Organic light-emitting compound and organic electroluminescent element comprising the same

Abstract

The present application relates to a novel compound and an organic electroluminescent element comprising the same, and by using the compound of the present application in an organic layer, preferably a light-emitting layer, a light-emitting auxiliary layer, an electron-transport auxiliary layer, or an electron-transport layer, of an organic electroluminescent element, it is possible to improve the light-emitting efficiency, driving voltage, lifespan, and the like of the organic electroluminescent element.

Description

Technical Field

[0001] This invention relates to novel organic light-emitting compounds and organic electroluminescent elements utilizing the same, and more specifically, to compounds with excellent electron transport and light emission capabilities, and organic electroluminescent elements whose luminous efficiency, driving voltage, lifetime, and other characteristics are improved by adding them to one or more organic layers. Background Technology

[0002] Starting with Bernanose's observations of organic thin-film luminescence in the 1950s, research was subsequently conducted on organic electroluminescent devices, which were developed in 1965 using the blue electroluminescence of anthracene single crystals. Then, in 1987, Tang proposed a layered organic electroluminescent device consisting of two functional layers: a hole layer and a light-emitting layer. Following this, to fabricate high-efficiency, long-lifetime organic electroluminescent devices, morphologies for introducing various characteristic organic layers within the device were developed, leading to the development of specialized materials for this purpose.

[0003] In organic electroluminescent devices, if a voltage is applied between two electrodes, holes are injected from the anode into the organic layer, and electrons are injected from the cathode. When the injected holes and electrons meet, they form excitons. When these excitons transition to the ground state, they emit light. The materials used in the organic layer can be categorized according to their function as light-emitting materials, hole-injecting materials, hole-transporting materials, electron-transporting materials, and electron-injecting materials.

[0004] The light-emitting layer materials of organic EL devices can be categorized into blue, green, and red light-emitting materials based on their emission color. Additionally, yellow and orange light-emitting materials are used to produce more natural colors. Furthermore, to increase color purity and luminous efficiency through energy transfer, a host / doped system can be used as the light-emitting material. Dopants can be classified into fluorescent dopants using organic materials and phosphorescent dopants using metal coordination compounds containing heavy atoms such as Ir and Pt. Since the development of such phosphorescent materials can theoretically improve luminous efficiency by up to four times compared to fluorescence, not only phosphorescent dopants but also phosphorescent host materials are attracting attention.

[0005] To date, NPB, BCP, and Alq3 are widely known as hole injection, hole transport, electron transport, and electron injection materials, while anthracene derivatives have been reported as luminescent materials. In particular, Ir-containing metal coordination compounds such as Firpic, Ir(ppy)3, and (acac)Ir(btp)2, which offer advantages in efficiency improvement for luminescent materials, have been used as blue, green, and red phosphorescent dopants, and 4,4-dicarbazolybiphenyl (CBP) has been used as a phosphorescent host material.

[0006]

[0007] However, conventional organic layer materials have low glass transition temperatures and poor thermal stability, as well as low triplet energies. Therefore, organic electroluminescent devices incorporating these materials in their organic layers cannot exhibit satisfactory levels of current efficiency and lifetime characteristics. Thus, there is a need to develop organic layer materials with superior performance.

[0008] Patent Document 1: Korean Patent Publication No. 2016-0078237 Summary of the Invention

[0009] Technical issues

[0010] The purpose of this invention is to provide novel compounds that possess excellent heat resistance, charge carrier transport capability, and luminescence capability, and can be used as organic layer materials, specifically luminescent layer materials, electron transport auxiliary layer materials, luminescence auxiliary layer materials, or electron transport layer materials, in organic electroluminescent elements.

[0011] Furthermore, the object of the present invention is to provide an organic electroluminescent element containing the above-mentioned novel compound, which has low driving voltage, high luminous efficiency, and improved lifetime.

[0012] Methods for solving problems

[0013] To achieve the above objectives, one example of the present invention provides a compound represented by the following chemical formula 1.

[0014] [Chemical Formula 1]

[0015]

[0016] In the above chemical formula 1,

[0017] Z1 to Z3 are either nitrogen or carbon, and contain at least two nitrogen atoms.

[0018] X is represented by the following chemical formula 2 or chemical formula 3.

[0019] [Chemical Formula 2]

[0020]

[0021] [Chemical Formula 3]

[0022]

[0023] Among the above chemical formulas 2 to 3,

[0024] One of Y1 to Y4 is nitrogen, and the rest are carbon; one of Y5 to Y6 is nitrogen, and the other is carbon.

[0025] The asterisk (*) indicates the portion that forms a bond with chemical formula 1 above.

[0026] n is an integer from 1 to 3.

[0027] L selects a free single key, C6~C 18 The group consists of arylene groups and heteroarylene groups with 5 to 18 nuclei.

[0028] A is represented by the following chemical formula 4.

[0029] [Chemical Formula 4]

[0030]

[0031] In the above chemical formula 4,

[0032] R a and R b They are the same or different from each other, and each is independently classified as C1 to C2. 40 Alkyl or C6-C 60 The aryl groups, or those that combine with each other to form a condensation ring,

[0033] R1 and R2 may be the same as or different from each other, and are independently chosen from hydrogen, deuterium, halogen group, cyano group, nitro group, amino group, C1-C2. 40 Alkyl groups, C2-C 40 alkenyl, C2~C 40 alkynyl group, C3~C 40 Cycloalkyl groups, heterocyclic alkyl groups with 3 to 40 nuclei, C6 to C4 cycloalkyl groups 60 aryl, heteroaryl with 5 to 60 nuclei, C1 to C 40 alkoxy groups, C6-C 60 aryloxy groups, C1-C 40 alkylsilyl, C6-C 60 arylsilyl, C1-C 40 alkylboron group, C6-C 60 arylboryl, C1-C 40 Phosphine group, C1-C 40Phosphine oxide and C6-C 60 A group composed of arylamine groups, or a condensation ring formed by combining with adjacent groups.

[0034] c is an integer from 0 to 4, and d is an integer from 0 to 3.

[0035] The asterisk (*) indicates the portion that forms a bond with chemical formula 1 above.

[0036] The above R a R b The alkyl, aryl, alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylsilyl, arylsilyl, alkylboronyl, arylboronyl, phosphinyl, phosphine oxide, arylamino, and the arylene and heteroarylene of L are each independently selected from deuterium, halogen, cyano, nitro, amino, C1-C1. 40 Alkyl groups, C2-C 40 alkenyl, C2~C 40 alkynyl group, C3~C 40 Cycloalkyl groups, heterocyclic alkyl groups with 3 to 40 nuclei, C6 to C4 cycloalkyl groups 60 aryl, heteroaryl with 5 to 60 nuclei, C1 to C 40 alkoxy groups, C6-C 60 aryloxy groups, C1-C 40 alkylsilyl, C6-C 60 arylsilyl, C1-C 40 alkylboron group, C6-C 60 arylboryl, C1-C 40 Phosphine group, C1-C 40 Phosphine oxide and C6-C 60 One or more substituents in the group consisting of arylamine groups are substituted or unsubstituted, and when there are multiple substituents, the multiple substituents are the same or different from each other.

[0037] Furthermore, the present invention provides an organic electroluminescent element comprising an anode, a cathode, and one or more organic layers between the anode and the cathode, wherein at least one of the organic layers comprises a compound represented by Chemical Formula 1. The organic layer comprising the compound represented by Chemical Formula 1 can be selected from the group consisting of a hole injection layer, a hole transport layer, a light-emitting auxiliary layer, a light-emitting layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer. In this case, the compound represented by Chemical Formula 1 can be used as an electron transport material for the electron transport layer and the electron transport auxiliary layer.

