TRIAZINE COMPOUND AND ORGANIC ELECTROLUMINESTENT ELEMENT SO THAT

Description

Technical Field

[0001] The present invention relates to an organic compound and an organic electroluminescent element comprising the same.Background Art

[0002] In an organic electroluminescent element, the application of a voltage across two opposite electrodes induces the injection of holes from the anode and electrons from the cathode into an organic layer. The injected holes and electrons recombine with each other to generate excitons which then return to the ground state, emitting light. The materials for use in the organic layer can be classified as luminescent materials, hole injection materials, hole transport materials, electron transport materials, and electron injection materials according to functions.

[0003] Widely known are NPB, BCP and Alq 3 as materials for hole injection, hole transport and electron transport, and anthracene derivatives and Ir-bearing metal complexes, such as Firpic, Ir(ppy) 3 , (acac)Ir(btp) 2 etc., as luminescent materials.

[0004] However, not only are such materials poor in thermal stability due to their low glass transition temperatures, but also organic electroluminescent elements having the materials introduced into organic layers thereof exhibit only an unsatisfactory level of current efficiency and lifespan because the materials are of low triplet energy.

[0005] KR 2012 0046778 A discloses a cyclic azine derivative useful as an organic compound layer in a fluorescent and phosphorescent organic electroluminescent device.

[0006] JP 2014 125449 A1 provides an industrial manufacturing method of efficiently manufacturing a polysubstituted cyclic azine compound with high purity.

[0007] WO 2014 / 171541 A1 provides a cyclic azine compound for an organic electroluminescence element having exceptional service life characteristics.

[0008] KR 2011 0008892 A relates to the provision of an organic electroluminescent compound and an organic electroluminescent device using the same to ensure excellent luminous efficiency and lifetime property of materials and to obtain an OLED devices with good driving durability.

[0009] In KR 2014 0101661 A, an organic EL device having an anode, a light emitting layer, an electron transport band, and a cathode in this order is described, the electron transport band containing an aromatic heterocyclic derivative.

[0010] WO 2015 / 152633 A1 provides a heterocyclic compound and an organic light-emitting device comprising the same.

[0011] WO 2015 / 152634 A1 relates to an organic light-emitting device comprising: a cathode; an anode; a light-emitting layer provided between the cathode and the anode; and a heterocyclic compound.Disclosure Technical Problem

[0012] In order to solve the problems encountered in related art, the present invention provides an organic compound that can impart an organic electroluminescent element with an improvement in driving voltage, current efficiency, and lifespan.

[0013] Also, the present invention provides an organic electroluminescent element comprising the organic compound.Technical Solution

[0014] In order to accomplish the above purposes thereof, the present invention provides a compound represented by the following Formula 1: wherein, R a and R b are each independently a methyl or a phenyl or bond each other to form a fused ring represented by (* is a site where to bond), R 1 and R 2 may be the same or different from each other and are each independently selected from the group consisting of a hydrogen, a deuterium, a halogen, a cyano group, a nitro group, an amino group, a C 1 -C 40 alkyl group, a C 2 -C 40 alkenyl group, a C 2 -C 40 alkynyl group, a C 3 -C 40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C 6 -C 60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C 1 -C 40 alkyloxy group, a C 6 -C 60 aryloxy group, a C 1 -C 40 alkylsilyl group, a C 6 -C 60 arylsilyl group, a C 1 -C 40 alkylboron group, a C 6 -C 60 arylboron group, a C 1 -C 40 phosphine group, a C 1 -C 40 phosphine oxide group, and a C 6 -C 60 arylamine group, or in this case, adjacent ones of R 1 and R 2 are optionally respectively to each other to form a fused ring, R 3 is hydrogen, c and e are each an integer of 0 to 4, d is an integer of 0 to 3, m is 1 and n is 1 or 2, the structure represented by (* is a site where to bond with L) in Formula 1 is C-9, R 4 are different from each other and are selected from a C 6 -C 60 aryl group that is optionally substituted with a C 6 -C 60 aryl group, wherein L is a structure represented by the following L-1(* is a site where to bond):

[0015] In addition, the present invention provides an organic electroluminescent element comprising an anode, a cathode, and at least one organic layer interposed therebetween, wherein at least one of the organic layer comprises the compound represented by Formula 1.Advantageous Effects

[0016] Having excellent thermal stability and emitting properties, the compound, represented by Formula 1, of the present invention can be available for use in an organic layer of an organic electroluminescent element. Particularly when used as a material for a light-emitting layer or an auxiliary electron transport layer, the compound, represented by Formula 1, of the present invention can impart excellent emission performance, low driving voltage, high efficiency and long lifespan to the organic electroluminescent element, thereby allowing for the fabrication of a full-color display panel improved in performance and lifespan.Mode for Invention

[0017] Below, a detailed description is given of the present invention.1. Organic Compound

[0018] The organic compound of the present invention has a framework, represented by Formula 1, in which a fluorene moiety is bonded to a 6-membered heterocyclic ring through a linker (biphenylene or terphenylene).

[0019] The fluorene moiety serves as an electron donor group (EDG) with high electron donating ability. When the fluorene moiety is connected via a linker to a 6-membered heterocyclic ring that serves as an electron withdrawing group (EWG) with high electron withdrawing ability (e.g., pyridine, pyrimidine, triazine, etc.), the overall molecule exhibits a bipolar property. Accordingly, the compound of the present invention can improve hole-electron recombination.

[0020] In addition, since the linker, e.g., biphenylene or terphenylene, functions to minimize interaction between the electron donor group and the electron withdrawing group, the compound of the present invention into which the linker is introduced has a wide bandgap and a high triplet energy. Hence, the compound of the present invention, if applied to an organic layer, minimizes the diffusion of excitons to adjacent other organic layers. An organic electroluminescent element comprising such an organic layer can be improved in light emission efficiency and lifespan, compared to that comprising an organic layer lacking the linker. Further, with the introduction of a linker thereto, the compound of the present invention has a higher molecular weight than those lacking the linker, thus improving in thermal stability.

[0021] Such effects may be more intensified when bonds between an electron donor group and a linker, between linkers, and between a linker and an electron drawing group are more twisted structure formed thereof.

[0022] In the compound represented by Formula 1 of the present invention, the structure (substituent) represented by (* is a site where to bond with L) is embodied by C-9. wherein, R 4 is the same as defined in Formula 1 and a plurality of R 4 's are different.

[0023] In greater detail, the compound, represented by Formula 1, of the present invention may be represented by the following Formula 5: wherein, R a , R b , R 1 to R 4 , L, c, d, e, m, and n are the same as defined in Formula 1, respectively. When account is taken of properties of organic electroluminescent device, R a and R b in the compound represented Formula 1 of the present invention are each independently a methyl or a phenyl, or bond each other to form a fused ring represented by (* is a site where to bond).

[0024] In the compound represented by Formula 1, R 1 and R 2 can be each independently selected from the group consisting of hydrogen, deuterium, a C 1 -C 40 alkyl group, a C 6 -C 60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, and a C 6 -C 60 arylamine group. In addition, m is 1 and n is 1 or 2.

[0025] In the compound represented by Formula 1 of the present invention, L is represented by the following L-1 (* is a site where to bond.

[0026] Concrete examples of the compound, represented by Formula 1, of the present invention include, but are not limited to, the following Compounds 197 to 204:

[0027] As used herein, the term "alkyl" refers to a monovalent substituent derived from linear or branched saturated hydrocarbon of 1 to 40 carbon atoms, including, for example, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, and the like.

[0028] As used herein, the term "alkenyl" refers to a monovalent substituent derived from a linear or branched unsaturated hydrocarbon with one more carbon-carbon double bonds, as exemplified by vinyl, allyl, isopropenyl, 2-butenyl, and the like.

[0029] As used herein, the term "alkynyl" refers to a monovalent substituent derived from a linear or branched unsaturated hydrocarbon of 2 to 40 carbon atoms with at least one carbon-carbon triple bond, as exemplified by ethynyl, 2-propynyl, and the like.

[0030] As used herein, the term "aryl" denotes a monovalent substituent derived from an aromatic hydrocarbon of 6 to 60 carbon atoms with a single ring or a combination of two or more rings in which two or more rings may simply be pendant to each other or fused together, as exemplified by phenyl, naphthyl, phenantryl, anthryl, etc.

[0031] As used herein, the term "heteroaryl" denotes a monovalent substituent derived from a mono- or polyheterocyclic aromatic hydrocarbon of 5 to 60 nuclear atoms in which at least one, particularly one to three carbon atoms of the ring are substituted by a heteroatom such as N, O, S or Se. Two or more rings of the heteroaryl, if present, may simply be pendant to each other or fused together or to an aryl group. Examples include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl, polycyclic rings such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, and carbazolyl, 2-furanyl, N-imidazolyl, 2-ixosazolyl, 2-pyridinyl, and 2-pyrimidinyl.

