Organic light-emitting compound and organic electroluminescent element using same

Abstract

The present invention relates to an organic light-emitting compound and an organic electroluminescent element using the same. The compound according to the present invention is used in an organic layer of an organic electroluminescent element, and thus can improve the luminous efficiency, driving voltage, lifespan, and the like of the organic electroluminescent element.

Description

[0001] This application is a divisional application of a Chinese patent application with an application date of February 13, 2019, an application number of 201980024512.2, and an invention title of "Organic Light-Emitting Compound and Organic Electroluminescent Element Using the Same". Technical Field

[0002] The present invention relates to a novel organic light-emitting compound that can be used as a material for an organic electroluminescent element and an organic electroluminescent element containing the same. Background Art

[0003] Starting from the observation of organic thin-film luminescence by Bernanose in the 1950s, research on organic electroluminescent (EL) elements (hereinafter, simply referred to as "organic EL elements") developed from the blue electroluminescence using anthracene single crystals in 1965 has been carried out. Subsequently, in 1987, Tang proposed an organic electroluminescent element having a stacked structure divided into two functional layers, a hole layer and a light-emitting layer (C.W. Tang, App. Phys. Lett. 1986, 48, 183; C.W. Tang and S.A. Van Slyke, App. Phys. Lett. 1987, 51, 913; A. Tsumura et al., App. Phys. Lett. 1986, 49, 1210). Thereafter, in order to manufacture high-efficiency and long-life organic electroluminescent elements, a form in which each characteristic organic layer is introduced into the element has been developed, and dedicated substances for this purpose have been developed.

[0004] Regarding an organic electroluminescent element, when a voltage is applied between two electrodes, holes are injected from the anode into the organic layer, and electrons are injected from the cathode into the organic layer. When the injected holes and electrons meet, an exciton is formed, and when this exciton transitions to the ground state, light is emitted. At this time, the substances used for the organic layer can be classified into a light-emitting substance, a hole injection substance, a hole transport substance, an electron transport substance, an electron injection substance, etc. according to their functions.

[0005] Light-emitting substances can be classified into blue, green, red light-emitting substances, and yellow and orange light-emitting substances for presenting more natural colors according to the emission color. In addition, in order to increase the luminescence efficiency through an increase in color purity and energy transfer, a host / dopant system can be used as the light-emitting substance.

[0006] Dopants can be classified into fluorescent dopants using organic substances and phosphorescent dopants using metal coordination compounds containing heavy atoms such as Ir and Pt. At this time, since the development of phosphorescent materials can theoretically improve the luminous efficiency by up to four times compared to fluorescence, a large amount of research is being conducted not only on phosphorescent dopants but also on phosphorescent host materials.

[0007] So far, as materials for the hole injection layer, hole transport layer, hole blocking layer, and electron transport layer, NPB, BCP, Alq3, etc. are well-known, and as materials for the light-emitting layer, anthracene derivatives have been reported. In particular, metal coordination compounds containing Ir such as Firpic, Ir(ppy)3, and (acac)Ir(btp)2, which have advantages in terms of efficiency improvement in the light-emitting layer material, have been used as phosphorescent dopant materials for blue, green, and red, and 4,4-dicarbazolybiphenyl (CBP) has been used as a phosphorescent host material.

[0008]

[0009] However, although conventional organic layer materials have advantages in terms of luminous characteristics, they have a low glass transition temperature and very poor thermal stability, so they cannot reach a satisfactory level in terms of the lifetime of organic electroluminescent elements. Therefore, the development of organic layer materials with excellent performance is required. Summary of the Invention

[0010] Technical Problem

[0011] An object of the present invention is to provide a novel organic compound that can be applied to an organic electroluminescent element and has excellent hole and electron injection and transport capabilities, light-emitting capabilities, etc.

[0012] In addition, another object of the present invention is to provide an organic electroluminescent element that contains the above novel organic compound, exhibits low-voltage driving and high luminous efficiency, and has an improved lifetime, and is used as a hole transport layer material and a hole transport auxiliary layer material.

[0013] Means for Solving the Problem

[0014] Basically, the structure of the spiroacridine system has very excellent electrochemical stability, a high glass transition temperature, and excellent carrier transport capabilities, especially very excellent hole transport capabilities, so that holes are smoothly transported to the light-emitting layer and the luminous efficiency is improved. The material represented by Chemical Formula 1 of the present invention is characterized by a structure of spirobifluorene and a spiroacridine nucleus plus an aromatic amine.

[0015] In addition, in the present invention, the selected linking group has low-voltage driving and high refractive index characteristics based on excellent hole transport ability, and thus exhibits physical characteristics of high efficiency and long life.

[0016] For this reason, since the compound represented by Chemical Formula 1 of the present invention has excellent light-emitting characteristics, it can be used as a material for any one of the organic layers of an organic electroluminescent element, namely, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer, and preferably can be used as a material for a hole transport layer and a hole transport auxiliary layer.

[0017] The present invention provides a compound represented by the following Chemical Formula 1:

[0018] [Chemical Formula 1]

[0019]

[0020] In the above Chemical Formula 1,

[0021] X is N, O, S or C,

[0022] L is a direct bond, or is selected from the group consisting of arylene groups having 6 to C 18 and heteroarylene groups having 5 to 18 ring nuclei;

[0023] Ar1 and Ar2 are each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, C1-C 40 alkyl groups, C2-C 40 alkenyl groups, C2-C 40 alkynyl groups, C3-C 40 cycloalkyl groups, heteroalkyl groups having 3 to 40 ring nuclei, C6-C 60 aryl groups, heteroaryl groups having 5 to 60 ring nuclei, C1-C 40 alkoxy groups, C6-C 60 aryloxy groups, C3-C 40 alkylsilyl groups, C6-C 60 arylsilyl groups, C1-C 40 alkylboron groups, C6-C 60 arylboron groups, C6-C 60 arylphosphine groups, C6-C 60 mono- or diarylphosphine groups, and C6-C 60 arylamine groups, and are symmetric or asymmetric to each other;

[0024] The alkyl, alkenyl, alkynyl, aryl, heteroaryl, aryloxy, alkoxy, cycloalkyl, heterocycloalkyl, arylamino, alkylsilyl, alkylboron, arylboron, arylphosphine, mono- or diarylphosphine, and arylsilyl groups of Ar1 and Ar2 as defined above are each independently selected from the group consisting of deuterium, halogen, cyano, nitro, C1-C 40 alkyl groups of, C2-C 40 alkenyl groups of, C2-C 40 alkynyl groups of, C6-C 60 aryl groups of, heteroaryl groups having 5 to 60 ring atoms, C6-C 60 aryloxy groups of, C1-C 40 alkoxy groups of, C6-C 60 aryl amino groups of, C3-C 40 cycloalkyl groups of, heterocycloalkyl groups having 3 to 40 ring atoms, C1-C 40 alkylsilyl groups of, C1-C 40 alkylboron groups of, C6-C 60 arylboron groups of, C6-C 60 arylphosphine groups of, C6-C 60 mono- or diarylphosphine groups of, and C6-C 60 aryl silyl groups of, and are substituted or unsubstituted with one or more substituents selected from the group, and when there are multiple substituents, they are the same or different from each other.

