A compound and an organic electroluminescent element containing the same

Abstract

The present invention relates to a compound and an organic electroluminescent element comprising the same. The compound is represented by Chemical Formula 1, wherein Z1 to Z3 are nitrogen or carbon, and contain at least two nitrogens, X is represented by the following Chemical Formula 2 or 3, wherein one of Y1 to Y4 is nitrogen and the rest are carbon, one of Y5 to Y6 is nitrogen and the other is carbon, n is an integer from 1 to 3, L is a single bond, and A is represented by the following Chemical Formula 4, wherein R a and R b are the same or different from each other, and are independently C1 to C 40 Alkyl or C6~C 60 R1 and R2 are the same or different from each other and are independently selected from hydrogen, deuterium, halogen, cyano, etc., c is an integer from 0 to 4, and d is an integer from 0 to 3. By using the compound of the present invention in the organic layer of an organic electroluminescent element, the luminous efficiency, driving voltage, life, etc. of the organic electroluminescent element can be improved.

Description

[0001] This application is a divisional application of the Chinese patent application with the application date of July 2, 2018, application number 201880048510.2, and invention name "Organic light-emitting compounds and organic electroluminescent elements containing the same". Technical Field

[0002] The present invention relates to novel organic light-emitting compounds and organic electroluminescent elements using the same. More specifically, it relates to compounds with excellent electron transport and light-emitting capabilities and organic electroluminescent elements with improved properties such as light-emitting efficiency, driving voltage and life by adding the compounds to one or more organic layers. Background Art

[0003] Starting from Bernanose's observation of organic thin film luminescence in the 1950s, research on organic electroluminescent devices developed from the blue electroluminescence of anthracene single crystals in 1965 was conducted, followed by Tang's proposal of an organic electroluminescent device with a stacked structure of two functional layers, a hole layer and a light-emitting layer, in 1987. Later, in order to manufacture high-efficiency and long-life organic electroluminescent devices, a form of introducing various characteristic organic layers into the device was developed, and then the development of special materials for this purpose was carried out.

[0004] In an organic electroluminescent element, 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 into the organic layer. When the injected holes and electrons meet, excitons are formed, and when the excitons transition to the ground state, light is emitted. At this time, the substances used for the organic layer can be divided into luminescent substances, hole injection substances, hole transport substances, electron transport substances, electron injection substances, etc. according to their functions.

[0005] The light-emitting layer forming materials of organic EL elements can be divided into blue, green and red light-emitting materials according to the light-emitting color. In addition, as light-emitting materials for presenting more natural colors, yellow and orange light-emitting materials are also used. In addition, in order to increase the color purity and increase the luminous efficiency through energy transfer, a host / dopant system can be used as a light-emitting material. Doping substances can be divided into fluorescent dopants using organic substances and phosphorescent dopants using metal coordination compounds containing heavy atoms (heavyatoms) such as Ir and Pt. Since the development of such phosphorescent materials can theoretically improve the luminous efficiency by up to 4 times compared with fluorescence, not only phosphorescent dopants but also phosphorescent host materials have received attention.

[0006] So far, NPB, BCP, Alq3 and the like are widely known as hole injection materials, hole transport materials, electron transport materials and electron injection materials, and anthracene derivatives have been reported as luminescent materials. In particular, metal coordination compounds containing Ir such as Firpic, Ir(ppy)3, (acac)Ir(btp)2, which have advantages in improving efficiency among luminescent materials, have been used as blue, green and red phosphorescent dopant materials, and 4,4-dicarbazolybiphenyl (CBP) has been used as a phosphorescent host material.

[0007]

[0008] However, conventional organic layer materials have low glass transition temperatures and poor thermal stability, and low triplet energy, so organic electroluminescent devices having these materials introduced into the organic layer cannot exhibit satisfactory current efficiency and life characteristics. Therefore, the development of organic layer materials with better performance is required.

[0009] Patent Document 1: Korean Patent Publication No. 2016-0078237 Summary of the invention

[0010] Technical issues

[0011] The object of the present invention is to provide a novel compound which has excellent heat resistance, carrier transport ability, luminescence ability, etc. and can be used as an organic layer material, specifically a luminescent layer material, an electron transport auxiliary layer material, a luminescence auxiliary layer material or an electron transport layer material of an organic electroluminescent element.

[0012] Another object of the present invention is to provide an organic electroluminescent device comprising the novel compound and having a low driving voltage, high luminous efficiency and improved life.

[0013] Solution to the problem

[0014] In order to achieve the above object, one example of the present invention provides a compound represented by the following Chemical Formula 1.

[0015] [Chemical formula 1]

[0016]

[0017] In the above chemical formula 1,

[0018] Z1 to Z3 are nitrogen or carbon, and contain at least two nitrogens,

[0019] X is represented by the following Chemical Formula 2 or Chemical Formula 3,

[0020] [Chemical formula 2]

[0021]

[0022] [Chemical formula 3]

[0023]

[0024] In the above Chemical Formulas 2 and 3,

[0025] One of Y1 to Y4 is nitrogen and the others are carbon, one of Y5 to Y6 is nitrogen and the other is carbon,

[0026] * means the part that forms a bond with the above chemical formula 1,

[0027] n is an integer from 1 to 3,

[0028] L is selected from a single bond, C6~C 18 and a heteroarylene group having an atomic nucleus number of 5 to 18,

[0029] A is represented by the following chemical formula 4,

[0030] [Chemical formula 4]

[0031]

[0032] In the above chemical formula 4,

[0033] R a and R b are the same or different from each other, and are independently C1 to C 40 Alkyl or C6~C 60 or they are combined with each other to form a condensed ring,

[0034] R1 and R2 are the same or different from each other and are independently selected from hydrogen, deuterium, halogen, cyano, nitro, amino, C1-C 40 Alkyl, C2~C 40 Alkenyl, C2~C 40 Alkynyl, C3~C 40 Cycloalkyl, heterocycloalkyl with 3 to 40 nuclei, C6~C 60 aryl, heteroaryl with 5 to 60 nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkyl silyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, C1~C 40 Phosphine, C1~C 40The phosphine oxide group and C6~C 60 or combines with an adjacent group to form a condensed ring, c is an integer from 0 to 4, d is an integer from 0 to 3,

[0035] * means the part that forms a bond with the above chemical formula 1,

[0036] The above R a , R b The alkyl, aryl, alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylsilyl, arylsilyl, alkylboryl, arylboryl, phosphino, phosphine oxide, arylamine, and the arylene and heteroarylene groups of L are independently selected from deuterium, halogen, cyano, nitro, amino, C1-C 40 Alkyl, C2~C 40 Alkenyl, C2~C 40 Alkynyl, C3~C 40 Cycloalkyl, heterocycloalkyl with 3 to 40 nuclei, C6~C 60 aryl, heteroaryl with 5 to 60 nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkyl silyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, C1~C 40 Phosphine, C1~C 40 The phosphine oxide group and C6~C 60 The arylamine group may be substituted or unsubstituted with one or more substituents. When there are multiple substituents, the multiple substituents may be the same as or different from each other.