[0032] As used herein, the term "aryloxy" refers to a monovalent substituent represented by RO- wherein R denotes an aryl of 6 to 60 carbon atoms, as exemplified by phenyloxy, naphthyloxy, diphenyloxy, etc.

[0033] As used herein, the term "alkyloxy" refers to a monovalant substituent represented by R'O- wherein R' means an alkyl of 1 to 40 carbon atoms and is construed to include a linear, branched or cyclic structure and examples of which include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy, etc.

[0034] As used herein, the term "arylamine" refers to an amine substituted with an aryl of 6 to 60 carbon atoms.

[0035] As used herein, the term "cycloalkyl" refers to a monovalent substituent derived from a mono- or polycyclic non-aromatic hydrocarbon of 3 to 40 carbon atoms, examples of which include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, and adamantine.

[0036] As used herein, the term "heterocycloalkyl" refers to a monovalent substituent derived from a non-aromatic hydrocarbon of 3 to 40 nuclear atoms in which at least one, particularly one to three carbon atoms of the ring are substituted by a heteroatom such as N, O, S or Se and examples of which include morpholinem, piperazine, and the like.

[0037] As used herein, the term "alkylsilyl" refers to a silyl substituent substituted with an alkyl of 1 to 40 carbon atoms, and the term "arylsilyl" refers to a silyl group substituted with an aryl of 6 to 60 carbon atoms.

[0038] As used herein, the term "fused ring" refers to a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring, a heteroaromatic ring, or a combination thereof.2. Organic Electroluminescent Element

[0039] The present invention provides an organic electroluminescent element comprising the compound represented by Formula 1.

[0040] In detail, the organic electroluminescent element of the present invention comprises an anode, a cathode, and at least one organic layer interposed therebetween wherein the at least one organic layer comprises the compound represented by Formula 1. Here, the compound may be a single kind or a combination of two or more different kinds.

[0041] The at least one organic layer may be selected from among a hole injection layer, a hole transport layer, an auxiliary light-emitting layer, an electron transport layer, an electron injection layer, and a combination thereof, and may comprise the compound represented by Formula 1. In detail, the organic layer comprising the compound represented by Formula 1 is particularly a light-emitting layer or an auxiliary electron transport layer (interposed between a light-emitting layer and an electron transport layer).

[0042] Meanwhile, the light-emitting layer may comprise a host. Here, the host may be the compound represented by Formula 1, alone or in combination with other compounds. In addition, the light-emitting layer may comprise a dopant based on a metal complex compound, together with the host.

[0043] No particular limitations are imparted to the structure of the organic electroluminescent element of the present invention. For example, the organic electroluminescent element may have a structure in which a substrate, an anode, a hole injection layer, a hole transport layer, an auxiliary light-emitting layer, a light-emitting layer, an auxiliary electron transport layer, an electron transport layer, and a cathode are sequentially deposited. Here, an electron injection layer may be further deposited on the electron transport layer. Moreover, an insulation layer or an adhesive layer may be introduced into the interface between the electrode (cathode or anode) and the organic layer.

[0044] The organic electroluminescent element of the present invention can be fabricated using materials and methods known in the art, with the exception that at least one of the organic layers comprises the compound represented by Formula 1.

[0045] The organic layer may be formed using a vacuum deposition method or a solution coating method. Examples of the solution coating method include spin coating, dip coating, doctor blade coating, inkjet printing and a thermal transfer method, but are not limited thereto.

[0046] The substrate used for the fabrication of the organic electroluminescent element of the present invention is not particularly limited, and may be a silicon wafer, quartz, a glass plate, a metal plate, or a plastic film.

[0047] As for the anode, its material is not particularly limited, but may be a metal such as vanadium, chromium, copper, zinc, gold, etc., or an alloy thereof; a metal oxide such as zinc oxide, indium oxide, indium tin oxide(ITO), and indium zinc oxide(IZO); a combination of metal and oxide such as ZnO:Al or SnO2:Sb; a conductive polymer such as polythiophene, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole or polyaniline; and carbon black.

[0048] Although no particular limitations are imparted thereto, a material available for the cathode may be a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or an alloy thereof; or a multilayer material such as LiF / Al or LiO2 / A.l.

[0049] In addition, the hole injection layer, the hole transport layer, the electron injection layer and the electron transport layer are not particularly limited, and may be made of conventional materials known in the art.

[0050] The present invention will be in greater detail described through the following examples that are set forth to illustrate, but are not to be construed as limiting the present invention.SYNTHESIS EXAMPLE 1 (reference example): Synthesis of Compound 1 (2-(3-(9, 9-dimethyl-9H-fluoren-2-yl)phenyl)-4,6-diphenyl-1,3,5-triazine)

[0051]

[0052] Under a nitrogen stream, 2-(3-bromophenyl)-4,6-diphenyl-[1,3,5]triazine (10.0 g, 0.026 mol), 9,9-dimethyl-9H-fluoren-2-yl-boronic acid (7.9 g, 0.033 mol), Pd(PPh 3 ) 4 (0.95 g, 0.001 mol), and potassium carbonate (7.65 g, 0.078 mol) were mixed and then stirred under reflux with 1,4-dioxane (80 ml) and H 2 O (20 ml). After completion of the reaction, an organic layer was separated with methylene chloride, and dried over MgSO 4 . The solvent was removed from the dehydrated organic layer, followed by purification through column chromatography [hexane: MC = 5:1 (v / v)] to afford Compound 1 (8.2 g, yield 63%) . HRMS [M]+: 501.62SYNTHESIS EXAMPLE 2 (reference example): Synthesis of Compound 3 (2-[3-(9,9-Dimethyl-9H-fluoren-3-yl)-phenyl]-4,6-diphenyl-[1,3,5]triazine)

[0053]

[0054] The same procedure was conducted as in Synthesis Example 1, with the exception of using 9,9-dimethyl-9H-fluoren-3-yl-boronic acid (7.9 g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid, to afford Compound 3. HRMS [M]+: 501.62SYNTHESIS EXAMPLE 3 (reference example): Synthesis of Compound 69 (2-[3-(9,9-Diphenyl-9H-fluoren-2-yl)-phenyl]-4,6-diphenyl-[1,3,5]triazine)

[0055]

[0056] The same procedure was conducted as in Synthesis Example 1, with the exception of using (9,9-diphenyl-9H-fluoren-2-yl)-boronic acid (11.9 g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid, to afford Compound 69. HRMS [M]+: 625.76SYNTHESIS EXAMPLE 4 (reference example): Synthesis of Compound 129 (2-[3-(9,9-Spirobi[9H-fluorene]--2-yl)-phenyl]-4, 6-diphenyl-[1,3,5]triazine)

[0057]

[0058] The same procedure was conducted as in Synthesis Example 1, with the exception of using 9,9'-spirobi[9H-fluorene]-2-yl-boronic acid (11.88g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid, to afford Compound 129. HRMS [M]+: 623.74SYNTHESIS EXAMPLE 5 (reference example): Synthesis of Compound 6 (4-[3-(9,9-Dimethyl-9H-fluoren-2-yl)-phenyl]-2, 6-diphenyl-pyrimidine

[0059]

[0060] The same procedure was conducted as in Synthesis Example 1, with the exception of using 4-(3-bromophenyl)-2,6-diphenylpyrimidine (10.0 g, 0.026 mol) instead of 2-(3-bromophenyl)-4,6-diphenyl-[1,3,5]triazine, to afford Compound 6. HRMS [M]+: 500.63SYNTHESIS EXAMPLE 6 (reference example): Synthesis of Compound 74 (4-[3-(9, 9-Diphenyl-9H-fluoren-2-yl)-phenyl]-2,6-diphenyl-pyrimidine)

[0061]

[0062] The same procedure was conducted as in Synthesis Example 5, with the exception of using (9,9-diphenyl-9H-fluoren-2-yl)-boronic acid (11.9 g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid, to afford Compound 74. HRMS [M]+: 624.77SYNTHESIS EXAMPLE 7 (reference example): Synthesis of Compound 134 (4-[3-(9,9-Spirobi[9H-fluorene]-2-yl)-phenyl]-2,6-diphenyl-pyrimidine

[0063]

[0064] The same procedure was conducted as in Synthesis Example 5, with the exception of using 9,9'-spirobi[9H-fluorene]-2-yl-boronic acid (12.77g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid, to afford Compound 134. HRMS [M]+: 622.75SYNTHESIS EXAMPLE 8 (reference example): Synthesis of Compound 7 (4-[3-(9,9-Dimethyl-9H-fluoren-2-yl)-phenyl]-2, 6-diphenyl-pyridine)