[0038] Invention Effects

[0039] According to an example of the present invention, the compound represented by chemical formula 1 has excellent heat resistance, charge carrier transport capability, luminescence capability, etc., and therefore can be used as an organic layer material for organic electroluminescent elements.

[0040] Furthermore, organic electroluminescent elements containing compounds according to an example of the present invention can be significantly improved in terms of luminous performance, driving voltage, lifetime, and efficiency, and such organic electroluminescent elements can be effectively used in full-color display panels, etc. Detailed Implementation

[0041] The present invention will now be described in detail.

[0042] <Organic Compounds>

[0043] The novel organic compounds of the present invention are compounds having a basic framework consisting of a fluorene moiety bonded to an electron-withdrawing group (EWG) of a pyridine compound attached to a triazine or pyrimidine, and are represented by the above-mentioned chemical formula 1.

[0044] The compound represented by Formula 1 exhibits excellent electrochemical stability due to the combination of pyrimidine (or triazine) with electron-withdrawing groups (EWGs) and pyridine. It not only possesses excellent electron transport properties but also exhibits high triplet energy, superior glass transition temperature, and excellent thermal stability. Furthermore, the compound represented by Formula 1 has a higher molecular weight than conventional organic EL element materials, resulting in a high glass transition temperature and excellent thermal stability.

[0045] Therefore, the compound represented by the above chemical formula 1 has excellent electron transport capability and luminescence properties, and can thus be used as a material for any of the following layers in an organic layer of an organic electroluminescent element: a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. Preferably, it can be used as a material for any of the following layers in green phosphorescence: a light-emitting layer, an electron transport layer, and an electron transport auxiliary layer additionally stacked on top of the electron transport layer.

[0046] Specifically, the compound represented by Formula 1 possesses high triplet energy and, due to its triplet-triplet fusion (TTF) effect, can be used as an electron transport auxiliary layer, thus exhibiting excellent efficiency improvements. Furthermore, it prevents excitons generated in the luminescent layer from diffusing into the adjacent electron transport or hole transport layer. The increased number of excitons contributing to luminescence in the luminescent layer improves the device's luminous efficiency, and the improved durability and stability effectively increase the device's lifetime. Organic electroluminescent devices utilizing this compound (Formula 1) can mostly achieve low-voltage operation, thereby exhibiting improved lifetime physical characteristics.

[0047] Therefore, when the compound represented by the above chemical formula 1 is used in organic electroluminescent devices, it can not only be expected to have excellent thermal stability and carrier transport capability (especially electron transport capability and light emission capability), but also improve the driving voltage, efficiency, lifetime and other aspects of the device.

[0048] Furthermore, the compound represented by Formula 1 not only exhibits excellent electron transport properties but also demonstrates long lifetime characteristics. The superior electron transport capabilities of such compounds can result in high efficiency and rapid mobility in organic electroluminescent devices, and the HOMO and LUMO energy levels can be easily tuned based on the orientation or position of the substituents. Therefore, organic electroluminescent devices using such compounds can exhibit high electron transport performance.

[0049] Specifically, the compound represented by chemical formula 1 of the present invention can be represented by any one of the following chemical formulas 5 to 10.

[0050] [Chemical Formula 5]

[0051]

[0052] [Chemical Formula 6]

[0053]

[0054] [Chemical Formula 7]

[0055]

[0056] [Chemical Formula 8]

[0057]

[0058] [Chemical Formula 9]

[0059]

[0060] [Chemical Formula 10]

[0061]

[0062] In the above chemical formulas 5 to 10, R a R b R1, R2, Y1 to Y6, L, c, d and n are the same as those defined in chemical formula 1.

[0063] Preferably, in the above chemical formula 1, X can be selected from the group consisting of the structures represented by X-1 to X-6 below.

[0064]

[0065] Preferably, in the above chemical formula 1, The structure represented by (* indicates the site of bonding) can be selected from the group consisting of the structures represented by Ar-1 to Ar-5 below.

[0066]

[0067] Preferably, the above-mentioned R a and R b Each can be independently methyl or phenyl, or they can be formed by combining with each other. (* indicates the condensation ring formed by the junction)

[0068] Preferably, in the above chemical formula 1, A can be selected from the group consisting of the structures represented by A-1 to A-6 below.

[0069]

[0070] Preferably, in the above chemical formula 1, L can be a single bond or a group selected from the structures represented by L-1 to L-7 below.

[0071]

[0072] The compounds represented by Chemical Formula 1 of the present invention described above can be further embodied by any of the compounds represented by compounds 1 to 750 exemplified below. However, the compounds represented by Chemical Formula 1 of the present invention are not limited to the compounds exemplified below.

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102] In this invention, "alkyl" means a monovalent functional group obtained by removing hydrogen atoms from a straight-chain or branched saturated hydrocarbon with 1 to 40 carbon atoms. Non-limiting examples include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, isopentyl, hexyl, etc.

[0103] In this invention, "alkenyl" means a monovalent substituent derived from a straight-chain or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and one or more carbon-carbon double bonds. Examples of such alkenyl groups include vinyl, allyl, isopropenyl, and 2-butenyl, but are not limited thereto.

[0104] In this invention, "alkynyl" means a monovalent substituent derived from a straight-chain or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and one or more carbon-carbon triple bonds. Examples of such alkynyl groups include ethynyl and 2-propynyl, but are not limited thereto.

[0105] In this invention, "aryl" means a monovalent substituent derived from an aromatic hydrocarbon with 6 to 60 carbon atoms, consisting of a single ring or a combination of two or more rings. Furthermore, it may also include forms where two or more rings are simply attached to each other or condensed together. Examples of such aryl groups include phenyl, naphthyl, phenanthryl, anthracene, etc., but are not limited thereto.

[0106] In this invention, "heteroaryl" means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon with 5 to 60 atomic nuclei. In this case, one or more carbons in the ring, preferably 1 to 3 carbons, are replaced by heteroatoms such as N, O, S, or Se. Furthermore, it may also include forms in which two or more rings are simply attached to or condensed together, and further may include forms condensed with an aryl group. Examples of such heteroaryl groups include six-membered monocyclic compounds such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl; phenyl... Polycyclic compounds such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, and carbazolyl; as well as 2-furanyl, N-imidazolyl, and 2-isocyanoyl groups. Azolyl, 2-pyridyl, 2-pyrimidinyl, etc., but not limited to these.

[0107] In this invention, "aryloxy group" means a 1-valent functional group represented by R"O-, where R" is an aryl group with 6 to 60 carbon atoms. Non-limiting examples of such aryloxy groups include phenoxy, naphthoxy, and diphenoxy groups.

[0108] In this invention, "alkoxy" means a monovalent functional group represented by R'O-, where R' is an alkyl group with 1 to 40 carbon atoms, and may include linear, branched, or cyclic structures. Non-limiting examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, 1-propoxy, tert-butoxy, n-butoxy, and pentoxy.

[0109] In this invention, "cycloalkyl" refers to a monovalent functional group obtained by removing hydrogen atoms from a monocyclic or polycyclic non-aromatic hydrocarbon (saturated cyclic hydrocarbon) with 3 to 40 carbon atoms. Non-limiting examples include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, and adamantine.

[0110] In this invention, "heterocyclic alkyl" means a monovalent functional group obtained by removing hydrogen atoms from a non-aromatic hydrocarbon (saturated cyclic hydrocarbon) with 3 to 40 atomic nuclei, wherein one or more carbons in the ring, preferably 1 to 3 carbons, are replaced by heteroatoms such as N, O, or S. Examples of its non-limiting properties include morpholinoyl and piperazineoyl groups.

