Novel compound and organic light-emitting element comprising same

Abstract

The present invention relates to a novel compound and an organic light-emitting element comprising same. The novel compound of the present invention can be used in: a first electrode and a second electrode and one or more organic material layers disposed between the first electrode and the second electrode, and can be used in an electron transport layer, a hole blocking layer, or a charge generation layer. According to the present invention, the low voltage, high efficiency, and long lifespan of the organic light-emitting element can be implemented.

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 and an organic light-emitting device comprising the same.

[0006] The object of the present invention is achieved by a novel 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] Ar1 is the structural formula A below,

[0010]

[0011] Ar2 is each independently hydrogen, deuterium, halogen, chloro group (-Cl), bromo group (-Br), 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, substituted or unsubstituted C2~C30 heteroaryl group, substituted or unsubstituted C6~C30 aryloxy group, substituted or unsubstituted C6~C30 arylthio group, substituted or unsubstituted Selected from the group consisting of a C6~C30 amine group, a substituted or unsubstituted arylsilyl group, and a substituted or unsubstituted arylphosphine oxide group,

[0012] L1 and L2 are each independently a direct bond, a substituted or unsubstituted C6~C30 arylene group, or a substituted or unsubstituted C2~C30 heteroarylene group,

[0013] In the above structural formula A,

[0014] X is O or S,

[0015] Y1 to Y8 are each independently N or CR, and the position at which they are bonded to chemical formula 1 is C,

[0016] Here, R is each independently selected from the group consisting of hydrogen, deuterium, halogen, chloro group (-Cl), bromo group (-Br), cyano group, nitro group, nitrile group, substituted or unsubstituted C1~C30 alkyl group, substituted or unsubstituted C6~C30 aryl group, and substituted or unsubstituted C2~C30 heteroaryl group.

[0017] According to the present invention, a novel compound and an organic light-emitting device comprising the same are provided. The novel compound of the present invention can be applied to an electron transport layer, a hole blocking layer, or a charge generation layer to realize an organic light-emitting device with low voltage, high efficiency, and long lifespan.

[0018] 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.

[0019] 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.

[0020] In this specification, examples of substituents are described below, but are not limited thereto.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] 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, and adamantyl groups.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] In the chemical formula or structural formula in this specification, * or indicates the binding position.

[0029] The novel compound of the present invention is described below.

[0030] The novel compound according to the present invention is represented by the following chemical formula 1.

[0031]

[0032] In the above chemical formula 1,

[0033] Ar1 is the structural formula A below,

[0034]

[0035] Ar2 is each independently hydrogen, deuterium, halogen, chloro group (-Cl), bromo group (-Br), 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, substituted or unsubstituted C2~C30 heteroaryl group, substituted or unsubstituted C6~C30 aryloxy group, substituted or unsubstituted C6~C30 arylthio group, substituted or unsubstituted Selected from the group consisting of a C6~C30 amine group, a substituted or unsubstituted arylsilyl group, and a substituted or unsubstituted arylphosphine oxide group,

[0036] L1 and L2 are each independently a direct bond, a substituted or unsubstituted C6~C30 arylene group, or a substituted or unsubstituted C2~C30 heteroarylene group,

[0037] In the above structural formula A,

[0038] X is O or S,

[0039] Y1 to Y8 are each independently N or CR, and the position at which they are bonded to chemical formula 1 is C,

[0040] Each R can be independently selected from the group consisting of hydrogen, deuterium, halogen, chloro group (-Cl), bromo group (-Br), cyano group, nitro group, nitrile group, substituted or unsubstituted C1~C30 alkyl group, substituted or unsubstituted C6~C30 aryl group, and substituted or unsubstituted C2~C30 heteroaryl group.

[0041] As such, the novel compound of the present invention is characterized by having a structure in which a heterocyclic group represented by structural formula A containing O or S is bonded to the 3-position of 1,5-naphthyridine. The heterocyclic group represented by structural formula A has an orbital distribution that is spread out throughout, so that electrons are injected well, and the naphthyridine group has a large electron affinity, so that the LUMO energy level is lowered, which reduces the energy gap, and thus not only has excellent electron transport ability but also has excellent durability due to its rigid structure. Therefore, the compound of the present invention combining these has the advantage of easy electron transfer due to excellent electron mobility and electron injection characteristics.

[0042] Specifically, the above chemical formula 1 may be the following chemical formula 2 or chemical formula 3. Chemical formula 2 represents a case where one 1,5-naphthyridine group is bonded to L1, and chemical formula 3 represents a case where two 1,5-naphthyridine groups are bonded to L1.

[0043]

[0044] In the above chemical formulas 2 and 3, Ar1, Ar2, L1 and L2 have the same definitions as in the above chemical formula 1.

[0045] In the above chemical formula 2, Ar1 and Ar2 may be the same or different. In the above chemical formula 3, Ar1 and Ar2 may also be the same or different, and Ar2 may also be the same or different.

[0046] According to one embodiment, the chemical formula 3 may be the following chemical formula 4.

[0047]

[0048] In the above chemical formula 4, Ar1, Ar2 and L2 are the same as defined in the above chemical formula 1,

[0049] X1 to X3 are each independently N or CH, and L3 may be a direct bond, a substituted or unsubstituted C6~C30 arylene group, or a substituted or unsubstituted C2~C30 heteroarylene group.

[0050] In one embodiment, X1 to X3 may all be CH, X1 to X3 may all be N, only X1 and X3 among X1 to X3 may be N, or only X2 among X1 to X3 may be N. That is, when two 1,5-naphthyridines are bonded to Ar1, they may be bonded using phenylene, triazinylene, pyrimidinylene, or pyridinylene as a linker.

