of H2O and refluxed for 11 hours. After the reaction was complete, the mixture was cooled to room temperature and extracted with dichloromethane and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography to obtain intermediate-37 (12.8 g, 75%).

[0244] Synthetic Example 11. Synthesis of Compound 246

[0245]

[0246] In a 500 mL round-bottomed flask, intermediate-37 (12.8 g, 17.5 mmol), Pd(OAc)2 (0.4 g, 1.8 mmol), triphenylphosphine (0.9 g, 3.5 mmol), triethylamine (10.6 g, 105.1 mmol), and formic acid (3.2 g, 70.1 mmol) were added to 180 mL of DMF and heated and stirred at 80 °C for 12 hours. After the reaction was completed, the mixture was extracted using dichloromethane and water. The organic layer was dried with MgSO4 and concentrated under reduced pressure. The resulting filtrate was purified by column chromatography and recrystallized to obtain compound 246 (4.9 g, 48%).

[0247] Fabrication of organic light-emitting devices

[0248] Comparative Example 1

[0249] After patterning the ITO substrate to have a light-emitting area of ​​2 mm Х 2 mm, it was cleaned with isopropyl alcohol and UV ozone, respectively. Afterwards, the ITO substrate was mounted on the substrate holder of a vacuum deposition device and the vacuum level was 1 Х 10 -7The pressure was set to 10 torr. Afterwards, plasma treatment was performed for 3 minutes under a N2 atmosphere. First, HAT-CN was vacuum-deposited to form a 7 nm thick layer. This material served as a hole injection layer. On top of this, NPB material was formed as a hole transport layer to a 90 nm thick layer. Then, α,β-ADN material as a host and TPPDA material as a dopant were vacuum-deposited to a thickness of 25 nm at a mass ratio of approximately 4% to form a blue light-emitting layer. On this light-emitting layer, BCP compound was formed as a hole-blocking layer to a thickness of 5 nm, and on this light-emitting layer, Bphen material was formed as an electron transport layer to a thickness of 20 nm. Afterwards, LiF material was deposited to form an electron injection layer to a thickness of 1 nm. Afterwards, Al was deposited as a 100 nm thick layer to form a cathode, and an organic EL device was manufactured. The HAT-CN, NPB, α,β-ADN, TPPDA, BCP, and Bphen used previously are shown in Table 1 below, respectively.

[0250] [Table 1]

[0251]

[0252] Comparative Examples 2 and 3

[0253] An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that Comparative Compounds 1 and 2 were used instead of BCP as the hole-blocking layer.

[0254]

[0255] Examples 1 to 11

[0256] An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that the compounds synthesized in Synthesis Examples 1 to 11 were used instead of BCP as the hole-blocking layer.

[0257] Experimental Example 1. Evaluation of Organic Light-Emitting Diodes (Applied to Hole-Blocking Layers)

[0258] The operating voltage, current efficiency, and lifespan of the previously fabricated organic light-emitting device were evaluated. The evaluation results are shown in Table 2 below.

[0259] [Table 2]

[0260]

[0261] As can be seen from the results in Table 2 above, the organic light-emitting device using the compounds of the present invention as a hole-blocking layer exhibited lower driving voltage and improved current efficiency and lifespan compared to the organic light-emitting devices of comparative examples.

[0262] Comparative Examples 4 and 5

[0263] An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that Comparative Compounds 1 and 2 were used instead of Bphen as the electron transport layer.

[0264] Examples 12 to 22

[0265] An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that the compounds synthesized in Synthetic Examples 1 to 11 were used instead of Bphen as the electron transport layer.

[0266] Experimental Example 2. Evaluation of Organic Light-Emitting Diodes (Applied to the Electron Transport Layer)

[0267] The operating voltage, current efficiency, and lifespan of the previously fabricated organic light-emitting device were evaluated. The evaluation results are shown in Table 3 below.

[0268] [Table 3]

[0269]

[0270] As can be seen from the results in Table 3 above, when the compound of the present invention was used as an electron transport layer, the examples also showed lower driving voltage and improved current efficiency and lifespan compared to the comparative examples.

[0271] In conclusion, as can be seen from the above experiments, the compound according to the present invention can realize low voltage, high efficiency, and long life of an organic light-emitting device when applied to a hole blocking layer or electron transport layer of the organic light-emitting device.

[0272] The novel compound of the present invention is characterized by having a core of spirobiindan, in which two indans are bonded in a spiro form, and an asymmetric chiral structure in which at least one substituent extends only to one of the benzenes on both sides. The novel compound of the present invention has high thermal stability due to the high rigidity of spirobiindan, and as a result, has the advantage of improving the lifespan of the device. In particular, due to the asymmetric structure in which the substituent extends only to one benzene, it has the characteristic of having a shallow LUMO energy level compared to a structure in which the substituent extends to both benzenes, so that electrons are smoothly transferred to the light-emitting layer, and since the light-emitting region is located within the light-emitting layer due to the wide energy band gap, it may be more preferable in terms of reducing the driving voltage, increasing the efficiency, and increasing the lifespan.