[0025] In addition, the present invention provides a compound represented by the following Chemical Formula 2:

[0026] [Chemical Formula 2]

[0027]

[0028] In the above Chemical Formula 2,

[0029] X, L, Ar1, and Ar2 are as defined in Chemical Formula 1 above;

[0030] R1 and R2 are each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, C1-C 40 alkyl groups of, C2-C 40 alkenyl groups of, C2-C 40 alkynyl groups of, C3-C 40 cycloalkyl groups of, heterocycloalkyl groups having 3 to 40 ring atoms, C6-C 60 aryl groups of, heteroaryl groups having 5 to 60 ring atoms, C1-C 40 alkoxy groups of, C6-C 60 aryloxy groups of, C3-C 40 alkylsilyl groups of, C6-C 60 arylsilyl groups of, C1-C 40An alkylboronyl group, C6-C 60 An arylboronyl group, C6-C 60 An arylphosphino group, C6-C 60 A mono- or diarylphosphino group, and C6-C 60 A group consisting of an arylamino group;

[0031] The alkyl, alkenyl, alkynyl, aryl, heteroaryl, aryloxy, alkoxy, cycloalkyl, heterocycloalkyl, arylamino, alkylsilyl, alkylboronyl, arylboronyl, arylphosphino, mono- or diarylphosphino, and arylsilyl groups of R1 and R2 are each independently selected from the group consisting of deuterium, halogen, cyano, nitro, C1-C 40 An alkyl group, C2-C 40 An alkenyl group, C2-C 40 An alkynyl group, C6-C 60 An aryl group, a heteroaryl group having 5 to 60 ring atoms, C6-C 60 An aryloxy group, C1-C 40 An alkoxy group, C6-C 60 An arylamino group, C3-C 40 A cycloalkyl group, a heterocycloalkyl group having 3 to 40 ring atoms, C1-C 40 An alkylsilyl group, C1-C 40 An alkylboronyl group, C6-C 60 An arylboronyl group, C6-C 60 An arylphosphino group, C6-C 60 A mono- or diarylphosphino group, and C6-C 60 An arylsilyl group, and is substituted or unsubstituted with one or more substituents selected from the group consisting of, and when there are a plurality of substituents, they may be the same as or different from each other.

[0032] The present invention provides an organic electroluminescent element comprising the above-described anode, cathode, and one or more organic layers interposed between the anode and the cathode, and at least one of the one or more organic layers contains a compound represented by Chemical Formula 1 or Chemical Formula 2.

[0033] In the present invention, "halogen" means fluorine, chlorine, bromine, or iodine.

[0034] In the present invention, "alkyl" means a monovalent substituent derived from a straight-chain or branched saturated hydrocarbon having 1 to 40 carbon atoms, and examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, isopentyl, hexyl, etc., but are not limited thereto.

[0035] "Alkenyl" in the present invention means a monovalent substituent derived from a straight-chain or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having more than 1 carbon-carbon double bond. Examples thereof include vinyl, allyl, isopropenyl, 2-butenyl, etc., but are not limited thereto.

[0036] "Alkynyl" in the present invention means a monovalent substituent derived from a straight-chain or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having more than 1 carbon-carbon triple bond. Examples thereof include ethynyl, 2-propynyl, etc., but are not limited thereto.

[0037] "Aryl" in the present invention means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 40 carbon atoms which is composed of a single ring or a combination of 2 or more rings. In addition, it may also include a monovalent substituent in which 2 or more rings are condensed with each other, contain only carbon as ring-forming atoms (for example, the number of carbon atoms may be 8 to 60), and the whole molecule has non-aromacity. Examples of such aryl include phenyl, naphthyl, phenanthryl, anthryl, fluorenyl, etc., but are not limited thereto.

[0038] "Heteroaryl" in the present invention means a monovalent substituent derived from a monocyclic or polycyclic aromatic hydrocarbon having 5 to 60 nuclear atoms. At this time, one or more carbons in the ring, preferably 1 to 3 carbons, are replaced by heteroatoms selected from N, O, P, S, and Se. In addition, it may also include a monovalent group in which 2 or more rings are simply attached or condensed with each other, contain heteroatoms selected from N, O, P, S, and Se in addition to carbon as ring-forming atoms, and the whole molecule has non-aromacity. Examples of such heteroaryl include 6-membered monocycles such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl; polycycles such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, carbazolyl; 2-furyl, N-imidazolyl, 2-iso oxazolyl, 2-pyridyl, 2-pyrimidinyl, etc., but are not limited thereto.

[0039] "Aryloxy" in the present invention means a monovalent substituent represented by RO-, wherein R is an aryl having 5 to 60 carbon atoms. Examples of such aryloxy include phenoxy, naphthyloxy, diphenoxy, etc., but are not limited thereto.

[0040] In the present invention, "alkoxy" means a monovalent substituent represented by R'O—, where R' is an alkyl group having 1 to 40 carbon atoms and may include a linear, branched, or cyclic structure. Examples of alkoxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, tert-butoxy, n-butoxy, pentyloxy, etc.

[0041] In the present invention, "arylamino" means an amino group substituted with an aryl group having 6 to 60 carbon atoms.

[0042] 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 include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, etc.

[0043] In the present invention, "heterocycloalkyl" means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, and one or more carbons in the ring, preferably 1 to 3 carbons, are substituted with heteroatoms such as N, O, S, or Se. Examples of such heterocycloalkyl include, but are not limited to, morpholinyl, piperazinyl, etc.

[0044] In the present invention, "alkylsilyl" means a silyl group substituted with an alkyl group having 1 to 40 carbon atoms, and "arylsilyl" means a silyl group substituted with an aryl group having 5 to 60 carbon atoms.

[0045] In the present invention, "condensed ring" means a form obtained by condensing an aliphatic ring, an aromatic ring, an aliphatic heterocycle, an aromatic heterocycle, or a combination thereof.

[0046] Advantages of the Invention

[0047] The compound of the present invention has extremely excellent hole transport ability based on the spiro dimethyl acridine structure, thereby showing a fast hole mobility and having excellent luminous efficiency.

[0048] In addition, due to the high glass transition temperature, it has thermal stability and has suitable HOMO and LUMO energy level characteristics between the hole injection layer and the light-emitting layer, so it can be driven at a low voltage and the lifetime is improved. Moreover, due to the amorphous crystallinity and high refractive index characteristics, it has the effect of further improving the luminous efficiency. Therefore, an organic electroluminescent element containing the compound of the present invention in the organic layer can be effectively applied to a transport layer material, a hole transport auxiliary layer, etc. Detailed Embodiments

[0049] The present invention will be described in detail below.

[0050] 1. Novel organic compound

[0051] The novel compound of the present invention can be represented by the following Chemical Formula 1:

[0052] [Chemical Formula 1]

[0053]

[0054] In the above Chemical Formula 1,

[0055] X is N, O, S or C,

[0056] L is a direct bond, or is selected from the group consisting of arylene having 6 to C 18 and heteroarylene having 5 to 18 ring nuclei;

[0057] Ar1 and Ar2 are each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, C1-C 40 alkyl, C2-C 40 alkenyl, C2-C 40 alkynyl, C3-C 40 cycloalkyl, heteroalkyl having 3 to 40 ring nuclei, C6-C 60 aryl, heteroaryl having 5 to 60 ring nuclei, C1-C 40 alkoxy, C6-C 60 aryloxy, C3-C 40 alkylsilyl, C6-C 60 arylsilyl, C1-C 40 alkylboron, C6-C 60 arylboron, C6-C 60 arylphosphine, C6-C 60 mono- or diarylphosphine, and C6-C 60 arylamine, and are symmetric or asymmetric to each other;

[0058] The alkyl, alkenyl, alkynyl, aryl, heteroaryl, aryloxy, alkoxy, cycloalkyl, heteroalkyl, arylamine, alkylsilyl, alkylboron, arylboron, arylphosphine, mono- or diarylphosphine, and arylsilyl of the above Ar1 and Ar2 are each independently selected from the group consisting of deuterium, halogen, cyano, nitro, C1-C 40 alkyl, C2-C 40 alkenyl, C2-C 40 alkynyl, C6-C 60 aryl, heteroaryl having 5 to 60 ring nuclei, C6-C 60 aryloxy, C1-C40 an alkoxy group, C6-C 60 an arylamino group, C3-C 40 a cycloalkyl group, a heterocycloalkyl group having 3 to 40 ring atoms, C1-C 40 an alkylsilyl group, C1-C 40 an alkylboron group, C6-C 60 an arylboron group, C6-C 60 an arylphosphino group, C6-C 60 a mono- or diarylphosphino group and C6-C 60 substituted or unsubstituted with one or more substituents selected from the group consisting of an arylsilyl group, and when there are a plurality of substituents, they may be the same as or different from each other.