[0051] Meanwhile, according to one embodiment, the structural formula A may be any one selected from the structural formulas A-1 to A-4 below.

[0052]

[0053] In the above structural formulas A-1 to A-4, X and Y1 to Y8 are as defined in the above structural formula A.

[0054] More specifically, the structural formula A may be any one selected from the structural formulas A-10 to A-46 below, and may be structural formula A-10 according to one embodiment.

[0055]

[0056]

[0057] In the above structural formulas A-10 to A-46, X and R have the same definitions as in the above structural formula A, and m can each independently be an integer from 0 to 2. More specifically, m can be 0 or 1.

[0058] According to one embodiment, the structural formula A may be any one of the structural formulas below. In the structural formulas below, R has the same definition as in the structural formula A.

[0059]

[0060]

[0061] Meanwhile, specifically, R may each independently be hydrogen, deuterium, a chloro group (-Cl), a bromo group (-Br), a C1~C20 alkyl group, a C6~C20 aryl group, or a C2~C20 heteroaryl group, and according to one embodiment, may be hydrogen, or if not hydrogen, may be one of the structural formulas R-1 to R-28 below. More specifically, it may be hydrogen or a phenyl group of structural formula R-1, because the π-conjugation lengthens and the band gap decreases, and thus the reorganization energy decreases and the electron transport capacity increases.

[0062]

[0063] Meanwhile, the above Ar2 may be any one selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C1~C30 alkyl group, a substituted or unsubstituted C3~C30 cycloalkyl group, a substituted or unsubstituted C2~C30 heterocycloalkyl group, a substituted or unsubstituted C6~C30 aryl group, and a substituted or unsubstituted C2~C30 heteroaryl group, and more specifically, may be hydrogen, deuterium, a substituted or unsubstituted C6~C20 aryl group, or a substituted or unsubstituted C2~C20 heteroaryl group.

[0064] In one embodiment, Ar2 may be hydrogen, and if not hydrogen, may be any one of the structural formulae B-1 to B-68 below.

[0065]

[0066]

[0067] Meanwhile, the above L1 to L3 may each independently be a direct bond, or may be formed by combining one or two or more selected from the structural formulae L-1 to L-21 below. In the present specification, the meaning of being formed by a combination of two or more means a combination of two or more identical or different structural formulae, and as an example, the case may include a case where two structural formulae L-1 are combined, a case where structural formulae L-1 and L-2 are combined, a case where two structural formulae L-1 and one L-2 are combined, etc.

[0068]

[0069] According to one embodiment, L1 to L3 may be a direct bond or a combination of one, two, or three of the following structural formulas. In the case of an asymmetric structure among the structural formulas below, the left and right are not fixed and may be changed.

[0070]

[0071] The novel compound of the present invention may be selected from compounds consisting of compounds 1 to 140 below.

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080] The novel compound of the present invention described so far includes a core structure in which a substituent, such as dibenzofuran, dibenzothiophene, or benzofuropyridine, in which one or more carbon positions of dibenzofuran or dibenzothiophene are substituted with nitrogen (N), is bonded to the 3-position of 1,5-naphthyridine, and is characterized in that an additional substituent can be bonded to the 7-position of 1,5-naphthyridine. Such a novel compound of the present invention has a particularly excellent electron transport ability.

[0081] 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, and specifically, can be applied to one or more of the organic layers.

[0082] Below, the organic light-emitting device is described in more detail.

[0083] An organic light-emitting device has an organic layer positioned between two 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] Meanwhile, the configuration of the organic light-emitting device can vary. For example, it can be a tandem structure in which two or more light-emitting layers (or light-emitting units) are provided. In the case of a tandem structure, in addition to the above-mentioned organic layers, a charge generation layer (CGL) can be further included as one of the organic layers. Generally, 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.

[0092] 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 to a host of an N-type charge generation layer.

[0093] An organic light-emitting device in which the novel compound of 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.

[0094] The present invention is described in more detail below through synthetic examples, embodiments, and experimental examples.

[0095] Synthesis of compounds

[0096] Synthesis of intermediate-1

[0097]

[0098] 3,7-dibromo-1,5-naphthyridine (10.0 g, 34.73 mmol), phenanthren-9-ylboronic acid (8.5 g, 38.20 mmol), potassium carbonate (14.4 g, 104.19 mmol), and tetrakis(triphenylphophine)palladium (2.0 g, 1.74 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 100 mL of 1,4-dioxane and 50 mL of water. After the reaction was complete, the mixture was cooled to room temperature and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was extracted with ethyl acetate and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was purified by column chromatography to obtain intermediate-1 (9.1 g, 68.0%).

[0099] Synthesis of intermediate-2

[0100]

[0101] Intermediate-1 (9.1 g, 23.62 mmol), bis(pinacolato)diboron (7.2 g, 28.34 mmol), potassium acetate (7.0 g, 70.86 mmol), [1,1'-Bis(diphenylphosphino)ferrocene]dichloropalladium(II) (1.1 g, 1.30 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 140 mL of 1,4-dioxane. The organic layer was dried with MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was dissolved in dichloromethane, filtered through silica gel and Celite under reduced pressure, and concentrated under reduced pressure to obtain intermediate-2 (9.6 g, 94.0%).