[0037] In addition, 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, and at least one of the one or more organic layers comprises the compound represented by the above chemical formula 1. The organic layer comprising the compound represented by the above chemical formula 1 can be selected from the group consisting of a hole injection layer, a hole transport layer, a luminescent auxiliary layer, a luminescent layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer. In this case, the compound represented by the above chemical formula 1 can be used as an electron transport material for the electron transport layer and the electron transport auxiliary layer.

[0038] Effects of the Invention

[0039] The compound represented by Chemical Formula 1 according to one example of the present invention has excellent heat resistance, carrier transport capability, light emitting capability, etc., and thus can be used as an organic layer material of an organic electroluminescent element.

[0040] In addition, an organic electroluminescent element including the compound according to one example of the present invention can significantly improve light emitting performance, driving voltage, life, efficiency, etc., and such an organic electroluminescent element can be effectively used in full-color display panels, etc. DETAILED DESCRIPTION

[0041] Hereinafter, the present invention will be described in detail.

[0042] <Organic compounds>

[0043] The novel organic compound of the present invention is a compound having a basic skeleton structure in which a fluorene part is bonded to an electron-withdrawing group (EWG) of a pyridine compound bonded to triazine or pyrimidine, and is represented by the above chemical formula 1.

[0044] The compound represented by the above chemical formula 1 is electrochemically stable because pyrimidine (or triazine) with excellent electron-withdrawing group (EWG) properties is combined with pyridine, and not only has excellent electron transport properties, but also has high triplet energy, excellent glass transition temperature and excellent thermal stability. In addition, the compound represented by the chemical formula 1 has a higher molecular weight than conventional organic EL element materials, so it has a high glass transition temperature and excellent thermal stability.

[0045] Therefore, the compound represented by the above chemical formula 1 has excellent electron transport ability and luminescent properties, and can be used as a material for any layer of the hole injection layer, hole transport layer, luminescent layer, electron transport layer and electron injection layer of the organic layer of the organic electroluminescent element. Preferably, it can be used as a material for any layer of the green phosphorescent luminescent layer, electron transport layer and electron transport auxiliary layer stacked on the electron transport layer.

[0046] Specifically, the compound represented by the above chemical formula 1 has a high triplet energy and is used as a material for an electron transport auxiliary layer due to the triplet-triplet fusion (TTF) effect, thereby being able to show excellent efficiency improvement. In addition, it is possible to prevent the excitons generated in the light-emitting layer from diffusing to the electron transport layer or hole transport layer adjacent to the light-emitting layer. The luminous efficiency of the element can be improved due to the increase in the number of excitons that contribute to luminescence in the light-emitting layer, and the life of the element can be effectively increased due to the improved durability and stability of the element. Most of the organic electroluminescent elements to which the compound represented by the chemical formula 1 is applied can achieve low-voltage driving, thereby showing physical characteristics of improved life.

[0047] Therefore, when the compound represented by the above Chemical Formula 1 is used in an organic electroluminescent element, not only excellent thermal stability and carrier transport ability (especially electron transport ability and luminescence ability) can be expected, but also the driving voltage, efficiency, life span, etc. of the element can be improved.

[0048] In addition, the compound represented by the above chemical formula 1 is not only very conducive to electron transport, but also shows long life characteristics. The excellent electron transport ability of such a compound can have high efficiency and fast mobility in an organic electroluminescent element, and it is easy to adjust the HOMO and LUMO energy levels according to the direction or position of the substituent. Therefore, in an organic electroluminescent element using such a compound, high electron transport can be exhibited.

[0049] Specifically, the compound represented by Chemical Formula 1 of the present invention may 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] 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 defined in Chemical Formula 1, respectively.

[0062] Preferably, in the above Chemical Formula 1, X may be selected from the group consisting of structures represented by the following X-1 to X-6.

[0063]

[0064] Preferably, in the above chemical formula 1, The structure represented by (* represents a bonding site) can be selected from the group consisting of the structures represented by the following Ar-1 to Ar-5.

[0065]

[0066] Preferably, the above R a and R b Each independently may be a methyl group or a phenyl group, or may be combined with each other to form (* indicates the site of bonding) represents a condensed ring.

[0067] Preferably, in the above Chemical Formula 1, A may be selected from the group consisting of structures represented by the following A-1 to A-6.

[0068]

[0069] Preferably, in the above Chemical Formula 1, L may be a single bond or a group consisting of structures represented by the following L-1 to L-7.

[0070]

[0071] The compound represented by the above-described Chemical Formula 1 of the present invention can be further embodied by a compound represented by any one of the following compounds 1 to 750. However, the compound represented by the Chemical Formula 1 of the present invention is not limited to the compounds exemplified below.

[0072]

[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] In the present invention, "alkyl" means a monovalent functional group obtained by removing a hydrogen atom from a straight-chain or branched saturated hydrocarbon having 1 to 40 carbon atoms, and non-limiting examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, isopentyl, hexyl, and the like.

[0102] In the present invention, "alkenyl" means a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon double bonds. Examples of such alkenyl groups include, but are not limited to, vinyl, allyl, isopropenyl, and 2-butenyl.

[0103] In the present invention, "alkynyl" means a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon triple bonds. Examples of such alkynyl groups include, but are not limited to, ethynyl and 2-propynyl.