[0111] In this invention, "alkylsilyl" means silyl group substituted with an alkyl group having 1 to 40 carbon atoms, "arylsilyl" means silyl group substituted with an aryl group having 6 to 60 carbon atoms, "alkylboryl" means boron group substituted with an alkyl group having 1 to 40 carbon atoms, "arylboryl" means boron group substituted with an aryl group having 6 to 60 carbon atoms, "arylphosphinyl" means phosphinyl group substituted with an aryl group having 1 to 60 carbon atoms, and "arylamine" means amine group substituted with an aryl group having 6 to 60 carbon atoms.

[0112] In this invention, "condensed ring" means a morphology consisting of a condensed aliphatic ring, a condensed aromatic ring, a condensed aliphatic heterocycle, a condensed aromatic heterocycle, or a combination thereof.

[0113] The compounds represented by Chemical Formula 1 of this invention can be synthesized in a variety of ways with reference to the synthesis procedures in the following examples. Detailed synthesis procedures for the compounds of this invention will be specifically described in the synthesis examples described later.

[0114] Organic electroluminescent elements

[0115] The present invention provides an organic electroluminescent element comprising the compound represented by the above chemical formula 1.

[0116] More specifically, the organic electroluminescent element of the present invention comprises an anode, a cathode, and one or more organic layers between the anode and the cathode, wherein at least one of the organic layers comprises a compound represented by chemical formula 1. In this case, the compound may be used alone or in combination of two or more.

[0117] The aforementioned organic layers (one or more) can be any one or more of a hole injection layer, a hole transport layer, a light-emitting auxiliary layer, a light-emitting layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer, wherein at least one organic layer may contain a compound represented by Chemical Formula 1. Specifically, the organic layer containing the compound of Chemical Formula 1 is preferably a light-emitting layer, an electron transport auxiliary layer, and an electron transport layer.

[0118] The light-emitting layer of the organic electroluminescent element of the present invention may comprise a host material (preferably a phosphorescent host material). Furthermore, the light-emitting layer of the organic electroluminescent element of the present invention may comprise a compound other than the compound of Formula 1 described above as a host.

[0119] The structure of the organic electroluminescent element of the present invention is not particularly limited. As a non-limiting example, it can be a structure in which a substrate, an anode, a hole injection layer, a hole transport layer, a light-emitting auxiliary layer, a light-emitting layer, an electron transport layer, and a cathode are sequentially stacked. In this case, one or more of the aforementioned hole injection layer, hole transport layer, light-emitting auxiliary layer, light-emitting layer, and electron transport layer may contain a compound represented by Chemical Formula 1. Preferably, the light-emitting layer or electron transport layer may contain a compound represented by Chemical Formula 1. Here, an electron injection layer may be further stacked on the electron transport layer. Furthermore, the structure of the organic electroluminescent element of the present invention can be a structure in which an electron transport auxiliary layer is added together with the electrode and the aforementioned organic layer. In this case, one or more of the aforementioned hole injection layer, hole transport layer, light-emitting auxiliary layer, light-emitting layer, electron transport auxiliary layer, and electron transport layer may contain a compound represented by Chemical Formula 1. Preferably, the light-emitting layer, electron transport auxiliary layer, or electron transport layer may contain a compound represented by Chemical Formula 1.

[0120] On the other hand, the organic electroluminescent element of the present invention, except that one or more of the organic layers contain the compound represented by the above chemical formula 1, can be formed and manufactured using materials and methods known in the art to form and manufacture the organic layers and electrodes.

[0121] The aforementioned organic layer can be formed by vacuum evaporation or solution coating. Examples of solution coating methods include spin coating, dip coating, blade coating, inkjet printing, or thermal transfer printing, but are not limited to these.

[0122] The substrate used in manufacturing organic electroluminescent elements according to the present invention is not particularly limited, and silicon wafers, quartz, glass plates, metal plates, plastic films and sheets, etc. can be used.

[0123] In addition, as anode materials, examples include metals such as vanadium, chromium, copper, zinc, and gold, or their alloys; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; conductive polymers such as polythiophene, poly(3-methylthiophene), poly[3,4-(ethylidene-1,2-dioxothiophene] (PEDT), polypyrrole, or polyaniline; and carbon black, but are not limited to these.

[0124] In addition, examples of cathode materials include metals or alloys thereof such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead; as well as multilayer materials such as LiF / Al or LiO2 / Al, but are not limited to these.

[0125] Furthermore, the hole injection layer, hole transport layer, and luminescent auxiliary layer are not particularly limited and can be made of materials known in the art.

[0126] The present invention will now be described in detail through examples. However, the following examples are merely illustrative and the present invention is not limited to these examples.

[0127] [Preparation Example 1] Synthesis of PPY-1

[0128] <Step 1> Synthesis of PPY-1

[0129]

[0130] 45.0 g of 4,6-dichloro-2-phenylpyrimidine, 40.0 g of (4-(pyridin-3-yl)phenyl)boronic acid, 6.0 g of tetrakis(triphenylphosphine)palladium(O), and 42 g of K₂CO₃ were added to 800 ml of toluene, 200 ml of ethanol, and 200 ml of water, and the mixture was heated under reflux with stirring for 2 hours. After the reaction was completed, the solution was deactivated with sufficient water, transferred to a separatory funnel, and extracted with dichloromethane. The organic layer was dried with magnesium sulfate, concentrated, and purified by column chromatography to obtain PPY-139.8 g (yield 58%).

[0131] 1H-NMR: δ9.24(s,1H),8.70(d,1H),8.42-8.30(m,5H),7.57-7.50(m,4H),7.25(d,2H)7.03(s,1H)

[0132] Mass: [(M+H)] + ]:344

[0133] [Preparation Example 2] Synthesis of PPY-2 to PPY-3

[0134] <Step 1> Synthesis of (E)-1-(4-bromophenyl)-3-(4-pyridin-3-yl)phenyl)prop-2-en-1-one

[0135]

[0136] 50.0 g of 4-(pyridin-3-yl)benzaldehyde, 49.1 g of 1-(4-bromophenyl)ethane-1-one, and 18.2 g of sodium methoxide were added to 800 ml of ethanol and stirred for 8 hours. After the reaction was completed, the mixture was stirred at room temperature for 1 hour, then extracted with ethyl acetate. The organic layer was dried with magnesium sulfate, concentrated, and purified by column chromatography to obtain 36.4 g of (E)-1-(4-bromophenyl)-3-(4-pyridin-3-yl)phenyl)prop-2-en-1-one (yield 72%).

[0137] 1H-NMR: δ9.24(s,1H),8.50(d,1H),8.38(d,1H),8.08-8.01(m,3H),7.75(d,2H),7.60-7.45(m,6H)

[0138] Mass: [(M+H)] + ]:364

[0139] <Step 2> Synthesis of PPY-2

[0140]

[0141] 36.4 g of (E)-1-(4-bromophenyl)-3-(4-pyridin-3-yl)phenyl)prop-2-en-1-one, 24.1 g of benzylamidin hydrochloride, and 14.2 g of sodium hydroxide were added to 500 ml of ethanol, and the mixture was heated under reflux with stirring for 4 hours. After the reaction was completed, the reactants were concentrated under reduced pressure to 250 ml, deactivated with sufficient water, and the solution was transferred to a separatory funnel and extracted with dichloromethane. The organic layer was dried with magnesium sulfate, concentrated, and purified by column chromatography to obtain 36.2 g of PPY-2 (yield 79%).