[0102] Synthetic Example 1. Synthesis of Compound 4

[0103]

[0104] 2-Bromobenzo[b,d]furan (5.0 g, 20.24 mmol), intermediate-2 (9.6 g, 22.26 mmol), potassium carbonate (8.4 g, 60.71 mmol), and tetrakis(triphenylphophine)palladium (1.2 g, 1.01 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 50 mL of 1,4-dioxane and 25 mL of water. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in dichlorobenzene, and the filtrate was filtered through silica gel and Celite under reduced pressure to obtain a filtrate. The obtained filtrate was concentrated under reduced pressure, dissolved in dichlorobenzene, and recrystallized with acetone to obtain compound 4 (5.6 g, 58.6%).

[0105] Synthesis of intermediate-3

[0106]

[0107] 5'-Bromo-1,1':3',1''-terphenyl (15.0 g, 48.51 mmol), bis(pinacolato)diboron (14.8 g, 58.21 mmol), potassium acetate (14.3 g, 145.53 mmol), [1,1'-Bis(diphenylphosphino)ferrocene]dichloropalladium(II)(1.2 g, 1.46 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 225 mL of 1,4-dioxane. The organic layer was dried with MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was dissolved in dichloromethane, filtered through silica gel and Celite under reduced pressure, and concentrated under reduced pressure to obtain intermediate-3 (15.8 g, 91.4%).

[0108] Synthesis of intermediate-4

[0109]

[0110] 3,7-dibromo-1,5-naphthyridine (10.0 g, 34.73 mmol), phenanthren-9-ylboronic acid (13.6 g, 38.20 mmol), potassium carbonate (14.4 g, 104.19 mmol), and tetrakis(triphenylphophine)palladium (2.0 g, 1.74 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 100 mL of 1,4-dioxane and 50 mL of water. After the reaction was complete, the mixture was cooled to room temperature and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was extracted with ethyl acetate and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was purified by column chromatography to obtain intermediate-4 (10.5 g, 69.1%).

[0111] Synthesis of intermediate-5

[0112]

[0113] Intermediate-4 (10.5 g, 24.01 mmol), bis(pinacolato)diboron (7.3 g, 28.81 mmol), potassium acetate (7.1 g, 72.03 mmol), [1,1'-Bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.6 g, 0.72 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 160 mL of 1,4-dioxane. The organic layer was dried with MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was dissolved in dichloromethane, filtered through silica gel and Celite under reduced pressure, and concentrated under reduced pressure to obtain intermediate-5 (10.9 g, 93.7%).

[0114] Synthesis Example 2. Synthesis of Compound 5

[0115]

[0116] 2-Bromobenzo[b,d]furan (5.0 g, 20.24 mmol), intermediate-5 (10.8 g, 22.26 mmol), potassium carbonate (8.4 g, 60.71 mmol), and tetrakis(triphenylphophine)palladium (1.2 g, 1.01 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 50 mL of 1,4-dioxane and 25 mL of water. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in dichlorobenzene, and the filtrate was filtered under reduced pressure through silica gel and Celite to obtain a filtrate. The filtrate was concentrated under reduced pressure, dissolved in dichlorobenzene, and recrystallized with acetone to obtain compound 5 (6.4 g, 60.3%).

[0117] Synthesis of intermediate-6

[0118]

[0119] 1-Bromo-4-iodobenzene (10.0 g, 35.35 mmol), intermediate-5 (18.8 g, 38.88 mmol), potassium carbonate (14.7 g, 106.04 mmol), and tetrakis(triphenylphophine)palladium (2.0 g, 1.77 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 100 mL of 1,4-dioxane and 50 mL of water. After the reaction was complete, the mixture was cooled to room temperature and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was extracted with ethyl acetate and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was purified by column chromatography to obtain intermediate-6 (12.3 g, 67.8%).

[0120] Synthesis of intermediate-7

[0121]

[0122] Intermediate-6 (12.3 g, 23.96 mmol), bis(pinacolato)diboron (7.3 g, 28.75 mmol), potassium acetate (7.1 g, 71.87 mmol), [1,1'-Bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.6 g, 0.72 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 160 mL of 1,4-dioxane. The organic layer was dried with MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was dissolved in dichloromethane, filtered through silica gel and Celite under reduced pressure, and concentrated under reduced pressure to obtain intermediate-7 (12.5 g, 93.1%).

[0123] Synthetic Example 3. Synthesis of Compound 24

[0124]

[0125] 2-Bromobenzo[b,d]furan (5.0 g, 20.24 mmol), intermediate-7 (12.5 g, 22.26 mmol), potassium carbonate (8.4 g, 60.71 mmol), and tetrakis(triphenylphophine)palladium (1.2 g, 1.01 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 50 mL of 1,4-dioxane and 25 mL of water. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in dichlorobenzene, and the filtrate was filtered under reduced pressure through silica gel and Celite to obtain a filtrate. The filtrate was concentrated under reduced pressure, dissolved in dichlorobenzene, and recrystallized with acetone to obtain compound 24 (8.1 g, 66.6%).

[0126] Synthesis of intermediate-8

[0127]

[0128] 4-Bromopyridine (15.0 g, 94.94 mmol), bis(pinacolato)diboron (28.9 g, 113.92 mmol), potassium acetate (28.0 g, 284.81 mmol), [1,1'-Bis(diphenylphosphino)ferrocene]dichloropalladium(II)(2.3 g, 2.85 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 225 mL of 1,4-dioxane. The organic layer was dried with MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was dissolved in dichloromethane, filtered through silica gel and Celite under reduced pressure, and concentrated under reduced pressure to obtain intermediate-8 (16.4 g, 84.2%).