[0059] In addition, the novel compound of the present invention can be represented by the following Chemical Formula 2.

[0060] [Chemical Formula 2]

[0061]

[0062] In the above Chemical Formula 2,

[0063] X, L, Ar1 and Ar2 are the same as defined in the above Chemical Formula 1;

[0064] R1 and R2 are each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, C1-C 40 an alkyl group, C2-C 40 an alkenyl group, C2-C 40 an alkynyl group, C3-C 40 a cycloalkyl group, a heterocycloalkyl group having 3 to 40 ring atoms, C6-C 60 an aryl group, a heteroaryl group having 5 to 60 ring atoms, C1-C 40 an alkoxy group, C6-C 60 an aryloxy group, C3-C 40 an alkylsilyl group, C6-C 60 an arylsilyl group, C1-C 40 an alkylboron group, C6-C 60 an arylboron group, C6-C 60 an arylphosphino group, C6-C 60 a mono- or diarylphosphino group and C6-C 60 an arylamino group;

[0065] The alkyl, alkenyl, alkynyl, aryl, heteroaryl, aryloxy, alkoxy, cycloalkyl, heterocycloalkyl, arylamino, alkylsilyl, alkylboron, arylboron, arylphosphine, mono- or diarylphosphine, and arylsilyl of R1 and R2 as described above are each independently selected from the group consisting of deuterium, halogen, cyano, nitro, C1-C 40 alkyl of 40 C2-C 40 alkenyl of 60 C2-C 60 alkynyl of 40 C6-C 60 aryl of 40 heteroaryl having 5 to 60 ring atoms, C6-C 40 aryloxy of 40 C1-C 60 alkoxy of 60 C6-C 60 arylamino of 60 C3-C

[0066] In one embodiment of the present invention, R1 and R2 as described above are each independently selected from the group consisting of C1-C 40 alkyl of 60 C6-C 40 aryl of 60 and heteroaryl having 5 to 60 ring atoms. The alkyl, aryl, and heteroaryl of R1 and R2 are each independently selected from the group consisting of C1-C

[0067] In a preferred embodiment of the present invention, R1 and R2 are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, phenyl, biphenyl, pyridyl, pyrimidinyl, and triazinyl. The methyl, ethyl, propyl, butyl, pentyl, phenyl, biphenyl, pyridyl, pyrimidinyl, and triazinyl of R1 and R2 are each independently selected from the group consisting of C1-C 40 alkyl of 60 C6-C

[0068] In one embodiment of the present invention, the above-mentioned L may be a direct bond or one or more linking groups selected from the group consisting of the following Chemical Formulas 3 to 8.

[0069] [Chemical Formula 3]

[0070]

[0071] [Chemical Formula 4]

[0072]

[0073] [Chemical Formula 5]

[0074]

[0075] [Chemical Formula 6]

[0076]

[0077] [Chemical Formula 7]

[0078]

[0079] [Chemical Formula 8]

[0080]

[0081] In one embodiment of the present invention, the above-mentioned Ar1 and Ar2 are selected from the group consisting of alkyl groups having C1 to C 40 aryl groups having C6 to C 60 and heteroaryl groups having 5 to 60 nuclei. The alkyl groups, aryl groups, and heteroaryl groups of the above-mentioned Ar1 and Ar2 are each independently selected from the group consisting of alkyl groups having C1 to C 40 aryl groups having C6 to C 60 and heteroaryl groups having 5 to 60 nuclei, and are either unsubstituted or substituted by one or more substituents selected from the group. When there are multiple substituents, they may be the same or different from each other.

[0082] In a preferred embodiment of the present invention, the above-mentioned Ar1 and Ar2 are selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, phenyl, biphenyl, fluorenyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, pyridyl, pyrimidinyl, triazinyl, naphthyl, triazolopyridyl, quinolinyl, isoquinolinyl, cinnolinyl, quinoxalinyl, and quinazolinyl. The methyl, ethyl, propyl, butyl, pentyl, phenyl, biphenyl, fluorenyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, pyridyl, pyrimidinyl, triazinyl, naphthyl, triazolopyridyl, quinolinyl, isoquinolinyl, cinnolinyl, quinoxalinyl, and quinazolinyl of the above-mentioned Ar1 and Ar2 are each independently selected from the group consisting of alkyl groups having C1 to C 40 aryl groups having C6 to C 60substituted or unsubstituted with one or more substituents selected from the group consisting of aryl groups and heteroaryl groups having 5 to 60 nuclear atoms, and when there are a plurality of substituents, they may be the same as or different from each other.

[0083] In one embodiment of the present invention, the compound represented by the above Chemical Formula 1 or Chemical Formula 2 may be a compound represented by the following chemical formula, which is 7-(10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]-3'-yl)-N,N-diphenyldibenzo[b,d]furan-2-amine or N,N-di([1,1'-biphenyl]-4-yl)-7-(10-phenyl-10H-spiro[acridine-9,9'-fluorene]-2'-yl)phenanthrene-2-amine.

[0084]

[0085] In one embodiment of the present invention, the compound represented by the above Chemical Formula 1 or Chemical Formula 2 may be selected from the group consisting of the following compounds, but is not limited thereto:

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092] The compound of Chemical Formula 1 of the present invention can be synthesized according to a general synthesis method (refer to Chem. Rev., 60:313 (1960); J. Chem. SOC. 4482 (1955); Chem. Rev. 95:2457 (1995), etc.). The detailed synthesis process of the compound of the present invention will be specifically described in the synthesis examples described later.

[0093] 2. Organic electroluminescent element

[0094] In addition, the present invention relates to an organic electroluminescent element (organic EL element) containing the compound represented by the above Chemical Formula 1 or Chemical Formula 2 of the present invention.

[0095] Specifically, the organic electroluminescent element of the present invention includes an anode, a cathode, and one or more organic layers interposed between the anode and the cathode, and at least one of the one or more organic layers contains the compound represented by Chemical Formula 1 or Chemical Formula 2. At this time, the above compounds can be used alone or in combination of two or more.

[0096] The one or more organic layers may be any one or more of a hole injection layer, a hole transport layer, a hole transport auxiliary layer, an electron injection layer, an electron transport layer, an electron transport auxiliary layer, or a light emitting layer, and at least one of the organic layers may contain the compound represented by Chemical Formula 1.

[0097] The structure of the organic electroluminescent element of the present invention described above is not particularly limited. For example, it may include an anode and a cathode facing each other and an organic layer located between the anode and the cathode. Here, the organic layer may include a hole transport layer, a light emitting layer, and an electron transport layer. In addition, a hole transport auxiliary layer may be included between the hole transport layer and the light emitting layer, and an electron transport auxiliary layer may be included between the electron transport layer and the light emitting layer.

[0098] In addition, the organic layer may further include a hole injection layer between the hole transport layer and the anode, and an electron injection layer may be additionally included between the electron transport layer and the cathode.