[0104] In the present invention, "aryl" means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms and composed of a single ring or a combination of two or more rings. In addition, it may also include a form in which two or more rings are simply attached to each other (pendant) or condensed. Examples of such aryl groups include, but are not limited to, phenyl, naphthyl, phenanthrenyl, anthracenyl, etc.

[0105] In the present invention, "heteroaryl" means a monovalent substituent derived from a monocyclic heterocyclic or polycyclic aromatic hydrocarbon having an atomic nucleus number of 5 to 60. In this case, one or more carbon atoms, preferably 1 to 3 carbon atoms, in the ring are substituted by heteroatoms such as N, O, S or Se. In addition, it may also include a form in which two or more rings are simply attached (pendant) or condensed to each other, and further may include a form condensed with an aromatic group. Examples of such heteroaryl groups include six-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl; phenanthroline; polycyclic rings such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, carbazolyl, and 2-furyl, N-imidazolyl, 2-isothiazolyl, oxazolyl, 2-pyridyl, 2-pyrimidinyl, etc., but are not limited thereto.

[0106] In the present invention, "aryloxy" means a monovalent functional group represented by R"O-, wherein R" is an aryl group having 6 to 60 carbon atoms. Non-limiting examples of such aryloxy include phenoxy, naphthoxy, diphenoxy, and the like.

[0107] In the present invention, "alkoxy" means a monovalent functional group represented by R'O-, wherein R' is an alkyl group having 1 to 40 carbon atoms, and may include a linear, branched or cyclic structure. Non-limiting examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, 1-propoxy, tert-butoxy, n-butoxy, pentoxy, and the like.

[0108] In the present invention, "cycloalkyl" means a monovalent functional group obtained by removing a hydrogen atom from a monocyclic or polycyclic non-aromatic hydrocarbon (saturated cyclic hydrocarbon) having 3 to 40 carbon atoms. Non-limiting examples thereof include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, and adamantine.

[0109] In the present invention, "heterocycloalkyl" means a monovalent functional group obtained by removing a hydrogen atom from a non-aromatic hydrocarbon (saturated cyclic hydrocarbon) having a nucleus number of 3 to 40, wherein one or more carbon atoms, preferably 1 to 3 carbon atoms in the ring are substituted with a heteroatom such as N, O or S. Non-limiting examples thereof include morpholinyl and piperazinyl.

[0110] In the present invention, "alkylsilyl" means a silyl group substituted by an alkyl group having 1 to 40 carbon atoms, "arylsilyl" means a silyl group substituted by an aryl group having 6 to 60 carbon atoms, "alkylboryl" means a boron group substituted by an alkyl group having 1 to 40 carbon atoms, "arylboryl" means a boron group substituted by an aryl group having 6 to 60 carbon atoms, "arylphosphino" means a phosphino group substituted by an aryl group having 1 to 60 carbon atoms, and "arylamino" means an amino group substituted by an aryl group having 6 to 60 carbon atoms.

[0111] In the present invention, the "condensed ring" means a condensed aliphatic ring, a condensed aromatic ring, a condensed aliphatic heterocycle, a condensed aromatic heterocycle or a combination thereof.

[0112] The compound represented by the chemical formula 1 of the present invention can be synthesized in various ways by referring to the synthesis process of the following examples. The detailed synthesis process of the compound of the present invention will be specifically described in the synthesis examples described below.

[0113] <Organic electroluminescent element>

[0114] The present invention provides an organic electroluminescent device comprising the compound represented by the above Chemical Formula 1.

[0115] 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, and at least one of the one or more organic layers comprises the compound represented by the above chemical formula 1. In this case, the above compounds can be used alone or in combination of two or more.

[0116] The one or more organic layers may be any one or more of a hole injection layer, a hole transport layer, a luminescent auxiliary layer, a luminescent layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer, wherein at least one organic layer may contain the compound represented by the above Chemical Formula 1. Specifically, the organic layer containing the compound of the above Chemical Formula 1 is preferably a luminescent layer, an electron transport auxiliary layer, and an electron transport layer.

[0117] The light-emitting layer of the organic electroluminescent device of the present invention may contain a host material (preferably a phosphorescent host material). In addition, the light-emitting layer of the organic electroluminescent device of the present invention may contain a compound other than the compound of the above Chemical Formula 1 as a host.

[0118] 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 luminescence auxiliary layer, a luminescent layer, an electron transport layer and a cathode are stacked in sequence. At this time, one or more of the hole injection layer, the hole transport layer, the luminescence auxiliary layer, the luminescent layer and the electron transport layer may contain the compound represented by the above-mentioned chemical formula 1, and preferably the luminescent layer or the electron transport layer may contain the compound represented by the above-mentioned chemical formula 1. Here, an electron injection layer may be further stacked on the above-mentioned electron transport layer. In addition, the structure of the organic electroluminescent element of the present invention may be a structure in which an electron transport auxiliary layer is added together with the electrode and the above-mentioned organic layer. At this time, one or more of the hole injection layer, the hole transport layer, the luminescence auxiliary layer, the luminescent layer, the electron transport auxiliary layer and the electron transport layer may contain the compound represented by the above-mentioned chemical formula 1, and preferably the luminescent layer, the electron transport auxiliary layer or the electron transport layer may contain the compound represented by the above-mentioned chemical formula 1.

[0119] On the other hand, the organic electroluminescent element of the present invention can form and manufacture the organic layers and electrodes by using materials and methods known in the art, except that at least one of the organic layers contains the compound represented by the above Chemical Formula 1.

[0120] The organic layer may be formed by vacuum deposition or solution coating, and examples of the solution coating method include spin coating, dip coating, blade coating, inkjet printing, thermal transfer, etc., but are not limited thereto.

[0121] The substrate used in the production of the organic electroluminescent element of the present invention is not particularly limited, and a silicon wafer, quartz, a glass plate, a metal plate, a plastic film or sheet, etc. can be used.

[0122] In addition, as anode materials, metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; 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-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole, or polyaniline; and carbon black, etc., but are not limited to these.

[0123] In addition, as cathode materials, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead, or alloys thereof; and multilayer structure materials such as LiF / Al or LiO2 / Al, etc. can be listed, but are not limited to these.

