Organic compound and organic electroluminescent element using same

Abstract

The present invention relates to a novel organic compound and an organic electroluminescent element using the same. The present invention relates to a compound having excellent electron injection and transport capabilities, and an organic electroluminescent element having improved characteristics such as luminous efficiency, driving voltage, lifetime, and progressive driving voltage by including the compound in one or more organic material layers.

Description

Technical Field

[0001] The present invention relates to a novel organic compound and an organic electroluminescent element using the same. More specifically, the present invention relates to a compound having excellent electron transport capability and an organic electroluminescent element in which the luminous efficiency, driving voltage, life and other characteristics as well as the progressive driving voltage are improved by including the compound in one or more organic layers. Background Art

[0002] When voltage is applied across two electrodes of an organic electroluminescent device (hereinafter referred to as an "organic EL device"), 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. When these excitons transition to the ground state, light is emitted. The materials used in the organic layer can be categorized by their function as light-emitting materials, hole-injecting materials, hole-transporting materials, electron-transporting materials, and electron-injecting materials.

[0003] The materials forming the light-emitting layer of organic EL elements can be divided into blue, green, and red light-emitting materials according to the color of the light. In addition, yellow and orange light-emitting materials are also used as light-emitting materials for presenting more natural colors. In addition, in order to increase the luminous efficiency by increasing the color purity and energy transfer, a host / dopant system can be used as a light-emitting material. Dopant substances can be divided into fluorescent dopants using organic substances and phosphorescent dopants using metal coordination compounds containing heavy atoms such as Ir and Pt. Since the development of such phosphorescent materials can theoretically increase the luminous efficiency by up to 4 times compared to fluorescence, not only phosphorescent dopants but also phosphorescent host materials have attracted attention.

[0004] To date, NPB, BCP, and Alq3, represented by the following chemical formula, are widely known for use as hole-injection layers, hole-transport layers, hole-blocking layers, and electron-transport layers. Anthracene derivatives have been reported as fluorescent dopants / host materials for luminescent materials. In particular, as phosphorescent materials offering significant advantages in terms of efficiency, Ir-containing metal coordination compounds such as Firpic, Ir(ppy)3, and (acac)Ir(btp)2 have been used as dopants for blue, green, and red luminescent materials. For this reason, CBP currently exhibits excellent properties as a phosphorescent host material.

[0005] However, while conventional organic layer materials have advantages in terms of luminescence properties, they have low glass transition temperatures and very poor thermal stability, making them unsatisfactory in terms of the lifespan of organic EL devices. Therefore, there is a demand for the development of organic layer materials with superior performance. Summary of the Invention

[0006] Technical issues

[0007] The object of the present invention is to provide a novel organic compound having excellent electron injection and transport capabilities, electrochemical stability, thermal stability, etc. and capable of being used as an organic layer material of an organic electroluminescent element, specifically an electron transport layer material or an N-type charge generation layer material.

[0008] Another object of the present invention is to provide an organic electroluminescent device that exhibits low driving voltage and high luminous efficiency and has an improved lifespan by containing the novel organic compound.

[0009] Solutions to Problems

[0010] In order to achieve the above object, the present invention provides an organic compound represented by the following Chemical Formula 1:

[0011] [Chemical Formula 1]

[0012]

[0013] (In the above chemical formula 1,

[0014] Ar1 is a C9~C 40 Heteroaryl,

[0015] n is an integer from 1 to 3,

[0016] L1 is C6~C 40 arylene,

[0017] a is an integer from 0 to 7,

[0018] Ar2 is selected from hydrogen, deuterium (D), 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 atomic nuclei, C6~C 60 aryl, heteroaryl with 5 to 60 atomic nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkylsilyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, C6~C 60 Arylphosphine, C6~C 60 Aryl phosphine oxide group, C6~C 60 Arylamine, C6~C 60A group consisting of an (aryl) (heteroaryl) amine group and a heteroarylamine group having 5 to 60 atomic nuclei, or condensed with an adjacent group to form a condensed ring,

[0019] The heteroaryl group of Ar1, the arylene group of L1 and the alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylsilyl, arylsilyl, alkylboryl, arylboryl, arylphosphino, arylphosphine oxide, arylamine, (aryl)(heteroaryl)amine and heteroarylamine groups of Ar2 are each independently selected from deuterium (D), 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 atomic nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkylsilyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, C6~C 60 Arylphosphine, C6~C 60 Aryl phosphine oxide group, C6~C 60 Arylamine, C6~C 60 The amino group may be substituted or unsubstituted with one or more substituents in the group consisting of (aryl)(heteroaryl)amine groups and heteroarylamine groups having 5 to 60 atomic nuclei; in this case, when there are multiple substituents, they may be the same as or different from each other).

[0020] The present invention also provides an organic electroluminescent device comprising an anode, a cathode, and one or more organic layers interposed between the anode and cathode, wherein at least one of the one or more organic layers comprises the organic compound. In this case, the organic layer comprising the compound may be an electron transport layer.

[0021] In addition, the present invention provides an organic electroluminescent element, which includes: an anode and a cathode arranged to be separated from each other; a plurality of light-emitting units between the above-mentioned anode and cathode; an N-type charge generation layer and a P-type charge generation layer between adjacent light-emitting units, each of the above-mentioned light-emitting units includes a hole transport layer, a light-emitting layer and an electron transport layer, and the above-mentioned N-type charge generation layer includes the above-mentioned compound.

[0022] Effects of the Invention

[0023] The compounds of the present invention exhibit excellent electron transport, luminescence, electrochemical stability, and thermal stability, and therefore can be used as organic layer materials in organic electroluminescent devices. In particular, when the compounds of the present invention are used as at least one of the electron transport layer material and the N-type charge generation layer material, organic electroluminescent devices can be produced that exhibit superior luminescence performance, low driving voltage, high efficiency, and long life compared to conventional materials. Furthermore, full-color display panels with improved performance and life can be produced. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is a cross-sectional view schematically showing the organic electroluminescent element according to the first embodiment of the present invention.

[0025] Figure 2 This is a cross-sectional view schematically showing an organic electroluminescent element according to a second embodiment of the present invention.

[0026] Figure 3 This is a cross-sectional view schematically showing an organic electroluminescent element according to a third embodiment of the present invention.

[0027] Figure 4 This is a cross-sectional view schematically showing an organic electroluminescent element according to a fourth embodiment of the present invention.

[0028] <Description of symbols>

[0029] 100: anode, 200: cathode,

[0030] 300: organic layer, 310: hole injection layer,

[0031] 320: hole transport layer, 330: light emitting layer,

[0032] 340: electron transport layer, 350: electron injection layer,

[0033] 360: electron transport auxiliary layer, 400: first light-emitting unit,

[0034] 410: first hole transport layer, 420: first light emitting layer,

[0035] 430: first electron transport layer, 440: hole injection layer,

[0036] 500: second light-emitting unit, 510: second hole transport layer,

[0037] 520: second light-emitting layer, 530: second electron transport layer,

[0038] 600: charge generation layer, 610: N-type charge generation layer,

[0039] 620: P-type charge generation layer. DETAILED DESCRIPTION

[0040] Hereinafter, the present invention will be described.

[0041] <New Compounds>

[0042] The compound of the present invention is represented by the above-mentioned chemical formula 1, and its structure includes a pyridine portion substituted with an N-containing heteroaryl group and a phenanthroline portion connected to the above-mentioned pyridine portion via a linking group. Such a compound has excellent electron injection and transport capabilities, electrochemical stability, thermal stability, etc., and can be used as an organic layer material for an organic electroluminescent element. In particular, when the compound of the present invention is used as at least one of an electron transport layer material and an N-type charge generation layer material of an organic electroluminescent element, an organic electroluminescent element having excellent luminescent performance, low driving voltage, high efficiency and long life characteristics compared to the past can be manufactured, and thus a full-color display panel with improved performance and life can also be manufactured.

[0043] Specifically, in the compound represented by Chemical Formula 1, the pyridine moiety and the phenanthroline moiety are electron-withdrawing groups (EWGs) with strong electron-withdrawing properties. Therefore, the compound of Chemical Formula 1 has a structure in which electron-withdrawing groups (EWGs) are present on both sides of the molecule, and these two electron-withdrawing groups (EWGs) are connected by a linking group (e.g., a phenylene group, a naphthylene group, etc.). Therefore, the compound of the present invention has excellent electron injection and transport capabilities, electrochemical stability, and thermal stability.

[0044] In addition, one hydrogen of the pyridine part is replaced by a nitrogen (N) heteroaryl group. At this time, since the N-containing heteroaryl group is introduced into the ortho position of the nitrogen (N) of the pyridine part, the pyridine part can form a metal bond. On the other hand, the phenanthroline part is also a structure in which two nitrogens are adjacent to each other, so it can form a covalent bond with the surrounding hydrogen (H) or form a coordination bond with an alkali metal or alkaline earth metal such as Li, Yb. That is, the compound of the present invention includes a part that can form two metal bonds. Therefore, the compound of the present invention can be combined with a dopant of the N-type charge generation layer, that is, a metal such as an alkali metal, an alkaline earth metal (for example: Li, Yb, etc.) to form a band gap state, so when used as an N-type charge generation layer material, the electron transfer characteristics to the electron transport layer can be improved. In particular, even if the compound of the present invention is not mixed with other host materials and is used alone as a host material of the N-type charge generation layer, it is possible to smoothly transfer electrons from the N-type charge generation layer to the electron transport layer through the band gap state. Furthermore, when the compounds of the present invention are used as materials for an N-type charge generation layer, the pyridine and phenanthroline moieties bind to the alkali metal or alkaline earth metal within the N-type charge generation layer, thereby preventing the alkali metal or alkaline earth metal from diffusing into the P-type charge generation layer. Therefore, when the compounds of the present invention are used as materials for an N-type charge generation layer, the driving voltage of an organic electroluminescent device can be reduced while improving luminous efficiency and achieving a longer lifespan.

[0045] As described above, the electron injection and electron transport capabilities of the compound of the present invention are excellent. Therefore, the compound of the present invention can be used as an organic layer of an organic electroluminescent element, specifically an electron transport layer material. In addition, the compound of the present invention can also be used as an N-type charge generation layer material of a tandem organic electroluminescent element. Therefore, in the case of applying the compound represented by Chemical Formula 1 of the present invention as an electron transport layer material or an N-type charge generation layer material of an organic electroluminescent element, not only can the driving voltage, luminous efficiency and life of the element be improved, but also the rise of the progressive driving voltage can be prevented, thereby also maximizing the performance of a full-color organic light-emitting panel applying the above-mentioned organic electroluminescent element.

[0046] In the compound represented by the above chemical formula 1, Ar1 can be a C9-C 40 The heteroaryl group (i.e., a 10-membered to 40-membered heteroaryl group containing one N) can be specifically a C9-C 18 The inclusion of such a nitrogen-containing heteroaryl group can enhance the binding force between the compound of the present invention and the metal and improve the electron transport capability, thereby reducing the driving voltage of the organic electroluminescent element, improving the luminous efficiency, and achieving a long life.