[0142] 1H-NMR: δ9.21(s,1H),8.70(d,1H),8.42-8.30(m,6H),7.76(d,2H),7.59-7.55(m,6H),7.25(d,2H)

[0143] Mass: [(M+H)] + ]:464

[0144] <Step 3> Synthesis of PPY-3

[0145]

[0146] 15.0 g of PPY-2, 6.1 g of (3-chlorophenyl)boric acid, 0.9 g of tetraphenylphosphine palladium(0), and 7.0 g of K2CO3 were added to 300 ml of toluene, 60 ml of ethanol, and 60 ml of water. The mixture was heated under reflux with stirring for 2 hours. After the reaction was complete, the solution was deactivated with sufficient water, transferred to a separatory funnel, and extracted with dichloromethane. The organic layer was dried with magnesium sulfate, concentrated, and purified by column chromatography to obtain 10.9 g of PPY-3 (yield 68%).

[0147] 1H-NMR: δ9.21(s,1H),8.70(d,1H),8.42-8.30(m,6H),7.97(s,1H),7.76(d,2H),7.59-7.55(m,6H),7.48(m,2H),7.39(d,1H),7.25(d,2H)

[0148] Mass: [(M+H)] + ]:496

[0149] [Preparation Example 3] Synthesis of PPY-4 to PPY-6

[0150] <Step 1> Synthesis of (E)-1-(3-bromophenyl)-3-(4-pyridin-3-yl)phenyl)prop-2-en-1-one

[0151]

[0152] 50.0 g of 4-(pyridin-3-yl)benzaldehyde, 49.1 g of 1-(3-bromophenyl)ethane-1-one, and 18.2 g of sodium methoxide were added to 800 ml of ethanol and stirred for 8 hours. After the reaction was completed, the mixture was stirred gently at room temperature for 1 hour, then extracted with ethyl acetate. The organic layer was dried with magnesium sulfate, concentrated, and purified by column chromatography to obtain 38.2 g of (E)-1-(3-bromophenyl)-3-(4-pyridin-3-yl)phenyl)prop-2-en-1-one (yield 74%).

[0153] 1H-NMR: δ9.24(s,1H),8.50(d,1H),8.38(d,1H),8.08-8.01(m,3H),7.82(d,1H),7.60-7.45(m,7H)

[0154] Mass: [(M+H)] + ]:364

[0155] <Step 2> Synthesis of PPY-4

[0156]

[0157] 38.2 g of (E)-1-(3-bromophenyl)-3-(4-pyridin-3-yl)phenyl)prop-2-en-1-one, 25.0 g of benzylamine hydrochloride, and 14.8 g of sodium hydroxide were added to 500 ml of ethanol, and the mixture was heated under reflux with stirring for 4 hours. After the reaction was completed, the reactants were concentrated under reduced pressure to 250 ml, deactivated with sufficient water, and the solution was transferred to a separatory funnel and extracted with dichloromethane. The organic layer was dried with magnesium sulfate, concentrated, and purified by column chromatography to obtain 34.2 g of PPY-4 (yield 75%).

[0158] 1H-NMR: δ9.24(s,1H),8.70(d,1H),8.42-8.30(m,6H),7.78(d,1H),7.67(d,1H)7.50-7.43(m,6H),7.25(d,2H)

[0159] Mass: [(M+H)] + ]:464

[0160] <Step 3> Synthesis of PPY-5

[0161]

[0162] 15.0 g of PPY-4, 6.1 g of (3-chlorophenyl)boric acid, 0.9 g of tetraphenylphosphine palladium(0), and 7.0 g of K2CO3 were added to 300 ml of toluene, 60 ml of ethanol, and 60 ml of water. The mixture was heated under reflux with stirring for 2 hours. After the reaction was complete, the solution was deactivated with sufficient water, transferred to a separatory funnel, and extracted with dichloromethane. The organic layer was dried with magnesium sulfate, concentrated, and purified by column chromatography to obtain 10.1 g of PPY-5 (yield 67%).

[0163] 1H-NMR: δ9.24(s,1H),8.70(d,1H),8.42-8.30(m,6H),7.97(s,1H),7.78(d,1H),7.67(d,1H)7.50-7.43(m,8H),7.35(d,1H),7.25(d,2H)

[0164] Mass: [(M+H)] + ]:496

[0165] <Step 4> Synthesis of PPY-6

[0166]

[0167] 10.0 g of PPY-5, 4.1 g of (3-chlorophenyl)boric acid, 0.1 g of Pd(OAc)2, 0.4 g of XPhos, and 4.5 g of Cs2CO3 were added to 200 ml of toluene, 40 ml of ethanol, and 40 ml of water. The mixture was heated under reflux with stirring for 2 hours. After the reaction was complete, the solution was deactivated with sufficient water, transferred to a separatory funnel, and extracted with dichloromethane. The organic layer was dried with magnesium sulfate, concentrated, and purified by column chromatography to obtain 6.7 g of PPY-6 (yield 66%).

[0168] 1H-NMR: δ9.24(s,1H),8.70(d,1H),8.42-8.30(m,6H),7.97(s,1H),7.90(s ,1H),7.78(d,1H),7.67(d,1H)7.50-7.40(m,10H),7.35(d,2H),7.25(d,2H)

[0169] Mass: [(M+H)] + ]:572

[0170] [Preparation Example 4] Synthesis of PPY-7~8

[0171] <Step 1> Synthesis of PPY-7

[0172]

[0173] 45.0 g of 4,6-dichloro-2-phenylpyrimidine, 38.7 g of (6-phenylpyridin-3-yl)boric acid, 6.0 g of tetrakis(triphenylphosphine)palladium(O), and 42 g of K₂CO₃ were added to 800 ml of toluene, 200 ml of ethanol, and 200 ml of water, and the mixture was heated under reflux with stirring for 2 hours. After the reaction was completed, the solution was deactivated with sufficient water, transferred to a separatory funnel, and extracted with dichloromethane. The organic layer was dried with magnesium sulfate, concentrated, and purified by column chromatography to obtain 40.7 g of PPY-7 (yield 61%).

[0174] 1H-NMR: δ9.23(s,1H),8.62(d,1H),8.42-8.30(m,3H),7.96(d,2H),7.73(s,1H),7.54-7.48(m,4H),7.31(d,2H)

[0175] Mass: [(M+H)] + ]:344

[0176] <Step 2> Synthesis of PPY-8

[0177]

[0178] 15.0 g of PPY-7, 6.1 g of (3-chlorophenyl)boric acid, 0.9 g of tetraphenylphosphine palladium(0), and 7.1 g of K₂CO₃ were added to 300 ml of toluene, 60 ml of ethanol, and 60 ml of water. The mixture was heated under reflux with stirring for 2 hours. After the reaction was complete, the solution was deactivated with sufficient water, transferred to a separatory funnel, and extracted with dichloromethane. The organic layer was dried with magnesium sulfate, concentrated, and purified by column chromatography to obtain 13.7 g of PPY-8 (yield 72%).