[0065]

[0066] The same procedure was conducted as in Synthesis Example 1, with the exception of using 4-(3-bromophenyl)-2,6-diphenyl-pyridine (10.0g, 0.026 mol) instead of 2-(3-bromophenyl)-4,6-diphenyl-[1,3,5]triazine, to afford Compound 7. HRMS [M]+: 499.64SYNTHESIS EXAMPLE 9 (reference example): Synthesis of Compound 75 (4-[3-(9,9-Diphenyl-9H-fluoren-2-yl)-phenyl]-2,6-diphenyl-pyridine

[0067]

[0068] The same procedure was conducted as in Synthesis Example 8, with the exception of using (9,9-diphenyl-9H-fluoren-2-yl)-boronic acid (11.9 g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid, to afford Compound 75. HRMS [M]+: 623.78SYNTHESIS EXAMPLE 10 (reference example): Synthesis of Compound 135 (4-[3-(9,9-Spirobi[9H-fluorene]-2-yl)-phenyl]-2,6-diphenyl-pyridine

[0069]

[0070] The same procedure was conducted as in Synthesis Example 8, with the exception of using 9,9'-spirobi[9H-fluorene]-2-yl-boronic acid (12.77g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid, to afford Compound 135. HRMS [M]+: 622.71SYNTHESIS EXAMPLE 11 (reference example): Synthesis of Compound 21 (2-(3'-(9,9-dimethyl-9H-fluoren-2-yl)biphenyl-3-yl)-4,6-diphenyl-1,3,5-triazine)

[0071] <Step 1> Synthesis of Intermediate 1-A (2-(3'-chlorobiphenyl-3-yl)-4,6-diphenyl-1,3,5-triazine)

[0072] Under a nitrogen stream, 2-(3-bromophenyl)-4,6-diphenyl-[1,3,5]triazine (12.0 g, 0.031 mol), 3-chlorophenylboronic acid (6.3 g, 0.040 mol), Pd(PPh 3 ) 4 (1.15 g, 0.001 mol), and potassium carbonate (12.85 g, 0.093 mol) were mixed and then stirred under reflux with 1,4-dioxane (100 ml) and H 2 O (25 ml).

[0073] After completion of the reaction, an organic layer was separated with methylene chloride and dried over MgSO 4 . The solvent was removed from the dehydrated organic layer, followed by purification through column chromatography [hexane: MC = 5:1 (v / v)] to afford Intermediate 1-A (11.0g, yield 83%).<Step2> Synthesis of Compound 21 (2-(3'-(9,9-dimethyl-9H-fluoren-2-yl)biphenyl-3-yl)-4,6-diphenyl-1,3,5-triazine)

[0074] Under a nitrogen stream, Intermediate 1-A (11.0 g, 0.026 mol) obtained in Step 1, 9,9-dimethyl-9H-fluoren-2-yl-boronic acid (7.9 g, 0.033 mol), Pd (OAc) 2 (0.29 g, 0.001 mol), cesium carbonate (25.4 g, 0.078 mol), and Xphos (1.23 g, 0.003 mol) were mixed and then stirred under reflux with toluene (100 ml) / ethanol (20ml) / H 2 O (20 ml).

[0075] After completion of the reaction, an organic layer was separated with methylene chloride and dried over MgSO 4 . The solvent was removed from the dehydrated organic layer, followed by purification through column chromatography [hexane: MC = 5:1 (v / v)] to afford Compound 21 (8.2 g, yield 63%). HRMS [M]+: 577.72SYNTHESIS EXAMPLE 12 (reference example): Synthesis of Compound 23 (2-[3'-(9,9-Dimethyl-9H-fluoren-3-yl)-biphenyl-3-yl]-4,6-diphenyl-[1,3,5]triazine

[0076]

[0077] The same procedure was conducted as in Synthesis Example 11, with the exception of using 9,9-dimethyl-9H-fluoren-3-yl-boronic acid (7.9 g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid used in Step 2 of Synthesis Example 11, to afford Compound 23. HRMS [M]+: 577.72SYNTHESIS EXAMPLE 13 (reference example): Synthesis of Compound 89 (2-[3'-(9,9-Diphenyl-9H-fluoren-2-yl)-biphenyl-3-yl]-4,6-diphenyl-[1,3,5]triazine

[0078]

[0079] The same procedure was conducted as in Synthesis Example 11, with the exception of using (9,9-diphenyl-9H-fluoren-2-yl)-boronic acid (7.9 g, 0.033 mol) instead of 9,9-Dimethyl-9H-fluoren-2-yl-boronic acid used in Step 2 of Synthesis Example 11. HRMS [M]+:701.85SYNTHESIS EXAMPLE 14 (reference example): Synthesis of Compound 91 (2-(3'-(9,9-diphenyl-9H-fluoren-3-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine

[0080]

[0081] The same procedure was conducted as in Synthesis Example 11, with the exception of using (9,9-diphenyl-9H-fluoren-3-yl)boronic acid (7.9 g, 0.033 mol) instead of (9,9-dimethyl-9H-fluoren-2-yl)boronic acid used in Step 2 of Synthesis Example 11, to afford Compound 91. HRMS [M]+: 701.85SYNTHESIS EXAMPLE 15 (reference example): Synthesis of Compound 149 (2-[3'-(9,9-Spirobi[9H-fluorene]-2-yl)biphenyl-3-yl]-4,6-diphenyl-[1,3,5]triazine

[0082]

[0083] The same procedure was conducted as in Synthesis Example 11, with the exception of using 9,9'-Spirobi[9H-fluorene]-2-yl-boronic acid (12.77g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid used in Step 2 of Synthesis Example 11, to afford Compound 149. HRMS [M]+: 699.84SYNTHESIS EXAMPLE 16 (reference example): Synthesis of Compound 151 (2-(3'-(9,9'-spirobi[fluoren]-3-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine

[0084]

[0085] The same procedure was conducted as in Synthesis Example 11, with the exception of using 9,9'-spirobi[fluoren]-3-yl-boronic acid (12.77g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid used in Step 2 of Synthesis Example 11, to afford Compound 151. HRMS [M]+: 699.84SYNTHESIS EXAMPLE 17 (reference example): Synthesis of Compound 31 (4-[3'-(9,9-Dimethyl-9H-fluoren-2-yl)-biphenyl-3-yl]-2,6-diphenyl-pyrimidine

[0086] <Step 1> Synthesis of Intermediate 2-A (4-(3'-Chlorobiphenyl-3-yl)-2,6-diphenyl-pyrimidine

[0087] The same procedure was conducted as in Step 1 of Synthesis Example 11, with the exception of using 4-(3-bromophenyl)-2,6-diphenyl-pyrimidine (12.0g, 0.031 mol) instead of 2-(3-bromophenyl)-4,6-diphenyl-[1,3,5]triazine used in Step 1 of Synthesis Example 11, to afford Intermediate 2-A.<Step2> Synthesis of Compound 31 4-[3'-(9,9-Dimethyl-9H-fluoren-2-yl)-biphenyl-3-yl]-2,6-diphenyl-pyrimidine

[0088] The same procedure was conducted as in Step 2 of Synthesis Example 11, with the exception of using Intermediate 2-A (11.0g, 0.026 mol) synthesized in Step 1 instead of Intermediate 1-A used in Step 2 of Synthesis Example 11, to afford Compound 31. HRMS [M]+: 576.73SYNTHESIS EXAMPLE 18 (reference example): Synthesis of Compound 35 (4-[3'-(9,9-Dimethyl-9H-fluoren-3-yl)-biphenyl-3-yl]-2,6-diphenyl-pyrimidine

[0089]

[0090] The same procedure was conducted as in Synthesis Example 17, with the exception of using 9,9-dimethyl-9H-fluoren-3-yl-boronic acid (7.9 g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid used in Step 2 of Synthesis Example 17, to afford Compound 35. HRMS [M]+: 576.73SYNTHESIS EXAMPLE 19 (reference example): Synthesis of Compound 99 (4-[3'-(9,9-Diphenyl-9H-fluoren-2-yl)-biphenyl-3-yl]-2,6-diphenyl-pyrimidine

[0091]

[0092] The same procedure was conducted as in Synthesis Example 17, with the exception of using (9,9-diphenyl-9H-fluoren-2-yl)-boronic acid (11.9 g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid used in Step 2 of Synthesis Example 17, to afford Compound 99. HRMS [M]+: 687.85SYNTHESIS EXAMPLE 20 (reference example): Synthesis of Compound 159 (4-[3'-(9,9-Spirobi[9H-fluorene]-2-yl)biphenyl-3-yl]-2,6-diphenyl-pyrimidine