[0047] The heteroaryl group of Ar1 can be selected from deuterium (D), halogen (e.g., -F, -Cl, -Br, -I, etc.), cyano (-CN), nitro (-NO2), amino (-NH2), 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 atomic nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkylsilyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, C6~C 60 Arylphosphine, C6~C 60 Aryl phosphine oxide group, C6~C 60 Arylamine, C6~C 60 The amine group may be substituted or unsubstituted with one or more substituents selected from the group consisting of an (aryl) (heteroaryl) amine group and a heteroarylamine group having 5 to 60 atomic nuclei. In this case, when there are multiple substituents, they may be the same or different from each other.

[0048] According to one example, Ar1 may be a substituent represented by the following chemical formula S1-1 or S1-2, but is not limited thereto.

[0049] [Chemical formula S1-1]

[0050]

[0051] [Chemical formula S1-2]

[0052]

[0053] In the above chemical formulas S1-1 and S1-2,

[0054] * refers to the part forming a bond with Chemical Formula 1,

[0055] Cy1 and Cy2 can each independently be C6~C 30 The condensed aromatic rings, specifically, each of which can be C6 to C 18 The condensed aromatic ring,

[0056] The condensed aromatic rings of Cy1 and Cy2 are independently selected from deuterium (D), halogen, cyano, nitro, amino, C1-C 40Alkyl, 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 atomic nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkylsilyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, C6~C 60 Arylphosphine, C6~C 60 Aryl phosphine oxide group, C6~C 60 Arylamine, C6~C 60 The amino group may be substituted or unsubstituted with one or more substituents selected from the group consisting of (aryl)(heteroaryl)amino groups and heteroarylamino groups having 5 to 60 atomic nuclei. In this case, when there are multiple substituents, they may be the same as or different from each other.

[0057] According to another example, Ar1 can be selected from the group consisting of the following substituents S2-1 to S2-9, but is not limited thereto.

[0058]

[0059] In the above substituents S2-1 to S2-9,

[0060] * indicates a portion forming a bond with Chemical Formula 1.

[0061] The hydrogen of the above substituents S2-1 to S2-9 can be selected from deuterium (D), halogen (e.g., -F, -Cl, -Br, -I, etc.), cyano (-CN), nitro (-NO2), amino (-NH2), C1~C 12 Alkyl (eg methyl, ethyl, propyl, butyl, etc.), C6~C 10 The aryl group may be substituted or unsubstituted with one or more substituents selected from the group consisting of aryl groups (for example, phenyl, biphenyl, terphenyl, monovalent naphthyl, etc.) and heteroaryl groups having 5 to 10 atomic nuclei (monovalent pyrazinyl, monovalent pyrimidinyl, monovalent pyridazinyl, monovalent triazinyl, etc.).

[0062] In the compound represented by the above Chemical Formula 1, n is an integer of 1 to 3.

[0063] When n is an integer from 1 to 3, L1 is a divalent linker group, which can be C6 to C 40The arylene group can be C6 to C 18 wherein multiple L1s may be the same as or different from each other.

[0064] In this case, the arylene group of L1 can be selected from deuterium (D), halogen (e.g., -F, -Cl, -Br, -I, etc.), cyano (-CN), nitro (-NO2), amino (-NH2), 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 atomic nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkylsilyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, C6~C 60 Arylphosphine, C6~C 60 Aryl phosphine oxide group, C6~C 60 Arylamine, C6~C 60 The amine group may be substituted or unsubstituted with one or more substituents selected from the group consisting of an (aryl) (heteroaryl) amine group and a heteroarylamine group having 5 to 60 atomic nuclei. In this case, when there are multiple substituents, they may be the same or different from each other.

[0065] According to one example, one or more L1 are the same or different from each other and can be independently selected from the group consisting of phenylene, biphenylene, terphenylene, naphthylene, phenanthrylene, anthracene, triphenylene, fluorenylene and combinations thereof. The hydrogen of phenylene, biphenylene, terphenylene, naphthylene, phenanthrylene, triphenylene and fluorenylene can be selected from deuterium (D), halogen (e.g., -F, -Cl, -Br, -I, etc.), cyano (-CN), nitro (-NO2), amino (-NH2), C1~C 12 Alkyl, C6~C 10 The aryl group may be substituted or unsubstituted with one or more substituents selected from the group consisting of an aryl group having 5 to 10 atomic nuclei and a heteroaryl group having 5 to 10 atomic nuclei.

[0066] According to another example, one or more L1 groups are the same or different and can be independently selected from the group consisting of the following linking groups L1-1 to L1-3. However, the present invention is not limited thereto.

[0067]

[0068] In the above-mentioned linking groups L1-1 to L1-3,

[0069] b is an integer from 0 to 4,

[0070] c is an integer from 0 to 6,

[0071] d is an integer from 0 to 8,

[0072] R1 can be selected from deuterium (D), halogen (e.g., -F, -Cl, -Br, -I, etc.), cyano (-CN), nitro (-NO2), amino (-NH2), 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 atomic nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkylsilyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, C6~C 60 Arylphosphine, C6~C 60 Aryl phosphine oxide group, C6~C 60 Arylamine, C6~C 60 The group consisting of (aryl) (heteroaryl) amine groups and heteroaryl amine groups having 5 to 60 atomic nuclei, specifically, deuterium (D), cyano (-CN), C1~C 40 Alkyl, C3~C 40 Cycloalkyl, heterocycloalkyl with 3 to 40 nuclei, C6~C 60 aromatic groups, heteroaryl groups with 5 to 60 atomic nuclei, and C6~C 60 A group composed of arylamine groups.

[0073] According to another example, one or more L1 groups are the same or different and can be independently selected from the group consisting of the following linking groups L2-1 to L2-22. However, the present invention is not limited thereto.

[0074]

[0075] The hydrogen of the linking groups L2-1 to L2-22 can be selected from deuterium (D), halogen (e.g., -F, -Cl, -Br, -I, etc.), cyano (-CN), nitro (-NO2), amino (-NH2), C1-C 12Alkyl (eg methyl, ethyl, propyl, butyl, etc.), C6~C 10 The aryl group may be substituted or unsubstituted with one or more substituents selected from the group consisting of aryl groups (for example, phenyl, biphenyl, terphenyl, monovalent naphthyl, etc.) and heteroaryl groups having 5 to 10 atomic nuclei (monovalent pyrazinyl, monovalent pyrimidinyl, monovalent pyridazinyl, monovalent triazinyl, etc.).

[0076] In the compound represented by the above Chemical Formula 1, a may be an integer from 0 to 7, specifically, a may be an integer from 0 to 3, more specifically, a may be 0 or 1.

[0077] Here, when a is 0, it means that hydrogen is not replaced by the substituent Ar2. On the other hand, when a is an integer from 1 to 7, it means that hydrogen is replaced by the substituent Ar2. In this case, when there are multiple Ar2, the multiple Ar2 are the same or different.

[0078] Ar2 can be selected from hydrogen, deuterium (D), halogen (e.g., -F, -Cl, -Br, -I, etc.), cyano (-CN), nitro (-NO2), amino (-NH2), C1~C 40 Alkyl, C2~C 40 Alkenyl, C2~C 40 Alkynyl, C3~C 40 Cycloalkyl, heterocycloalkyl with 3 to 40 atomic nuclei, C6~C 60 aryl, heteroaryl with 5 to 60 atomic nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkylsilyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, C6~C 60 Arylphosphine, C6~C 60 Aryl phosphine oxide group, C6~C 60 Arylamine, C6~C 60 A group consisting of an (aryl) (heteroaryl) amine group and a heteroarylamine group having 5 to 60 atomic nuclei, or condensed with an adjacent group (for example: Ar2-Ar2, Ar2-L1) to form a condensed ring, specifically, it can be selected from hydrogen, deuterium (D), cyano (-CN), C1~C 40 Alkyl, C3~C 40 Cycloalkyl, heterocycloalkyl with 3 to 40 atomic nuclei, C6~C 60 aromatic groups, heteroaryl groups with 5 to 60 atomic nuclei, and C6~C 60 A group composed of arylamine groups.

[0079] At this time, the alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylsilyl, arylsilyl, alkylboryl, arylboryl, arylphosphino, arylphosphine oxide, arylamine, (aryl)(heteroaryl)amine and heteroarylamine groups of Ar2 can be independently selected from deuterium (D), 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 atomic nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkylsilyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, C6~C 60 Arylphosphine, C6~C 60 Aryl phosphine oxide group, C6~C 60 Arylamine, C6~C 60 The amine group may be substituted or unsubstituted with one or more substituents selected from the group consisting of an (aryl) (heteroaryl) amine group and a heteroarylamine group having 5 to 60 atomic nuclei. In this case, when there are multiple substituents, they may be the same or different from each other.

[0080] Depending on the type of Ar1 and the position of L1, the compound represented by the above Chemical Formula 1 may be a compound represented by any one of the following Chemical Formulas 2 to 7. However, the present invention is not limited thereto.

[0081] [Chemical Formula 2]

[0082]

[0083] [Chemical Formula 3]

[0084]

[0085] [Chemical Formula 4]

[0086]

[0087] [Chemical Formula 5]

[0088]

[0089] [Chemical Formula 6]

[0090]

[0091] [Chemical Formula 7]

[0092]

[0093] In the above chemical formulas 2 to 7,

[0094] n, L1, a and Ar2 are each the same as those defined in the above chemical formula 1,

[0095] Cy1 and Cy2 can each independently be C6~C 30 The condensed aromatic rings, specifically, each of which can be C6 to C 18 The condensed aromatic ring,

[0096] The condensed aromatic rings of Cy1 and Cy2 are independently selected from deuterium (D), 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 atomic nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkylsilyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, C6~C 60 Arylphosphine, C6~C 60 Aryl phosphine oxide group, C6~C 60 Arylamine, C6~C 60 The amino group may be substituted or unsubstituted with one or more substituents selected from the group consisting of (aryl)(heteroaryl)amino groups and heteroarylamino groups having 5 to 60 atomic nuclei. In this case, when there are multiple substituents, they may be the same as or different from each other.

[0097] The compound represented by Chemical Formula 1 of the present invention can be further embodied as the following compounds 001 to 146, but is not limited thereto.

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106] In the present invention, "alkyl" means a monovalent substituent derived from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, isopentyl, and hexyl.

[0107] 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 thereof include vinyl, allyl, isopropenyl, and 2-butenyl, but are not limited thereto.

[0108] 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 thereof include, but are not limited to, ethynyl and 2-propynyl.

[0109] In the present invention, "cycloalkyl" means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl groups include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl.

[0110] In the present invention, "heterocycloalkyl" means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclei, wherein one or more carbon atoms, preferably 1 to 3 carbon atoms, in the ring are substituted with a heteroatom such as N, O, S, or Se. Examples of such heterocycloalkyl groups include, but are not limited to, morpholinyl and piperazinyl.