[0099] In the present invention, the hole injection layer laminated between the hole transport layer and the anode is a layer that not only improves the interfacial characteristics between ITO used as the anode and the organic substance used as the hole transport layer, but also makes the surface of ITO smooth by coating on the upper part of the uneven ITO surface. As long as it is a hole injection layer commonly used in the art, it can be used without particular limitation. For example, an amine compound can be used, but it is not limited thereto.

[0100] In addition, the above electron injection layer is a layer laminated on the upper part of the electron transport layer that functions to facilitate the injection of electrons from the cathode and ultimately improve the power efficiency. As long as it is an electron injection layer commonly used in the art, it can be used without particular limitation. For example, substances such as LiF, Liq, NaCl, CsF, Li2O, and BaO can be used.

[0101] In addition, a light emitting auxiliary layer may be further included between the hole transport auxiliary layer and the light emitting layer. The light emitting auxiliary layer can function to transport holes to the light emitting layer and adjust the thickness of the organic layer. The light emitting auxiliary layer may contain a hole transport substance and may be made of the same substance as the hole transport layer.

[0102] In addition, a lifetime improvement layer may be further included between the above-mentioned electron transport auxiliary layer and the light-emitting layer. It functions to block holes that move toward the light-emitting layer with the ionization energy level within the organic light-emitting element at the high energy barrier of the lifetime improvement layer and prevent them from diffusing or moving toward the electron transport layer. As a result, the holes are confined to the light-emitting layer. This function of confining holes to the light-emitting layer prevents holes from diffusing into the electron transport layer where electrons move due to reduction, and suppresses the phenomenon of lifetime reduction caused by irreversible decomposition reactions through oxidation, thus contributing to the improvement of the lifetime of the organic light-emitting element.

[0103] Basically, the structure of the spiroacridine-based compound has very excellent electrochemical stability, a high glass transition temperature, and excellent carrier transport ability, especially very excellent hole transport ability, so that holes can be smoothly transported to the light-emitting layer and the light-emitting efficiency can be improved.

[0104] Basically, the structure of the spiroacridine-based compound has very excellent electrochemical stability, a high glass transition temperature, and excellent carrier transport ability, especially very excellent hole transport ability, so that holes can be smoothly transported to the light-emitting layer and the light-emitting efficiency can be improved.

[0105] In the present invention, the compound represented by Chemical Formula 1 is characterized by a structure of spirobifluorene plus arylamine, and has the characteristics of low-voltage driving and high refractive index, thereby exhibiting physical characteristics of high efficiency and long lifetime.

[0106] Therefore, the compound represented by Chemical Formula 1 of the representative structure claimed in the present invention has excellent light-emitting characteristics, and thus can be used as a material for any one of the organic layers of the organic electroluminescent element, namely, the hole injection layer, the hole transport layer, the hole transport auxiliary layer, the electron injection layer, the electron transport layer, the electron transport auxiliary layer, and the light-emitting layer. Preferably, it can be used as a material for the hole transport layer and the hole transport auxiliary layer.

[0107] In addition, in the present invention, as described above, the above-mentioned organic electroluminescent element may not only have an anode, one or more organic layers, and a cathode laminated in sequence, but also an insulating layer or an adhesive layer may be additionally included at the interface between the electrode and the organic layer.

[0108] For the organic electroluminescent element of the present invention, except that one or more of the above-mentioned organic layers (for example, the electron transport auxiliary layer) contain the compound represented by Chemical Formula 1, other organic layers and electrodes can be formed and manufactured using materials and methods known in the art.

[0109] The above-mentioned organic layer can be formed by vacuum evaporation or solution coating. Examples of the above-mentioned solution coating method include spin coating, dip coating, blade coating, inkjet printing, or thermal transfer printing, etc., but are not limited thereto.

[0110] The substrates that can be used in the present invention are not particularly limited, and silicon wafers, quartz, glass plates, metal plates, plastic films and sheets, etc. can be used.

[0111] In addition, as the anode material, for example, it can be made of a conductor with a high work function to facilitate hole injection, such as metals or their alloys like vanadium, chromium, copper, zinc, gold; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), 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-(ethylenedioxy)thiophene] (PEDT), polypyrrole or polyaniline; and carbon black, etc., but not limited thereto.

[0112] In addition, as the cathode material, for example, it can be made of a conductor with a low work function to facilitate electron injection, such as metals or their alloys like magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead; and multilayer structure materials such as LiF / Al or LiO2 / Al, etc., but not limited thereto.

[0113] Hereinafter, the present invention will be described in detail by way of examples, as follows. However, the following examples are only illustrative of the present invention, and the present invention is not limited by the following examples.

[0114] Examples

[0115] [Preparation Example 1] Synthesis of 2'-(4-chloronaphthalen-1-yl)-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]

[0116]

[0117] To 15.0 g (38.2 mmol) of 2'-chloro-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene] and 9.5 g (45.9 mmol) of (4-chloronaphthalen-1-yl)boronic acid were added 200 mL of toluene (Tol.), 50 mL of EtOH, and 50 mL of H2O. After adding 2.3 g (2.0 mmol) of Pd(PPh3)4 and 10.6 g (76.4 mmol) of K2CO3, the mixture was heated under reflux at 100 °C for 3 hours. The temperature was cooled to room temperature, and the reaction was terminated by adding 300 mL of purified water to the reaction solution. The mixture was extracted with 1.0 L of E.A and then washed with distilled water. The obtained organic layer was dried over anhydrous MgSO4, then distilled under reduced pressure, and purified by silica gel column chromatography to obtain 12.3 g of the target compound (yield 62%).

[0118] [LCMS]: 519

[0119] [Preparation Example 2] Synthesis of 3'-(4-chloronaphthalen-1-yl)-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]

[0120]

[0121] As a reactant, 3'-chloro-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene] was used, and the same procedure as in the above [Preparation Example 1] was carried out, whereby 19.5 g (49%) of the target compound was obtained.

[0122] [LCMS]: 519

[0123] [Preparation Example 3] Synthesis of 4'-(4-chloronaphthalen-1-yl)-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]

[0124]

[0125] As a reactant, 4'-bromo-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene] was used, and the same procedure as in the above [Preparation Example 1] was carried out, whereby 20.4 g (69%) of the target compound was obtained.

[0126] [LCMS]: 519

[0127] [Preparation Example 4] Synthesis of 2'-(4-chloronaphthalen-1-yl)-10,10-diphenyl-10H-spiro[anthracene-9,9'-fluorene]

[0128]

[0129] As a reactant, 2'-chloro-10,10-diphenyl-10H-spiro[anthracene-9,9'-fluorene] was used, and the same procedure as in the above [Preparation Example 1] was carried out, whereby 18.6 g (55%) of the target compound was obtained.

[0130] [LCMS]: 643

[0131] [Preparation Example 5] Synthesis of 2'-(4-chloronaphthalen-1-yl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene]

[0132]

[0133] As a reactant, 2'-bromo-10-phenyl-10H-spiro[acridine-9,9'-fluorene] was used, and the same procedure as in the above [Preparation Example 1] was carried out, whereby 21.5 g (68%) of the target compound was obtained.

[0134] [LCMS]: 568

[0135] [Preparation Example 6] Synthesis of 3'-(4-chloronaphthalen-1-yl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene]

[0136]

[0137] As a reactant, 3'-bromo-10-phenyl-10H-spiro[acridine-9,9'-fluorene] was used, and the same procedure as in the above [Preparation Example 1] was carried out, whereby 18.0 g (61%) of the target compound was obtained.

[0138] [LCMS]: 568

[0139] [Preparation Example 7] Synthesis of 3'-(4-chloronaphthalen-1-yl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene]

[0140]

[0141] As a reactant, 4'-chloro-10-phenyl-10H-spiro[acridine-9,9'-fluorene] was used, and except for this, the same procedure as in the above [Preparation Example 1] was carried out to obtain 11.3 g (42%) of the target compound.