[0093]

[0094] The same procedure was conducted as in Synthesis Example 17, with the exception of using 9,9'-spirobi[9H-fluorene]-2-yl-boronic acid (11.88g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid used in Step 2 of Synthesis Example 17, to afford Compound 159. HRMS [M]+: 698.85SYNTHESIS EXAMPLE 21 (reference example): Synthesis of Compound 45 (4-[3'-(9,9-Dimethyl-9H-fluoren-2-yl)-biphenyl-3-yl]-2,6-diphenyl-pyridine <Step 1> Synthesis of Intermediate 3-A (4-(3'-Chlorobiphenyl-3-yl)-2,6-diphenyl-pyridine

[0095] The same procedure was conducted as in Step 1 of Synthesis Example 11, with the exception of using 4-(3-bromophenyl)-2,6-diphenyl-pyridine (12.0g, 0.031 mol) instead of 2-(3-bromophenyl)-4,6-diphenyl-[1,3,5]triazine used in Step 1 of Synthesis Example 11, to afford Intermediate 3-A.<Step2> Synthesis of Compound 45 (4-[3'-(9,9-Dimethyl-9H-fluoren-2-yl)-biphenyl-3-yl]-2,6-diphenyl-pyridine

[0096] The same procedure was conducted as in Step 2 of Synthesis Example 11, with the exception of using Intermediate 3-A (11.0g, 0.026 mol) synthesized in Step 1 instead of Intermediate 1-A used in Step 2 of Synthesis Example 11, to afford Compound 45.SYNTHESIS EXAMPLE 22 (reference example): Synthesis of Compound 53 (4-[3'-(9,9-Dimethyl-9H-fluoren-3-yl)-biphenyl-3-yl]-2,6-diphenyl-pyridine

[0097]

[0098] The same procedure was conducted as in Synthesis Example 21, with the exception of using 9,9-dimethyl-9H-fluoren-3-yl-boronic acid (7.9 g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid used in Step 2 of Synthesis Example 21, to afford Compound 53. HRMS [M]+: 501.62SYNTHESIS EXAMPLE 23 (reference example): Synthesis of Compound 113 (4-[3'-(9,9-Diphenyl-9H-fluoren-2-yl)-biphenyl-3-yl]-2,6-diphenyl-pyridine

[0099]

[0100] The same procedure was conducted as in Synthesis Example 21, with the exception of using (9,9-diphenyl-9H-fluoren-2-yl)-boronic acid (11.9 g, 0.033 mol) instead of 9,9-Dimethyl-9H-fluoren-2-yl-boronic acid used in Step 2 of Synthesis Example 21, to afford Compound 113. HRMS [M]+: 699.88SYNTHESIS EXAMPLE 24 (reference example): Synthesis of Compound 173 (4-[3'-(9,9-Spirobi[9H-fluorene]-2-yl)-biphenyl-3-yl]-2,6-diphenyl-pyridine

[0101]

[0102] The same procedure was conducted as in Synthesis Example 21, with the exception of using 9,9'-spirobi[9H-fluorene]-2-yl-boronic acid (11.88g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid used in Step 2 of Synthesis Example 21, to afford Compound 173. HRMS [M]+: 697.86SYNTHESIS EXAMPLE 25 (reference example): Synthesis of Compound 61 (2-(3"-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1':3',1"-terphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine)

[0103] <Step 1> Synthesis of Intermediate 1-B (2-(3"-chloro-[1,1':3',1"-terphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine)

[0104] Under a nitrogen stream, Intermediate 1-A (11.0 g, 0.026 mol), 3-Chlorophenylboronic acid (4.8 g, 0.031 mol), Pd(OAc) 2 (0.29 g, 0.001 mol), Cesium carbonate (25.4 g, 0.078 mol), and Xphos (0.3 g, 0.003 mol) were mixed and then stirred under reflux with toluene (100 ml) / ethanol (20ml) / H 2 O (20 ml).

[0105] After completion of the reaction, an organic layer was separated with methylene chloride and dried over MgSO 4 . The solvent was removed from the dehydrated organic layer, followed by purification through column chromatography [hexane: MC = 5:1 (v / v)] to afford Intermediate 1-B (7.5 g, yield 58%).<Step2> Synthesis of Compound 61 (2-(3"-(9, 9-dimethyl-9H-fluoren-2-yl)-[1,1':3',1''-terphenyl]-3-yl)-4,6-diphenyl-1, 3, 5-triazine)

[0106] Under a nitrogen stream, Intermediate 1-B (7.5 g, 0.015 mol) obtained in Step 1, 9,9-dimethyl-9H-fluoren-2-yl-boronic acid (4.3 g, 0.018 mol), Pd(OAc) 2 (0.17 g, 0.75 mmol), cesium carbonate (14.6 g, 0.045 mol), and Xphos (0.7 g, 1.5 mmol) were mixed and stirred under reflux with toluene (60 ml) / ethanol (15 ml) / H 2 O (15 ml).

[0107] After completion of the reaction, an organic layer was separated with methylene chloride and dried over MgSO 4 . The solvent was removed from the dehydrated organic layer, followed by purification through column chromatography [hexane: MC = 4:1 (v / v)] to afford Compound 61 (8.1 g, yield 83%). HRMS [M]+: 653.83SYNTHESIS EXAMPLE 26 (reference example): Synthesis of Compound 62 (2-(3"-(9,9-dimethyl-9H-fluoren-3-yl)-[1,1':3',1"-terphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine

[0108]

[0109] The same procedure was conducted as in Synthesis Example 25, with the exception of using (9,9-dimethyl-9H-fluoren-3-yl)boronic acid (4.3 g, 0.018 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid used in Step 2 of Synthesis Example 25, to afford Compound 62. HRMS [M]+: 653.83SYNTHESIS EXAMPLE 27 (reference example): Synthesis of Compound 63 (4-(3"-(9, 9-dimethyl-9H-fluoren-2-yl)-[1,1':3",1''-terphenyl]-3-yl)-2,6-diphenylpyrimidine

[0110] <Step 1> Synthesis of Intermediate 2-B (4-(3"-chloro-[1,1':3',1"-terphenyl]-3-yl)-2,6-diphenylpyrimidine

[0111] Under a nitrogen stream, Intermediate 2-A (11.0 g, 0.026 mol), 3-chlorophenylboronic acid (4.8 g, 0.031 mol), Pd(OAc) 2 (0.29 g, 0.001 mol), Cesium carbonate (25.4 g, 0.078 mol), and Xphos (0.3 g, 0.003 mol) were mixed and then stirred under reflux with toluene (100 ml) / ethanol (20ml) / H 2 O (20 ml) .

[0112] After completion of the reaction, an organic layer was separated with methylene chloride and then dried over MgSO 4 . The solvent was removed from the dehydrated organic layer, followed by purification through column chromatography [hexane: MC = 5:1 (v / v)] to afford Intermediate 2-B (7.5 g, yield 58%).<Step2> Synthesis of Compound 63 (4-(3"-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1':3',1"-terphenyl]-3-yl)-2,6-diphenylpyrimidine

[0113] Under a nitrogen stream, Intermediate 2-B (7.5 g, 0.015 mol), 9,9-dimethyl-9H-fluoren-2-yl-boronic acid (4.3 g, 0.018 mol) obtained in Step 1, Pd(OAc) 2 (0.17 g, 0.75 mmol), cesium carbonate (14.6 g, 0.045 mol), and Xphos (0.7 g, 1.5 mmol) were mixed and then mixed and then stirred under reflux with toluene (60 ml) / Ethanol (15 ml) / H 2 O (15 ml).