[0124] In addition, the hole injection layer, the hole transport layer and the light-emitting auxiliary layer are not particularly limited, and common materials known in the art can be used.

[0125] Hereinafter, the present invention will be described in detail by way of examples. However, the following examples are merely illustrative of the present invention, and the present invention is not limited to the following examples.

[0126] [Preparation Example 1] Synthesis of PPY-1

[0127] <Step 1> Synthesis of PPY-1

[0128]

[0129] 45.0 g of 4,6-dichloro-2-phenylpyrimidine, 40.0 g of (4-(pyridin-3-yl)phenyl)boric acid, 6.0 g of tetrakistriphenylphosphine palladium (0), and 42 g of K2CO3 were added to 800 ml of toluene, 200 ml of ethanol, and 200 ml of water, and heated under reflux and stirring for 2 hours. After the reaction was completed, the solution was deactivated with a sufficient amount of water, transferred to a separatory funnel, extracted with dichloromethane, and the organic layer was dried with magnesium sulfate, concentrated, and purified by column chromatography to obtain 39.8 g of PPY-1 (yield 58%).

[0130] 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)

[0131] Mass: [(M+H) + ]:344

[0132] [Preparation Example 2] Synthesis of PPY-2 to 3

[0133] <Step 1> Synthesis of (E)-1-(4-bromophenyl)-3-(4-pyridin-3-yl)phenyl)prop-2-en-1-one

[0134]

[0135] 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, extracted with ethyl acetate, and the organic layer was dried over magnesium sulfate and concentrated. The mixture was purified by column chromatography to obtain 36.4 g (yield 72%) of (E)-1-(4-bromophenyl)-3-(4-pyridin-3-yl)phenyl)prop-2-en-1-one.

[0136] 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)

[0137] Mass: [(M+H) + ]:364

[0138] <Step 2> Synthesis of PPY-2

[0139]

[0140] 36.4 g of (E)-1-(4-bromophenyl)-3-(4-pyridin-3-yl)phenyl)prop-2-en-1-one, 24.1 g of benzamidine hydrochloride, and 14.2 g of sodium hydroxide were added to 500 ml of ethanol and heated under reflux with stirring for 4 hours. After the reaction was completed, the reactant was concentrated under reduced pressure to 250 ml, inactivated with a sufficient amount of 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%).

[0141] 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)

[0142] Mass: [(M+H) + ]:464

[0143] <Step 3> Synthesis of PPY-3

[0144]

[0145] 15.0 g of PPY-2, 6.1 g of (3-chlorophenyl)boric acid, 0.9 g of tetrakistriphenylphosphine palladium (0), and 7.0 g of K2CO3 were added to 300 ml of toluene, 60 ml of ethanol, and 60 ml of water, and heated under reflux and stirring for 2 hours. After the reaction was completed, the solution was deactivated with a sufficient amount of water, transferred to a separatory funnel, extracted with dichloromethane, and the organic layer was dried with magnesium sulfate, concentrated, and purified by column chromatography to obtain 10.9 g of PPY-3 (yield 68%).

[0146] 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)

[0147] Mass: [(M+H) + ]:496

[0148] [Preparation Example 3] Synthesis of PPY-4 to 6

[0149] <Step 1> Synthesis of (E)-1-(3-bromophenyl)-3-(4-pyridin-3-yl)phenyl)prop-2-en-1-one

[0150]

[0151] 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 at room temperature for 1 hour, extracted with ethyl acetate, and the organic layer was dried over magnesium sulfate and concentrated. The mixture was purified by column chromatography to obtain 38.2 g (yield 74%) of (E)-1-(3-bromophenyl)-3-(4-pyridin-3-yl)phenyl)prop-2-en-1-one.

[0152] 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)

[0153] Mass: [(M+H) + ]:364

[0154] <Step 2> Synthesis of PPY-4

[0155]

[0156] 38.2 g of (E)-1-(3-bromophenyl)-3-(4-pyridin-3-yl)phenyl)prop-2-en-1-one, 25.0 g of benzamidine hydrochloride, and 14.8 g of sodium hydroxide were added to 500 ml of ethanol, and the mixture was heated under reflux and stirred for 4 hours. After the reaction was completed, the reactant was concentrated under reduced pressure to 250 ml, inactivated with a sufficient amount of 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%).

[0157] 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)

[0158] Mass: [(M+H) + ]:464

[0159] <Step 3> Synthesis of PPY-5

[0160] 15.0 g of PPY-4, 6.1 g of (3-chlorophenyl)boric acid, 0.9 g of tetrakistriphenylphosphine palladium (0), and 7.0 g of K2CO3 were added to 300 ml of toluene, 60 ml of ethanol, and 60 ml of water, and heated under reflux with stirring for 2 hours. After the reaction was completed, the solution was deactivated with a sufficient amount of water, transferred to a separatory funnel, extracted with dichloromethane, and the organic layer was dried with magnesium sulfate, concentrated, and purified by column chromatography to obtain 10.1 g of PPY-5 (yield 67%).

[0161] 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)

[0162] Mass: [(M+H) + ]:496

[0163] <Step 4> Synthesis of PPY-6

[0164]

[0165] 10.0 g of PPY-5, 4.1 g of (3-chlorophenyl)boronic 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, and heated under reflux and stirring for 2 hours. After the reaction was completed, the solution was deactivated with a sufficient amount of water, transferred to a separatory funnel, extracted with dichloromethane, and the organic layer was dried with magnesium sulfate, concentrated, and purified by column chromatography to obtain 6.7 g of PPY-6 (yield 66%).

[0166] 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)

[0167] Mass: [(M+H) + ]:572

[0168] [Preparation Example 4] Synthesis of PPY-7 to 8

[0169] <Step 1> Synthesis of PPY-7

[0170] 45.0 g of 4,6-dichloro-2-phenylpyrimidine, 38.7 g of (6-phenylpyridin-3-yl)boric acid, 6.0 g of tetrakistriphenylphosphine palladium (0), and 42 g of K2CO3 were added to 800 ml of toluene, 200 ml of ethanol, and 200 ml of water, and heated under reflux and stirring for 2 hours. After the reaction was completed, the solution was deactivated with a sufficient amount of water, transferred to a separatory funnel, extracted with dichloromethane, and the organic layer was dried with magnesium sulfate, concentrated, and purified by column chromatography to obtain 40.7 g of PPY-7 (yield 61%).