[0142] [LCMS]: 568

[0143] [Preparation Example 8] Synthesis of 2'-(6-chloronaphthalen-2-yl)-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]

[0144]

[0145] As a reactant, 4'-chloro-10-phenyl-10H-spiro[acridine-9,9'-fluorene] and (6-chloronaphthalen-2-yl)boronic acid were used, and except for this, the same procedure as in the above [Preparation Example 1] was carried out to obtain 15.5 g (39%) of the target compound.

[0146] [LCMS]: 519

[0147] [Preparation Example 9] Synthesis of 4'-(6-chloronaphthalen-2-yl)-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]

[0148]

[0149] As a reactant, 4'-bromo-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene] was used, and except for this, the same procedure as in the above [Preparation Example 8] was carried out to obtain 23.4 g (62%) of the target compound.

[0150] [LCMS]: 519

[0151] [Preparation Example 10] Synthesis of 3'-(6-chloronaphthalen-2-yl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene]

[0152]

[0153] As a reactant, 3'-bromo-10-phenyl-10H-spiro[acridine-9,9'-fluorene] was used, and except for this, the same procedure as in the above [Preparation Example 8] was carried out to obtain 28.0 g (75%) of the target compound.

[0154] [LCMS]: 568

[0155] [Preparation Example 11] Synthesis of 2'-(7-chlorophenanthren-2-yl)-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]

[0156]

[0157] As reactants, 2'-chloro-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene] and (7-chlorophenanthren-2-yl)boronic acid were used, and in other respects, the same procedure as in the above [Preparation Example 1] was carried out, whereby 13.3 g (44%) of the target compound was obtained.

[0158] [LCMS]: 569

[0159] [Preparation Example 12] Synthesis of 2'-(7-chlorophenanthren-2-yl)-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]

[0160]

[0161] As reactants, 4'-bromo-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene] was used, and in other respects, the same procedure as in the above [Preparation Example 11] was carried out, whereby 17.5 g (70%) of the target compound was obtained.

[0162] [LCMS]: 569

[0163] [Preparation Example 13] Synthesis of 4'-(7-chlorophenanthren-2-yl)-10,10-diphenyl-10H-spiro[anthracene-9,9'-fluorene]

[0164]

[0165] As reactants, 4'-bromo-10,10-diphenyl-10H-spiro[anthracene-9,9'-fluorene] was used, and in other respects, the same procedure as in the above [Preparation Example 11] was carried out, whereby 20.2 g (75%) of the target compound was obtained.

[0166] [LCMS]: 693

[0167] [Preparation Example 14] Synthesis of 2'-(7-chlorophenanthren-2-yl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene]

[0168]

[0169] As reactants, 2'-bromo-10-phenyl-10H-spiro[acridine-9,9'-fluorene] was used, and in other respects, the same procedure as in the above [Preparation Example 11] was carried out, whereby 14.4 g (68%) of the target compound was obtained.

[0170] [LCMS]: 618

[0171] [Preparation Example 15] Synthesis of 4-bromo-6-(10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]-2'-yl)dibenzo[b,d]furan [Preparation Example 16] Synthesis of 4-bromo-6-(10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]-4'-yl)dibenzo[b,d]furan

[0172]

[0173] As reactants, 2-(10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]-2'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane and 4,6-dibromodibenzo[b,d]furan were used, and the same procedure as in the above [Preparation Example 1] was carried out to obtain 10.5 g (59%) of the target compound.

[0174] [LCMS]: 603

[0175] [Preparation Example 17] Synthesis of 2-chloro-8-(10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]-2'-yl)dibenzo[b,d]furan [Preparation Example 18] Synthesis of 4'-(6-bromodibenzo[b,d]furan-4-yl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene]

[0176]

[0177] As reactants, 2-(10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]-4'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was used, and the same procedure as in the above [Preparation Example 15] was carried out to obtain 12.5 g (51%) of the target compound.

[0178] [LCMS]: 603

[0179] [Preparation Example 19] Synthesis of 4'-(8-chlorodibenzo[b,d]furan-2-yl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene] [Preparation Example 20] 4-bromo-6-(10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]-2'-yl)dibenzo[b,d]thiophene

[0180]

[0181] As reactants, 2-(10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]-2'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane and 2-bromo-8-chlorodibenzo[b,d]furan were used, and the same procedure as in the above [Preparation Example 1] was carried out to obtain 20.2 g (62%) of the target compound.

[0182] [LCMS]: 559

[0183] ​ ​

[0184]

[0185] As reactants, 10-phenyl-4'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-spiro[acridine-9,9'-fluorene] and 4,6-dibromodibenzo[b,d]furan were used, and the same procedure as in the above [Preparation Example 15] was carried out to obtain 9.7 g (38%) of the target compound.

[0186] [LCMS]: 652

[0187] ​ ​

[0188]

[0189] As reactants, 10-phenyl-4'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-spiro[acridine-9,9'-fluorene] and 2-bromo-8-chlorodibenz[b,d]furan were used. Except for this, the same procedure as in the above [Preparation Example 1] was carried out to obtain 14.4 g (68%) of the target compound.

[0190] [LCMS]: 608

[0191] ​ Synthesis of Phenanthrene

[0192]

[0193] As reactants, 2-(10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]-2'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborane and 4,6-dibromodibenz[b,d]thiophene were used. Except for this, the same procedure as in the above [Preparation Example 1] was carried out to obtain 8.5 g (42%) of the target compound.

[0194] [LCMS]: 619

[0195] [Preparation Example 21] 2-Chloro-8-(10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]-4'-yl)dibenzothiophene Synthesis of Phenanthrene

[0196]

[0197] As reactants, 2-(10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]-4'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborane and 2-bromo-8-chlorodibenz[b,d]thiophene were used. Except for this, the same procedure as in the above [Preparation Example 1] was carried out to obtain 19.0 g (66%) of the target compound.

[0198] [LCMS]: 575

[0199] [Preparation Example 22] 2'-(8-Chlorodibenzothiophen-2-yl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene] Synthesis

[0200]

[0201] As reactants, 10-phenyl-2'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-spiro[acridine-9,9'-fluorene] and 2-bromo-8-chlorodibenzothiophene were used, and otherwise, the same procedure as in the above [Preparation Example 1] was carried out to obtain 12.5 g (60%) of the target compound.

[0202] [LCMS]: 624

[0203] [Preparation Example 23] 3'-(7-Bromo-9,9-dimethyl-9H-fluoren-2-yl)-10,10-dimethyl-10H-spiro[anthracene-9, 9'-fluorene] Synthesis

[0204]

[0205] As reactants, 2-(10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]-3'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane and 2,7-dibromo-9,9-dimethyl-9H-fluorene were used, and otherwise, the same procedure as in the above [Preparation Example 1] was carried out to obtain 8.8 g (45%) of the target compound.

[0206] [LCMS]: 629

[0207] [Preparation Example 24] 2'-(7-Bromo-9,9-dimethyl-9H-fluoren-2-yl)-10,10-diphenyl-10H-spiro[anthracene-9, 9'-fluorene] Synthesis

[0208]

[0209] As reactants, 2-(10,10-diphenyl-10H-spiro[anthracene-9,9'-fluorene]-2'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane and 2,7-dibromo-9,9-dimethyl-9H-fluorene were used, and otherwise, the same procedure as in the above [Preparation Example 1] was carried out to obtain 4.1 g (39%) of the target compound.