[0129] Synthesis of intermediate-9

[0130]

[0131] 3,7-dibromo-1,5-naphthyridine (15.0 g, 52.09 mmol), intermediate-8 (11.8 g, 57.30 mmol), potassium carbonate (21.6 g, 156.28 mmol), and tetrakis(triphenylphophine)palladium (3.0 g, 2.60 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 150 mL of 1,4-dioxane and 75 mL of water. After the reaction was complete, the mixture was cooled to room temperature and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was extracted with ethyl acetate and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was purified by column chromatography to obtain intermediate-9 (10.1 g, 67.8%).

[0132] Synthesis of intermediate-10

[0133]

[0134] Intermediate-9 (10.1 g, 35.30 mmol), bis(pinacolato)diboron (10.8 g, 42.36 mmol), potassium acetate (10.4 g, 105.90 mmol), [1,1'-Bis(diphenylphosphino)ferrocene]dichloropalladium(II)(0.9 g, 1.06 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 155 mL of 1,4-dioxane. The organic layer was dried with MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was dissolved in dichloromethane, filtered through silica gel and Celite under reduced pressure, and concentrated under reduced pressure to obtain intermediate-10 (10.5 g, 89.3%).

[0135] Synthesis of intermediate-11

[0136]

[0137] 1-Bromo-4-iodobenzene (8.0 g, 28.28 mmol), intermediate-10 (10.4 g, 31.11 mmol), potassium carbonate (11.7 g, 84.83 mmol), and tetrakis(triphenylphophine)palladium (1.6 g, 1.41 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 80 mL of 1,4-dioxane and 40 mL of water. After the reaction was complete, the mixture was cooled to room temperature and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was extracted with ethyl acetate and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was purified by column chromatography to obtain intermediate-11 (7.5 g, 73.2%).

[0138] Synthesis of intermediate-12

[0139]

[0140] Intermediate-11 (7.5 g, 20.71 mmol), bis(pinacolato)diboron (6.3 g, 24.85 mmol), potassium acetate (6.1 g, 62.12 mmol), and [1,1'-Bis(diphenylphosphino)ferrocene]dichloropalladium(II)(0.5 g, 0.62 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 115 mL of 1,4-dioxane. The organic layer was dried with MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was dissolved in dichloromethane, filtered through silica gel and celite under reduced pressure, and concentrated under reduced pressure to obtain intermediate-12 (8.0 g, 94.4%).

[0141] Synthetic Example 4. Synthesis of Compound 27

[0142]

[0143] 2-Bromobenzo[b,d]furan (4.0 g, 16.19 mmol), intermediate-12 (7.3 g, 17.81 mmol), potassium carbonate (6.7 g, 48.57 mmol), and tetrakis(triphenylphophine)palladium (0.9 g, 0.81 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 40 mL of 1,4-dioxane and 20 mL of water. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in dichlorobenzene, and the filtrate was filtered under reduced pressure through silica gel and Celite to obtain a filtrate. The filtrate was concentrated under reduced pressure, dissolved in dichlorobenzene, and recrystallized with acetone to obtain compound 27 (5.1 g, 70.1%).

[0144] Synthesis of intermediate-13

[0145]

[0146] 3,7-dibromo-1,5-naphthyridine (20.0 g, 69.46 mmol), phenylboronic acid (9.3 g, 76.40 mmol), potassium carbonate (28.8 g, 208.38 mmol), and tetrakis(triphenylphophine)palladium (4.0 g, 3.47 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 200 mL of 1,4-dioxane and 100 mL of water. After the reaction was complete, the mixture was cooled to room temperature and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was extracted with ethyl acetate and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was purified by column chromatography to obtain intermediate-13 (15.4 g, 77.8%).

[0147] Synthesis of intermediate-14

[0148]

[0149] Intermediate-13 (15.4 g, 54.01 mmol), bis(pinacolato)diboron (16.5 g, 64.81 mmol), potassium acetate (15.9 g, 162.03 mmol), [1,1'-Bis(diphenylphosphino)ferrocene]dichloropalladium(II)(1.3 g, 1.62 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 235 mL of 1,4-dioxane. The organic layer was dried with MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was dissolved in dichloromethane, filtered through silica gel and Celite under reduced pressure, and concentrated under reduced pressure to obtain intermediate-14 (16.1 g, 89.7%).

[0150] Synthesis of intermediate-15

[0151]

[0152] 1-Bromo-3-iodobenzene (10.0 g, 35.35 mmol), intermediate-14 (12.9 g, 38.88 mmol), potassium carbonate (14.7 g, 106.04 mmol), and tetrakis(triphenylphophine)palladium (2.0 g, 1.77 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 100 mL of 1,4-dioxane and 50 mL of water. After the reaction was complete, the mixture was cooled to room temperature and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was extracted with ethyl acetate and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was purified by column chromatography to obtain intermediate-15 (9.2 g, 72.1%).

[0153] Synthesis of intermediate-16

[0154]

[0155] Intermediate-15 (9.2 g, 25.47 mmol), bis(pinacolato)diboron (7.8 g, 30.56 mmol), potassium acetate (7.5 g, 76.40 mmol), and [1,1'-Bis(diphenylphosphino)ferrocene]dichloropalladium(II)(0.6 g, 0.76 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 115 mL of 1,4-dioxane. The organic layer was dried with MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was dissolved in dichloromethane, filtered through silica gel and Celite under reduced pressure, and concentrated under reduced pressure to obtain intermediate-16 (9.4 g, 90.4%).

