KR20200004253A - A plurality of host materials and organic electroluminescent device comprising the same - Google Patents

Abstract

An application of the present invention relates to multiple types of host materials and an organic electroluminescent element including the same which comprise a first host material comprising a compound represented by chemical formula 1 and a second host material comprising a compound represented by chemical formula 1 wherein the first host compound and the second host compound are different. By comprising the multiple types of host materials comprising a specific combination of compounds, the organic electroluminescent element having good thermal stability, low driving voltage, high light emitting efficiency and/or improved lifespan characteristic can be manufactured.

Description

A plurality of host materials and an organic electroluminescent device comprising the same {A PLURALITY OF HOST MATERIALS AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME}

The present application relates to a plurality of host materials and organic electroluminescent devices comprising the same.

Since Eastman Kodak's Tang et al. Developed the first TPD / Alq3 double-layer low molecular green organic electroluminescent device (OLED) consisting of a light emitting layer and a charge transfer layer in 1987, research on organic electroluminescent devices is rapidly and rapidly commercialized. Reached. Currently, organic electroluminescent devices mainly use phosphorescent materials having excellent luminous efficiency in panel implementation. There is a need for OLEDs having high luminous efficiency and / or long life for long time use and high resolution of displays.

Various materials or concepts have been proposed in the organic layer of the organic electroluminescent device in order to improve luminous efficiency, driving voltage and / or lifetime, but they are not satisfactory for practical use.

Korean Patent Publication No. 2015-0121337 discloses a compound in which azulene, carbazole and the like are fused, but does not specifically disclose that the compound is used as a plurality of host compounds, and still does not provide a host material for improving the performance of OLED devices. Development is required.

Korean Patent Publication No. 2015-0121337 (published Oct. 29, 2015)

It is an object of the present invention to provide an organic electroluminescent device having good thermal stability, low drive voltage, high luminous efficiency and / or improved lifetime characteristics by including a plurality of types of host materials comprising specific combinations of compounds.

The light emitting layer including the phosphorescent dopant is excellent in the hole and electron current characteristics of the light emitting layer material for low voltage, high efficiency and long life, and excellent thermal stability of the material to improve the life. In addition, by using a light emitting material having a narrow energy band gap for efficient energy transfer from the host of the light emitting layer to the dopant, the charge trap can be minimized to contribute to the driving voltage and the light emitting efficiency. The azulene derivative included in the device of the present invention originally had a slow internal conversion transition constant of S ₂ → S ₁ as 7 * 10 ⁻⁸ s, while the internal conversion transition constant of S ₁ → S ₀ was 7 * 10. ^As fast as ^-12 s, the fluorescence quantum yield of S ₂ → S ₀ increases, which is one of the representative materials that violates Kasha's rule. Non Patent Literature [Phys. Chem. Chem. Phys. 2015, 17, 23573, J. Phys. Chem. A, Vol. 103, No. 15, 1999 2529], Azulene's S ₂ and S ₁ levels are 3.565 eV and 1.771 eV, respectively, whereas the T ₁ → S ₀ transition is 1.711 eV, which shows a very small level difference between T ₁ and S ₀ . In addition, it has been reported that the intersystem crossing transition from S ₂ to T _n may be improved according to the polarity of the substitution material and the solvent, and the transition to triplet may be increased, thereby improving the phosphorescence properties. These azulene derivatives have a small S ₁ → T ₁ energy gap and may have a narrow energy band gap because of relatively high HOMO characteristics compared to carbazole or benzocarbazole compounds. The present inventors have found that by using the azulene derivative of the present application as a light emitting layer material by mixing the light emitting layer as the first and second hosts as appropriate, it can exhibit the characteristics of low driving voltage, high efficiency and / or long life. Specifically, a plurality of host materials including at least one first host compound and at least one second host compound, wherein the first host compound and the second host compound are represented by the following Formula 1, and the first host The present invention has been completed by discovering that the host material achieves the above-mentioned object, wherein the compound and the second host compound are different.