[0179] 1H-NMR: δ9.15(s,1H),8.73(d,1H),8.43-8.12(m,4H),8.13(s,1H),7.99-7.97(m,3H),7.52-7.41(m,6H),7.11(d,2H)

[0180] Mass: [(M+H)] + ]:420

[0181] [Preparation Example 5] Synthesis of PTZ-1 to 2

[0182] <Step 1> Synthesis of PTZ-1

[0183]

[0184] 45.0 g of 2,4-dichloro-6-phenyl-1,3,5-triazine, 39.2 g of (4-(pyridin-3-yl)phenyl)boronic acid, 6.0 g of tetrakis(triphenylphosphine)palladium(O), and 42 g of K₂CO₃ were added to 800 ml of toluene, 200 ml of ethanol, and 200 ml of water. The mixture was heated under reflux with stirring for 2 hours. After the reaction was complete, the solution was deactivated with sufficient water, transferred to a separatory funnel, and extracted with dichloromethane. The organic layer was dried with magnesium sulfate, concentrated, and purified by column chromatography to obtain 36.2 g of PTZ-1 (yield 53%).

[0185] 1H-NMR: δ9.24(s,1H),8.70(d,1H),8.42-8.30(m,3H),7.96(d,2H),7.57-7.50(m,4H),7.25(d,2H)

[0186] Mass: [(M+H)] + ]:345

[0187] <Step 2> Synthesis of PTZ-2

[0188]

[0189] PTZ-1 10.0 g, (3-chlorophenyl)boric acid 4.1 g, tetrakis(triphenylphosphine)palladium(0) 0.6 g, and K₂CO₃ 4.7 g were added to 200 ml of toluene, 40 ml of ethanol, and 40 ml of water, and the mixture was heated under reflux with stirring for 2 hours. After the reaction was complete, the solution was deactivated with sufficient water, transferred to a separatory funnel, and extracted with dichloromethane. The organic layer was dried with magnesium sulfate, concentrated, and purified by column chromatography to obtain PTZ-2 8.7 g (yield 71%).

[0190] 1H-NMR: δ9.24(s,1H),8.70(d,1H),8.42-8.30(m,3H),8.16(s,1H),7.96-7.95(m,3H),7.50-7.43(m,6H),7.25(d,2H)

[0191] Mass: [(M+H)] + ]:421

[0192] [Preparation Example 6] Synthesis of PTZ-3

[0193]

[0194] 45.0 g of 2-([1,1'-biphenyl]-3-yl)-4,6-dichloro-1,3,5-triazine, 38.1 g of (4-(pyridin-2-yl)phenyl)boronic acid, 6.0 g of tetraphenylphosphine palladium(O), and 42 g of K₂CO₃ were added to 800 ml of toluene, 200 ml of ethanol, and 200 ml of water. The mixture was heated under reflux with stirring for 2 hours. After the reaction was completed, the solution was deactivated with sufficient water, transferred to a separatory funnel, and extracted with dichloromethane. The organic layer was dried with magnesium sulfate, concentrated, and purified by column chromatography to obtain PTZ-340.4 g (yield 65%).

[0195] 1H-NMR: δ9.23(s,1H),8.70(d,1H),8.42-8.30(m,3H),7.96(d,2H),7.75(d,2H)7.67-7.43(m,7H),7.23(d,2H)

[0196] Mass: [(M+H)] + ]:421

[0197] [Synthesis Example 1] Synthesis of Compound 1

[0198]

[0199] 3.0 g of PPY-1 was mixed with 4.3 g of (9,9-dimethyl-9H-fluorene-2-yl)boric acid and 3.3 g of K2CO3. 60 ml of toluene, 12 ml of ethanol, and 12 ml of water were added, followed by 500 mg of tetraphenylphosphine palladium(O). The mixture was heated and stirred for 4 hours. After the reaction was complete, the temperature was lowered to room temperature, and the mixture was filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried using MgSO4. After concentration under reduced pressure, column chromatography was performed at an MC:Hex ratio of 2:1 to obtain 2.8 g of a white solid of compound 1 (yield 55%).

[0200] Mass: [(M+H)] + ]:502

[0201] [Synthetic Example 2] Synthesis of Compound 2

[0202]

[0203] 3.0 g of PPY-1 was mixed with 5.1 g of 9,9'-spirobis[fluorene]-2-ylboronic acid and 3.3 g of K2CO3. 60 ml of toluene, 12 ml of ethanol, and 12 ml of water were added, followed by 500 mg of tetra(triphenylphosphine)palladium(O). The mixture was heated and stirred for 4 hours. After the reaction was complete, the temperature was lowered to room temperature, and the mixture was filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried using MgSO4. After concentration under reduced pressure, column chromatography was performed at an MC:Hex ratio of 2:1 to obtain 3.2 g of a white solid of compound 2 (yield 58%).

[0204] Mass: [(M+H)] + ]:624

[0205] [Synthetic Example 3] Synthesis of Compound 4

[0206]

[0207] 3.1 g of PPY-1 was mixed with 4.8 g of (7,7-dimethyl-7H-benzo[c]fluorene-9-yl)boric acid and 3.3 g of K2CO3. 60 ml of toluene, 12 ml of ethanol, and 12 ml of water were added, followed by 500 mg of tetra(triphenylphosphine)palladium(O). The mixture was heated and stirred for 4 hours. After the reaction was complete, the temperature was lowered to room temperature, and the mixture was filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried using MgSO4. After concentration under reduced pressure, column chromatography was performed at an MC:Hex ratio of 2:1 to obtain 3.5 g of a white solid (56% yield) of compound 4.

[0208] Mass: [(M+H)] + ]:551

[0209] [Synthetic Example 4] Synthesis of Compound 42

[0210]

[0211] PTZ-1 3.0 g was mixed with 9,9'-spirobis[fluorene]-4-ylboronic acid 5.1 g and K2CO3 3.3 g. Then, 60 ml of toluene, 12 ml of ethanol and 12 ml of water were added, followed by 500 mg of tetrakis(triphenylphosphine)palladium(O). The mixture was heated and stirred for 4 hours. After the reaction was complete, the temperature was lowered to room temperature, and then filtered. The filtrate was poured into water, and the resulting solid was filtered. The solid was dissolved in sufficient MC, concentrated under reduced pressure, and then subjected to column chromatography at MC:Hex = 2:1 to obtain 4.1 g of a white solid of compound 42 (yield 75%).

[0212] Mass: [(M+H)] + ]:625

[0213] [Synthetic Example 5] Synthesis of Compound 45

[0214]

[0215] PTZ-1 3.2g was mixed with (7,7-dimethyl-7H-benzo[c]fluorene-7-yl)boric acid 4.9g and K2CO3 3.3g. Then, 60ml of toluene, 12ml of ethanol, and 12ml of water were added, followed by 520mg of tetrakis(triphenylphosphine)palladium(O). The mixture was heated and stirred for 4 hours. After the reaction was complete, the temperature was lowered to room temperature, and the mixture was filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried using MgSO4. After concentration under reduced pressure, column chromatography was performed at MC:Hex = 2:1 to obtain 3.8g of a white solid of compound 45 (yield 57%).

[0216] Mass: [(M+H)] + ]:553

[0217] [Synthetic Example 6] Synthesis of Compound 111

[0218]

[0219] 2.0 g of PPY-2 was mixed with 2.1 g of (9,9-dimethyl-9H-fluorene-3-yl)boric acid and 1.8 g of K2CO3. Then, 50 ml of toluene, 10 ml of ethanol, and 10 ml of water were added, followed by 200 mg of tetra(triphenylphosphine palladium(O). The mixture was heated and stirred for 4 hours. After the reaction was complete, the temperature was lowered to room temperature, and the mixture was filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried using MgSO4. After concentration under reduced pressure, column chromatography was performed using MC to obtain 1.8 g of a white solid of compound 111 (76% yield).