[0111] In the present invention, "aryl" means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms, which is a single ring or a combination of two or more rings. Furthermore, it also includes forms in which two or more rings are simply attached (pendant) or condensed. Examples of such aryl groups include, but are not limited to, phenyl, naphthyl, phenanthrenyl, and anthracenyl.

[0112] In the present invention, "heteroaryl" means a monovalent substituent derived from a monocyclic heterocyclic or polycyclic aromatic hydrocarbon having an atomic 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 to each other (pendant) or condensed, and further include a form condensed with an aryl group. Examples of such heteroaryl groups include six-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl; polycyclic rings such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, and carbazolyl; and 2-furyl, N-imidazolyl, 2-isoxazolyl, 2-pyridyl, 2-pyrimidinyl, but are not limited thereto.

[0113] In the present invention, "alkoxy" refers to a monovalent substituent represented by R'O-, where R' represents an alkyl group having 1 to 40 carbon atoms and may have a linear, branched, or cyclic structure. Examples of such alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, tert-butoxy, n-butoxy, and pentoxy.

[0114] In the present invention, "aryloxy" is a monovalent substituent represented by RO-, where R is an aryl group having 5 to 40 carbon atoms. Examples of such aryloxy groups include, but are not limited to, phenoxy, naphthyloxy, and diphenoxy.

[0115] In the present invention, "alkylsilyl" means a silyl group substituted with an alkyl group having 1 to 40 carbon atoms, and includes not only monoalkylsilyl groups but also dialkylsilyl groups and trialkylsilyl groups. Furthermore, "arylsilyl" means a silyl group substituted with an aryl group having 5 to 60 carbon atoms, and includes not only monoarylsilyl groups but also polyarylsilyl groups such as diarylsilyl groups and triarylsilyl groups.

[0116] In the present invention, an "alkylboryl group" means a boron group substituted by an alkyl group having 1 to 40 carbon atoms, and an "arylboryl group" means a boron group substituted by an aryl group having 6 to 60 carbon atoms.

[0117] In the present invention, "alkylphosphinyl" means a phosphinyl group substituted with an alkyl group having 1 to 40 carbon atoms, and includes not only monoalkylphosphinyl groups but also dialkylphosphinyl groups. In addition, in the present invention, "arylphosphinyl" means a phosphinyl group substituted with a monoaryl or diaryl group having 6 to 60 carbon atoms, and includes not only monoarylphosphinyl groups but also diarylphosphinyl groups.

[0118] In the present invention, the "arylamine group" means an amine group substituted with an aryl group having 6 to 60 carbon atoms, and includes not only a monoarylamine group but also a diarylamine group.

[0119] In the present invention, the "heteroarylamine group" means an amine group substituted with a heteroaryl group having 5 to 60 atomic nuclei, and includes not only a monoheteroarylamine group but also a diheteroarylamine group.

[0120] In the present invention, the (aryl)(heteroaryl)amino group means an amino group substituted with an aryl group having 6 to 60 carbon atoms and a heteroaryl group having 5 to 60 atomic nuclei.

[0121] In the present invention, "condensed ring" means a condensed aliphatic ring having 3 to 40 carbon atoms, a condensed aromatic ring having 6 to 60 carbon atoms, a condensed aliphatic heterocyclic ring having 3 to 60 atomic nuclei, a condensed aromatic heterocyclic ring having 5 to 60 atomic nuclei, or a combination thereof.

[0122] In the present invention, "nuclear number" means the number of ring atoms constituting a ring structure, and the nucleus may be carbon or a heteroatom selected from the group consisting of N, O, S, and Se. For example, the number of nuclei of pyridine means 6, including the 5 C atoms and 1 N atoms constituting the pyridine ring.

[0123] <Organic Electroluminescent Element>

[0124] In another aspect, the present invention provides an organic electroluminescent device (hereinafter referred to as “organic EL device”) comprising the compound represented by the above Chemical Formula 1.

[0125] Figures 1 to 4 These are cross-sectional views schematically showing organic electroluminescent elements according to first to fourth embodiments of the present invention.

[0126] Below, refer to Figures 1 to 3 The organic electroluminescent elements according to the first to third embodiments of the present invention will be described in detail.

[0127] like Figures 1 to 3As shown, the organic electroluminescent element of the present invention includes an anode 100, a cathode 200, and one or more organic layers 300 interposed between the anode and the cathode, wherein at least one of the one or more organic layers includes the compound represented by Chemical Formula 1. In this case, the above compounds can be used alone or in combination of two or more.

[0128] The above-mentioned one or more organic layers 300 may include any one or more of a hole injection layer 310, a hole transport layer 320, a light-emitting layer 330, an electron transport auxiliary layer 360, an electron transport layer 340, and an electron injection layer 350, wherein at least one organic layer 300 includes the compound represented by the above-mentioned chemical formula 1. Specifically, the organic layer including the compound of the above-mentioned chemical formula 1 may be the electron transport layer 340. That is, the compound represented by the above-mentioned chemical formula 1 is included in the organic electroluminescent element as an electron transport layer substance. In such an organic electroluminescent element, due to the compound of the above-mentioned chemical formula 1, electrons can be easily injected from the cathode or the electron injection layer into the electron transport layer, and quickly migrate from the electron transport layer to the light-emitting layer, so that the binding force between holes and electrons in the light-emitting layer is strong. Therefore, the organic electroluminescent element of the present invention has excellent luminous efficiency, power efficiency, brightness, etc. In addition, the compound of the above-mentioned chemical formula 1 has excellent thermal stability and electrochemical stability, thereby improving the performance of the organic electroluminescent element.

[0129] The compound of Chemical Formula 1 can be used alone or mixed with electron transport layer materials known in the art.

[0130] In the present invention, the electron transport layer material that can be mixed with the compound of the above chemical formula 1 includes an electron transport material generally known in the art. As non-limiting examples of usable electron transport materials, there are oxazole compounds, isoxazole compounds, triazole compounds, isothiazole compounds, oxadiazole compounds, thiadiazole compounds, perylene compounds, aluminum complexes (for example: Alq3, tris (8-hydroxyquinoline) -aluminum (tris (8-quinolinolato) -aluminium)), gallium complexes (for example: Gaq'2OPiv, Gaq'2OAc, 2 (Gaq'2)), etc. They can be used alone or in combination of two or more.

[0131] In the present invention, when the compound of Chemical Formula 1 and the electron transport layer material are mixed, their mixing ratio is not particularly limited and can be appropriately adjusted within the range known in the art.

[0132] The structure of the organic electroluminescent element of the present invention is not particularly limited. For example, an anode 100, one or more organic layers 300, and a cathode 200 may be sequentially stacked on a substrate (see FIG. Figures 1 to 3 Although not shown in the figure, an insulating layer or an adhesive layer may be inserted at the interface between the electrode and the organic layer.

[0133] According to one example, Figure 1 As shown, the organic electroluminescent element may have a structure in which an anode 100, a hole injection layer 310, a hole transport layer 320, a light emitting layer 330, an electron transport layer 340 and a cathode 200 are sequentially stacked on a substrate. Figure 2 As shown, an electron injection layer 350 may be provided between the electron transport layer 340 and the cathode 200. In addition, an electron transport auxiliary layer 360 (see Figure 3 ).

[0134] In the organic electroluminescent element of the present invention, at least one layer of the organic layer 300 (for example, the electron transport layer 340 ) contains the compound represented by the above Chemical Formula 1. In addition, the organic layer and the electrode can be formed and manufactured using materials and methods known in the art.

[0135] The organic layer may be formed by vacuum deposition or solution coating, such as spin coating, dip coating, doctor blade coating, inkjet printing, or thermal transfer, but is not limited thereto.

[0136] The substrate that can be used in the present invention is not particularly limited, and non-limiting examples include silicon wafers, quartz, glass plates, metal plates, plastic films and sheets, and the like.

[0137] In addition, examples of anode materials include 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, but are not limited to these.

[0138] In addition, examples of cathode materials include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver (Ag), tin or lead, or alloys thereof; and multilayer structure materials such as LiF / Al or LiO2 / Al, but are not limited to these.

[0139] The hole injection layer, hole transport layer, light emitting layer, and electron injection layer are not particularly limited, and common materials known in the art can be used.

[0140] Below, refer to Figure 4 Next, an organic electroluminescent element according to a fourth embodiment of the present invention will be described.

[0141] like Figure 4 As shown, the organic electroluminescent element according to the fourth embodiment of the present invention is a tandem element, which includes, on a substrate (not shown), an anode 100 and a cathode 200 facing each other; a plurality of light-emitting units 400 and 500 interposed between the anode 100 and the cathode 200; and a charge generation layer 600 interposed between adjacent light-emitting units 400 and 500 and including an N-type charge generation layer 610 and a P-type charge generation layer 620. In this case, the N-type charge generation layer 610 includes the compound represented by Chemical Formula 1.

[0142] In such a tandem organic electroluminescent element, the number of light-emitting units is at least two, and the number of light-emitting units can be increased by inserting a charge generation layer between adjacent light-emitting units.

[0143] According to one example, the plurality of light-emitting units may include a first light-emitting unit 400, a second light-emitting unit 500, ..., and an mth light-emitting unit (m is an integer greater than or equal to 3, specifically 3 to 4). In this case, a charge generation layer 600 including an N-type charge generation layer 610 and a P-type charge generation layer 620 is disposed between adjacent light-emitting units. The N-type charge generation layer 610 includes the compound represented by Chemical Formula 1.

[0144] Specifically, the organic electroluminescent element of the present invention includes: an anode 100 and a cathode 200 facing each other; a first light-emitting unit 400 disposed on the anode 100; a second light-emitting unit 500 disposed on the first light-emitting unit 400; and a charge generation layer 600 interposed between the first and second light-emitting units 400 and 500 and including an N-type charge generation layer 610 and a P-type charge generation layer 620. In this case, the N-type charge generation layer 610 includes the compound represented by Chemical Formula 1.

[0145] Each light-emitting unit 400, 500 includes a hole transport layer 410, 510, a light-emitting layer 420, 520, and an electron transport layer 430, 530. Specifically, the first light-emitting unit 400 may include a first hole transport layer 410, a first light-emitting layer 420, and a first electron transport layer 430, and the second light-emitting unit 500 may include a hole transport layer 510, a light-emitting layer 520, and an electron transport layer 530. Optionally, the first light-emitting unit 400 may further include a hole injection layer 440.

[0146] The hole transport layers 410 and 510 , the light emitting layers 420 and 520 , the electron transport layers 430 and 530 , and the hole injection layer 440 are not particularly limited, and any common materials known in the art may be used.

[0147] The charge generation layer (CGL) 600 is disposed between the adjacent light emitting units 400 and 500 , so that the charges between the light emitting units 400 and 500 are adjusted to achieve charge balance.