[0171] 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)

[0172] Mass: [(M+H) + ]:344

[0173] <Step 2> Synthesis of PPY-8

[0174]

[0175] 15.0 g of PPY-7, 6.1 g of (3-chlorophenyl)boric acid, 0.9 g of tetrakistriphenylphosphine palladium (0), and 7.1 g of K2CO3 were added to 300 ml of toluene, 60 ml of ethanol, and 60 ml of water, and heated under reflux with stirring for 2 hours. After the reaction was completed, the solution was deactivated with a sufficient amount of water, transferred to a separatory funnel, extracted with dichloromethane, and the organic layer was dried with magnesium sulfate, concentrated, and purified by column chromatography to obtain 13.7 g of PPY-8 (yield 72%).

[0176] 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)

[0177] Mass: [(M+H) + ]:420

[0178] [Preparation Example 5] Synthesis of PTZ-1 to 2

[0179] <Step 1> Synthesis of PTZ-1

[0180] 45.0 g of 2,4-dichloro-6-phenyl-1,3,5-triazine, 39.2 g of (4-(pyridin-3-yl)phenyl)boric acid, 6.0 g of tetrakistriphenylphosphine palladium (0), and 42 g of K2CO3 were added to 800 ml of toluene, 200 ml of ethanol, and 200 ml of water, and heated under reflux and stirring for 2 hours. After the reaction was completed, the mixture was deactivated with a sufficient amount of water, and then 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 PTZ-1 (yield 53%).

[0181] 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)

[0182] Mass: [(M+H) + ]:345

[0183] <Step 2> Synthesis of PTZ-2

[0184]

[0185] 10.0 g of PTZ-1, 4.1 g of (3-chlorophenyl)boric acid, 0.6 g of tetrakistriphenylphosphine palladium (0), and 4.7 g of K2CO3 were added to 200 ml of toluene, 40 ml of ethanol, and 40 ml of water, and heated under reflux and stirring for 2 hours. After the reaction was completed, the solution was deactivated with a sufficient amount of water, transferred to a separatory funnel, extracted with dichloromethane, and the organic layer was dried with magnesium sulfate, concentrated, and purified by column chromatography to obtain 8.7 g of PTZ-2 (yield 71%).

[0186] 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)

[0187] Mass: [(M+H) + ]:421

[0188] [Preparation Example 6] Synthesis of PTZ-3

[0189] 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)boric acid, 6.0 g of tetrakistriphenylphosphine palladium (0), and 42 g of K2CO3 were added to 800 ml of toluene, 200 ml of ethanol, and 200 ml of water, and heated under reflux and stirring for 2 hours. After the reaction was completed, the solution was deactivated with a sufficient amount of water, transferred to a separatory funnel, extracted with dichloromethane, and the organic layer was dried with magnesium sulfate, concentrated, and purified by column chromatography to obtain 40.4 g of PTZ-3 (yield 65%).

[0190] 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)

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

[0192] [Synthesis Example 1] Synthesis of Compound 1

[0193]

[0194] 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. After adding 60 ml of toluene, 12 ml of ethanol and 12 ml of water, 500 mg of tetrakistriphenylphosphine palladium (0) was added, and the mixture was heated and stirred for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried with MgSO4. After it was concentrated under reduced pressure, column chromatography was performed with MC:Hex=2:1 to obtain 2.8 g of white solid of compound 1 (yield 55%).

[0195] Mass: [(M+H) + ]:502

[0196] [Synthesis Example 2] Synthesis of Compound 2

[0197] 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. After adding 60 ml of toluene, 12 ml of ethanol and 12 ml of water, 500 mg of tetrakistriphenylphosphine palladium (0) was added and heated and stirred for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried using MgSO4. After it was concentrated under reduced pressure, column chromatography was performed with MC:Hex=2:1 to obtain 3.2 g of white solid of compound 2 (yield 58%).

[0198] Mass: [(M+H) + ]:624

[0199] [Synthesis Example 3] Synthesis of Compound 4

[0200]

[0201] 3.1 g of PPY-1 was mixed with 4.8 g of (7,7-dimethyl-7H-benzo[c]fluoren-9-yl)boric acid and 3.3 g of K2CO3. After adding 60 ml of toluene, 12 ml of ethanol and 12 ml of water, 500 mg of tetrakistriphenylphosphine palladium (0) was added and heated and stirred for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried with MgSO4. After it was concentrated under reduced pressure, column chromatography was performed with MC:Hex=2:1 to obtain 3.5 g of compound 4 as a white solid (yield 56%).

[0202] Mass: [(M+H) + ]:551

[0203] [Synthesis Example 4] Synthesis of Compound 42

[0204]

[0205] 3.0 g of PTZ-1 was mixed with 5.1 g of 9,9'-spirobi[fluorene]-4-ylboronic acid and 3.3 g of K2CO3, and 60 ml of toluene, 12 ml of ethanol and 12 ml of water were added, and 500 mg of tetrakistriphenylphosphine palladium (0) was added, and the mixture was heated and stirred for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, and the generated solid was filtered. The generated solid was dissolved in a sufficient amount of MC, concentrated under reduced pressure, and column chromatography was performed with MC:Hex=2:1 to obtain 4.1 g of compound 42 as a white solid (yield 75%).

[0206] Mass: [(M+H) + ]:625

[0207] [Synthesis Example 5] Synthesis of Compound 45

[0208]

[0209] 3.2 g of PTZ-1 was mixed with 4.9 g of (7,7-dimethyl-7H-benzo[c]fluoren-7-yl)boric acid and 3.3 g of K2CO3. After adding 60 ml of toluene, 12 ml of ethanol and 12 ml of water, 520 mg of tetrakistriphenylphosphine palladium (0) was added, and the mixture was heated and stirred for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried with MgSO4. After it was concentrated under reduced pressure, column chromatography was performed with MC:Hex=2:1 to obtain 3.8 g of compound 45 as a white solid (yield 57%).