[0210] [LCMS]: 753

[0211] [Preparation Example 25] 4'-(7-Bromo-9,9-dimethyl-9H-fluoren-2-yl)-10-phenyl-10H-spiro[acridine-9,9'- fluorene] Synthesis

[0212]

[0213] As reactants, 10-phenyl-4'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-spiro[acridine-9,9'-fluorene] and 2,7-dibromo-9,9-dimethyl-9H-fluorene were used, and otherwise, the same procedure as in the above [Preparation Example 1] was carried out to obtain 5.0 g (46%) of the target compound.

[0214] [LCMS]: 678

[0215] [Synthesis Example 1] Synthesis of Compound 1

[0216]

[0217] To 10.2 g (19.6 mmol) of Preparation Example 1 and 3.0 g (17.8 mmol) of diphenylamine, 100 mL of toluene was added. 0.82 g (0.9 mmol) of Pd2(dba)3, 0.86 g (1.8 mmol) of XPhos, and 2.6 g (26.7 mmol) of NaOt-Bu were added to the reaction solution, and the mixture was heated under reflux at 120 °C for 5 hours. The temperature was cooled to room temperature, and the reaction was terminated by adding 300 mL of purified water to the reaction solution. After extracting the mixture with 500 mL of EA, it was washed with distilled water. The obtained organic layer was dried over anhydrous MgSO4, then distilled under reduced pressure, and purified by silica gel column chromatography to obtain 8.5 g of the target compound (yield 73%).

[0218] [LCMS]: 651

[0219] [Synthesis Example 2] Synthesis of Compound 2

[0220]

[0221] Using 2'-(4-chloronaphthalen-1-yl)-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene] of Preparation Example 1 and N-phenyl-[1,1'-biphenyl]-4-amine, the same procedure as in [Synthesis Example 1] was carried out except for this, to obtain 10.5 g of the target compound (yield 80%).

[0222] [LCMS]: 727

[0223] [Synthesis Example 3] Synthesis of Compound 8

[0224]

[0225] Using 3'-(4-chloronaphthalen-1-yl)-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene] of Preparation Example 2 and bis([1,1'-biphenyl]-4-yl)amine, the same procedure as in [Synthesis Example 1] was carried out except for this, to obtain 7.7 g of the target compound (yield 52%).

[0226] [LCMS]: 804

[0227] [Synthesis Example 4] Synthesis of Compound 9

[0228]

[0229] Using 3'-(4-chloronaphthalen-1-yl)-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene] and N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-2-amine of Preparation Example 2, except for this, the same process as in [Synthesis Example 1] was carried out to obtain 7.7 g of the target compound (yield 52%).

[0230] [LCMS]: 804

[0231] [Synthesis Example 5] Synthesis of Compound 12

[0232]

[0233] Using 4'-(4-chloronaphthalen-1-yl)-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene] and N-phenyl-[1,1'-biphenyl]-4-amine of Preparation Example 3, except for this, the same process as in [Synthesis Example 1] was carried out to obtain 3.8 g of the target compound (yield 72%).

[0234] [LCMS]: 727

[0235] [Synthesis Example 6] Synthesis of Compound 15

[0236]

[0237] Using 4'-(4-chloronaphthalen-1-yl)-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene] and N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine of Preparation Example 3, except for this, the same process as in [Synthesis Example 1] was carried out to obtain 5.0 g of the target compound (yield 60%).

[0238] [LCMS]: 844

[0239] [Synthesis Example 7] Synthesis of Compound 16

[0240]

[0241] Using 2'-(4-chloronaphthalen-1-yl)-10,10-diphenyl-10H-spiro[anthracene-9,9'-fluorene] and diphenylamine of Preparation Example 4, except for this, the same process as in [Synthesis Example 1] was carried out to obtain 6.3 g of the target compound (yield 75%).

[0242] [LCMS]: 776

[0243] [Synthesis Example 8] Synthesis of Compound 22

[0244]

[0245] Using 2'-(4-chloronaphthalen-1-yl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene] of Preparation Example 5 and N-phenyl-[1,1'-biphenyl]-4-amine, except for this, the same process as in [Synthesis Example 1] was carried out to obtain 4.4 g of the target compound (yield 69%).

[0246] [LCMS]: 776

[0247] [Synthesis Example 9] Synthesis of Compound 24

[0248]

[0249] Using 2'-(4-chloronaphthalen-1-yl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene] of Preparation Example 5 and N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-2-amine, except for this, the same process as in [Synthesis Example 1] was carried out to obtain 8.4 g of the target compound (yield 59%).

[0250] [LCMS]: 853

[0251] [Synthesis Example 10] Synthesis of Compound 28

[0252]

[0253] Using 3'-(4-chloronaphthalen-1-yl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene] of Preparation Example 6 and bis([1,1'-biphenyl]-4-yl)amine, except for this, the same process as in [Synthesis Example 1] was carried out to obtain 5.2 g of the target compound (yield 69%).

[0254] [LCMS]: 853

[0255] [Synthesis Example 11] Synthesis of Compound 31

[0256]

[0257] Using 4'-(4-chloronaphthalen-1-yl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene] of Preparation Example 7 and diphenylamine, except for this, the same process as in [Synthesis Example 1] was carried out to obtain 3.3 g of the target compound (yield 59%).

[0258] [LCMS]: 700

[0259] [Synthesis Example 12] Synthesis of Compound 35

[0260]

[0261] Using 4'-(4-chloronaphthalen-1-yl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene] and N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluorene-2-amine of Preparation Example 7, and otherwise carrying out the same procedure as in [Synthesis Example 1], 5.1 g (yield 62%) of the target compound was obtained.

[0262] [LCMS]: 893

[0263] [Synthesis Example 13] Synthesis of Compound 37

[0264]

[0265] Using 2'-(6-chloronaphthalen-2-yl)-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene] and N-phenyl-[1,1'-biphenyl]-4-amine of Preparation Example 8, and otherwise carrying out the same procedure as in [Synthesis Example 1], 5.5 g (yield 70%) of the target compound was obtained.

[0266] [LCMS]: 727

[0267] [Synthesis Example 14] Synthesis of Compound 39

[0268]

[0269] Using 2'-(6-chloronaphthalen-2-yl)-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene] and N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-2-amine of Preparation Example 8, and otherwise carrying out the same procedure as in [Synthesis Example 1], 3.9 g (yield 65%) of the target compound was obtained.

[0270] [LCMS]: 804

[0271] [Synthesis Example 15] Synthesis of Compound 48

[0272]

[0273] Using 4'-(6-chloronaphthalen-2-yl)-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene] and bis([1,1'-biphenyl]-4-yl)amine of Preparation Example 9, and otherwise carrying out the same procedure as in [Synthesis Example 1], 5.1 g (yield 49%) of the target compound was obtained.

[0274] [LCMS]: 804

[0275] [Synthesis Example 16] Synthesis of Compound 50

[0276]

[0277] Using 4'-(6-chloronaphthalen-2-yl)-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene] and N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluorene-2-amine of Preparation Example 9, except for this, the same process as in [Synthesis Example 1] was carried out to obtain 3.3 g of the target compound (yield 65%).

[0278] [LCMS]: 844

[0279] [Synthesis Example 17] Synthesis of Compound 57

[0280]

[0281] Using 3'-(6-chloronaphthalen-2-yl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene] and N-phenyl-[1,1'-biphenyl]-4-amine of Preparation Example 10, except for this, the same process as in [Synthesis Example 1] was carried out to obtain 4.0 g of the target compound (yield 62%).

[0282] [LCMS]: 776

[0283] [Synthesis Example 18] Synthesis of Compound 58

[0284]

[0285] Using 3'-(6-chloronaphthalen-2-yl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene] and bis([1,1'-biphenyl]-4-yl)amine of Preparation Example 10, except for this, the same process as in [Synthesis Example 1] was carried out to obtain 2.9 g of the target compound (yield 66%).