[0220] Mass: [(M+H)] + ]:578

[0221] [Synthetic Example 7] Synthesis of Compound 112

[0222]

[0223] 2.0 g of PPY-2 was mixed with 2.5 g of 9,9'-spirobis[fluorene]-3-ylboronic acid and 2.0 g of K2CO3. Then, 50 ml of toluene, 12 ml of ethanol, and 12 ml of water were added, followed by 200 mg of tetra(triphenylphosphine)palladium(O). The mixture was heated and stirred for 4 hours. After the reaction was complete, the temperature was lowered to room temperature, and the mixture was filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried using MgSO4. After concentration under reduced pressure, column chromatography was performed using THF:Hex = 1:5 to obtain 1.5 g of a white solid of compound 112 (yield 55%).

[0224] Mass: [(M+H)] + ]:700

[0225] [Synthetic Example 8] Synthesis of Compound 121

[0226]

[0227] PPY-4 2.1 g was mixed with (9,9-dimethyl-9H-fluorene-2-yl)boric acid 2.2 g and K2CO3 1.9 g. Then, 50 ml toluene, 10 ml ethanol, and 10 ml water were added, followed by 220 mg tetraphenylphosphine palladium(O). The mixture was heated and stirred for 4 hours. After the reaction was complete, the temperature was lowered to room temperature, and then filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried using MgSO4. After concentration under reduced pressure, column chromatography was performed using MC to obtain 1.6 g of a white solid of compound 121 (yield 72%).

[0228] Mass: [(M+H)] + ]:578

[0229] [Synthetic Example 9] Synthesis of Compound 133

[0230]

[0231] 2.1 g of PPY-4 was mixed with 2.7 g of (9,9-diphenyl-9H-fluorene-4-yl)boric acid and 2.1 g of K2CO3. Then, 50 ml of toluene, 12 ml of ethanol, and 12 ml of water were added, followed by 210 mg of tetra(triphenylphosphine-palladium(O). The mixture was heated and stirred for 4 hours. After the reaction was complete, the temperature was lowered to room temperature, and the mixture was filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried using MgSO4. After concentration under reduced pressure, column chromatography was performed using MC with a small amount of pyridine added to obtain 2.1 g of a white solid of compound 133 (68% yield).

[0232] Mass: [(M+H)] + ]:702

[0233] [Synthetic Example 10] Synthesis of Compound 151

[0234]

[0235] PTZ-2.3g was mixed with (9,9-dimethyl-9H-fluorene-2-yl)boric acid 2.3g and Cs₂CO₃ 3.0g. Then, 60ml toluene, 12ml ethanol, and 12ml water were added, followed by 250mg Pd(OAc) and 230mg Xphos. The mixture was heated and stirred for 4 hours. After the reaction was complete, the temperature was lowered to room temperature, and the mixture was filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried using MgSO₄. After concentration under reduced pressure, column chromatography was performed using MC to obtain 2.2g of a white solid of compound 151 (75% yield).

[0236] Mass: [(M+H)] + ]:579

[0237] [Synthetic Example 11] Synthesis of Compound 156

[0238]

[0239] PTZ-22.1g was mixed with 2.2g of (9,9-dimethyl-9H-fluorene-3-yl)boric acid and 2.8g of Cs₂CO₃. Then, 60ml of toluene, 12ml of ethanol, and 12ml of water were added, followed by 248mg of Pd(OAc) and 200mg of Xphos. The mixture was heated and stirred for 4 hours. After the reaction was complete, the temperature was lowered to room temperature, and the mixture was filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried using MgSO₄. After concentration under reduced pressure, column chromatography was performed using MC to obtain 2.0g of a white solid of compound 156 (71% yield).

[0240] Mass: [(M+H)] + ]:579

[0241] [Synthetic Example 12] Synthesis of Compound 346

[0242]

[0243] 2.5 g of PPY-3 was mixed with 2.4 g of (9,9-dimethyl-9H-fluorene-2-yl)boric acid and 3.3 g of Cs₂CO₃. 60 ml of toluene, 12 ml of ethanol, and 12 ml of water were added, followed by 57 mg of Pd(OAc)₂ and 250 mg of Xphos. The mixture was heated and stirred for 4 hours. After the reaction was complete, the temperature was lowered to room temperature, and the mixture was filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried using MgSO₄. After concentration under reduced pressure, column chromatography was performed using MC to obtain 2.3 g of a white solid of compound 346 (70% yield).

[0244] Mass: [(M+H)] + ]:654

[0245] [Synthetic Example 13] Synthesis of Compound 350

[0246]

[0247] 2.5 g of PPY-3 was mixed with 2.8 g of (7,7-dimethyl-7H-benzo[c]fluorene-9-yl)boric acid and 3.3 g of Cs₂CO₃. 60 ml of toluene, 12 ml of ethanol, and 12 ml of water were added, followed by 57 mg of Pd(OAc)₂ and 250 mg of Xphos. The mixture was heated and stirred for 4 hours. After the reaction was complete, the temperature was lowered to room temperature, and the mixture was filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried using MgSO₄. After concentration under reduced pressure, column chromatography was performed using MC to obtain 2.5 g of a white solid of compound 350 (71% yield).

[0248] Mass: [(M+H)] + ]:704

[0249] [Synthetic Example 14] Synthesis of Compound 376

[0250]

[0251] 2.2 g of PPY-5 was mixed with 2.3 g of (9,9-dimethyl-9H-fluorene-2-yl)boric acid and 3.0 g of Cs₂CO₃. 60 ml of toluene, 12 ml of ethanol, and 12 ml of water were added, followed by 50 mg of Pd(OAc)₂ and 230 mg of Xphos. The mixture was heated and stirred for 4 hours. After the reaction was complete, the temperature was lowered to room temperature, and the mixture was filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried using MgSO₄. After concentration under reduced pressure, column chromatography was performed using MC to obtain 2.0 g of a white solid of compound 376 (66% yield).

[0252] Mass: [(M+H)] + ]:654

[0253] [Synthetic Example 15] Synthesis of Compound 377

[0254]

[0255] 2.0 g of PPY-5 was mixed with 2.5 g of (9,9-dimethyl-9H-fluorene-2-yl)boric acid and 3.0 g of Cs₂CO₃. 60 ml of toluene, 12 ml of ethanol, and 12 ml of water were added, followed by 50 mg of Pd(OAc)₂ and 230 mg of Xphos. The mixture was heated and stirred for 4 hours. After the reaction was complete, the temperature was lowered to room temperature, and the mixture was filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried using MgSO₄. After concentration under reduced pressure, column chromatography with a THF:Hex ratio of 1:2 was performed to obtain 2.3 g of a white solid of compound 377 (66% yield).

[0256] Mass: [(M+H)] + ]:776

[0257] [Synthetic Example 16] Synthesis of Compound 380

[0258]

[0259] PPY-52.1g was mixed with (11,11-dimethyl-11H-benzo[a]fluorene-9-yl)boric acid 2.4g and Cs₂CO₃ 2.9g. 60ml of toluene, 12ml of ethanol, and 12ml of other solvents were added, followed by 253mg of Pd(OAc) and 240mg of Xphos. The mixture was heated and stirred for 4 hours. After the reaction was complete, the temperature was lowered to room temperature, and the mixture was filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried using MgSO₄. After concentration under reduced pressure, column chromatography was performed using MC to obtain 1.9g of a white solid of compound 380 (63% yield).