[0210] Mass: [(M+H) + ]:553

[0211] [Synthesis Example 6] Synthesis of Compound 111

[0212] 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. After adding 50 ml of toluene, 10 ml of ethanol and 10 ml of water, 200 mg of tetrakistriphenylphosphine palladium (0) was added and heated and stirred for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried using MgSO4. After it was concentrated under reduced pressure, column chromatography was performed with MC to obtain 1.8 g of a white solid of compound 111 (yield 76%).

[0213] Mass: [(M+H)+ ]:578

[0214] [Synthesis Example 7] Synthesis of Compound 112

[0215]

[0216] PPY-2 2.0g was mixed with 9,9'-spirobi[fluorene]-3-ylboronic acid 2.5g and K2CO3 2.0g, and 50ml of toluene, 12ml of ethanol and 12ml of water were added, and 200mg of tetrakistriphenylphosphine palladium (0) was added, and the mixture was heated and stirred for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried using MgSO4. After it was concentrated under reduced pressure, column chromatography was performed with THF:Hex=1:5 to obtain 1.5g (yield 55%) of white solid of compound 112.

[0217] Mass: [(M+H) + ]:700

[0218] [Synthesis Example 8] Synthesis of Compound 121

[0219]

[0220] 2.1 g of PPY-4 was mixed with 2.2 g of (9,9-dimethyl-9H-fluorene-2-yl)boric acid and 1.9 g of K2CO3. After adding 50 ml of toluene, 10 ml of ethanol and 10 ml of water, 220 mg of tetrakistriphenylphosphine palladium (0) was added and heated and stirred for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried using MgSO4. After it was concentrated under reduced pressure, column chromatography was performed with MC to obtain 1.6 g of a white solid of compound 121 (yield 72%).

[0221] Mass: [(M+H) + ]:578

[0222] [Synthesis Example 9] Synthesis of Compound 133

[0223]

[0224] 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, and 50 ml of toluene, 12 ml of ethanol and 12 ml of water were added. Then, 210 mg of tetrakistriphenylphosphine palladium (0) was added and heated and stirred for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried using MgSO4. After it was concentrated under reduced pressure, column chromatography was performed with MC to which a small amount of pyridine was added to obtain 2.1 g (yield 68%) of white solid of compound 133.

[0225] Mass: [(M+H) + ]:702

[0226] [Synthesis Example 10] Synthesis of Compound 151

[0227]

[0228] 2.3 g of PTZ- was mixed with 2.3 g of (9,9-dimethyl-9H-fluorene-2-yl)boric acid and 3.0 g of Cs2CO3. After adding 60 ml of toluene, 12 ml of ethanol and 12 ml of water, 50 mg of Pd(OAc)2 and 230 mg of Xphos were added, and the mixture was heated and stirred for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried using MgSO4. After it was concentrated under reduced pressure, column chromatography was performed using MC to obtain 2.2 g of a white solid of compound 151 (yield 75%).

[0229] Mass: [(M+H) + ]:579

[0230] [Synthesis Example 11] Synthesis of Compound 156

[0231]

[0232] 2.1 g of PTZ-2 was mixed with 2.2 g of (9,9-dimethyl-9H-fluorene-3-yl)boric acid and 2.8 g of Cs2CO3. After adding 60 ml of toluene, 12 ml of ethanol and 12 ml of water, 48 mg of Pd(OAc)2 and 200 mg of Xphos were added, and the mixture was heated and stirred for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried using MgSO4. After it was concentrated under reduced pressure, column chromatography was performed using MC to obtain 2.0 g of a white solid of compound 156 (yield 71%).

[0233] Mass: [(M+H) + ]:579

[0234] [Synthesis Example 12] Synthesis of Compound 346

[0235] 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. After adding 60 ml of toluene, 12 ml of ethanol and 12 ml of water, 57 mg of Pd(OAc)2 and 250 mg of Xphos were added, and the mixture was heated and stirred for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried using MgSO4. After it was concentrated under reduced pressure, column chromatography was performed using MC to obtain 2.3 g of a white solid of compound 346 (yield 70%).

[0236] Mass: [(M+H) + ]:654

[0237] [Synthesis Example 13] Synthesis of Compound 350

[0238]

[0239] 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. After adding 60 ml of toluene, 12 ml of ethanol and 12 ml of water, 57 mg of Pd(OAc)2 and 250 mg of Xphos were added, and the mixture was heated and stirred for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried using MgSO4. After it was concentrated under reduced pressure, column chromatography was performed using MC to obtain 2.5 g of a white solid of compound 350 (yield 71%).

[0240] Mass: [(M+H) + ]:704

[0241] [Synthesis Example 14] Synthesis of Compound 376

[0242] 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. After adding 60 ml of toluene, 12 ml of ethanol and 12 ml of water, 50 mg of Pd(OAc)2 and 230 mg of Xphos were added, and the mixture was heated and stirred for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried using MgSO4. After it was concentrated under reduced pressure, column chromatography was performed with MC to obtain 2.0 g of a white solid of compound 376 (yield 66%).

[0243] Mass: [(M+H) + ]:654

[0244] [Synthesis Example 15] Synthesis of Compound 377

[0245]

[0246] 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. After adding 60 ml of toluene, 12 ml of ethanol and 12 ml of water, 50 mg of Pd(OAc)2 and 230 mg of Xphos were added, and the mixture was heated and stirred for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried using MgSO4. After it was concentrated under reduced pressure, column chromatography was performed with THF:Hex=1:2 to obtain 2.3 g (yield 66%) of white solid of compound 377.

[0247] Mass: [(M+H) + ]:776

[0248] [Synthesis Example 16] Synthesis of Compound 380

[0249]

[0250] 2.1 g of PPY-5 was mixed with 2.4 g of (11,11-dimethyl-11H-benzo[a]fluorene-9-yl)boric acid and 2.9 g of Cs2CO3. After adding 60 ml of toluene, 12 ml of ethanol and 12 ml of ethanol, 53 mg of Pd(OAc)2 and 240 mg of Xphos were added, and the mixture was heated and stirred for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried using MgSO4. After it was concentrated under reduced pressure, column chromatography was performed using MC to obtain 1.9 g of a white solid of compound 380 (yield 63%).