[0148] The charge generation layer 600 includes an N-type charge generation layer 610 disposed adjacent to the first light emitting unit 400 to supply electrons to the first light emitting unit 400 , and a P-type charge generation layer 620 disposed adjacent to the second light emitting unit 500 to supply holes to the second light emitting unit 500 .

[0149] The N-type charge generation layer 610 includes the compound represented by Chemical Formula 1. The compound of Chemical Formula 1 has excellent electron mobility, resulting in excellent electron injection and transport capabilities. Therefore, when the compound of Chemical Formula 1 is used as an N-type charge generation layer material in an organic electroluminescent device, a gradual increase in the device's driving voltage and a decrease in its lifespan can be prevented.

[0150] According to one example, the N-type charge generation layer 610 includes a host having electron transport properties, wherein the host is a compound represented by Chemical Formula 1. Unlike N-type charge generation layers including two hosts, the N-type charge generation layer 610 of the present invention can improve process efficiency when manufactured by co-evaporation.

[0151] The N-type charge generation layer 610 may further include an N-type dopant.

[0152] The N-type dopant that can be used in the present invention is not particularly limited as long as it is a substance commonly used in the art for the N-type charge generation layer, for example, there are alkali metals such as Li, Na, K, Rb, Cs, Fr, etc.; alkaline earth metals such as Be, Mg, Ca, Sr, Ba, Ra, etc.; Group 15 metals such as bismuth (Bi), antimony (Sb), etc.; lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), etc. Lanthanide metals such as promethium (Pm), samarium (Sm), europium (europium), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu); and compounds of more than one of the above metals. Alternatively, an organic N-type dopant may be one that has electron donor properties and is capable of donating at least a portion of the electron charge to an organic host (e.g., the compound of Chemical Formula 1) to form a charge transfer complex with the organic host. Examples thereof include bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) and tetrathiafulvalene (TTF).

[0153] The thickness of the N-type charge generation layer 610 is not particularly limited, and may be, for example, in the range of about 5 to 30 nm.

[0154] The above-mentioned P-type charge generation layer 620 can be composed of a metal or a P-type doped organic substance. Here, the above-mentioned metals include Al, Cu, Fe, Pb, Zn, Au, Pt, W, In, Mo, Ni and Ti, etc., which can be used alone or in alloys of two or more. In addition, the P-type dopant and the main substance used in the above-mentioned P-type doped organic substance are not particularly limited as long as they are commonly used substances. For example, the above-mentioned P-type dopants include 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-quinodimethane (2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-quinodimethane, F4-TCNQ), iodine, FeCl3, FeF3 and SbCl5, etc., which can be used alone or in a mixture of two or more. In addition, non-limiting examples of the above-mentioned main body include N,N'-bis(naphthaen-1-yl)-N,N'-bis(phenyl)-benzidine (NPB), N,N'-bis(3-methylphenyl)N,N'-bis(phenyl)-benzidine (TPD), and N,N,N',N'-tetra-naphthalenyl-benzidine (TNB), which can be used alone or in combination of two or more.

[0155] The description of the anode 100 and the cathode 200 is the same as that in the first to third embodiments, and thus is omitted.

[0156] Hereinafter, the present invention will be described in detail by way of examples, which are as follows. However, the following examples are merely illustrative of the present invention and the present invention is not limited thereto.

[0157] [Preparation Example 1] Synthesis of 2-(6-chloropyridin-2-yl)quinoline (A-1)

[0158]

[0159] Step 1. Synthesis of 2-(tributylstannyl)quinoline

[0160] 2-Bromoquinoline (10.0 g, 48.1 mmol) was dissolved in 150 ml of dry THF and cooled to -78 ° C under a nitrogen atmosphere, and then n-BuLi (30.0 mL of a 1.6 M hexane solution, 48.1 mmol) was slowly added dropwise. After stirring at -78 ° C for 1 hour, tributyltin chloride (15.6 g, 48.1 mmol) was added and reacted for 3 hours. The reaction was terminated by NH4Cl solution at room temperature. The reaction-terminated mixture was extracted with EtOAc and then washed with brine (Brine). The organic layer after washing was concentrated to obtain 2-(tributyltinalkyl)quinoline (18.3 g, 43.8 mmol, yield 91%).

[0161] Mass: [(M+H) + ]:419

[0162] Step 2. Synthesis of 2-(6-chloropyridin-2-yl)quinoline

[0163] 2-(tributylstannyl)quinoline (18.3 g, 43.8 mmol) and 2-bromo-6-chloropyridine (8.4 g, 43.8 mmol) synthesized in Step 1 of Preparation Example 1 were added to dry DMF, and Pd(PPh3)2Cl2 (3.1 g, 4.4 mmol) was added, followed by heating and stirring at 110°C for 18 hours. After completion of the reaction, the mixture was diluted with EtOAc and washed with water. The organic layer was dehydrated with magnesium sulfate and concentrated, and then purified by column chromatography to obtain 2-(6-chloropyridin-2-yl)quinoline (4.2 g, 17.5 mmol, 40% yield).

[0164] Mass: [(M+H) + ]:242

[0165] [Preparation Example 2] Synthesis of 6-(6-chloropyridin-2-yl)phenanthridine (A-2)

[0166]

[0167] Step 1. Synthesis of 6-(tributylstannyl)phenanthridine

[0168] After dissolving 6-bromophenanthridine (10.0 g, 38.7 mmol) in 150 ml of dry THF, the mixture was cooled to -78 ° C under a nitrogen atmosphere, and then n-BuLi (24.2 mL of 1.6 M hexane solution, 38.7 mmol) was slowly added dropwise. After stirring at -78 ° C for 1 hour, tributyltin chloride (12.6 g, 38.7 mmol) was added and reacted for 3 hours. The reaction was terminated by NH4Cl solution at room temperature. The reaction-terminated mixture was extracted with EtOAc and then washed with brine. The organic layer after washing was concentrated to obtain 6-(tributyltin alkyl)phenanthridine (16.1 g, 34.5 mmol, yield 89%).

[0169] Mass: [(M+H) + ]:469

[0170] Step 2. Synthesis of 6-(6-chloropyridin-2-yl)phenanthridine

[0171] 6-(tributylstannyl)phenanthridine (16.1 g, 34.5 mmol) and 2-bromo-6-chloropyridine (6.6 g, 34.5 mmol) synthesized in Step 1 of Preparation Example 2 were added to dry DMF and Pd(PPh3)2Cl2 (2.4 g, 3.4 mmol) was added, followed by heating and stirring at 110°C for 18 hours. After completion of the reaction, the mixture was diluted with EtOAc and washed with water. The organic layer was dehydrated with magnesium sulfate and concentrated, and then purified by column chromatography to obtain 6-(6-chloropyridin-2-yl)phenanthridine (4.2 g, 14.4 mmol, 42% yield).

[0172] Mass: [(M+H) + ]:292

[0173] [Preparation Example 3] Synthesis of 6-(6-chloropyridin-2-yl)benzo[c]phenanthridine (A-3)

[0174]

[0175] Step 1. Synthesis of 6-(tributylstannyl)benzo[c]phenanthridine

[0176] 6-bromobenzo[c]-phenanthridine (10.0 g, 32.4 mmol) was dissolved in 150 ml of dry THF and cooled to -78 ° C under a nitrogen atmosphere, and then n-BuLi (20.3 mL of a 1.6 M hexane solution, 32.4 mmol) was slowly added dropwise. After stirring at -78 ° C for 1 hour, tributyltin chloride (10.6 g, 32.4 mmol) was added and reacted for 3 hours. The reaction was terminated with NH4Cl solution at room temperature. The reaction-terminated mixture was extracted with EtOAc and then washed with brine. The organic layer after washing was concentrated to obtain 6-(tributyltin alkyl)benzo[c]phenanthridine (15.0 g, 28.9 mmol, yield 89%).

[0177] Mass: [(M+H) + ]:519

[0178] Step 2. Synthesis of 6-(6-chloropyridin-2-yl)benzo[c]phenanthridine

[0179] 6-(tributylstannyl)benzo[c]phenanthridine (15.0 g, 28.9 mmol) and 2-bromo-6-chloropyridine (5.6 g, 28.9 mmol) synthesized in Step 1 of Preparation Example 3 were added to dry DMF, and Pd(PPh3)2Cl2 (2.0 g, 2.9 mmol) was added, followed by heating and stirring at 110°C for 18 hours. After completion of the reaction, the mixture was diluted with EtOAc and washed with water. The organic layer was dehydrated with magnesium sulfate and concentrated, and then purified by column chromatography to obtain 6-(6-chloropyridin-2-yl)benzo[c]phenanthridine (3.9 g, 11.6 mmol, 40% yield).

[0180] Mass: [(M+H) + ]:342

[0181] [Preparation Example 4] Synthesis of 2-(6-(3-chlorophenyl)pyridin-2-yl)quinoline (B-1)

[0182]

[0183] Compound A-1 (10.0 g, 41.5 mmol) synthesized by the method of Preparation Example 1, (3-chlorophenyl)boronic acid (6.5 g, 41.5 mmol), Pd(PPh3)4 (1.4 g, 1.2 mmol), and K2CO3 (17.2 g, 124.6 mmol) were added to 100 ml of toluene, 15 ml of EtOH, and 15 ml of water, and heated under reflux with stirring for 2 hours. After the reaction was completed, the organic layer was extracted with dichloromethane, and the extracted organic layer was dehydrated with magnesium sulfate, concentrated, and crystallized using acetone and MeOH to obtain 2-(6-(3-chlorophenyl)pyridin-2-yl)quinoline (11.2 g, 35.3 mmol, yield 85%).

[0184] Mass: [(M+H) + ]:318

[0185] [Preparation Example 5] Synthesis of 6-(6-(3-chlorophenyl)pyridin-2-yl)phenanthridine (B-2)

[0186]

[0187] Compound A-2 (10 g, 34.4 mmol) synthesized by the method of Preparation Example 2, (3-chlorophenyl)boronic acid (5.4 g, 34.4 mmol), Pd(PPh3)4 (1.2 g, 1.0 mmol), and K2CO3 (14.3 g, 103.2 mmol) were added to 100 ml of toluene, 15 ml of EtOH, and 15 ml of water, and heated under reflux with stirring for 2 hours. After the reaction was completed, the organic layer was extracted with dichloromethane, and the extracted organic layer was dehydrated with magnesium sulfate, concentrated, and crystallized using acetone and MeOH to obtain 6-(6-(3-chlorophenyl)pyridin-2-yl)phenanthridine (11.0 g, 29.9 mmol, yield 87%).