[0114] After completion of the reaction, an organic layer was separated with methylene chloride and then dried over MgSO 4 . The solvent was removed from the dehydrated organic layer, followed by purification through column chromatography [hexane: MC = 4:1 (v / v)] to afford Compound 63 (8.1 g, yield 83%). HRMS [M]+: 652.84SYNTHESIS EXAMPLE 28 (reference example): Synthesis of Compound 64 (4-(3"-(9,9-dimethyl-9H-fluoren-3-yl)-[1,1':3",1''-terphenyl]--3-yl)-2,6-diphenylpyrimidine

[0115]

[0116] The same procedure was conducted as in Synthesis Example 27, with the exception of using (9,9-dimethyl-9H-fluoren-3-yl)boronic acid (4.3 g, 0.018 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid used in Step 2 of Synthesis Example 27, to afford Compound 64. HRMS [M]+: 652.84SYNTHESIS EXAMPLE 29: Synthesis of Compound 200 (2 2-([1,1'-biphenyl]-4-yl)-4-(3'-(9,9-diphenyl-9H-fluoren-2-yl)-[1,1'-biphenyl]-3-yl)-6-phenyl-1,3,5-triazine

[0117] <Step 1> Synthesis of Intermediate 4-A

[0118] The same procedure was conducted as in Step 1 of Synthesis Example 11, with the exception of using 2-([1,1'-biphenyl]-4-yl)-4-(3-bromophenyl)-6-phenyl-1,3,5-triazine (14.4 g, 0.031 mol) instead of 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine used in Step 1 of Synthesis Example 11, to afford Intermediate 4-A.<Step 2> Synthesis of Compound 200 (2 2-([1,1'-biphenyl]-4-yl)-4-(3'-(9,9-diphenyl-9H-fluoren-2-yl)-[1,1'-biphenyl]-3-yl)-6-phenyl-1,3,5-triazine

[0119] The same procedure was conducted as in Step 2 of Synthesis Example 11, with the exception of using (9,9-diphenyl-9H-fluoren-2-yl)-boronic acid (11.9 g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid used in Step 2 of Synthesis Example 11, to afford Compound 200. HRMS [M]+:777.97SYNTHESIS EXAMPLE 30 (reference example): Synthesis of Compound 206 (4-([1,1'-biphenyl]-4-yl)-6-(3'-(9,9-diphenyl-9H-fluoren-2-yl)-[1,1'-biphenyl]-3-yl)-2-phenylpyrimidine

[0120] <Step 1> Synthesis of Intermediate 5-A

[0121] The same procedure was conducted as in Step 1 of Synthesis Example 11, with the exception of using 4-([1,1'-biphenyl]-4-yl)-6-(3-bromophenyl)-2-phenylpyrimidine (14.3 g, 0.031 mol) instead of 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine used in Step 1 of Synthesis Example 11, to afford Intermediate 5-A.<Step 2> Synthesis of Compound 206 (4-([1,1'-biphenyl]-4-yl)-6-(3'-(9,9-diphenyl-9H-fluoren-2-yl)-[1,1'-biphenyl]-3-yl)-2-phenylpyrimidine

[0122] The same procedure was conducted as in Step 2 of Synthesis Example 11, with the exception of using (9,9-diphenyl-9H-fluoren-2-yl)-boronic acid (11.9 g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid used in Step 2 of Synthesis Example 11, to afford Compound 206. HRMS [M]+:776.98SYNTHESIS EXAMPLE 31 (reference example): Synthesis of Compound 217 (2-(3'-(9,9-dimethyl-9H-fluoren-1-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1, 3, 5-triazine

[0123] <Step 1> Intermediate I-1 (2-(3'-chloro-biphenyl-3-yl)-4,6-diphenyl-1,3,5-triazine

[0124] Under a nitrogen stream, 2-(3-Bromo-phenyl)-4,6-diphenyl-[1,3,5]triazine (12.0 g, 0.031 mol), 3-Chlorophenylboronic acid (6.3 g, 0.040 mol), Pd(PPh 3 ) 4 (1.15 g, 0.001 mol) and potassium carbonate (12.85 g, 0.093 mol) were mixed and then stirred under reflux with, 1,4-dioxane (100 ml) and H 2 O (25 ml).

[0125] After completion of the reaction, an organic layer was separated with methylene chloride and then dried over MgSO 4 . The solvent was removed from the dehydrated organic layer, followed by purification through column chromatography [hexane: MC = 5:1 (v / v)] to afford Intermediate I-1 (11.0g, yield 83%).<Step2> Synthesis of Compound 217 (2-(3'-(9,9-dimethyl-9H-fluoren-1-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine

[0126] Under a nitrogen stream, Intermediate I-1 (11.0 g, 0.026 mol) obtained in Step 1, (9,9-dimethyl-9H-fluoren-1-yl)boronic acid (7.9 g, 0.033 mol), Pd(OAc) 2 (0.29 g, 0.001 mol), Cesium carbonate (25.4 g, 0.078 mol), and Xphos (1.23 g, 0.003 mol) were mixed and then stirred under reflux with toluene (100 ml), ethanol (20ml) and H 2 O (20 ml).

[0127] After completion of the reaction, an organic layer was separated with methylene chloride and then dried over MgSO 4 . The solvent was removed from the dehydrated organic layer, followed by purification through column chromatography [hexane: MC = 5:1 (v / v)] to afford Compound 217 (8.2 g, yield 63%) . HRMS [M]+: 577.25SYNTHESIS EXAMPLE 32 (reference example): Synthesis of Compound 218 (2-(3'-(9,9-diphenyl-9H-fluoren-1-yl)-[1,1'-biphenyl]-3-yl)-4, 6-diphenyl-1, 3, 5- triazine

[0128]

[0129] The same procedure was conducted as in Synthesis Example 31, with the exception of using (9,9-diphenyl-9H-fluoren-1-yl)boronic acid (12.0 g, 0.033 mol) instead of (9,9-dimethyl-9H-fluoren-1-yl)boronic acid used in Step 2 of Synthesis Example 31, to afford Compound 218. HRMS [M]+: 701.28SYNTHESIS EXAMPLE 33 (reference example): Synthesis of Compound 220 (2-(3'-(9,9'-spirobi[fluoren]-1-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine

[0130]

[0131] The same procedure was conducted as in Synthesis Example 31, with the exception of using (9,9'-spirobi[fluoren]-1-yl)boronic acid (11.9 g, 0.033 mol) instead of (9,9-dimethyl-9H-fluoren-1-yl)boronic acid used in Step 2 of Synthesis Example 31, to afford Compound 220. HRMS [M]+: 699.27SYNTHESIS EXAMPLE 34 (reference example): Synthesis of Compound 21 (2-(3'-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine

[0132]

[0133] The same procedure was conducted as in Synthesis Example 31, with the exception of using (9,9-dimethyl-9H-fluoren-2-yl)boronic acid (7.9, 0.033 mol) instead of (9,9-dimethyl-9H-fluoren-1-yl)boronic acid used in Step 2 of Synthesis Example 31, to afford Compound 21. HRMS [M]+: 577.25SYNTHESIS EXAMPLE 35 (reference example): Synthesis of Compound 189 (2-(3'-(9-methyl-9-phenyl-9H-fluoren-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine

[0134]

[0135] The same procedure was conducted as in Synthesis Example 31, with the exception of using (9-methyl-9-phenyl-9H-fluoren-2-yl)boronic acid (9.9, 0.033 mol) instead of (9,9-dimethyl-9H-fluoren-1-yl)boronic acid used in Step 2 of Synthesis Example 31, to afford Compound 189. HRMS [M]+: 639.27SYNTHESIS EXAMPLE 36 (reference example): Synthesis of Compound 193 (2-(3'-(7,7-dimethyl-7H-benzo[c]fluoren-9-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine

[0136]

[0137] The same procedure was conducted as in Synthesis Example 31, with the exception of using (7,7-dimethyl-7H-benzo[c]fluoren-9-yl)boronic acid (9.5, 0.033 mol) instead of (9,9-dimethyl-9H-fluoren-1-yl)boronic acid used in Step 2 of Synthesis Example 31, to afford Compound 193. HRMS [M]+: 627.27SYNTHESIS EXAMPLE 37 (reference example): Synthesis of Compound 65 (2-(3'-(9,9-dimethyl-7-phenyl-9H-fluoren-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine

[0138]

[0139] The same procedure was conducted as in Synthesis Example 31, with the exception of using (9,9-dimethyl-7-phenyl-9H-fluoren-2-yl)boronic acid (10.4 g, 0.033 mol) instead of (9,9-dimethyl-9H-fluoren-1-yl)boronic acid used in Step 2 of Synthesis Example 31, to afford Compound 65. HRMS [M]+: 653.28SYNTHESIS EXAMPLE 38 (reference example): Synthesis of Compound 231 (2,4-diphenyl-6-(3'-(spiro[benzo[c]fluorene-7,9'-fluoren]-9-yl)-[1,1'-biphenyl]-3-yl)-1,3,5-triazine

[0140]

[0141] The same procedure was conducted as in Synthesis Example 31, with the exception of using (spiro[benzo[c]fluorene-7,9'-fluoren]-9-yl)boronic acid (13.5 g, 0.033 mol) instead of (9,9-dimethyl-9H-fluoren-1-yl)boronic acid used in Step 2 of Synthesis Example 31, to afford Compound 231. HRMS [M]+: 749.28SYNTHESIS EXAMPLE 39 (reference example): Synthesis of Compound 234 (2-(3'-(13,13-dimethyl-13H-indeno[1,2-l]phenanthren-10-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine

[0142]