[0260] Mass: [(M+H)] + ]:704

[0261] [Synthetic Example 17] Synthesis of Compound 409

[0262]

[0263] PPY-6 2.0 g was mixed with (7,7-dimethyl-7H-benzo[c]fluorene-9-yl)boric acid 2.1 g and Cs₂CO₃ 2.5 g. Then, 60 ml of toluene, 12 ml of ethanol, and 12 ml of water were added, followed by 248 mg of Pd(OAc) and 210 mg of Xphos. The mixture was heated and stirred for 4 hours. After the reaction was complete, the temperature was lowered to room temperature, and the mixture was filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried using MgSO₄. After concentration under reduced pressure, column chromatography was performed at MC:MeOH = 100:1 to give 2.1 g of a white solid of compound 409 (yield 66%).

[0264] Mass: [(M+H)] + ]:780

[0265] [Synthetic Example 18] Synthesis of Compound 411

[0266]

[0267] PPY-6 2.0 g was mixed with (9,9-dimethyl-9H-fluorene-3-yl)boric acid 2.0 g and Cs₂CO₃ 2.5 g. Then, 60 ml of toluene, 12 ml of ethanol, and 12 ml of water were added, followed by 248 mg of Pd(OAc) and 210 mg of Xphos. The mixture was heated and stirred for 4 hours. After the reaction was complete, the temperature was lowered to room temperature, and the mixture was filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried using MgSO₄. After concentration under reduced pressure, column chromatography was performed at MC:MeOH = 100:1 to give 1.6 g of a white solid of compound 411 (yield 59%).

[0268] Mass: [(M+H)] + ]:730

[0269] [Synthetic Example 19] Synthesis of Compound 436

[0270]

[0271] 3.0 g of PPY-7 was mixed with 4.6 g of (9,9'-dimethyl-9H-fluorene-2-yl)boric acid and 3.2 g of K2CO3. 60 ml of toluene, 12 ml of ethanol, and 12 ml of water were added, followed by 500 mg of tetra(triphenylphosphine palladium(O). The mixture was heated and stirred for 4 hours. After the reaction was complete, the temperature was lowered to room temperature, and the mixture was filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried using MgSO4. After concentration under reduced pressure, column chromatography was performed at an MC:Hex ratio of 2:1 to obtain 3.0 g of a white solid of compound 436 (65% yield).

[0272] Mass: [(M+H)] + ]:502

[0273] [Synthetic Example 20] Synthesis of Compound 448

[0274]

[0275] 2.9 g of PPY-7 was mixed with 5.0 g of (9,9'-diphenyl-9H-fluorene-4-yl)boric acid and 3.1 g of K2CO3. 60 ml of toluene, 12 ml of ethanol, and 12 ml of water were added, followed by 500 mg of tetra(triphenylphosphine-palladium(O). The mixture was heated and stirred for 4 hours. After the reaction was complete, the temperature was lowered to room temperature, and the mixture was filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried using MgSO4. After concentration under reduced pressure, column chromatography was performed at an MC:Hex ratio of 2:1 to obtain 3.9 g of a white solid of compound 448 (62% yield).

[0276] Mass: [(M+H)] + ]:626

[0277] [Synthetic Example 21] Synthesis of Compound 518

[0278]

[0279] PTZ-3 2.6g was mixed with (9,9'-diphenyl-9H-fluorene-3-yl)boric acid 4.6g and K2CO3 3.3g. Then, 60ml of toluene, 12ml of ethanol and 12ml of water were added, followed by 480mg of tetraphenylphosphine palladium(O). The mixture was heated and stirred for 4 hours. After the reaction was complete, the temperature was lowered to room temperature, and then filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried using MgSO4. After concentration under reduced pressure, column chromatography was performed at MC:Hex = 2:1 to obtain 4.2g of a white solid of compound 518 (yield 72%).

[0280] Mass: [(M+H)] + ]:703

[0281] [Synthetic Example 22] Synthesis of Compound 524

[0282]

[0283] PTZ-3 2.0 g was mixed with (7,7-dimethyl-7H-benzo[c]fluorene-11-yl)boric acid 3.6 g and K2CO3 2.3 g. Then, 50 ml of toluene, 10 ml of ethanol and 10 ml of water were added, followed by 400 mg of tetraphenylphosphine palladium(O). The mixture was heated and stirred for 4 hours. After the reaction was complete, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried using MgSO4. After concentration under reduced pressure, column chromatography was performed at MC:Hex = 2:1 to obtain 4.2 g of a white solid of compound 524 (yield 72%).

[0284] Mass: [(M+H)] + ]:629

[0285] [Synthetic Example 23] Synthesis of Compound 542

[0286]

[0287] 2.2 g of PPY-8 was mixed with 2.6 g of 9,9'-spirobis[fluorene]2-ylboronic acid and 2.9 g of Cs₂CO₃. 60 ml of toluene, 12 ml of ethanol, and 12 ml of water were added, followed by 50 mg of Pd(OAc)₂ and 230 mg of Xphos. The mixture was heated and stirred for 4 hours. After the reaction was complete, the temperature was lowered to room temperature, and the mixture was filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried using MgSO₄. After concentration under reduced pressure, column chromatography was performed using MC to obtain 2.1 g of a white solid of compound 542 (53% yield).

[0288] Mass: [(M+H)] + ]:700

[0289] [Synthetic Example 24] Synthesis of Compound 545

[0290]

[0291] 2.3 g of PPY-8 was mixed with 2.4 g of (11,11-dimethyl-11H-benzo[a]fluorene-9-yl)boric acid and 3.0 g of Cs₂CO₃. 60 ml of toluene, 12 ml of ethanol, and 12 ml of water were added, followed by 55 mg of Pd(OAc)₂ and 250 mg of Xphos. The mixture was heated and stirred for 4 hours. After the reaction was complete, the temperature was lowered to room temperature, and the mixture was filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried using MgSO₄. After concentration under reduced pressure, column chromatography was performed using THF:Hex = 1:3 to obtain 2.6 g of a white solid of compound 545 (63% yield).

[0292] Mass: [(M+H)] + ]:628

[0293] [Examples 1 to 13] Fabrication of Blue Organic Electroluminescent Element

[0294] The compounds 1, 2, 4, 42, 45, 111, 112, 121, 133, 151, 156, 346, and 350 synthesized in the synthesis example were purified to high purity by sublimation using commonly known methods, and then blue organic electroluminescent elements were fabricated as follows.

[0295] First, will be Glass substrates coated with a thin film of indium tin oxide (ITO) were ultrasonically washed with distilled water. After washing with distilled water, they were ultrasonically washed with solvents such as isopropanol, acetone, and methanol, and then dried. They were then transferred to a UV ozone cleaner (Power sonic 405, HwashinTech) and cleaned with UV light for 5 minutes. After that, the substrates were transferred to a vacuum evaporation machine.

[0296] On the ITO transparent electrode prepared above, DS-205 (Doosan Electron Co., Ltd., 80nm) / NPB (15nm) / ADN+5%DS-405 (Doosan Electron Co., Ltd., 30nm) / compounds 1, 2, 4, 42, 45, 111, 112, 121, 133, 151, 156, 346, 360 (30nm) / LiF (1nm) / Al (200nm) are sequentially stacked to fabricate an organic electroluminescent element.

[0297] [Comparative Example 1] Fabrication of a blue organic electroluminescent element

[0298] Alq3 was used instead of compound 1 as the electron transport layer material, and the blue organic electroluminescent element was fabricated in the same manner as in Example 1 above.

[0299] [Comparative Example 2] Fabrication of a Blue Organic Electroluminescent Element

[0300] As the electron transport layer material, compound 1 is not used. Otherwise, the blue organic electroluminescent element is fabricated in the same manner as in Example 1 above.