[0188] Mass: [(M+H) + ]:368

[0189] [Preparation Example 6] Synthesis of 6-(6-(3-chlorophenyl)pyridin-2-yl)benzo[c]phenanthridine (B-3)

[0190]

[0191] Compound A-3 (10.0 g, 29.3 mmol) synthesized by the method of Preparation Example 3, (3-chlorophenyl)boronic acid (4.6 g, 29.3 mmol), Pd(PPh3)4 (1.0 g, 0.9 mmol), and K2CO3 (12.2 g, 88.0 mmol) were added to 100 ml of toluene, 15 ml of EtOH, and 15 ml of water, and heated under reflux with stirring for 2 hours. After the reaction was completed, the organic layer was extracted with dichloromethane, and the extracted organic layer was dehydrated with magnesium sulfate, concentrated, and crystallized using acetone and MeOH to obtain 6-(6-(3-chlorophenyl)pyridin-2-yl)benzo[c]phenanthridine (10.3 g, 24.6 mmol, yield 84%).

[0192] Mass: [(M+H) + ]:418

[0193] [Preparation Example 7] Synthesis of 6-(6-(4-chlorophenyl)pyridin-2-yl)phenanthridine (B-4)

[0194]

[0195] Compound A-2 (10.0 g, 34.4 mmol) synthesized by the method of Preparation Example 2, (4-chlorophenyl)boronic acid (5.4 g, 34.4 mmol), Pd(PPh3)4 (1.2 g, 1.0 mmol), and K2CO3 (14.3 g, 103.2 mmol) were added to 100 ml of toluene, 15 ml of EtOH, and 15 ml of water, and heated under reflux with stirring for 2 hours. After the reaction was completed, the organic layer was extracted with dichloromethane, and the extracted organic layer was dehydrated with magnesium sulfate, concentrated, and crystallized using acetone and MeOH to obtain 6-(6-(4-chlorophenyl)pyridin-2-yl)phenanthridine (10.5 g, 28.5 mmol, yield 83%).

[0196] Mass: [(M+H) + ]:368

[0197] [Preparation Example 8] Synthesis of 6-(6-(3-chloronaphthalen-1-yl)pyridin-2-yl)phenanthridine (B-5)

[0198]

[0199] Compound A-2 (10.0 g, 34.4 mmol) synthesized by the method of Preparation Example 2, (3-chloronaphthalene-1-yl)boric acid (7.1 g, 34.4 mmol), Pd(PPh3)4 (1.2 g, 1.0 mmol), and K2CO3 (14.3 g, 103.2 mmol) were added to 100 ml of toluene, 15 ml of EtOH, and 15 ml of water, and heated under reflux with stirring for 2 hours. After the reaction was completed, the organic layer was extracted with dichloromethane, and the extracted organic layer was dehydrated with magnesium sulfate, concentrated, and crystallized from acetone and MeOH to obtain 6-(6-(3-chloronaphthalene-1-yl)pyridin-2-yl)phenanthridine (11.9 g, 28.5 mmol, yield 83%).

[0200] Mass: [(M+H) + ]:418

[0201] [Preparation Example 9] Synthesis of 6-(6-(7-chloronaphthalen-2-yl)pyridin-2-yl)phenanthridine (B-6)

[0202]

[0203] Compound A-2 (10.0 g, 34.4 mmol) synthesized by the method of Preparation Example 2, (7-chloronaphthalene-2-yl)boric acid (7.1 g, 34.4 mmol), Pd(PPh3)4 (1.2 g, 1.0 mmol), and K2CO3 (14.3 g, 103.2 mmol) were added to 100 ml of toluene, 15 ml of EtOH, and 15 ml of water, and heated under reflux with stirring for 2 hours. After the reaction was completed, the organic layer was extracted with dichloromethane, and the extracted organic layer was dehydrated with magnesium sulfate, concentrated, and crystallized from acetone and MeOH to obtain 6-(6-(7-chloronaphthalene-2-yl)pyridin-2-yl)phenanthridine (11.6 g, 27.9 mmol, yield 81%).

[0204] Mass: [(M+H) + ]:418

[0205] [Preparation Example 10] Synthesis of 6-(6-(7-chloronaphthalen-2-yl)pyridin-2-yl)benzo[c]phenanthridine (B-7)

[0206]

[0207] Compound A-3 (10.0 g, 29.3 mmol) synthesized by the method of Preparation Example 3, (7-chloronaphthalene-2-yl)boric acid (6.1 g, 29.3 mmol), Pd(PPh3)4 (1.0 g, 0.9 mmol), and K2CO3 (12.2 g, mmol) were added to 100 ml of toluene, 15 ml of EtOH, and 15 ml of water, and heated under reflux with stirring for 2 hours. After the reaction was completed, the organic layer was extracted with dichloromethane, and the extracted organic layer was dehydrated with magnesium sulfate, concentrated, and crystallized from acetone and MeOH to obtain 6-(6-(7-chloronaphthalene-2-yl)pyridin-2-yl)benzo[c]phenanthridine (11.8 g, 25.2 mmol, yield 86%).

[0208] Mass: [(M+H) + ]:468

[0209] [Preparation Example 11] Synthesis of 2-(6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyridine-2-yl)quinoline (C-1)

[0210]

[0211] Compound B-1 (10 g, 31.6 mmol) synthesized by the method of Preparative Example 4, bis(pinacolato)diboron (10.4 g, 41.0 mmol), Pd(dppf)Cl2 (0.7 g, 0.9 mmol), X-Phos (0.9 g, 1.9 mmol), and KOAc (6.2 g, 63.1 mmol) were added to 100 ml of 1,4-dioxane and heated under reflux with stirring for 6 hours. After the reaction was completed, the KOAc was removed by filtration. The organic layer was concentrated and crystallized from acetone and MeOH to obtain 2-(6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyridin-2-yl)quinoline (11.6 g, 28.4 mmol, 90% yield).

[0212] Mass: [(M+H) + ]:409

[0213] [Preparation Example 12] Synthesis of 6-(6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyridin-2-yl)phenanthridine (C-2)

[0214]

[0215] Compound B-2 (10 g, 27.3 mmol) synthesized by the method of Preparative Example 5, bis(pinacolato)diboron (9.0 g, 35.4 mmol), Pd(dppf)Cl2 (0.6 g, 0.8 mmol), X-Phos (0.8 g, 1.6 mmol), and KOAc (5.4 g, 54.5 mmol) were added to 100 ml of 1,4-dioxane and heated under reflux with stirring for 6 hours. After the reaction was completed, the KOAc was removed by filtration. The organic layer was concentrated and crystallized from acetone and MeOH to obtain 6-(6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyridin-2-yl)phenanthridine (11.4 g, 24.8 mmol, 91% yield).

[0216] Mass: [(M+H) + ]:459

[0217] [Preparation Example 13] Synthesis of 6-(6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyridin-2-yl)benzo[c]phenanthridine (C-3)

[0218]

[0219] Compound B-3 (10 g, 24.0 mmol) synthesized by the method of Preparative Example 6, bis(pinacolato)diboron (7.9 g, 31.2 mmol), Pd(dppf)Cl2 (0.5 g, 0.7 mmol), X-Phos (0.7 g, 1.4 mmol), and KOAc (4.7 g, 48.0 mmol) were added to 100 ml of 1,4-dioxane and heated under reflux with stirring for 6 hours. After the reaction was completed, the KOAc was removed by filtration. The organic layer was concentrated and crystallized from acetone and MeOH to obtain 6-(6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyridin-2-yl)benzo[c]phenanthridine (10.9 g, 21.3 mmol, 89% yield).

[0220] Mass: [(M+H) + ]:509

[0221] [Preparation Example 14] Synthesis of 6-(6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyridin-2-yl)phenanthridine (C-4)

[0222]

[0223] Compound B-4 (10 g, 27.3 mmol) synthesized by the method of Preparative Example 7, bis(pinacolato)diboron (9.0 g, 35.4 mmol), Pd(dppf)Cl2 (0.6 g, 0.8 mmol), X-Phos (0.8 g, 1.6 mmol), and KOAc (5.4 g, 54.5 mmol) were added to 100 ml of 1,4-dioxane and heated under reflux with stirring for 6 hours. After the reaction was completed, the KOAc was removed by filtration. The organic layer was concentrated and crystallized from acetone and MeOH to obtain 6-(6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyridin-2-yl)phenanthridine (11.1 g, 24.3 mmol, 89% yield).

[0224] Mass: [(M+H) + ]:459

[0225] [Preparation Example 15] Synthesis of 6-(6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)naphthalen-1-yl)pyridin-2-yl)phenanthridine (C-5)

[0226]

[0227] Compound B-5 (10 g, 24.0 mmol) synthesized by the method of Preparative Example 8, bis(pinacolato)diboron (7.9 g, 31.2 mmol), Pd(dppf)Cl2 (0.5 g, 0.7 mmol), X-Phos (0.7 g, 1.4 mmol), and KOAc (4.7 g, 48.0 mmol) were added to 100 ml of 1,4-dioxane and heated under reflux with stirring for 6 hours. After the reaction was completed, the KOAc was removed by filtration. The organic layer was concentrated and crystallized from acetone and MeOH to obtain 6-(6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)naphthalen-1-yl)pyridin-2-yl)phenanthridine (11.0 g, 21.6 mmol, 90% yield).

[0228] Mass: [(M+H) + ]:509

[0229] [Preparation Example 16] Synthesis of 6-(6-(7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)naphthalen-2-yl)pyridin-2-yl)phenanthridine (C-6)

[0230]

[0231] Compound B-6 (10 g, 24.0 mmol) synthesized by the method of Preparative Example 9, bis(pinacolato)diboron (7.9 g, 31.2 mmol), Pd(dppf)Cl2 (0.5 g, 0.7 mmol), X-Phos (0.7 g, 1.4 mmol), and KOAc (4.7 g, 48.0 mmol) were added to 100 ml of 1,4-dioxane and heated under reflux with stirring for 6 hours. After the reaction was completed, the KOAc was removed by filtration. The organic layer was concentrated and crystallized from acetone and MeOH to obtain 6-(6-(7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)naphthalen-2-yl)pyridin-2-yl)phenanthridine (11.2 g, 22.1 mmol, 92% yield).

[0232] Mass: [(M+H) + ]:509

[0233] [Preparation Example 17] Synthesis of 6-(6-(7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)naphthalen-2-yl)pyridin-2-yl)benzo[c]phenanthridine (C-7)

[0234]

[0235] Compound B-7 (10 g, 21.4 mmol) synthesized by the method of Preparative Example 10, bis(pinacolato)diboron (7.1 g, 27.8 mmol), Pd(dppf)Cl2 (0.5 g, 0.6 mmol), X-Phos (0.6 g, 1.3 mmol), and KOAc (4.2 g, 42.8 mmol) were added to 100 ml of 1,4-dioxane and heated under reflux with stirring for 6 hours. After the reaction was completed, the KOAc was removed by filtration. The organic layer was concentrated and crystallized from acetone and MeOH to obtain 6-(6-(7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)naphthalen-2-yl)pyridin-2-yl)benzo[c]phenanthridine (10.2 g, 18.2 mmol, 85% yield).