Claims

1. An asymmetric spirobiindane compound represented by the following chemical formula 1: In the above chemical formula 1, R1 to R4 are each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano group, nitro group, nitrile group, substituted or unsubstituted C1~C30 alkyl group, substituted or unsubstituted C2~C30 alkenyl group, substituted or unsubstituted C1~C30 alkynyl group, substituted or unsubstituted C3~C30 cycloalkyl group, substituted or unsubstituted C2~C30 heterocycloalkyl group, substituted or unsubstituted C1~C30 alkoxy group, substituted or unsubstituted C1~C30 sulfide group, substituted or unsubstituted C6~C30 aryl group, or substituted or unsubstituted C2~C30 heteroaryl group, and adjacent groups may or may not combine with each other to form a ring. L is each independently a direct bond, a substituted or unsubstituted C6~C30 arylene group, or a substituted or unsubstituted C2~C30 heteroarylene group, Ar is each independently selected from the group consisting of deuterium, halogen, cyano group, nitro group, nitrile group, substituted or unsubstituted C1~C30 alkyl group, substituted or unsubstituted C2~C30 alkenyl group, substituted or unsubstituted C1~C30 alkynyl group, substituted or unsubstituted C3~C30 cycloalkyl group, substituted or unsubstituted C2~C30 heterocycloalkyl group, substituted or unsubstituted C1~C30 alkoxy group, substituted or unsubstituted C1~C30 sulfide group, substituted or unsubstituted C2~C30 amine group, substituted or unsubstituted C6~C30 aryl group, or substituted or unsubstituted C2~C30 heteroaryl group, n is an integer from 1 to 4.

2. In paragraph 1, The above chemical formula 1 is characterized by being one of the following chemical formulas 1-1 to 1-4. Asymmetric spirobindan compounds: In the above chemical formulas 1-1 to 1-4, R1 to R4, L and Ar are the same as defined in the above chemical formula 1.

3. In paragraph 1, The above Ar is characterized by being one of the structural formulas A-1 to A-5 below. Asymmetric spirobindan compounds: In the above structural formulas A-1 to A-5, a1 to a5 are each independently N or CR5, b1 to b8 are each independently N or CR6, and the binding position is C, c1 to c10 are each independently N or CR7, and the binding position is C, d1 to d5 are each independently N or CR8, and the binding position is C, d6 is O, S, N or NR9, but if it is N, it is a binding site, e1 to e8 are each independently N or CR10, and the binding position is C, e9 is O, S, N or NR11, but if it is N, it is a binding site, The above R5 to R11 are each independently hydrogen, deuterium, a substituted or unsubstituted C1~C30 alkyl group, a substituted or unsubstituted C6~C30 aryl group, or a substituted or unsubstituted C2~C30 heteroaryl group.

4. In paragraph 3, The above structural formula A-1 is characterized by being one of the following structural formulas A-1-1 to A-1-11. Asymmetric spirobindan compounds: In the above structural formulas A-1-1 to A-1-11, R5 is the same as defined in the above structural formula A-1, o is an integer from 0 to 2, each independently.

5. In paragraph 4, The above R5 is characterized in that each independently represents a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracene group, a phenanthrene group, a dimethylfluorene group, a diphenylfluorene group, a spirobifluorene group, a quinoline group, an isoquinoline group, a quinazoline group, a quinoxaline group, a phthalazine group, a naphthyridine group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a benzoimidazole group, a benzoxazole group, a benzothiazole group, a benzofuran group, a benzothiophene group, a dibenzofuran group, a dibenzothiophene group, a phenanthroline group, or a combination of one or more of these. Asymmetric spirobindan compounds.

6. In paragraph 4, The above o is 2, and the two R5s are characterized in that they have a meta bonding position to each other. Asymmetric spirobindan compounds.

7. In paragraph 1, The compound represented by the above chemical formula 1 is characterized in that it is one of the compounds 1 to 246 below. Asymmetric spirobindan compounds:

8. First electrode and second electrode; It comprises one or more organic layers disposed between the first electrode and the second electrode, An organic light-emitting device, characterized in that at least one of the organic layers comprises a compound according to any one of claims 1 to 7.

9. In paragraph 8, An organic light-emitting device, characterized in that the organic layer containing the compound is an electron transport layer, a hole blocking layer, or a charge generation layer.

Images