[0286] [LCMS]: 853

[0287] [Synthesis Example 19] Synthesis of Compound 66

[0288]

[0289] Using 2'-(7-chlorophenanthren-2-yl)-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene] and diphenylamine of Preparation Example 11, except for this, the same process as in [Synthesis Example 1] was carried out to obtain 4.1 g of the target compound (yield 60%).

[0290] [LCMS]: 701

[0291] [Synthesis Example 20] Synthesis of Compound 70

[0292]

[0293] Using 2'-(7-chlorophenanthren-2-yl)-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene] and N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluorene-2-amine of Preparation Example 11, except for this, the same procedure as in [Synthesis Example 1] was carried out to obtain 5.3 g of the target compound (yield 65%).

[0294] [LCMS]: 894

[0295] [Synthesis Example 21] Synthesis of Compound 77

[0296]

[0297] Using 4'-(7-chlorophenanthren-2-yl)-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene] and N-phenyl-[1,1'-biphenyl]-4-amine of Preparation Example 12, except for this, the same procedure as in [Synthesis Example 1] was carried out to obtain 2.5 g of the target compound (yield 69%).

[0298] [LCMS]: 778

[0299] [Synthesis Example 22] Synthesis of Compound 79

[0300]

[0301] Using 4'-(7-chlorophenanthren-2-yl)-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene] and N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-2-amine of Preparation Example 12, except for this, the same procedure as in [Synthesis Example 1] was carried out to obtain 5.9 g of the target compound (yield 50%).

[0302] [LCMS]: 854

[0303] [Synthesis Example 23] Synthesis of Compound 86

[0304]

[0305] Using 4'-(7-chlorophenanthren-2-yl)-10,10-diphenyl-10H-spiro[anthracene-9,9'-fluorene] and diphenylamine of Preparation Example 13, except for this, the same procedure as in [Synthesis Example 1] was carried out to obtain 3.5 g of the target compound (yield 44%).

[0306] [LCMS]: 826

[0307] [Synthesis Example 24] Synthesis of Compound 88

[0308]

[0309] Using 4'-(7-chlorophenanthren-2-yl)-10,10-diphenyl-10H-spiro[anthracene-9,9'-fluorene] and bis([1,1'-biphenyl]-4-yl)amine of Preparation Example 13, and otherwise carrying out the same process as in [Synthesis Example 1], 4.1 g of the target compound was obtained (yield 39%).

[0310] [LCMS]: 978

[0311] [Synthesis Example 25] Synthesis of Compound 94

[0312]

[0313] Using 2'-(7-chlorophenanthren-2-yl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene] and N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-2-amine of Preparation Example 14, and otherwise carrying out the same process as in [Synthesis Example 1], 8.5 g of the target compound was obtained (yield 60%).

[0314] [LCMS]: 903

[0315] [Synthesis Example 26] Synthesis of Compound 102

[0316]

[0317] Using 4-bromo-6-(10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]-2'-yl)dibenzo[b,d]furan and N-phenyl-[1,1'-biphenyl]-4-amine of Preparation Example 15, and otherwise carrying out the same process as in [Synthesis Example 1], 6.6 g of the target compound was obtained (yield 49%).

[0318] [LCMS]: 767

[0319] [Synthesis Example 27] Synthesis of Compound 103

[0320]

[0321] Using 4-bromo-6-(10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]-2'-yl)dibenzo[b,d]furan and bis([1,1'-biphenyl]-4-yl)amine of Preparation Example 15, and otherwise carrying out the same process as in [Synthesis Example 1], 9.6 g of the target compound was obtained (yield 59%).

[0322] [LCMS]: 844

[0323] [Synthesis Example 28] Synthesis of Compound 109

[0324]

[0325] Using 4-bromo-6-(10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]-4'-yl)dibenz[b,d]furan of Preparation Example 16 and N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-2-amine, and otherwise carrying out the same process as in [Synthesis Example 1], 8.4 g (yield 59%) of the target compound was obtained.

[0326] [LCMS]: 844

[0327] [Synthesis Example 29] Synthesis of Compound 110

[0328]

[0329] Using 4-bromo-6-(10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]-4'-yl)dibenz[b,d]furan of Preparation Example 16 and N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluorene-2-amine, and otherwise carrying out the same process as in [Synthesis Example 1], 5.6 g (yield 68%) of the target compound was obtained.

[0330] [LCMS]: 884

[0331] [Synthesis Example 30] Synthesis of Compound 113

[0332]

[0333] Using 2-chloro-8-(10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]-2'-yl)dibenz[b,d]furan of Preparation Example 17 and bis([1,1'-biphenyl]-4-yl)amine, and otherwise carrying out the same process as in [Synthesis Example 1], 4.0 g (yield 69%) of the target compound was obtained.

[0334] [LCMS]: 884

[0335] [Synthesis Example 31] Synthesis of Compound 126

[0336]

[0337] Using 4'-(6-bromodibenz[b,d]furan-4-yl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene] of Preparation Example 18 and diphenylamine, and otherwise carrying out the same process as in [Synthesis Example 1], 5.1 g (yield 60%) of the target compound was obtained.

[0338] [LCMS]: 740

[0339] [Synthesis Example 32] Synthesis of Compound 129

[0340]

[0341] Using 4'-(6-bromodibenzo[b,d]furan-4-yl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene] and N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-2-amine of Preparation Example 18, and otherwise carrying out the same procedure as in [Synthesis Example 1], 3.0 g of the target compound was obtained (yield 72%).

[0342] [LCMS]: 893

[0343] [Synthesis Example 33] Synthesis of Compound 138

[0344]

[0345] Using 4'-(8-chlorodibenzo[b,d]furan-2-yl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene] and bis([1,1'-biphenyl]-4-yl)amine of Preparation Example 19, and otherwise carrying out the same procedure as in [Synthesis Example 1], 5.9 g of the target compound was obtained (yield 60%).

[0346] [LCMS]: 893

[0347] [Synthesis Example 34] Synthesis of Compound 142

[0348]

[0349] Using 4-bromo-6-(10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]-2'-yl)dibenzo[b,d]thiophene and N-phenyl-[1,1'-biphenyl]-4-amine of Preparation Example 20, and otherwise carrying out the same procedure as in [Synthesis Example 1], 4.5 g of the target compound was obtained (yield 63%).

[0350] [LCMS]: 784

[0351] [Synthesis Example 35] Synthesis of Compound 145

[0352]

[0353] Using 4-bromo-6-(10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]-2'-yl)dibenzo[b,d]thiophene and N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluorene-2-amine of Preparation Example 20, and carrying out the same procedure as in [Synthesis Example 1], 2.8 g of the target compound was obtained (yield 70%).

[0354] [LCMS]: 900

[0355] [Synthesis Example 36] Synthesis of Compound 156

[0356]

[0357] Using 2-chloro-8-(10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]-4'-yl)dibenzothiophene and diphenylamine of Preparation Example 21, and otherwise carrying out the same process as in [Synthesis Example 1], 3.5 g of the target compound was obtained (yield 62%).

[0358] [LCMS]: 707

[0359] [Synthesis Example 37] Synthesis of Compound 157

[0360]

[0361] Using 2-chloro-8-(10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene]-4'-yl)dibenzothiophene and N-phenyl-[1,1'-biphenyl]-4-amine of Preparation Example 21, and otherwise carrying out the same process as in [Synthesis Example 1], 3.0 g of the target compound was obtained (yield 72%).