[Formula 1]

In Chemical Formula 1,

, O 또는 S이고;M is

, O or S;

X ₁ to X ₁₂ are each independently N or CR ₁ ;

La is a single bond, substituted or unsubstituted (C1-C30) alkylene, substituted or unsubstituted (C6-C30) arylene, substituted or unsubstituted (3- to 30-membered) heteroarylene, or substituted or unsubstituted Ring (C3-C30) cycloalkylene;

Ar and R ₁ are each independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3-30 Heteroaryl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted tri (C1-C30) alkylsilyl, substituted or unsubstituted di (C1-C30) alkyl (C6-C30) arylsilyl, substituted or unsubstituted (C1-C30) alkyldi (C6-C30) arylsilyl, substituted or unsubstituted tri (C6-C30) arylsilyl, substituted or Unsubstituted mono- or di- (C1-C30) alkylamino, substituted or unsubstituted mono- or di- (C6-C30) arylamino, or substituted or unsubstituted (C1-C30) alkyl (C6-C30) Arylamino; Adjacent Ar are connected to each other to form a ring, or may form a ring are connected to each other, the adjacent R _1, if R ₁ is plural, each of R ₁ are the same or may be different from one another, and;

a is an integer of 1 or 2, and when a is 2, each Ar may be the same or different.

By including a plurality of host materials according to the present application, an organic electroluminescent device having good thermal stability, low driving voltage, high luminous efficiency and / or improved lifespan characteristics is provided, and manufacturing of a display device or a lighting device using the same It is possible.

The present application is described in more detail below, but for the purpose of description and should not be construed to limit the scope of the present application.

As used herein, "organic electroluminescent material" means a material that can be used in an organic electroluminescent device, and may include one or more compounds, and may be included in any layer constituting the organic electroluminescent device as needed. For example, the organic electroluminescent material may be a hole injection material, a hole transport material, a hole auxiliary material, a light emission auxiliary material, an electron blocking material, a light emitting material (including a host material and a dopant material), an electron buffer material, a hole blocking material, Electron transport material, electron injection material, and the like.

As used herein, "plural kinds of organic electroluminescent materials" means organic electroluminescent materials in which two or more compounds that can be included in any layer constituting the organic electroluminescent device are combined, and before being included in the organic electroluminescent device ( For example, it can mean both before and after the deposition (eg, after deposition). For example, the plurality of organic electroluminescent materials may include one of a hole injection layer, a hole transport layer, a hole auxiliary layer, a light emitting auxiliary layer, an electron blocking layer, a light emitting layer, an electron buffer layer, a hole blocking layer, an electron transport layer, and an electron injection layer. The compound which may be included in the above layer may be a combination of two or more kinds. These two or more compounds may be included in the same layer or in different layers and may be mixed or co-deposited or deposited separately.

As used herein, "plural species of host material" means a host material comprising a combination of two or more compounds that may be included in any light emitting layer constituting the organic electroluminescent device, and is not included in the organic electroluminescent device (e.g., For example, before and after the deposition (eg, after deposition), the material may mean both. In one example, the plurality of host materials of the present application is a combination of two or more host materials, optionally, may further include a conventional material included in the organic electroluminescent material. The plurality of host materials of the present application may be included in any light emitting layer constituting the organic electroluminescent device, and two or more compounds included in the plurality of host materials may be included together in one light emitting layer, and may be included in different light emitting layers, respectively. May be included. When two or more host materials are included in one layer, for example, they may be mixed-deposited to form a layer, or they may be separately co-deposited simultaneously to form a layer.

Hereinafter, the compound represented by Chemical Formula 1 will be described in more detail.