[0143] The same procedure was conducted as in Synthesis Example 31, with the exception of using (13,13-dimethyl-13H-indeno[1,2-l]phenanthren-11-yl)boronic acid (11.2 g, 0.033 mol) instead of (9,9-dimethyl-9H-fluoren-1-yl)boronic acid used in Step 2 of Synthesis Example 31, to afford Compound 234. HRMS [M]+: 677.28SYNTHESIS EXAMPLE 40 (reference example): Synthesis of Compound 250 (2-(3'-(9,9-di-p-tolyl-9H-fluoren-4-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine

[0144]

[0145] The same procedure was conducted as in Synthesis Example 31, with the exception of using (9,9-di-p-tolyl-9H-fluoren-4-yl)boronic acid (12.9 g, 0.033 mol) instead of (9,9-dimethyl-9H-fluoren-1-yl)boronic acid used in Step 2 of Synthesis Example 31, to afford Compound 250. HRMS [M]+: 729.31SYNTHESIS EXAMPLE 41 (reference example): Synthesis of Compound 252 (2,4-diphenyl-6-(3 '-(4 '-phenyl-9,9'-spirobi[fluoren]-4-yl)-[1,1'-biphenyl]-3-yl)-1,3,5-triazine

[0146]

[0147] The same procedure was conducted as in Synthesis Example 31, with the exception of using (4'-phenyl-9,9'-spirobi[fluoren]-4-yl)boronic acid (14.4 g, 0.033 mol) instead of (9,9-dimethyl-9H-fluoren-1-yl)boronic acid used in Step 2 of Synthesis Example 31, to afford Compound 252. HRMS [M]+: 775.30SYNTHESIS EXAMPLE 42 (reference example): Synthesis of Compound 5 (2-(3-(9,9-dimethyl-9H-fluoren-2-yl)phenyl)-4,6-diphenylpyrimidine

[0148]

[0149] Under a nitrogen stream, 2-(3-bromophenyl)-4,6-diphenylpyrimidine (10.0 g, 0.026 mol), 9,9-dimethyl-9H-fluoren-2-yl-boronic acid (7.9 g, 0.033 mol), Pd(PPh 3 ) 4 (0.95 g, 0.001 mol), and potassium carbonate (7.65 g, 0.078 mol) were mixed and then stirred under reflux with 1,4-dioxane (80 ml) and H 2 O (20 ml). After completion of the reaction, an organic layer was separated with methylene chloride and then dried over MgSO 4 . The solvent was removed from the dehydrated organic layer, followed by purification through column chromatography [hexane: MC = 5:1 (v / v)] to afford Compound 5 (8.5 g, yield 66%). HRMS [M]+: 500.23SYNTHESIS EXAMPLE 43 (reference example): Synthesis of Compound 13 (2-(3-(9,9-dimethyl-9H-fluoren-3-yl)phenyl)-4,6-diphenylpyrimidine

[0150]

[0151] The same procedure was conducted as in Synthesis Example 42, with the exception of using 9,9-dimethyl-9H-fluoren-3-yl-boronic acid (7.9 g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid, to afford Compound 13. HRMS [M]+: 500.23SYNTHESIS EXAMPLE 44 (reference example): Synthesis of Compound 73 (2-(3-(9,9-diphenyl-9H-fluoren-2-yl)phenyl)-4,6-diphenylpyrimidine

[0152]

[0153] The same procedure was conducted as in Synthesis Example 42, with the exception of using (9,9-diphenyl-9H-fluoren-2-yl)-boronic acid (11.9 g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid to afford Compound 73. HRMS [M]+: 624.26SYNTHESIS EXAMPLE 45 (reference example): Synthesis of Compound 133 (2-(3-(9,9'-spirobi[fluoren]-2-yl)phenyl)-4,6-diphenylpyrimidine

[0154]

[0155] The same procedure was conducted as in Synthesis Example 42, with the exception of using 9,9'-Spirobi[9H-fluorene]-2-yl-boronic acid (11.88g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid to afford Compound 133. HRMS [M]+: 622.24SYNTHESIS EXAMPLE 46 (reference example): Synthesis of Compound 134 (4-[3-(9,9-Spirobi[9H-fluorene]-2-yl)-phenyl]-2,6-diphenyl-pyrimidine

[0156]

[0157] The same procedure was conducted as in Synthesis Example 42, with the exception of using 4-(3-bromophenyl)-2,6-diphenylpyrimidine (10.0 g, 0.026 mol) and 9,9'-Spirobi[9H-fluorene]-2-yl-boronic acid (12.77g, 0.033 mol) instead of 2-(3-bromophenyl)-4,6-diphenylpyrimidine and 9,9-dimethyl-9H-fluoren-2-yl-boronic acid, respectively, to afford Compound 134. HRMS [M]+: 622.24SYNTHESIS EXAMPLE 47 (reference example): Synthesis of Compound 29 (2-(3'-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenylpyrimidine

[0158] <Step 1> Synthesis of Intermediate 1-A (2-(3'-chloro-[1,1'-biphenyl]-3-yl)-4,6-diphenylpyrimidine

[0159] Under a nitrogen stream, 2-(3-bromophenyl)-4,6-diphenylpyrimidine (12.0 g, 0.031 mol), 3-chlorophenylboronic acid (6.3 g, 0.040 ol), Pd(PPh 3 ) 4 (1.15 g, 0.001 mol), and potassium carbonate (12.85 g, 0.093 mol) were mixed and then stirred under reflux with 1,4-dioxane (100 ml) and H 2 O (25 ml) .

[0160] After completion of the reaction, an organic layer was separated with methylene chloride and then dried over MgSO 4 . The solvent was removed from the dehydrated organic layer, followed by purification through column chromatography [hexane: MC = 5:1 (v / v)] to afford Intermediate 1-A (11.0g, yield 83%).<Step2> Synthesis of Compound 29 (2-(3'-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenylpyrimidine

[0161] Under a nitrogen stream, Intermediate 1-A (11.0 g, 0.026 mol) obtained in Step 1, 9,9-dimethyl-9H-fluoren-2-yl-boronic acid (7.9 g, 0.033 mol), Pd(OAc) 2 (0.29 g, 0.001 mol), Cesium carbonate (25.4 g, 0.078 mol), and Xphos (1.23 g, 0.003 mol) were mixed and then stirred under reflux with toluene (100 ml), ethanol (20ml), and H 2 O (20 ml).

[0162] After completion of the reaction, an organic layer was separated with methylene chloride and then dried over MgSO 4 . The solvent was removed from the dehydrated organic layer, followed by purification through column chromatography [hexane: MC = 5:1 (v / v)] to afford Compound 29 (11.2 g, yield 74%) . HRMS [M]+: 576.26SYNTHESIS EXAMPLE 48 (reference example): Synthesis of Compound 33 (2-(3'-(9,9-dimethyl-9H-fluoren-3-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenylpyrimidine

[0163]

[0164] The same procedure was conducted as in Synthesis Example 47, with the exception of using 9,9-dimethyl-9H-fluoren-3-yl-boronic acid (7.9 g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid used in Step 2 of Synthesis Example 47 to afford Compound 33. HRMS [M]+: 576.26SYNTHESIS EXAMPLE 49 (reference example): Synthesis of Compound 97 (2-(3'-(9,9-diphenyl-9H-fluoren-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenylpyrimidine

[0165]

[0166] The same procedure was conducted as in Synthesis Example 47, with the exception of using (9, 9-diphenyl-9H-fluoren-2-yl)-boronic acid (12.0 g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid used in Step 2 of Synthesis Example 47 to afford Compound 97. HRMS [M]+:700.29SYNTHESIS EXAMPLE 50 (reference example): Synthesis of Compound 101 (2-(3'-(9,9-diphenyl-9H-fluoren-3-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenylpyrimidine

[0167]

[0168] The same procedure was conducted as in Synthesis Example 47, with the exception of using (9,9-diphenyl-9H-fluoren-3-yl)boronic acid (12.0 g, 0.033 mol) instead of (9,9-dimethyl-9H-fluoren-2-yl)boronic acid used in Step 2 of Synthesis Example 47 to afford Compound 101. HRMS [M]+: 700.29SYNTHESIS EXAMPLE 51 (reference example): Synthesis of Compound 157 (2-(3'-(9,9'-spirobi[fluoren]-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenylpyrimidine

[0169]

[0170] The same procedure was conducted as in Synthesis Example 47, with the exception of using 9,9'-Spirobi[9H-fluorene]-2-yl-boronic acid (11.9g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid used in Step 2 of Synthesis Example 47 to afford Compound 157. HRMS [M]+: 698.27SYNTHESIS EXAMPLE 52 (reference example): Synthesis of Compound 161 (2-(3'-(9,9'-spirobi[fluoren]-3-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenylpyrimidine

[0171]

[0172] The same procedure was conducted as in Synthesis Example 47, with the exception of using 9,9'-spirobi[fluoren]-3-yl-boronic acid (11.9g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid used in Step 2 of Synthesis Example 47 to afford Compound 161. HRMS [M]+: 698.27SYNTHESIS EXAMPLE 53 (reference example): Synthesis of Compound 282 (4-(3'-(9, 9-dimethyl-9H-fluoren-4-yl)-[1,1'-biphenyl]-3-yl)-2,6-diphenylpyrimidine

[0173] <Step 1> Synthesis of Intermediate 2-A (4-(3'-chloro-[1,1'-biphenyl]-3-yl)-2,6-diphenylpyrimidine

[0174] The same procedure was conducted as in Step 1 of Synthesis Example 47, with the exception of using 4-(3-bromophenyl)-2,6-diphenylpyrimidine (12.0g, 0.031 mol) instead of 2-(3-bromophenyl)-4,6-diphenylpyrimidine used in Step 1 of Synthesis Example 47 to afford Intermediate 2-A.<Step2> Synthesis of Compound 282 (4-(3'-(9,9-dimethyl-9H-fluoren-4-yl)-[1,1'-biphenyl]-3-yl)-2,6-diphenylpyrimidine

[0175] The same procedure was conducted as in Step 2 of Synthesis Example 47, with the exception of using Intermediate 2-A (11.0g, 0.026 mol) synthesized in Step 1 and (9,9-dimethyl-9H-fluoren-4-yl)boronic acid (7.9 g, 0.033 mol)instead of Intermediate 1-A used in Step 2 of Synthesis Example 47 and 9,9-dimethyl-9H-fluoren-2-yl-boronic acid, respectively, to afford Compound 282. HRMS [M]+: 576.26SYNTHESIS EXAMPLE 54 (reference example): Synthesis of Compound 159 (4-(3'-(9,9'-spirobi[fluoren]-2-yl)-[1,1'-biphenyl]-3-yl)-2,6-diphenylpyrimidine

[0176]

[0177] The same procedure was conducted as in Synthesis Example 53, with the exception of using 9,9'-spirobi[9H-fluorene]-2-yl-boronic acid (11.9g, 0.033 mol) instead of (9,9-dimethyl-9H-fluoren-4-yl)boronic acid used in Step 2 of Synthesis Example 53 to afford Compound 159. HRMS [M]+: 698.27SYNTHESIS EXAMPLE 55 (reference example): Synthesis of Compound 205 (4-([1,1'-biphenyl]-4-yl)-6-(3'-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1'-biphenyl]-3-yl)-2-phenylpyrimidine

[0178] <Step 1> Synthesis of Intermediate 3-A (4-([1,1'-biphenyl]-4-yl)-6-(3'-chloro-[1,1'-biphenyl]-3-yl)-2-phenylpyrimidine

[0179] The same procedure was conducted as in Step 1 of Synthesis Example 53, with the exception of using 4-([1,1'-biphenyl]-4-yl)-6-(3-bromophenyl)-2-phenyl-pyrimidine (14.4 g, 0.031 mol) instead of 4-(3-bromo-phenyl)-2,6-diphenylpyrimidine used in Step 1 of Synthesis Example 53 to afford Intermediate 3-A.<Step2> Synthesis of Compound 205 (4-([1,1'-biphenyl]-4-yl)-6-(3'-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1'-biphenyl]-3-yl)-2-phenylpyrimidine

[0180] The same procedure was conducted as in Step 2 of Synthesis Example 53, with the exception of using Intermediate 3-A (12.9g, 0.026 mol) synthesized in Step 1 and (9,9-dimethyl-9H-fluoren-2-yl)boronic acid instead of Intermediate 2-A used in Step 2 of Synthesis Example 53 and (9,9-dimethyl-9H-fluoren-4-yl)boronic acid, respectively, to afford Compound 205. HRMS [M]+:652.29SYNTHESIS EXAMPLE 56 (reference example): Synthesis of Compound 206 (4-([1,1'-biphenyl]-4-yl)-6-(3'-(9,9-diphenyl-9H-fluoren-2-yl)-[1,1'-biphenyl]-3-yl)-2-phenylpyrimidine

[0181]

[0182] The same procedure was conducted as in Synthesis Example 55, with the exception of using (9,9-diphenyl-9H-fluoren-2-yl)-boronic acid (11.9 g, 0.033 mol) instead of 9,9-dimethyl-9H-fluoren-2-yl-boronic acid used in Step 2 of Synthesis Example 55, to afford Compound 206. HRMS [M]+:776.32SYNTHESIS EXAMPLE 57 (reference example): Synthesis of Compound 336 (2-(3"-(9,9-dimethyl-9H-fluoren-3-yl)-[1,1':3',1"-terphenyl]-3-yl)-4,6-diphenylpyrimidine

[0183] <Step 1> Intermediate 1-B (2-(3"-chloro-[1,1':3',1"-terphenyl]-3-yl)-4,6-diphenylpyrimidine

[0184] Under a nitrogen stream, Intermediate 1-A (11.0 g, 0.026 mol), 3-chlorophenylboronic acid (4.8 g, 0.031 mol), Pd(OAc) 2 (0.29 g, 0.001 mol), Cesium carbonate (25.4 g, 0.078 mol), and Xphos (0.3 g, 0.003 mol) were mixed and then stirred under reflux with toluene (100 ml), ethanol (20ml) and H 2 O (20 ml).

[0185] After completion of the reaction, an organic layer was separated with methylene chloride and then dried over MgSO 4 . The solvent was removed from the dehydrated organic layer, followed by purification through column chromatography [hexane: MC = 5:1 (v / v)] to afford Intermediate 1-B (7.5 g, yield 58%).<Step2> Synthesis of Compound 336 (2-(3"-(9,9-dimethyl-9H-fluoren-3-yl)-[1,1':3',1"-terphenyl]-3-yl)-4,6-diphenylpyrimidine

[0186] Under a nitrogen stream, Intermediate 1-B (7.5 g, 0.015 mol) synthesized in Step 1, 9,9-dimethyl-9H-fluoren-3-yl-boronic acid (4.3 g, 0.018 mol), Pd(OAc) 2 (0.17 g, 0.75 mmol), Cesium carbonate (14.6 g, 0.045 mol), and Xphos (0.7 g, 1.5 mmol) were mixed and then stirred under reflux with toluene (60 ml), ethanol (15 ml) and H 2 O (15 ml).

[0187] After completion of the reaction, an organic layer was separated with methylene chloride and then dried over MgSO 4 . The solvent was removed from the dehydrated organic layer, followed by purification through column chromatography [hexane: MC = 4:1 (v / v)] to afford Compound 336 (8.1 g, yield 83%). HRMS [M]+: 652.29EXAMPLES 1 TO 41 (1-28 and 30-41 reference examples): Fabrication of Green Organic Electroluminescent Element

[0188] The compounds synthesized in the Synthesis Examples were purified by sublimation to a high degree of purity using a conventional method known in the art before being applied to the fabrication of green organic electroluminescent elements as follows.

[0189] First, a glass substrate coated with an ITO (indium tin oxide) thin film 1500 Å thick was cleansed by ultrasonication in distilled water and then in a solvent such as isopropyl alcohol, acetone, methanol, etc. and then dried. The glass substrate was transferred to a UV OZONE cleaner (Power sonic 405, Hwashin Tech) and cleaned for 5 min using UV, and transferred to a vacuum evaporator.

[0190] On the transparent ITO substrate (electrode) thus obtained, m-MTDATA (60 nm) / TCTA (80 nm) / 90% of each of the compounds synthesized in Synthesis Examples 1 to 41 + 10% of Ir(ppy) 3 (30 nm) / BCP (10nm) / Alq 3 (30 nm) / LiF (1 nm) / Al (200nm) were deposited in that order to fabricate organic electroluminescent elements.