[0156] Synthetic Example 5. Synthesis of Compound 28

[0157]

[0158] 2-Bromobenzo[b,d]furan (5.0 g, 20.24 mmol), intermediate-16 (9.1 g, 22.26 mmol), potassium carbonate (8.4 g, 60.71 mmol), and tetrakis(triphenylphophine)palladium (1.2 g, 1.01 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 50 mL of 1,4-dioxane and 25 mL of water. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in dichlorobenzene, and the filtrate was filtered through silica gel and Celite under reduced pressure to obtain a filtrate. The obtained filtrate was concentrated under reduced pressure, dissolved in dichlorobenzene, and recrystallized with acetone to obtain compound 28 (5.6 g, 61.7%).

[0159] Synthesis of intermediate-17

[0160]

[0161] 3-Bromo-1,5-naphthyridine (10.0 g, 47.84 mmol), bis(pinacolato)diboron (14.6 g, 57.40 mmol), potassium acetate (14.1 g, 143.51 mmol), [1,1'-Bis(diphenylphosphino)ferrocene]dichloropalladium(II) (1.2 g, 1.44 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 150 mL of 1,4-dioxane. The organic layer was dried with MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was dissolved in dichloromethane, filtered through silica gel and Celite under reduced pressure, and concentrated under reduced pressure to obtain intermediate-17 (10.1 g, 82.4%).

[0162] Synthesis of intermediate-18

[0163]

[0164] 1-Bromo-3-iodobenzene (10.0 g, 35.35 mmol), intermediate-17 (10.0 g, 38.88 mmol), potassium carbonate (14.7 g, 106.04 mmol), and tetrakis(triphenylphophine)palladium (2.0 g, 1.77 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 100 mL of 1,4-dioxane and 50 mL of water. After the reaction was complete, the mixture was cooled to room temperature and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was extracted with ethyl acetate and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was purified by column chromatography to obtain intermediate-18 (7.6 g, 75.4%).

[0165] Synthesis of intermediate-19

[0166]

[0167] Intermediate-18 (7.6 g, 26.65 mmol), bis(pinacolato)diboron (8.1 g, 31.98 mmol), potassium acetate (7.8 g, 79.96 mmol), [1,1'-Bis(diphenylphosphino)ferrocene]dichloropalladium(II)(0.7 g, 0.80 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 115 mL of 1,4-dioxane. The organic layer was dried with MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was dissolved in dichloromethane, filtered through silica gel and Celite under reduced pressure, and concentrated under reduced pressure to obtain intermediate-19 (8.2 g, 92.6%).

[0168] Synthetic Example 6. Synthesis of Compound 48

[0169]

[0170] 3-Bromodibenzo[b,d]furan (5.0 g, 20.24 mmol), intermediate-19 (7.4 g, 22.26 mmol), potassium carbonate (8.4 g, 60.71 mmol), and tetrakis(triphenylphophine)palladium (1.2 g, 1.01 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 50 mL of 1,4-dioxane and 25 mL of water. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in dichlorobenzene, and the filtrate was filtered under reduced pressure through silica gel and Celite to obtain a filtrate. The filtrate was concentrated under reduced pressure, dissolved in dichlorobenzene, and recrystallized with acetone to obtain compound 48 (5.3 g, 58.4%).

[0171] Synthetic Example 7. Synthesis of Compound 49

[0172]

[0173] In a round-bottomed flask were added 3-bromodibenzo[b,d]fura (10.0 g, 40.47 mmol), intermediate-16 (18.2 g, 44.52 mmol), potassium carbonate (16.8 g, 121.41 mmol), and tetrakis(triphenylphophine)palladium (2.3 g, 2.02 mmol), and the mixture was stirred overnight while refluxing in 100 mL of 1,4-dioxane and 50 mL of water. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in dichlorobenzene, and the filtrate was filtered through silica gel and Celite under reduced pressure to obtain a filtrate. The obtained filtrate was concentrated under reduced pressure, dissolved in dichlorobenzene, and recrystallized with acetone to obtain compound 49 (8.3 g, 45.7%).

[0174] Synthesis Example 8. Synthesis of Compound 60

[0175]

[0176] 2-Bromobenzo[b,d]thiophene (10.0 g, 38.00 mmol), intermediate-2 (18.1 g, 41.80 mmol), potassium carbonate (15.8 g, 114.00 mmol), and tetrakis(triphenylphophine)palladium (2.2 g, 1.90 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 100 mL of 1,4-dioxane and 50 mL of water. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in dichlorobenzene, and the filtrate was filtered through silica gel and Celite under reduced pressure to obtain a filtrate. The obtained filtrate was concentrated under reduced pressure, dissolved in dichlorobenzene, and recrystallized with acetone to obtain compound 60 (9.5 g, 51.2%).

[0177] Synthetic Example 9. Synthesis of Compound 61

[0178]

[0179] 2-Bromobenzo[b,d]thiophene (10.0 g, 38.00 mmol), intermediate-5 (20.2 g, 41.80 mmol), potassium carbonate (15.8 g, 114.00 mmol), and tetrakis(triphenylphophine)palladium (2.2 g, 1.90 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 100 mL of 1,4-dioxane and 50 mL of water. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in dichlorobenzene, and the filtrate was filtered under reduced pressure through silica gel and Celite to obtain a filtrate. The obtained filtrate was concentrated under reduced pressure, dissolved in dichlorobenzene, and recrystallized with acetone to obtain compound 61 (9.6 g, 46.7%).