[0236] Mass: [(M+H) + ]:560

[0237] [Preparation Example 18] Synthesis of 2-chloro-9-phenyl-1,10-phenanthroline (S-1)

[0238]

[0239] After dissolving bromobenzene (7.3 g, 46.6 mmol) in 150 ml of dry THF, the mixture was cooled to -78°C under a nitrogen atmosphere, and then n-BuLi (29.1 mL of a 1.6 M hexane solution, 46.6 mmol) was slowly added dropwise. After stirring at -78°C for 1 hour, 2-chloro-1,10-phenanthroline (10.0 g, 46.6 mmol) was added and reacted for 3 hours. The reaction was terminated with NH4Cl solution at room temperature. The reaction mixture was extracted with EtOAc and then washed with brine. After washing, the organic layer was concentrated and dissolved in 150 ml of dichloromethane. MnO2 (40.5 g, 465.8 mmol) was added and heated under reflux with stirring for 12 hours. After the reaction, the mixture was filtered to remove MnO 2 , washed with water, and the organic layer was concentrated and then crystallized using acetone and MeOH to obtain 2-chloro-9-phenyl-1,10-phenanthroline (12.3 g, 42.4 mmol, yield 91%).

[0240] Mass: [(M+H)+]: 292

[0241] [Preparation Example 19] Synthesis of 7-chloro-2-phenyl-1,10-phenanthroline (S-2)

[0242]

[0243] Step 1. 2,2-Dimethyl-5-(((2-phenylquinolin-8-yl)amino)methylene)-1,3-dioxane-4,6-diol Synthesis of ketones

[0244] Meldrum's acid (7.4 g, 51.2 mmol) was added to trimethoxymethane (81.6 g, 768.5 mmol) and heated under reflux with stirring for 2 hours, then cooled, and then 2-phenylquinolin-8-amine (10.0 g, 46.6 mmol) was added and the solution was heated under reflux for 1.5 hours. After the reaction was completed, it was cooled to room temperature and then terminated with NH4Cl solution. The reaction-terminated mixture was extracted with EtOAc and then washed with brine. The washed organic layer was concentrated after dehydration with magnesium sulfate and then recrystallized with EtOH to obtain 2,2-dimethyl-5-(((2-phenylquinolin-8-yl)amino)methylene)-1,3-dioxane-4,6-dione (12.2 g, 32.6 mmol, yield 70%).

[0245] Mass: [(M+H)+]: 375

[0246] Step 2. Synthesis of 9-phenyl-1,10-phenanthroline-4-ol

[0247] 2,2-Dimethyl-5-(((2-phenylquinolin-8-yl)amino)methylene)-1,3-dioxane-4,6-dione (12.2 g, 32.6 mmol) synthesized in Step 1 of Preparation Example 19 was added to 122 ml of diphenyl ether and heated under reflux with stirring for 1 hour. After the reaction, the mixture was cooled and crystallized by adding petroleum ether. The resulting crystals were filtered to obtain 9-phenyl-1,10-phenanthroline-4-ol (6.3 g, 23.1 mmol, 71% yield).

[0248] Mass: [(M+H)+]: 273

[0249] Step 3. Synthesis of 7-chloro-2-phenyl-1,10-phenanthroline

[0250] 9-Phenyl-1,10-phenanthroline-4-ol (6.3 g, 23.1 mmol) synthesized in Step 2 of Preparation Example 19 was added to POCl3 (71.0 g, 463.0 mmol) and heated under reflux with stirring for 1 hour. After cooling the solution, it was slowly poured into 200 ml of water, and then adjusted to pH 13 with a 20% aqueous NaOH solution. After extraction with dichloromethane, the water was removed with magnesium sulfate and concentrated to obtain 7-chloro-2-phenyl-1,10-phenanthroline (6.4 g, 22.0 mmol, 95% yield).

[0251] Mass: [(M+H)+]: 292

[0252] [Preparation Example 20] Synthesis of 2-chloro-9-(naphthalen-2-yl)-1,10-phenanthroline (S-4)

[0253]

[0254] 2-Bronaphthalene (9.6 g, 46.6 mmol) was dissolved in 150 ml of dry THF and cooled to –78°C under a nitrogen atmosphere. Then, n-BuLi (29.1 mL of a 1.6 M hexane solution, 46.6 mmol) was slowly added dropwise. After stirring at –78°C for 1 hour, 2-chloro-1,10-phenanthroline (10.0 g, 46.6 mmol) was added and reacted for 3 hours. The reaction was terminated with NH4Cl solution at room temperature. The reaction mixture was extracted with EtOAc and washed with brine. The washed organic layer was concentrated and dissolved in 150 ml of dichloromethane. MnO2 (40.5 g, 465.8 mmol) was added and heated under reflux with stirring for 12 hours. After the reaction, the mixture was filtered to remove MnO2, washed with water, and the organic layer was concentrated. The mixture was then crystallized using acetone and MeOH to obtain 2-chloro-9-(naphthalen-2-yl)-1,10-phenanthroline (14.0 g, 41.0 mmol, yield 88%).

[0255] Mass: [(M+H)+]: 342

[0256] [Preparation Example 21] Synthesis of 2-([1,1':2',1"-terphenyl]-4'-yl)-9-chloro-1,10-phenanthroline (S-3)

[0257]

[0258] 4'-Bromo-1,1':2',1"-terphenyl (14.4 g, 46.6 mmol) was dissolved in 150 ml of dry THF and cooled to -78 ° C under a nitrogen atmosphere. Then, n-BuLi (29.1 mL of a 1.6 M hexane solution, 46.6 mmol) was slowly added dropwise. After stirring at -78 ° C for 1 hour, 2-chloro-1,10-phenanthroline (10.0 g, 46.6 mmol) was added and reacted for 3 hours. The reaction was terminated with NH4Cl solution at room temperature. The mixture was quenched with EtOAc. The product was extracted and then washed with brine. The washed organic layer was concentrated and dissolved in 150 ml of dichloromethane. MnO2 (40.5 g, 465.8 mmol) was added and heated under reflux with stirring for 12 hours. After the reaction was completed, the MnO2 was removed by filtration. After washing with water, the organic layer was concentrated and then crystallized using acetone and MeOH to obtain 2-([1,1':2',1"-terphenyl]-4'-yl)-9-chloro-1,10-phenanthroline (18.8 g, 42.4 mmol, yield 91%).

[0259] Mass: [(M+H)+]: 444

[0260] [Preparation Example 22] Synthesis of 4-chloro-7-phenyl-1,10-phenanthroline (S-5)

[0261]

[0262] Step 1. 2,2-Dimethyl-5-(((4-phenylquinolin-8-yl)amino)methylene)-1,3-dioxane-4,6-diol Synthesis of ketones

[0263] Michaelis acid (7.4 g, 51.2 mmol) was added to trimethoxymethane (81.6 g, 768.5 mmol) and heated under reflux with stirring for 2 hours, then cooled, and then 4-phenylquinolin-8-amine (10.0 g, 46.6 mmol) was added and the solution was heated under reflux for 1.5 hours. After the reaction was completed, it was cooled to room temperature and then terminated with NH4Cl solution. The reaction-terminated mixture was extracted with EtOAc and then washed with brine. The washed organic layer was concentrated after dehydration with magnesium sulfate and then recrystallized with EtOH to obtain 2,2-dimethyl-5-(((4-phenylquinolin-8-yl)amino)methylene)-1,3-dioxane-4,6-dione (12.7 g, 34.0 mmol, yield 73%).

[0264] Mass: [(M+H)+]: 375

[0265] Step 2. Synthesis of 7-phenyl-1,10-phenanthroline-4-ol

[0266] 2,2-Dimethyl-5-(((4-phenylquinolin-8-yl)amino)methylene)-1,3-dioxane-4,6-dione (12.7 g, 34.0 mmol) synthesized in Step 1 of Preparation Example 22 was added to 128 ml of diphenyl ether and heated under reflux with stirring for 1 hour. After the reaction was completed, the mixture was cooled, petroleum ether was added for crystallization, and the resulting crystals were filtered to obtain 7-phenyl-1,10-phenanthroline-4-ol (6.7 g, 24.5 mmol, 72% yield).

[0267] Mass: [(M+H)+]: 273

[0268] Step 3. Synthesis of 4-chloro-7-phenyl-1,10-phenanthroline

[0269] 7-Phenyl-1,10-phenanthroline-4-ol (6.7 g, 24.5 mmol) synthesized in Step 2 of Preparation Example 22 was added to POCl3 (75.1 g, 489.6 mmol) and heated under reflux with stirring for 1 hour. After cooling the solution, it was slowly added to 200 ml of water, and then adjusted to pH 13 with a 20% aqueous NaOH solution. After extraction with dichloromethane, the water was removed with magnesium sulfate and concentrated to obtain 4-chloro-7-phenyl-1,10-phenanthroline (6.5 g, 22.5 mmol, 92% yield).

[0270] Mass: [(M+H)+]: 292

[0271] [Synthesis Example 1] Synthesis of 2-phenyl-9-(3-(6-(quinolin-2-yl)pyridin-2-yl)phenyl)-1,10-phenanthroline (001)

[0272]

[0273] Compound S-1 (10.0 g, 34.4 mmol) synthesized by the method of Preparation Example 18, compound C-1 (14.0 g, 34.4 mmol) synthesized by the method of Preparation Example 11, Pd(PPh3)4 (1.2 g, 1.0 mmol), and K2CO3 (14.3 g, 103.2 mmol) were added to 150 ml of toluene, 30 ml of EtOH, and 30 ml of water, and heated under reflux with stirring for 2 hours. After the reaction was completed, the organic layer was extracted with dichloromethane, and the extracted organic layer was dehydrated with magnesium sulfate, concentrated, and purified by column chromatography to obtain 2-phenyl-9-(3-(6-(quinolin-2-yl)pyridin-2-yl)phenyl)-1,10-phenanthroline (16.6 g, 30.9 mmol, yield 90%).

[0274] Mass: [(M+H)+]: 538

[0275] [Synthesis Example 2] Synthesis of 2-(3-(6-(phenanthridin-6-yl)pyridin-2-yl)phenyl)-9-phenyl-1,10-phenanthroline (002)

[0276]

[0277] Compound S-1 (10.0 g, 34.4 mmol) synthesized by the method of Preparation Example 18, compound C-2 (15.8 g, 34.4 mmol) synthesized by the method of Preparation Example 12, Pd(PPh3)4 (1.2 g, 1.0 mmol), and K2CO3 (14.3 g, 103.2 mmol) were added to 150 ml of toluene, 30 ml of EtOH, and 30 ml of water, and heated under reflux with stirring for 2 hours. After the reaction was completed, the organic layer was extracted with dichloromethane, and the extracted organic layer was dehydrated with magnesium sulfate, concentrated, and purified by column chromatography to obtain 2-(3-(6-(phenanthridin-6-yl)pyridin-2-yl)phenyl)-9-phenyl-1,10-phenanthroline (17.8 g, 30.3 mmol, yield 88%).