[0191] Structures of m-MTDATA, TCTA, Ir(ppy) 3 and BCP are as follows. COMPARATIVE EXAMPLE 1: Fabrication of Green Organic Electroluminescent Element

[0192] A green organic electroluminescent element was fabricated in the same manner as in Example 1, with the exception of using the following CBP instead of Compound 1 synthesized in Synthesis Example 1. COMPARATIVE EXAMPLE 2: Fabrication of Green Organic Electroluminescent Element

[0193] A green organic electroluminescent element was fabricated in the same manner as in Example 1, with the exception of using the following Compound A instead of Compound 1 synthesized in Synthesis Example 1. COMPARATIVE EXAMPLE 3: Fabrication of Green Organic Electroluminescent Element

[0194] A green organic electroluminescent element was fabricated in the same manner as in Example 1, with the exception of using the following Compound B instead of Compound 1 synthesized in Synthesis Example 1. EVALUATION EXAMPLE 1

[0195] The green organic electroluminescent elements fabricated in Examples 1 to 41 and Comparative Examples 1 to 3 were measured for driving voltage at a current density of 10 mA / cm 2< , current efficiency, and emitting peak, and the results are summarized in Table 1, below. TABLE 1Light-Emitting MaterialDriving Volt. (V)Emitting Peak (nm)Current Efficiency (cd / A)Example 1Compound 14.5051753.5Example 2Compound 34.6151551.5Example 3Compound 694.4551849.8Example 4Compound 1294.5751851.7Example 5Compound 64.6051849.6Example 6Compound 744.5951751.7Example 7Compound 1344.5651552.7Example 8Compound 75.1051849.8Example 9Compound 754.6551850.5Example 10Compound 1354.3551752.5Example 11Compound 214.1051563.4Example 12Compound 234.0551865.4Example 13Compound 894.1551861.5Example 14Compound 914.0551763.3Example 15Compound 1494.1551863.5Example 16Compound 1514.1151764.2Example 17Compound 314.2851558.3Example 18Compound 354.1551860.5Example 19Compound 994.4051855.5Example 20Compound 1594.3351856.6Example 21Compound 454.3051757.5Example 22Compound 534.2051556.5Example 23Compound 1134.3351851.5Example 24Compound 1734.3051852.7Example 25Compound 614.1551759.3Example 26Compound 624.1051862.7Example 27Compound 634.2051754.5Example 28Compound 644.2351556.5Example 29Compound 2004.6551646.9Example 30Compound 2064.2351747.2Example 31Compound 2174.1551761.8Example 32Compound 2184.2651862.5Example 33Compound 2204.3251859.8Example 34Compound 214.1051663.4Example 35Compound 1894.1551762.3Example 36Compound 1934.3551857.8Example 37Compound 654.5251852.3Example 38Compound 2314.4151851.3Example 39Compound 2344.5051852.6Example 40Compound 2504.3551857.6Example 41Compound 2524.4851854.6C. Example 1CBP6.9351638.2C. Example 2Compound A4.9851739.6C. Example 3Compound B5.0351637.3

[0196] As understood from Table 1, the organic electroluminescent elements employing the compounds of the present invention in the light-emitting layer thereof (Examples 1 to 41) are far superior in terms of current efficiency and driving voltage compared to that employing the conventional material CBP in the light-emitting layer thereof (Comparative Example 1).

[0197] In addition, when used in the light-emitting layer of an organic electroluminescent element, the compounds having the linker (Examples 1 to 41) decrease the driving voltage and increases current efficiency in the organic electroluminescent element, compared to those lacking the linker (Comparative Examples 2 and 3).EXAMPLES 42 TO 98 (42 to 69 and 71 to 98 reference examples): Fabrication of Blue Organic Electroluminescent Element

[0198] The compounds synthesized in the Synthesis Examples were purified by sublimation to a high degree of purity using a conventional method known in the art before being applied to the fabrication of blue organic electroluminescent elements having the structures listed in Table 2, below. TABLE 2Hole Injection LayerHole Transport LayerLight-emitting LayerAux. Electron Transport LayerElectron Transport LayerElectron Injection LayerCathodeMaterialDS-205 (Doosan Corporation)NPBADN+5% DS-405 (Doosan Corporation)Individual Cpd. Synthesized in Synthesis Examples 1 to 57Alq 3 LiFAlThick.80nm15nm30nm5nm25nm1nm200nm

[0199] The structures of NPB, ADN, and Alq 3 listed in Table 2 are as follows. COMPARATIVE EXAMPLE 4: Fabrication of Blue Organic Electroluminescent Element

[0200] A blue organic electroluminescent element was fabricated in the same manner as in Example 42, with the exception that an electron transport layer 30nm thick was deposited without using an auxiliary electron transport layer.COMPARATIVE EXAMPLE 5 : Fabrication of Blue Organic Electroluminescent Element

[0201] A blue organic electroluminescent element was fabricated in the same manner as in Example 42, with the exception of using the following BCP instead of Compound 1 synthesized in Synthesis Example 1. EVALUATION EXAMPLE 2

[0202] The blue organic electroluminescent elements fabricated in Examples 42 to 98 and Comparative Examples 4 and 5 were measured for driving voltage at a current density of 10 mA / cm 2< , current efficiency, and emitting peak, and the results are summarized in Table 3, below. TABLE 3Material of Aux. Electron Transport LayerDriving Volt. (V)Current Efficiency (cd / A)Emitting Peak (nm)Example 42Compound 14.76.6458Example 43Compound 34.56.3458Example 44Compound 694.26.6457Example 45Compound 1294.16.0458Example 46Compound 64.56.2458Example 47Compound 744.26.6458Example 48Compound 1344.16.3457Example 49Compound 74.46.2458Example 50Compound 754.36.1457Example 51Compound 1354.46.2458Example 52Compound 213.88.2458Example 53Compound 234.17.2458Example 54Compound 894.08.1458Example 55Compound 914.18.1457Example 56Compound 1494.08.0458Example 57Compound 1514.27.8458Example 58Compound 314.18.0458Example 59Compound 354.17.5457Example 60Compound 994.58.1458Example 61Compound 1594.27.6458Example 62Compound 454.56.1458Example 63Compound 534.66.2458Example 64Compound 1134.56.0458Example 65Compound 1734.26.1458Example 66Compound 614.16.8458Example 67Compound 624.16.9458Example 68Compound 634.57.3457Example 69Compound 644.27.6458Example 70Compound 2004.17.0458Example 71Compound 2064.37.7458Example 72Compound 2174.08.0458Example 73Compound 2184.18.1458Example 74Compound 2203.98.0457Example 75Compound 213.88.2458Example 76Compound 1894.08.2458Example 77Compound 1934.27.9458Example 78Compound 654.37.6457Example 79Compound 2314.47.2458Example 80Compound 2344.37.6458Example 81Compound 2504.17.6457Example 82Compound 2524.37.7458Example 83Compound 54.76.7458Example 84Compound 134.66.5458Example 85Compound 734.46.1457Example 86Compound 1334.66.9458Example 87Compound 1344.16.7457Example 88Compound 294.47.2458Example 89Compound 334.37.1457Example 90Compound 974.47.5458Example 91Compound 1014.37.6458Example 92Compound 1574.17.5458Example 93Compound 1614.27.3458Example 94Compound 2824.57.9458Example 95Compound 1594.18.3458Example 96Compound 2054.58.0457Example 97Compound 2064.67.7458Example 98Compound 3364.57.9458C. Example 4-4.75.6457C. Example 5BCP5.35.9458

[0203] As shown in Table 3, the compounds according to the present invention, when used in auxiliary electron transport layer of blue organic electroluminescent elements (Examples 42 to 98), impart excellent current efficiency and driving voltages to the blue organic electroluminescent elements.

Claims

1. A compound represented by the following Formula 1: wherein, Ra and Rb are each independently a methyl or a phenyl or bond each other to form a fused ring represented by (* is a site where to bond), R1 and R2 are the same or different from each other and are each independently selected from the group consisting of a hydrogen, a deuterium, a halogen, a cyano group, a nitro group, an amino group, a C1-C40 alkyl group, a C2-C40 alkyenyl group, a C2-C40 alkynyl group, a C3-C40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C6-C60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C1-C40 alkyloxy group, a C6-C60 aryloxy group, a C1-C40 alkylsilyl group, a C6-C60 arylsilyl group, a C1-C40 alkylboron group, a C6-C60 arylboron group, a C1-C40 phosphine group, a C1-C40 phosphine oxide group, and a C6-C60 arylamine group, or in this case, adjacent ones of R1 and R2 are optionally respectively to each other to form a fused ring, R3 is hydrogen, c and e are each an integer of 0 to 4, d is an integer of 0 to 3, m is 1 and n is 1 or 2, the structure represented by (* is a site where to bond with L) in Formula 1 is C-9, R4 are different from each other and are selected from a C6-C60 aryl group that is optionally substituted with a C6-C60 aryl group, wherein L is a structure represented by the following L-1(* is a site where to bond):

2. The Compound of claim 1, wherein the compound represented by Formula 1 is selected from the group consisting of the following Compounds 197 to 204:

3. An organic electroluminescent element, comprising an anode, a cathode, and at least one organic layer interposed there between, wherein at least one of the organic layer comprises the compound of claim 1 or 2.

4. The organic electroluminescent element of claim 3, wherein the organic layer comprising the compound is a light-emitting layer or an auxiliary electron transport layer.