[0301] The structures of NPB, AND, and Alq3 used in Examples 1 to 13 and Comparative Examples 1 and 2 are as follows.

[0302]

[0303] [Evaluation Example 1]

[0304] For each blue organic electroluminescent element prepared in Examples 1 to 13 and Comparative Examples 1 and 2, the current density was measured to be 10 mA / cm². 2 The driving voltage, current efficiency, and emission wavelength at that time are shown in Table 1 below.

[0305] [Table 1]

[0306] sample Electron transport layer Drive voltage (V) Emission peak (nm) Current efficiency (cd / A) Example 1 Compound 1 3.6 455 8.1 Example 2 Compound 2 3.8 451 8.6 Example 3 Compound 4 3.8 452 9.1 Example 4 Compound 42 3.6 452 8.5 Example 5 Compound 45 3.7 453 8.6 Example 6 Compound 111 3.6 451 8.8 Example 7 Compound 112 3.9 451 9.1 Example 8 Compound 121 3.4 453 7.7 Example 9 Compound 133 3.3 452 7.6 Example 10 Compound 151 3.1 451 7.1 Example 11 Compound 156 3.2 450 7.3 Example 12 Compound 346 4.3 451 8.9 Example 13 Compound 350 4.4 453 9.0 Comparative Example 1 <![CDATA[Alq3]]> 4.8 457 5.6 Comparative Example 2 - 4.7 459 6.1

[0307] As shown in Table 1 above, it can be seen that the blue organic electroluminescent elements (Examples 1 to 13) synthesized in the above synthesis examples using compounds 1, 2, 4, 42, 45, 111, 112, 121, 133, 151, 156, 346 and 350 of the present invention in the electron transport layer exhibit superior performance in terms of driving voltage, emission peak and current efficiency compared with conventional blue organic electroluminescent elements using Alq3 in the electron transport layer (Comparative Example 1) and blue organic electroluminescent elements without an electron transport layer (Comparative Example 2).

[0308] [Examples 14 to 24] Fabrication of Blue Organic Electroluminescent Element

[0309] After the compounds 376, 377, 380, 409, 411, 436, 448, 518, 524, 542, and 545 synthesized in the above synthesis examples were purified to high purity by sublimation using commonly known methods, blue organic electroluminescent elements were fabricated according to the following process.

[0310] First, will be Glass substrates coated with a thin film of indium tin oxide (ITO) were ultrasonically washed with distilled water. After washing with distilled water, they were ultrasonically washed with solvents such as isopropanol, acetone, and methanol, and then dried. They were then transferred to a UV ozone cleaner (Power sonic 405, HwashinTech) and cleaned with UV light for 5 minutes. After that, the substrates were transferred to a vacuum evaporation machine.

[0311] On the ITO transparent electrode prepared above, DS-205 (Doosan Electron Co., Ltd., 80nm) / NPB (15nm) / ADN+5%DS-405 (Doosan Electron Co., Ltd., 30nm) / compounds 376, 377, 380, 409, 411, 436, 448, 518, 524, 542, 546 (5nm) / Alq3 (25nm) / LiF (1nm) / Al (200nm) are sequentially stacked to fabricate an organic electroluminescent element.

[0312] [Comparative Example 3] Fabrication of a Blue Organic Electroluminescent Element

[0313] As the electron transport auxiliary layer material, compound 376 was not used, and Alq3 was deposited at 30 nm instead of 25 nm as the electron transport layer material. Otherwise, the same procedure as in Example 14 above was followed to fabricate a blue organic electroluminescent element.

[0314] [Evaluation Example 2]

[0315] For each organic electroluminescent element prepared in Examples 14 to 24 and Comparative Example 3, a current density of 10 mA / cm² was measured. 2 The driving voltage, emission wavelength, and current efficiency at that time are shown in Table 2 below.

[0316] [Table 2]

[0317] sample Electron transport auxiliary layer Drive voltage (V) Emission peak (nm) Current efficiency (cd / A) Example 14 Compound 376 3.7 456 9.0 Example 15 Compound 377 3.6 455 8.8 Example 16 Compound 380 3.5 456 8.6 Example 17 Compound 409 3.9 455 8.5 Example 18 Compound 411 3.4 456 9.1 Example 19 Compound 436 3.3 457 8.8 Example 20 Compound 448 3.6 455 9.1 Example 21 Compound 518 3.4 454 8.4 Example 22 Compound 524 3.7 455 8.6 Example 23 Compound 542 3.4 456 8.8 Example 24 Compound 545 3.6 455 9.3 Comparative Example 3 - 4.7 459 6.1

[0318] As shown in Table 2 above, it can be seen that the blue organic electroluminescent element (Examples 14 to 24) using the compounds of the present invention synthesized in the above synthesis examples with an electron transport auxiliary layer exhibits superior performance in terms of current efficiency, emission peak and driving voltage compared to the blue organic electroluminescent element without an electron transport auxiliary layer (Comparative Example 3).

[0319] As described above, preferred embodiments of the present invention have been described, but the present invention is not limited thereto. Various modifications can be made within the scope of the claims and the invention content, which also fall within the scope of the invention.

Claims

1. A compound represented by chemical formula 1: [Chemical Formula 1] In the chemical formula 1, Z1 to Z3 are nitrogen. X is represented by the following chemical formula 2. [Chemical Formula 2] In the chemical formula 2, One of Y1 to Y4 is nitrogen, and the rest are carbon. The asterisk (*) indicates the portion that forms a bond with chemical formula 1. n is 1, L can be selected freely from C6 to C. 18 The group consists of arylene groups and heteroarylene groups with 5 to 18 nuclei. Choose group A, which consists of structures represented by the chemical formulas A-4 to A-6. The asterisk (*) indicates the portion that forms a bond with the chemical formula 1.

2. The compound according to claim 1, wherein in chemical formula 1, X is selected from the group consisting of structures represented by X-1 to X-4 below. The asterisk (*) indicates the portion that forms a bond with the chemical formula 1.

3. The compound according to claim 1, wherein in chemical formula 1, The structure represented is denoted by the following Ar-1, where, * indicates the site where the bond is formed. In the Ar-1 structure, * means the part that forms a bond with the chemical formula 1.

4. The compound according to claim 1, wherein in chemical formula 1, L is selected from the group consisting of structures represented by L-1 to L-7 below. The asterisk (*) indicates the portion that forms a bond with the chemical formula 1.

5. The compound according to claim 1, wherein the compound represented by chemical formula 1 is selected from the following: 139, 140, 144, 145, 149, 150, 154, 155, 159, 160, 164, 165, 334, 335, 339, 340, 344, 345, 364, 365, 369, 370, 374, 375, 394, 395, 399, 400, 404, 405, 424, 425, 429. The group consisting of compounds represented by 430, 434, 435, 574, 575, 579, 580, 584, 585, 589, 590, 594, 595, 599, 600, 649, 650, 654, 655, 659, 660, 679, 680, 684, 685, 689, 690, 709, 710, 714, 715, 719, 720, 739, 740, 744, 745, 749, and 750. 。 6. An organic electroluminescent device comprising an anode, a cathode, and one or more organic layers between the anode and the cathode. At least one of the more than one organic layer comprises the compound according to any one of claims 1 to 5.

7. The organic electroluminescent element according to claim 6, wherein the organic layer comprising the compound is selected from the group consisting of a hole injection layer, a hole transport layer, a light-emitting auxiliary layer, a light-emitting layer, an electron transport layer, and an electron injection layer.

8. The organic electroluminescent element according to claim 6, wherein the organic layer comprising the compound is selected from the group consisting of an electron transport layer and an electron transport auxiliary layer.

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