[0251] Mass: [(M+H) + ]:704

[0252] [Synthesis Example 17] Synthesis of Compound 409

[0253]

[0254] 2.0 g of PPY-6 was mixed with 2.1 g of (7,7-dimethyl-7H-benzo[c]fluorene-9-yl)boric acid and 2.5 g of Cs2CO3. After adding 60 ml of toluene, 12 ml of ethanol and 12 ml of water, 48 mg of Pd(OAc)2 and 210 mg of Xphos were added, and the mixture was heated and stirred for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried with MgSO4. After it was concentrated under reduced pressure, column chromatography was performed with MC:MeOH=100:1 to obtain 2.1 g of compound 409 as a white solid (yield 66%).

[0255] Mass: [(M+H) + ]:780

[0256] [Synthesis Example 18] Synthesis of Compound 411

[0257]

[0258] 2.0 g of PPY-6 was mixed with 2.0 g of (9,9-dimethyl-9H-fluorene-3-yl)boric acid and 2.5 g of Cs2CO3. After adding 60 ml of toluene, 12 ml of ethanol and 12 ml of water, 48 mg of Pd(OAc)2 and 210 mg of Xphos were added, and the mixture was heated and stirred for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried with MgSO4. After it was concentrated under reduced pressure, column chromatography was performed with MC:MeOH=100:1 to obtain 1.6 g of white solid of compound 411 (yield 59%).

[0259] Mass: [(M+H) + ]:730

[0260] [Synthesis Example 19] Synthesis of Compound 436

[0261]

[0262] 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. After adding 60 ml of toluene, 12 ml of ethanol and 12 ml of water, 500 mg of tetrakistriphenylphosphine palladium (0) was added and heated and stirred for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried with MgSO4. After it was concentrated under reduced pressure, column chromatography was performed with MC:Hex=2:1 to obtain 3.0 g of white solid of compound 436 (yield 65%).

[0263] Mass: [(M+H)+ ]:502

[0264] [Synthesis Example 20] Synthesis of Compound 448

[0265]

[0266] 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. After adding 60 ml of toluene, 12 ml of ethanol and 12 ml of water, 500 mg of tetrakistriphenylphosphine palladium (0) was added and heated and stirred for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried with MgSO4. After it was concentrated under reduced pressure, column chromatography was performed with MC:Hex=2:1 to obtain 3.9 g of white solid of compound 448 (yield 62%).

[0267] Mass: [(M+H) + ]:626

[0268] [Synthesis Example 21] Synthesis of Compound 518

[0269]

[0270] 2.6 g of PTZ-3 was mixed with 4.6 g of (9,9'-diphenyl-9H-fluorene-3-yl)boric acid and 3.3 g of K2CO3. After adding 60 ml of toluene, 12 ml of ethanol and 12 ml of water, 480 mg of tetrakistriphenylphosphine palladium (0) was added, and the mixture was heated and stirred for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried with MgSO4. After it was concentrated under reduced pressure, column chromatography was performed with MC:Hex=2:1 to obtain 4.2 g of compound 518 as a white solid (yield 72%).

[0271] Mass: [(M+H) + ]:703

[0272] [Synthesis Example 22] Synthesis of Compound 524

[0273]

[0274] 2.0 g of PTZ-3 was mixed with 3.6 g of (7,7-dimethyl-7H-benzo[c]fluorene-11-yl)boric acid and 2.3 g of K2CO3. After adding 50 ml of toluene, 10 ml of ethanol and 10 ml of water, 400 mg of tetrakistriphenylphosphine palladium (0) was added, and the mixture was heated and stirred for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried with MgSO4. After it was concentrated under reduced pressure, column chromatography was performed with MC:Hex=2:1 to obtain 4.2 g of compound 524 as a white solid (yield 72%).

[0275] Mass: [(M+H) + ]:629

[0276] [Synthesis Example 23] Synthesis of Compound 542

[0277] PPY-8 2.2g was mixed with 9,9'-spirobis[fluorene]2-ylboronic acid 2.6g and Cs2CO3 2.9g, and after adding toluene 60ml, ethanol 12ml and water 12ml, Pd(OAc)2 50mg and Xphos 230mg were added, and heated and stirred for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried using MgSO4. After it was concentrated under reduced pressure, column chromatography was performed with MC to obtain 2.1g (yield 53%) of white solid of compound 542.

[0278] Mass: [(M+H) + ]:700

[0279] [Synthesis Example 24] Synthesis of Compound 545

[0280]

[0281] 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. After adding 60 ml of toluene, 12 ml of ethanol and 12 ml of water, 55 mg of Pd(OAc)2 and 250 mg of Xphos were added, and the mixture was heated and stirred for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried using MgSO4. After it was concentrated under reduced pressure, column chromatography was performed with THF:Hex=1:3 to obtain 2.6 g of compound 545 as a white solid (yield 63%).

[0282] Mass: [(M+H) + ]:628

[0283] [Examples 1 to 13] Preparation of blue organic electroluminescent elements

[0284] Compounds 1, 2, 4, 42, 45, 111, 112, 121, 133, 151, 156, 346, and 350 synthesized in Synthesis Examples were purified by sublimation to high purity by a commonly known method, and then a blue organic electroluminescent element was prepared as follows.

[0285] First, we will The glass substrate coated with a thin film of indium tin oxide (ITO) was washed with distilled water ultrasonically. After the distilled water washing, it was ultrasonically washed with isopropyl alcohol, acetone, methanol and other solvents and dried, and then transferred to a UV OZONE cleaning machine (Power sonic 405, HwashinTech), and the substrate was cleaned with UV for 5 minutes, and then transferred to a vacuum evaporator.

[0286] On the ITO transparent electrode prepared as above, DS-205 (Doosan Electronics, 80nm) / NPB (15nm) / ADN+5% DS-405 (Doosan Electronics, 30nm) / compounds 1, 2, 4, 42, 45, 111, 112, 121, 133, 151, 156, 346, 360 (30nm) / LiF (1nm) / Al (200nm) are stacked in sequence to produce an organic electroluminescent element.