[0362] [LCMS]: 784

[0363] [Synthesis Example 38] Synthesis of Compound 171

[0364]

[0365] Using 2'-(8-chlorodibenzothiophen-2-yl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene] of Preparation Example 22 and diphenylamine, and otherwise carrying out the same process as in [Synthesis Example 1], 6.4 g of the target compound was obtained (yield 62%).

[0366] [LCMS]: 756

[0367] [Synthesis Example 39] Synthesis of Compound 174

[0368]

[0369] Using 2'-(8-chlorodibenzothiophen-2-yl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene] of Preparation Example 22 and N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-2-amine, and otherwise carrying out the same process as in [Synthesis Example 1], 5.7 g of the target compound was obtained (yield 75%).

[0370] [LCMS]: 909

[0371] [Synthesis Example 40] Synthesis of Compound 187

[0372]

[0373] Using 3'-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene] and N-phenyl-[1,1'-biphenyl]-4-amine of Preparation Example 23, and carrying out the same process as in [Synthesis Example 1] except for this, 8.9 g of the target compound was obtained (yield 71%).

[0374] [LCMS]: 794

[0375] [Synthesis Example 41] Synthesis of Compound 198

[0376]

[0377] Using 2'-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-10,10-diphenyl-10H-spiro[anthracene-9,9'-fluorene] and bis([1,1'-biphenyl]-4-yl)amine of Preparation Example 24, and carrying out the same process as in [Synthesis Example 1] except for this, 5.8 g of the target compound was obtained (yield 66%).

[0378] [LCMS]: 994

[0379] [Synthesis Example 42] Synthesis of Compound 199

[0380]

[0381] Using 2'-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-10,10-diphenyl-10H-spiro[anthracene-9,9'-fluorene] and N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-2-amine of Preparation Example 24, and carrying out the same process as in [Synthesis Example 1] except for this, 7.3 g of the target compound was obtained (yield 68%).

[0382] [LCMS]: 994

[0383] [Synthesis Example 43] Synthesis of Compound 212

[0384]

[0385] Using 4'-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene] and N-phenyl-[1,1'-biphenyl]-4-amine of Preparation Example 25, and otherwise conducting the same process as in [Synthesis Example 1], 7.7 g (yield 62%) of the target compound was obtained.

[0386] [LCMS]: 843

[0387] [Examples 1 to 43] Fabrication of Organic Electroluminescent Devices

[0388] After subjecting Compounds 1, 2, 8, 9, 12, 15, 16, 22, 24, 28, 31, 35, 37, 39, 48, 50, 57, 58, 66, 70, 77, 79, 86, 88, 94, 102, 103, 109, 110, 113, 126, 129, 138, 142, 145, 156, 157, 171, 174, 187, 198, 199, 212 synthesized in the synthesis examples to high-purity sublimation purification by a generally known method, green organic electroluminescent devices were fabricated according to the following process.

[0389] First, a glass substrate coated with indium tin oxide (ITO) with a thickness film was ultrasonically washed with distilled water. After the distilled water washing was completed, it was ultrasonically washed with solvents such as isopropyl alcohol, acetone, and methanol and dried, and then transferred to an ultraviolet ozone (UV OZONE) cleaner (Power sonic 405, HwashinTech). After UV cleaning for 5 minutes, the coated glass substrate was transferred to a vacuum evaporation apparatus.

[0390] On the ITO transparent glass substrate (electrode) prepared in this way, m-MTDATA (60 nm) / 1, 2, 8, 9, 12, 15, 16, 22, 24, 28, 31, 35, 37, 39, 48, 50, 57, 58, 66, 70, 77, 79, 86, 88, 94, 102, 103, 109, 110, 113, 126, 129, 138, 142, 145, 156, 157, 171, 174, 187, 198, 199, 212 (80 nm) / DS-H522 + 5% DS-501 (300 nm) / BCP (10 nm) / Alq3 (30 nm) / LiF (1 nm) / Al (200 nm) were laminated in sequence to fabricate organic EL devices.

[0391] DS-H522 and DS-501 used in device fabrication are products of Doosan Electronics BG Co., Ltd. The structures of m-MTDATA, TCTA, CBP, Ir(ppy)3, and BCP are as follows.

[0392]

[0393] [Comparative Example 1] Fabrication of Organic Electroluminescent Device

[0394] As the hole transport layer material, NPB was used instead of Compound 1 used as the hole transport layer material when forming the hole transport layer in Example 1. Otherwise, the organic EL device was fabricated in the same manner as in Example 1 above. The structure of the NPB used is as follows.

[0395]

[0396] [Evaluation Example 1]

[0397] For each of the green organic electroluminescent devices fabricated in Examples 1 to 43 and Comparative Example 1, the driving voltage, current efficiency, and emission peak were measured at a current density of 10 mA / cm 2 The results are shown in Table 1 below.

[0398] [Table 1]

[0399] Sample Hole Transport Layer Driving Voltage (V) Current Efficiency (cd / A) Example 1 Compound 1 3.9 24.9 Example 2 Compound 2 4.1 25.1 Example 3 Compound 8 4.1 23.9 Example 4 Compound 9 4.2 25.2 Example 5 Compound 12 4.4 22.9 Example 6 Compound 15 3.9 24.5 Example 7 Compound 16 3.8 24.8 Example 8 Compound 22 4.1 23.5 Example 9 Compound 24 4.2 23.7 Example 10 Compound 28 3.9 22.9 Example 11 Compound 31 4.1 24.0 Example 12 Compound 35 3.7 22.8 Example 13 Compound 37 3.9 22.4 Example 14 Compound 39 4.3 25.1 Example 15 Compound 48 4.4 24.7 Example 16 Compound 50 4.1 24.1 Example 17 Compound 57 4.1 24.8 Example 18 Compound 58 3.9 20.3 Example 19 Compound 66 4.3 19.4 Example 20 Compound 70 4.6 21.5 Example 21 Compound 77 4.1 24.9 Example 22 Compound 79 4.0 25.0 Example 23 Compound 86 4.2 25.0 Example 24 Compound 88 4.1 24.0 Example 25 Compound 94 3.9 22.2 Example 26 Compound 102 4.1 22.5 Example 27 Compound 103 4.2 25.4 Example 28 Compound 109 4.1 24.8 Example 29 Compound 110 4.5 21.0 Example 30 Compound 113 4.4 24.3 Example 31 Compound 126 3.8 24.1 Example 32 Compound 129 4.5 21.2 Example 33 Compound 138 3.7 24.5 Example 34 Compound 142 4.4 23.5 Example 35 Compound 145 4.1 23.0 Example 36 Compound 156 4.2 24.5 Example 37 Compound 157 4.1 24.8 Example 38 Compound 171 3.8 24.5 Example 39 Compound 174 3.9 25.2 Example 40 Compound 187 4.4 23.1 Example 41 Compound 198 4.5 21.3 Example 42 Compound 199 4.8 24.9 Example 43 Compound 212 4.2 24.7 Comparative Example 1 NPB 5.2 18.2

[0400] As shown in Table 1 above, it can be seen that for the organic electroluminescent devices (organic electroluminescent devices fabricated in Examples 1 to 43 respectively) using the compound of the present invention in the hole transport layer, the current efficiency and driving voltage show excellent performance compared to the conventional case of using NBP (Comparative Example 1).

Claims

1. A compound, which is a compound selected from the group consisting of the following compounds:

2. An organic electroluminescent device, comprising (i) an anode, (ii) a cathode, and (iii) one or more organic layers interposed between the anode and the cathode, wherein at least one of the one or more organic layers contains the compound according to claim 1.

3. The organic electroluminescent element according to claim 2, wherein, The organic layer is one or more layers selected from a hole injection layer, a hole transport layer, a hole transport assisting layer, an electron injection layer, an electron transport layer, an electron transport assisting layer, and a light emitting layer.

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