[0278] Mass: [(M+H)+]: 588

[0279] [Synthesis Example 3] Synthesis of 6-(6-(3-(9-phenyl-1,10-phenanthroline-2-yl)phenyl)pyridin-2-yl)benzo[c]phenanthridine (003)

[0280]

[0281] Compound S-1 (10.0 g, 34.4 mmol) synthesized by the method of Preparation Example 18, compound C-3 (17.5 g, 34.4 mmol) synthesized by the method of Preparation Example 13, Pd(PPh3)4 (1.2 g, 1.0 mmol), and K2CO3 (14.3 g, 103.2 mmol) were added to 150 ml of toluene, 30 ml of EtOH, and 30 ml of water, and the mixture was heated under reflux with stirring for 2 hours. After the reaction was completed, the organic layer was extracted with dichloromethane, and the extracted organic layer was dehydrated with magnesium sulfate, concentrated, and purified by column chromatography to obtain 6-(6-(3-(9-phenyl-1,10-phenanthroline-2-yl)phenyl)pyridin-2-yl)benzo[c]phenanthridine (19.1 g, 29.9 mmol, yield 87%).

[0282] Mass: [(M+H)+]: 638

[0283] [Synthesis Example 4] Synthesis of 2-(4-(6-(phenanthridin-6-yl)pyridin-2-yl)phenyl)-9-phenyl-1,10-phenanthroline (011)

[0284]

[0285] Compound S-1 (10.0 g, 34.4 mmol) synthesized by the method of Preparation Example 18, compound C-4 (15.8 g, 34.4 mmol) synthesized by the method of Preparation Example 14, Pd(PPh3)4 (1.2 g, 1.0 mmol), and K2CO3 (14.3 g, 103.2 mmol) were added to 150 ml of toluene, 30 ml of EtOH, and 30 ml of water, and heated under reflux with stirring for 2 hours. After the reaction was completed, the organic layer was extracted with dichloromethane, and the extracted organic layer was dehydrated with magnesium sulfate, concentrated, and purified by column chromatography to obtain 2-(4-(6-(phenanthridin-6-yl)pyridin-2-yl)phenyl)-9-phenyl-1,10-phenanthroline (17.8 g, 30.3 mmol, yield 88%).

[0286] Mass: [(M+H)+]: 588

[0287] [Synthesis Example 5] Synthesis of 2-(4-(6-(phenanthridin-6-yl)pyridin-2-yl)naphthalen-2-yl)-9-phenyl-1,10-phenanthroline (013)

[0288]

[0289] Compound S-1 (10.0 g, 34.4 mmol) synthesized by the method of Preparation Example 18, compound C-5 (17.5 g, 34.4 mmol) synthesized by the method of Preparation Example 15, Pd(PPh3)4 (1.2 g, 1.0 mmol), and K2CO3 (14.3 g, 103.2 mmol) were added to 150 ml of toluene, 30 ml of EtOH, and 30 ml of water, and heated under reflux with stirring for 2 hours. After the reaction was completed, the organic layer was extracted with dichloromethane, and the extracted organic layer was dehydrated with magnesium sulfate, concentrated, and purified by column chromatography to obtain 2-(4-(6-(phenanthridin-6-yl)pyridin-2-yl)naphthalen-2-yl)-9-phenyl-1,10-phenanthroline (19.7 g, 30.9 mmol, yield 90%).

[0290] Mass: [(M+H)+]: 638

[0291] [Synthesis Example 6] Synthesis of 2-(7-(6-(phenanthridin-6-yl)pyridin-2-yl)naphthalen-2-yl)-9-phenyl-1,10-phenanthroline (022)

[0292]

[0293] Compound S-1 (10.0 g, 34.4 mmol) synthesized by the method of Preparation Example 18, compound C-6 (17.5 g, 34.4 mmol) synthesized by the method of Preparation Example 16, Pd(PPh3)4 (1.2 g, 1.0 mmol), and K2CO3 (14.3 g, 103.2 mmol) were added to 150 ml of toluene, 30 ml of EtOH, and 30 ml of water, and heated under reflux with stirring for 2 hours. After the reaction was completed, the organic layer was extracted with dichloromethane, and the extracted organic layer was dehydrated with magnesium sulfate, concentrated, and purified by column chromatography to obtain 2-(7-(6-(phenanthridin-6-yl)pyridin-2-yl)naphthalen-2-yl)-9-phenyl-1,10-phenanthroline (18.6 g, 29.2 mmol, yield 85%).

[0294] Mass: [(M+H)+]: 638

[0295] [Synthesis Example 7] Synthesis of 6-(6-(7-(9-phenyl-1,10-phenanthroline-2-yl)naphthalen-2-yl)pyridin-2-yl)benzo[c]phenanthridine (062)

[0296]

[0297] Compound S-1 (10.0 g, 34.4 mmol) synthesized by the method of Preparation Example 18, compound C-7 (19.2 g, 34.4 mmol) synthesized by the method of Preparation Example 17, Pd(PPh3)4 (1.2 g, 1.0 mmol), and K2CO3 (14.3 g, 103.2 mmol) were added to 150 ml of toluene, 30 ml of EtOH, and 30 ml of water, and the mixture was heated under reflux and stirred for 2 hours. After the reaction was completed, the organic layer was extracted with dichloromethane, and the extracted organic layer was dehydrated with magnesium sulfate, concentrated, and purified by column chromatography to obtain 6-(6-(7-(9-phenyl-1,10-phenanthroline-2-yl)naphthalen-2-yl)pyridin-2-yl)benzo[c]phenanthridine (20.1 g, 29.2 mmol, yield 85%).

[0298] Mass: [(M+H)+]: 688

[0299] [Synthesis Example 8] Synthesis of 6-(6-(3-(9-phenyl-1,10-phenanthroline-4-yl)phenyl)pyridin-2-yl)benzo[c]phenanthridine (072)

[0300]

[0301] Compound S-2 (10.0 g, 34.4 mmol) synthesized by the method of Preparation Example 19, compound C-3 (17.5 g, 34.4 mmol) synthesized by the method of Preparation Example 13, and Cs2CO3 (33.6 g, 103.2 mmol) were added to 150 ml of toluene, 30 ml of EtOH, and 30 ml of DIW. Pd(OAc)2 (0.2 g, 1.0 mmol) and X-Phos (1.0 g, 2.1 mmol) were then added and the mixture was heated under reflux with stirring for 4 hours. After the reaction was completed, the organic layer was extracted with dichloromethane, the extracted organic layer was dehydrated with magnesium sulfate, concentrated, and purified by column chromatography to obtain 6-(6-(3-(9-phenyl-1,10-phenanthroline-4-yl)phenyl)pyridin-2-yl)benzo[c]phenanthridine (18.8 g, 29.6 mmol, yield 86%).

[0302] Mass: [(M+H)+]: 638

[0303] [Synthesis Example 9] Synthesis of 6-(6-(3-(9-([1,1':2',1"-terphenyl]-4'-yl)-1,10-phenanthroline-2-yl)phenyl)pyridin-2-yl)benzo[c]phenanthridine (074)

[0304]

[0305] Compound S-3 (10.0 g, 22.6 mmol) synthesized by the method of Preparation Example 20, compound C-3 (11.5 g, 22.6 mmol) synthesized by the method of Preparation Example 13, Pd(PPh3)4 (0.8 g, 0.7 mmol), and K2CO3 (9.4 g, 67.7 mmol) were added to 150 ml of toluene, 30 ml of EtOH, and 30 ml of water, and the mixture was heated under reflux and stirred for 2 hours. After the reaction was completed, the organic layer was extracted with dichloromethane, and the extracted organic layer was dehydrated with magnesium sulfate, concentrated, and purified by column chromatography to obtain 6-(6-(3-(9-([1,1':2',1"-terphenyl]-4'-yl)-1,10-phenanthroline-2-yl)phenyl)pyridin-2-yl)benzo[c]phenanthridine (15.0 g, 19.0 mmol, yield 84%).

[0306] Mass: [(M+H)+]: 790

[0307] [Synthesis Example 10] Synthesis of 6-(6-(3-(9-(naphthalen-2-yl)-1,10-phenanthroline-2-yl)phenyl)pyridin-2-yl)benzo[c]phenanthridine (083)

[0308]

[0309] Compound S-4 (10.0 g, 29.3 mmol) synthesized by the method of Preparation Example 21, compound C-3 (14.9 g, 29.3 mmol) synthesized by the method of Preparation Example 13, Pd(PPh3)4 (1.0 g, 0.9 mmol), and K2CO3 (12.2 g, 88.0 mmol) were added to 150 ml of toluene, 30 ml of EtOH, and 30 ml of water, and the mixture was heated under reflux and stirred for 2 hours. After the reaction was completed, the organic layer was extracted with dichloromethane, and the extracted organic layer was dehydrated with magnesium sulfate, concentrated, and purified by column chromatography to obtain 6-(6-(3-(9-(naphthalen-2-yl)-1,10-phenanthroline-2-yl)phenyl)pyridin-2-yl)benzo[c]phenanthridine (17.1 g, 24.9 mmol, yield 85%).

[0310] Mass: [(M+H)+]: 688

[0311] [Synthesis Example 11] Synthesis of 4-(3-(6-(phenanthridin-6-yl)pyridin-2-yl)phenyl)-7-phenyl-1,10-phenanthroline (096)

[0312]

[0313] Compound S-5 (10.0 g, 34.4 mmol) synthesized by the method of Preparation Example 22, compound C-2 (15.8 g, 34.4 mmol) synthesized by the method of Preparation Example 12, and Cs2CO3 (33.6 g, 103.2 mmol) were added to 150 ml of toluene, 30 ml of EtOH, and 30 ml of DIW, followed by the addition of Pd(OAc)2 (0.2 g, 1.0 mmol) and X-Phos (1.0 g, 2.1 mmol), and the mixture was heated under reflux with stirring for 4 hours. After the reaction was completed, the organic layer was extracted with dichloromethane, the extracted organic layer was dehydrated with magnesium sulfate, concentrated, and purified by column chromatography to obtain 4-(3-(6-(phenanthridin-6-yl)pyridin-2-yl)phenyl)-7-phenyl-1,10-phenanthroline (16.7 g, 28.5 mmol, yield 83%).

[0314] Mass: [(M+H)+]: 588

[0315] [Example 1] Preparation of blue organic electroluminescent element

[0316] Compound 001 synthesized in Synthesis Example 1 was purified to high purity by sublimation according to a commonly known method, and then a blue organic electroluminescent device was prepared as follows.

[0317] First, we will A glass substrate coated with a thin film of indium tin oxide (ITO) was ultrasonically cleaned with distilled water. After the distilled water wash, the substrate was ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, or methanol, dried, and then transferred to a UV ozone cleaner (Power sonic 405, Hwashintech). Afterwards, the substrate was cleaned with UV light for 5 minutes and then transferred to a vacuum evaporator.