[0180] Synthetic Example 10. Synthesis of Compound 81

[0181]

[0182] 2-Bromobenzo[b,d]thiophene (10.0 g, 38.00 mmol), intermediate-7 (23.4 g, 41.80 mmol), potassium carbonate (15.8 g, 114.00 mmol), and tetrakis(triphenylphophine)palladium (2.2 g, 1.90 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 100 mL of 1,4-dioxane and 50 mL of water. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in dichlorobenzene, and the filtrate was filtered under reduced pressure through silica gel and Celite to obtain a filtrate. The obtained filtrate was concentrated under reduced pressure, dissolved in dichlorobenzene, and recrystallized with acetone to obtain compound 81 (11.2 g, 47.8%).

[0183] Synthetic Example 11. Synthesis of Compound 84

[0184]

[0185] 2-Bromobenzo[b,d]thiophene (10.0 g, 38.00 mmol), intermediate-7 (23.4 g, 41.80 mmol), potassium carbonate (15.8 g, 114.00 mmol), and tetrakis(triphenylphophine)palladium (2.2 g, 1.90 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 100 mL of 1,4-dioxane and 50 mL of water. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in dichlorobenzene, and the filtrate was filtered through silica gel and Celite under reduced pressure to obtain a filtrate. The obtained filtrate was concentrated under reduced pressure, dissolved in dichlorobenzene, and recrystallized with acetone to obtain compound 84 (8.0 g, 45.2%).

[0186] Synthesis Example 12. Synthesis of Compound 85

[0187]

[0188] 2-Bromobenzo[b,d]thiophene (10.0 g, 38.00 mmol), intermediate-16 (17.1 g, 41.80 mmol), potassium carbonate (15.8 g, 114.00 mmol), and tetrakis(triphenylphophine)palladium (2.2 g, 1.90 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 100 mL of 1,4-dioxane and 50 mL of water. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in dichlorobenzene, and the filtrate was filtered through silica gel and Celite under reduced pressure to obtain a filtrate. The obtained filtrate was concentrated under reduced pressure, dissolved in dichlorobenzene, and recrystallized with acetone to obtain compound 85 (8.3 g, 47.0%).

[0189] Synthetic Example 13. Synthesis of Compound 109

[0190]

[0191] In a round-bottomed flask were added 3-bromodibenzo[b,d]thiophene (10.0 g, 38.00 mmol), intermediate-16 (17.1 g, 41.80 mmol), potassium carbonate (15.8 g, 114.00 mmol), and tetrakis(triphenylphophine)palladium (2.2 g, 1.90 mmol), and the mixture was stirred overnight while refluxing in 100 mL of 1,4-dioxane and 50 mL of water. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in dichlorobenzene, and the filtrate was filtered under reduced pressure through silica gel and Celite to obtain a filtrate. The obtained filtrate was concentrated under reduced pressure, dissolved in dichlorobenzene, and recrystallized with acetone to obtain compound 109 (7.6 g, 43.0%).

[0192] Synthesis of intermediate-20

[0193]

[0194] 1,3-dibromo-5-chlorobenzene (10.0 g, 36.99 mmol), intermediate-17 (20.8 g, 81.38 mmol), potassium carbonate (20.4 g, 147.96 mmol), and tetrakis(triphenylphophine)palladium (3.0 g, 2.59 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 100 mL of 1,4-dioxane and 50 mL of water. After the reaction was complete, the mixture was cooled to room temperature and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was extracted with ethyl acetate and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was purified by column chromatography to obtain intermediate-20 (10.1 g, 74.0%).

[0195] Synthesis of intermediate-21

[0196]

[0197] Intermediate-20 (10.1 g, 27.38 mmol), bis(pinacolato)diboron (8.3 g, 32.86 mmol), potassium acetate (8.1 g, 82.15 mmol), [1,1'-Bis(diphenylphosphino)ferrocene]dichloropalladium(II)(0.7 g, 0.82 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 115 mL of 1,4-dioxane. The organic layer was dried with MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was dissolved in dichloromethane, filtered through silica gel and celite under reduced pressure, and concentrated under reduced pressure to obtain intermediate-21 (11.4 g, 90.4%).

[0198] Synthetic Example 14. Synthesis of Compound 121

[0199]

[0200] 3-Bromobenzo[b,d]furan (5.0 g, 20.24 mmol), intermediate-21 (10.2 g, 22.26 mmol), potassium carbonate (8.4 g, 60.71 mmol), and tetrakis(triphenylphophine)palladium (1.2 g, 1.01 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 50 mL of 1,4-dioxane and 25 mL of water. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in dichlorobenzene, and the filtrate was filtered under reduced pressure through silica gel and Celite to obtain a filtrate. The obtained filtrate was concentrated under reduced pressure, dissolved in dichlorobenzene, and recrystallized with acetone to obtain compound 121 (5.8 g, 57.3%).

[0201] Synthesis Example 15. Synthesis of Compound 122

[0202]

[0203] 2-Bromobenzo[b,d]furan (10.0 g, 40.47 mmol), intermediate-21 (20.5 g, 44.52 mmol), potassium carbonate (16.8 g, 121.41 mmol), and tetrakis(triphenylphophine)palladium (2.3 g, 2.02 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 100 mL of 1,4-dioxane and 50 mL of water. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in dichlorobenzene, and the filtrate was filtered through silica gel and Celite under reduced pressure to obtain a filtrate. The obtained filtrate was concentrated under reduced pressure, dissolved in dichlorobenzene, and recrystallized with acetone to obtain compound 122 (8.9 g, 43.9%).