[0287] [Comparative Example 1] Preparation of blue organic electroluminescent element

[0288] A blue organic electroluminescent element was produced in the same manner as in Example 1 except that Alq3 was used instead of Compound 1 as the electron transport layer material.

[0289] [Comparative Example 2] Preparation of blue organic electroluminescent element

[0290] A blue organic electroluminescent device was produced in the same manner as in Example 1 except that Compound 1 was not used as the electron transport layer material.

[0291] The structures of NPB, AND, and Alq3 used in Examples 1 to 13 and Comparative Examples 1 and 2 are as follows.

[0292]

[0293] [Evaluation Example 1]

[0294] The current density of each blue organic electroluminescent element prepared in Examples 1 to 13 and Comparative Examples 1 and 2 was measured at 10 mA / cm 2 The driving voltage, current efficiency and emission wavelength at the time of irradiation are shown in the following Table 1.

[0295] [Table 1]

[0296] sample Electron transport layer Driving voltage(V) Luminescence 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 Embodiment 11 Compound 156 3.2 450 7.3 Example 12 Compound 346 4.3 451 8.9 Embodiment 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

[0297] As shown in Table 1 above, it can be seen that the blue organic electroluminescent elements (Examples 1 to 13) using compounds 1, 2, 4, 42, 45, 111, 112, 121, 133, 151, 156, 346 and 350 of the present invention synthesized in the above synthesis examples for the electron transport layer show better performance in terms of driving voltage, luminescence peak and current efficiency than the previous blue organic electroluminescent elements (Comparative Example 1) using Alq3 for the electron transport layer and the blue organic electroluminescent elements without an electron transport layer (Comparative Example 2).

[0298] [Examples 14 to 24] Preparation of blue organic electroluminescent elements

[0299] Compounds 376, 377, 380, 409, 411, 436, 448, 518, 524, 542, and 545 synthesized in the above synthesis examples were purified by sublimation to high purity according to a commonly known method, and then a blue organic electroluminescent element was prepared according to the following process.

[0300] First, we will The glass substrate coated with a thin film of indium tin oxide (ITO) was washed with distilled water ultrasonically. After the distilled water washing, it was ultrasonically washed with isopropyl alcohol, acetone, methanol and other solvents and dried, and then transferred to a UV OZONE cleaning machine (Power sonic 405, HwashinTech), and the substrate was cleaned with UV for 5 minutes, and then transferred to a vacuum evaporator.

[0301] On the ITO transparent electrode prepared as above, DS-205 (Doosan Electronics, 80nm) / NPB (15nm) / ADN+5% DS-405 (Doosan Electronics, 30nm) / compounds 376, 377, 380, 409, 411, 436, 448, 518, 524, 542, 546 (5nm) / Alq3 (25nm) / LiF (1nm) / Al (200nm) are stacked in sequence to produce an organic electroluminescent element.

[0302] [Comparative Example 3] Preparation of blue organic electroluminescent element

[0303] A blue organic electroluminescent element was produced in the same manner as in Example 14, except that the compound 376 was not used as the electron transport auxiliary layer material and Alq3 was vapor-deposited in a thickness of 30 nm instead of 25 nm as the electron transport layer material.

[0304] [Evaluation Example 2]

[0305] For each of the organic electroluminescent devices prepared in Examples 14 to 24 and Comparative Example 3, the current density of 10 mA / cm 2 The driving voltage, emission wavelength and current efficiency at the time of irradiation are shown in the following Table 2.

[0306] [Table 2]

[0307] sample Electron transport auxiliary layer Driving voltage(V) Luminescence peak (nm) Current efficiency (cd / A) Embodiment 14 Compound 376 3.7 456 9.0 Embodiment 15 Compound 377 3.6 455 8.8 Example 16 Compound 380 3.5 456 8.6 Embodiment 17 Compound 409 3.9 455 8.5 Embodiment 18 Compound 411 3.4 456 9.1 Embodiment 19 Compound 436 3.3 457 8.8 Embodiment 20 Compound 448 3.6 455 9.1 Embodiment 21 Compound 518 3.4 454 8.4 Embodiment 22 Compound 524 3.7 455 8.6 Embodiment 23 Compound 542 3.4 456 8.8 Embodiment 24 Compound 545 3.6 455 9.3 Comparative Example 3 - 4.7 459 6.1

[0308] As shown in Table 2 above, it can be seen that the blue organic electroluminescent element (Examples 14 to 24) using the compound of the present invention synthesized in the above synthesis example for the electron transport auxiliary layer shows better performance in terms of current efficiency, luminescence peak and driving voltage than the blue organic electroluminescent element (Comparative Example 3) without the electron transport auxiliary layer.

[0309] As described above, the preferred embodiments of the present invention are described, but the present invention is not limited thereto, and can be implemented after being modified in various ways within the scope of the claims and the content of the invention, which of course also belongs to the category of the invention.

Claims

1. A compound represented by Chemical Formula 1: Chemical formula 1 In the chemical formula 1, Z1 to Z3 are all nitrogen, X is represented by the following X-3, In the X-3, * means the part that forms a bond with the chemical formula 1, n is 1, L is a single bond, A is represented by the following chemical formula 4, Chemical formula 4 In the chemical formula 4, R a and R b Combined with each other to form The condensed ring represented by * is the site where the bond is formed. R1 and R2 are each independently hydrogen, c is 4, d is 3, * means a part forming a bond with the chemical formula 1.

2. The compound according to claim 1, wherein in the chemical formula 1, the structure represented by A is the following A-2, wherein: * is the site where the bond is formed.

3. The compound according to claim 1, wherein the compound represented by Chemical Formula 1 is selected from the group consisting of compounds represented by the following 32, 37 and 42, 4. An organic electroluminescent element comprising an anode, a cathode and one or more organic layers between the anode and the cathode, At least one of the one or more organic layers comprises the compound according to any one of claims 1 to 3. 5 . The organic electroluminescent element according to claim 4 , wherein the organic layer containing the compound is selected from the group consisting of a hole injection layer, a hole transport layer, a luminescence auxiliary layer, a light emitting layer, an electron transport layer and an electron injection layer. 6 . The organic electroluminescent element according to claim 4 , wherein the organic layer containing the compound is selected from the group consisting of an electron transport layer and an electron transport auxiliary layer.

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