[0318] Compound 1 and Compound 2 were co-evaporated at a weight ratio of 98:2 on the ITO transparent electrode prepared as above to form After forming a hole injection layer with a thickness of 100 nm, compound 1 was evaporated on the upper portion of the hole injection layer to form a hole injection layer. A hole transport layer having a thickness of Thickness of the compound 3 was evaporated to form a hole transport auxiliary layer, and then the compound 4 and the compound 5 were co-evaporated at a weight ratio of 98:2 to form Then, compound 6 is evaporated on the upper part of the light-emitting layer to form After the electron transport auxiliary layer is formed, compound 001 and compound 7 are co-evaporated at a weight ratio of 1:1 to form The electron transport layer is formed by evaporating LiF on the upper portion of the electron transport layer. After the electron injection layer is formed, Al is evaporated on the upper part of the electron injection layer to form A cathode having a thickness of 1000 Å was prepared to produce a blue organic electroluminescent device. The structures of compounds 1 to 7 used in this process are as follows.

[0319]

[0320] [Examples 2 to 11] Preparation of blue organic electroluminescent elements

[0321] A blue organic electroluminescent element was produced in the same manner as in Example 1 except that the compounds listed in Table 1 below were used instead of Compound 001 used as the electron transport layer material in Example 1.

[0322] [Comparative Examples 1 to 5] Preparation of Blue Organic Electroluminescent Elements

[0323] A blue organic electroluminescent device was produced in the same manner as in Example 1 except that Compound A to Compound E were used instead of Compound 001 used as the electron transport layer material in Example 1.

[0324]

[0325] [Evaluation Example 1]

[0326] The current density of 10 mA / cm was measured for the blue organic electroluminescent devices prepared in Examples 1 to 11 and Comparative Examples 1 to 5. 2 The driving voltage, current efficiency, and emission wavelength under the conditions are shown in Table 1 below.

[0327] [Table 1]

[0328]

[0329]

[0330] As shown in Table 1 above, the compounds of the present invention have a structure in which a pyridine moiety substituted with a 10- to 40-membered N-containing heteroaryl group is connected to a phenanthroline moiety via a linker. The blue organic electroluminescent elements of Examples 1 to 11, which utilize such compounds of the present invention in the electron transport layer, exhibit superior driving voltage, luminescence peak, current efficiency, and device life compared to the organic electroluminescent elements of Comparative Examples 1 to 5, which utilize compounds not containing a pyridine moiety substituted with a 10- to 40-membered N-containing heteroaryl group in the electron transport layer.

[0331] [Example 12] Preparation of organic electroluminescent element

[0332] Compound 001 synthesized in Synthesis Example 1 was purified to high purity by sublimation according to a commonly known method, and then a blue organic electroluminescent device was prepared as follows.

[0333] First, we will A glass substrate coated with a thin film of indium tin oxide (ITO) was ultrasonically cleaned with distilled water. After the distilled water wash, the substrate was ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, or methanol, dried, and then transferred to a UV ozone cleaner (Power sonic 405, Hwashintech). Afterwards, the substrate was cleaned with UV light for 5 minutes and then transferred to a vacuum evaporator.

[0334] Compound 1 and Compound 2 were co-evaporated at a weight ratio of 98:2 on the ITO transparent electrode prepared as above to form After forming a hole injection layer with a thickness of 100 nm, compound 1 was evaporated on the upper portion of the hole injection layer to form a hole injection layer. A hole transport layer having a thickness of Thickness of the compound 3 was evaporated to form a hole transport auxiliary layer, and then the compound 4 and the compound 5 were co-evaporated at a weight ratio of 98:2 to form Then, on the light-emitting layer, Thickness of compound 7 is evaporated to form an electron transport region, and a thickness of Compound 001 was evaporated at a thickness of 1000 to form an N-type charge generation layer. Compound 1 and Compound 2 were co-evaporated at a weight ratio of 98:2 on the N-type charge generation layer to form a After forming a P-type charge generation layer with a thickness of 100 nm, compound 1 is evaporated on the P-type charge generation layer to form A hole transport layer having a thickness of After the hole transport auxiliary layer was formed by evaporating compound 3 at a thickness of 100 nm, compound 4 and compound 5 were co-evaporated at a weight ratio of 98:2 to form a hole transport auxiliary layer. Then, compound 6 is evaporated on the upper part of the light-emitting layer to form After forming an electron transport auxiliary layer with a thickness of 1:1, compound 7 and compound 8 were evaporated at a weight ratio of 1:1 to form an electron transport auxiliary layer. An electron transport layer is formed by evaporating LiF on the upper portion of the electron transport layer. After the electron injection layer is formed, Al is evaporated on the upper part of the electron injection layer to form The structures of the compounds 1 to 7 used in this process are the same as those described in Example 1, and the structure of the compound 8 is as follows.

[0335]

[0336] [Examples 13 to 22] Fabrication of organic electroluminescent elements

[0337] Organic electroluminescent devices were prepared in the same manner as in Example 12 except that the compounds listed in Table 2 were used instead of Compound 001 used as the charge generation layer material in Example 12.

[0338] [Comparative Examples 6 to 10] Preparation of Organic Electroluminescent Elements

[0339] Organic electroluminescent devices were prepared in the same manner as in Example 12 except that Compounds A to E were used instead of Compound 001 as the charge generating layer material. Compounds A to E used were the same as those described in Comparative Examples 1 to 5.

[0340] [Evaluation Example 2]

[0341] The current density of 10 mA / cm was measured for the organic electroluminescent devices prepared in Examples 12 to 22 and Comparative Examples 6 to 10. 2 The driving voltage, current efficiency, and emission wavelength under the conditions are shown in Table 2 below.

[0342] [Table 2]

[0343]

[0344]

[0345] As shown in Table 2 above, the compounds of the present invention have a structure in which a pyridine moiety substituted with a 10- to 40-membered N-containing heteroaryl group is connected to a phenanthroline moiety via a linker. The organic electroluminescent devices of Examples 12 to 22, which utilize such compounds of the present invention in the N-type charge generation layer, exhibit superior driving voltage, luminescence peak, current efficiency, and device life compared to the organic electroluminescent devices of Comparative Examples 6 to 10, which utilize compounds not containing a pyridine moiety substituted with a 10- to 40-membered N-containing heteroaryl group in the N-type charge generation layer.

Claims

1. A compound represented by the following chemical formula 1: [Chemical Formula 1] In the chemical formula 1, Ar1 is a C9~C 40 Heteroaryl, n is an integer from 1 to 3, L1 is C6~C 40 arylene, a is an integer from 0 to 7, Ar2 is selected from hydrogen, deuterium (D), 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 atomic nuclei, C6~C 60 aryl, heteroaryl with 5 to 60 atomic nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkylsilyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, C6~C 60 Arylphosphine, C6~C 60 Aryl phosphine oxide group, C6~C 60 Arylamine, C6~C 60 A group consisting of an (aryl) (heteroaryl) amine group and a heteroarylamine group having 5 to 60 atomic nuclei, or condensed with an adjacent group to form a condensed ring, The heteroaryl group of Ar1, the arylene group of L1 and the alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylsilyl, arylsilyl, alkylboryl, arylboryl, arylphosphino, arylphosphine oxide, arylamine, (aryl)(heteroaryl)amine and heteroarylamine of Ar2 are each independently selected from deuterium (D), 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 atomic nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkylsilyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, C6~C 60 Arylphosphine, C6~C 60 Aryl phosphine oxide group, C6~C 60 Arylamine, C6~C 60 The present invention may be substituted or unsubstituted with one or more substituents selected from the group consisting of (aryl)(heteroaryl)amine groups and heteroarylamine groups having 5 to 60 atomic nuclei. In this case, when there are multiple substituents, they may be the same as or different from each other.

2. The compound according to claim 1, wherein Ar1 is a substituent represented by the following chemical formula S1-1 or S1-2: [Chemical formula S1-1] [Chemical formula S1-2] In the chemical formulas S1-1 and S1-2, Cy1 and Cy2 are each independently C6~C 30 The condensed aromatic ring, The condensed aromatic rings of Cy1 and Cy2 are independently selected from deuterium (D), 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 atomic nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkylsilyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, C6~C 60 Arylphosphine, C6~C 60 Aryl phosphine oxide group, C6~C 60 Arylamine, C6~C 60 The present invention may be substituted or unsubstituted with one or more substituents selected from the group consisting of (aryl)(heteroaryl)amine groups and heteroarylamine groups having 5 to 60 atomic nuclei. In this case, when there are multiple substituents, they may be the same as or different from each other.

3. The compound according to claim 1, wherein Ar1 is selected from the group consisting of the following substituents S2-1 to S2-9:

4. The compound according to claim 1, wherein L1 is selected from the group consisting of the following linking groups L1-1 to L1-3: In the linking groups L1-1 to L1-3, b is an integer from 0 to 4, c is an integer from 0 to 6, d is an integer from 0 to 8, R1 is selected from hydrogen, deuterium (D), 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 atomic nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkylsilyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, C6~C 60 Arylphosphine, C6~C 60 Aryl phosphine oxide group, C6~C 60 Arylamine, C6~C 60 The group consisting of (aryl)(heteroaryl)amine groups and heteroarylamine groups having 5 to 60 atomic nuclei.

5. The compound according to claim 1, wherein the compound represented by Chemical Formula 1 is represented by any one of the following Chemical Formulas 2 to 7: [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] [Chemical Formula 7] In the chemical formulas 2 to 7, n, L1, a and Ar2 are each the same as defined in claim 1, Cy1 and Cy2 are each independently C6~C 30 The condensed aromatic ring, The condensed aromatic rings of Cy1 and Cy2 are independently selected from deuterium (D), 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 atomic nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkylsilyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, C6~C 60 Arylphosphine, C6~C 60 Aryl phosphine oxide group, C6~C 60 Arylamine, C6~C 60 The present invention may be substituted or unsubstituted with one or more substituents selected from the group consisting of (aryl)(heteroaryl)amine groups and heteroarylamine groups having 5 to 60 atomic nuclei. In this case, when there are multiple substituents, they may be the same as or different from each other.

6. The compound according to claim 1, wherein the compound represented by Chemical Formula 1 is selected from the group consisting of the following compounds 001 to 146:

7. 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 organic compound according to any one of claims 1 to 6. The organic electroluminescent element according to claim 7 , wherein the organic layer containing the organic compound is an electron transport layer.

9. An organic electroluminescent element, comprising: an anode and a cathode spaced apart from each other; a plurality of light-emitting units between the anode and the cathode; and The N-type charge generation layer and the P-type charge generation layer are located between adjacent light-emitting units. Each of the plurality of light-emitting units comprises a hole transport layer, a light-emitting layer and an electron transport layer, The N-type charge generation layer includes the organic compound according to any one of claims 1 to 6.

10. The organic electroluminescent element according to claim 9, wherein the N-type charge generation layer comprises a host having electron transport properties. The host is the organic compound according to any one of claims 1 to 6. The organic electroluminescent element according to claim 10 , wherein the N-type charge generation layer further comprises an N-type dopant.

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