[0204] Synthesis Example 16. Synthesis of Compound 123

[0205]

[0206] In a round-bottomed flask were added 3-bromodibenzo[b,d]thiophene (10.0 g, 38.00 mmol), intermediate-21 (19.2 g, 41.80 mmol), potassium carbonate (15.8 g, 114.00 mmol), and tetrakis(triphenylphophine)palladium (2.2 g, 1.90 mmol), and the mixture was stirred overnight under reflux in 100 mL of 1,4-dioxane and 50 mL of water. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in dichlorobenzene, and the filtrate was filtered under reduced pressure through silica gel and Celite to obtain a filtrate. The obtained filtrate was concentrated under reduced pressure, dissolved in dichlorobenzene, and recrystallized with acetone to obtain compound 123 (9.1 g, 46.4%).

[0207] Synthetic Example 17. Synthesis of Compound 124

[0208]

[0209] 2-Bromobenzo[b,d]thiophene (10.0 g, 38.00 mmol), intermediate-21 (19.2 g, 41.80 mmol), potassium carbonate (15.8 g, 114.00 mmol), and tetrakis(triphenylphophine)palladium (2.2 g, 1.90 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 100 mL of 1,4-dioxane and 50 mL of water. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in dichlorobenzene, and the filtrate was filtered through silica gel and Celite under reduced pressure to obtain a filtrate. The filtrate was concentrated under reduced pressure, dissolved in dichlorobenzene, and recrystallized with acetone to obtain compound 124 (9.3 g, 47.4%).

[0210] Synthesis of intermediate-22

[0211]

[0212] 1,3-dibromo-5-chlorobenzene (15.0 g, 55.48 mmol), intermediate-14 (40.6 g, 122.06 mmol), potassium carbonate (30.7 g, 221.93 mmol), and tetrakis(triphenylphophine)palladium (4.5 g, 3.88 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 150 mL of 1,4-dioxane and 75 mL of water. After the reaction was complete, the mixture was cooled to room temperature and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was extracted with ethyl acetate and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was purified by column chromatography to obtain intermediate-22 (17.6 g, 60.9%).

[0213] Synthesis of intermediate-23

[0214]

[0215] Intermediate-22 (17.6 g, 33.78 mmol), bis(pinacolato)diboron (10.3 g, 40.54 mmol), potassium acetate (9.9 g, 101.34 mmol), [1,1'-Bis(diphenylphosphino)ferrocene]dichloropalladium(II)(0.8 g, 1.01 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 265 mL of 1,4-dioxane. The organic layer was dried with MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was dissolved in dichloromethane, filtered through silica gel and celite under reduced pressure, and concentrated under reduced pressure to obtain intermediate-23 (15.3 g, 73.9%).

[0216] Synthetic Example 18. Synthesis of Compound 126

[0217]

[0218] 3-Bromobenzo[b,d]furan (5.0 g, 20.24 mmol), intermediate-23 (13.6 g, 22.26 mmol), potassium carbonate (8.4 g, 60.71 mmol), and tetrakis(triphenylphophine)palladium (1.2 g, 1.01 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 50 mL of 1,4-dioxane and 25 mL of water. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in dichlorobenzene, and the filtrate was filtered through silica gel and Celite under reduced pressure to obtain a filtrate. The obtained filtrate was concentrated under reduced pressure, dissolved in dichlorobenzene, and recrystallized with acetone to obtain compound 126 (6.7 g, 50.7%).

[0219] Synthetic Example 19. Synthesis of Compound 130

[0220]

[0221] 2-Bromobenzo[b,d]furan (5.0 g, 20.24 mmol), intermediate-23 (10.2 g, 22.26 mmol), potassium carbonate (8.4 g, 60.71 mmol), and tetrakis(triphenylphophine)palladium (1.2 g, 1.01 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 50 mL of 1,4-dioxane and 25 mL of water. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in dichlorobenzene, and the filtrate was filtered under reduced pressure through silica gel and Celite to obtain a filtrate. The obtained filtrate was concentrated under reduced pressure, dissolved in dichlorobenzene, and recrystallized with acetone to obtain compound 130 (5.9 g, 44.7%).

[0222] Synthetic Example 20. Synthesis of Compound 134

[0223]

[0224] 3-Bromobenzo[b,d]thiophene (5.0 g, 19.00 mmol), intermediate-23 (12.8 g, 20.90 mmol), potassium carbonate (7.9 g, 57.00 mmol), and tetrakis(triphenylphophine)palladium (1.1 g, 0.95 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 50 mL of 1,4-dioxane and 25 mL of water. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in dichlorobenzene, and the filtrate was filtered under reduced pressure through silica gel and Celite to obtain a filtrate. The obtained filtrate was concentrated under reduced pressure, dissolved in dichlorobenzene, and recrystallized with acetone to obtain compound 134 (6.8 g, 53.5%).

[0225] Synthetic Example 21. Synthesis of Compound 138

[0226]

[0227] 2-Bromobenzo[b,d]thiophene (5.0 g, 19.00 mmol), intermediate-23 (12.8 g, 20.90 mmol), potassium carbonate (7.9 g, 57.00 mmol), and tetrakis(triphenylphophine)palladium (1.1 g, 0.95 mmol) were added to a round-bottomed flask and stirred overnight under reflux in 50 mL of 1,4-dioxane and 25 mL of water. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in dichlorobenzene, and the filtrate was filtered through silica gel and celite under reduced pressure to obtain a filtrate. The filtrate was concentrated under reduced pressure, dissolved in dichlorobenzene, and recrystallized with acetone to obtain compound 138 (7.2 g, 56.7%).

[0228] Fabrication of organic light-emitting devices: Application to hole-blocking layers

[0229] Comparative Example 1

[0230] After patterning the ITO substrate to have a light-emitting area of ​​2 mm × 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 × 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-AND material was vacuum-deposited to a thickness of 25 nm with a mass ratio of approximately 4% as a host and TPPDA material as a dopant to form a blue light-emitting layer. On this light-emitting layer, BCP compound was formed to a thickness of 5 nm as a hole blocking layer. Bphen material was formed to a thickness of 20 nm as an electron transport layer. Afterwards, LiF material was deposited to form an electron injection layer to a thickness of 1 nm. Afterwards, Al was deposited to a thickness of 100 nm 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.

[0231] [Table 1]

[0232]

[0233] Comparison Example 2

[0234] An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that Comparative Compound 1 shown in Table 2 below was used instead of BCP as a hole-blocking layer.

[0235] [Table 2]

[0236]

[0237] Examples 1 to 21

[0238] 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 21 were used instead of BCP as the hole-blocking layer.

[0239] Experimental Example 1. Evaluation of Organic Light-Emitting Devices: Application of a Hole-Blocking Layer

[0240] 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.

[0241] [Table 3]

[0242]

[0243] As can be seen from the results in Table 3 above, examples using the compound of the present invention as a hole blocking layer showed improved characteristics in voltage, efficiency, and lifespan compared to comparative examples.

[0244] Fabrication of organic light-emitting devices: Application to electron transport layers

[0245] Comparative Example 3

[0246] An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that Comparative Compound 1 shown in Table 2 was used instead of Bphen as the electron transport layer.

[0247] Examples 22 to 42

[0248] 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 21 were used instead of Bphen as the electron transport layer.

[0249] Experimental Example 2. Evaluation of Organic Light-Emitting Devices: Application to the Electron Transport Layer

[0250] The operating voltage, current efficiency, and lifespan of the previously fabricated organic light-emitting device were evaluated. The evaluation results are shown in Table 4 below.

[0251] [Table 4]

[0252]

[0253] As shown in Table 4 above, when applied to the electron transport layer, the voltage, efficiency, and lifespan of the examples were also improved compared to the comparative examples. This is because the compounds of the present invention, due to their excellent electron injection and electron transport capabilities, can rapidly transport electrons from the electron injection layer to the hole blocking layer when applied to the electron transport layer.

[0254] The novel compound of the present invention is characterized by having a structure in which a heterocyclic group represented by structural formula A containing O or S is bonded to the 3-position of 1,5-naphthyridine. The heterocyclic group represented by structural formula A containing O or S has a characteristic of good electron injection because its orbital distribution is spread throughout, and the 1,5-naphthyridine group has a large electron affinity, so that the LUMO energy level is lowered, resulting in a small energy gap, and thus has excellent electron transport ability, and also has excellent durability due to its rigid structure. Therefore, the compound of the present invention combining these has the advantage of easy electron movement due to the characteristics of excellent electron mobility and good electron injection, and can be applied to an electron transport layer, a hole blocking layer, or a charge generation layer of an organic light-emitting device due to its excellent durability.

Claims

1. A novel compound represented by the following chemical formula 1: In the above chemical formula 1, Ar1 is the structural formula A below, Ar2 is each independently hydrogen, deuterium, halogen, chloro group (-Cl), bromo group (-Br), 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, substituted or unsubstituted C2~C30 heteroaryl group, substituted or unsubstituted C6~C30 aryloxy group, substituted or unsubstituted C6~C30 arylthio group, substituted or unsubstituted Selected from the group consisting of a C6~C30 amine group, a substituted or unsubstituted arylsilyl group, and a substituted or unsubstituted arylphosphine oxide group, L1 and L2 are each independently a direct bond, a substituted or unsubstituted C6~C30 arylene group, or a substituted or unsubstituted C2~C30 heteroarylene group, In the above structural formula A, X is O or S, Y1 to Y8 are each independently N or CR, and the position at which they are bonded to chemical formula 1 is C, Each R is independently selected from the group consisting of hydrogen, deuterium, halogen, chloro group (-Cl), bromo group (-Br), cyano group, nitro group, nitrile group, substituted or unsubstituted C1~C30 alkyl group, substituted or unsubstituted C6~C30 aryl group, and substituted or unsubstituted C2~C30 heteroaryl group.

2. In paragraph 1, The above chemical formula 1 is a novel compound characterized by the following chemical formula 2 or 3: In the above chemical formulas 2 and 3, Ar1, Ar2, L1 and L2 have the same definitions as in the above chemical formula 1.

3. In paragraph 2, The above chemical formula 3 is a novel compound characterized by the following chemical formula 4: In the above chemical formula 4, Ar1, Ar2 and L2 are the same as defined in the above chemical formula 1, X1 to X3 are each independently N or CH, L3 is a direct bond, a substituted or unsubstituted C6~C30 arylene group, or a substituted or unsubstituted C2~C30 heteroarylene group.

4. In paragraph 1, A novel compound characterized in that the structural formula A is one selected from the following structural formulas A-1 to A-4: In the above structural formulas A-1 to A-4, X and Y1 to Y8 are as defined in the above structural formula A.

5. In paragraph 1, A novel compound characterized in that the structural formula A is one selected from the following structural formulas A-10 to A-46: In the above structural formulas A-10 to A-46, X and R are the same as defined in the above structural formula A, m is an integer from 0 to 2, each independently.

6. In paragraph 1, A novel compound characterized in that each of the above Ar2 is independently hydrogen or selected from the following structural formulas B-1 to B-68:

7. In paragraph 1, The above compound is a novel compound characterized in that it is selected from compounds consisting of compounds 1 to 140 below:

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 novel 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