As used herein, "(C1-C30) alkyl (ene)" means a straight or branched chain alkyl (ene) having 1 to 30 carbon atoms constituting the chain, wherein the carbon number is preferably 1 to 20, more preferably Preferably it is 1-10. Specific examples of the alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. As used herein, "(C2-C30) alkenyl" means a straight or branched chain alkenyl having 2 to 30 carbon atoms constituting the chain, wherein the carbon number is preferably 2 to 20, more preferably 2 to 10. Specific examples of the alkenyl include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl and the like. As used herein, "(C2-C30) alkynyl" means a straight or branched chain alkynyl having 2 to 30 carbon atoms constituting the chain, wherein the carbon number is preferably 2 to 20, more preferably 2 to 10. Examples of the alkynyl include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl and the like. As used herein, "(C3-C30) cycloalkyl (ene)" means a monocyclic or polycyclic hydrocarbon having 3 to 30 ring skeleton carbon atoms, and the carbon number is preferably 3 to 20, more preferably 3 to 7 Dog. Examples of the cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. As used herein, "(3-7 membered) heterocycloalkyl" has 3 to 7, preferably 5 to 7 ring skeleton atoms, and is a group consisting of B, N, O, S, Si and P, preferably O , Cycloalkyl comprising at least one heteroatom selected from the group consisting of S and N, and examples thereof include tetrahydrofuran, pyrrolidine, thiolane, tetrahydropyran and the like. As used herein, "(C6-C30) aryl (ene)" means a monocyclic or fused ring radical derived from an aromatic hydrocarbon having 6 to 30 ring backbone carbon atoms, and may be partially saturated. The ring skeleton carbon number is preferably 6 to 25, more preferably 6 to 18. The aryl includes those having a spiro structure. Examples of the aryl include phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, phenylterphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzoflu Orenyl, phenanthrenyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetrasenyl, peryllenyl, chrysenyl, naphthacenyl, fluoranthenyl, spirobifluorenyl and the like. . More specifically, a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, benzanthryl group, 1-phenanthryl group, 2-phenanthryl Group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, naphthacenyl group, pyrenyl group, 1-crisenyl group, 2-crissenyl group, 3-crissenyl group, 4-crissenyl group , 5-crisenyl group, 6-crisenyl group, benzo [c] phenanthryl group, benzo [g] chrysenyl group, 1-triphenylenyl group, 2-triphenylenyl group, 3-triphenylenyl group, 4-triphenylenyl group, 1-fluorenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 9-fluorenyl group, benzofluorenyl group, dibenzofluorenyl group, 2- Biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, o-terphenyl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, p- Terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-quaterphenyl group, 3-fluoranthenyl group, 4-fluoranthenyl group, 8-fluoranthenyl group , 9- Laurantenyl group, benzofluoranthenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 3,4-xylyl group, 2,5-xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, pt-butylphenyl group, p- (2-phenylpropyl) phenyl group, 4'-methylbiphenylyl group, 4 "-t-butyl-p-terphenyl- 4-yl group, 9,9-dimethyl-1-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, 9,9-dimethyl-3-fluorenyl group, 9,9-dimethyl-4-fluore Neyl group, 9,9-diphenyl-1-fluorenyl group, 9,9-diphenyl-2-fluorenyl group, 9,9-diphenyl-3-fluorenyl group, 9,9-diphenyl-4- Fluorenyl group is mentioned.

As used herein, "(3- to 30-membered) heteroaryl (ene)" is an aryl group having 3 to 30 ring skeleton atoms and containing at least one heteroatom selected from the group consisting of B, N, O, S, Si and P. it means. The number of heteroatoms is preferably 1 to 4, and may be a single ring system or a fused ring system condensed with one or more benzene rings, and may be partially saturated. In addition, the heteroaryl (ene) herein also includes a form in which one or more heteroaryl or an aryl group is connected to a heteroaryl group by a single bond, and includes a spiro structure. Examples of the heteroaryl include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxdiazolyl, triazinyl, tetrazinyl Monocyclic heteroaryl such as triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, di Benzothiophenyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzooxazolyl, isoindolinyl, indolyl, benzoindolyl, indazolyl, benzothiadiazolyl, quinolyl, iso Quinolyl, cinnolinyl, quinazolinyl, benzoquinazolinyl, quinoxalinyl, benzoquinoxalinyl, naphthyridinyl, carbazolyl, benzocarbazolyl, dibenzocarbazolyl, phenoxazylyl, phenothiazineyl, Such as phenanthridinyl, benzodioxolyl, dihydroacridinyl It must include heteroaryl ring systems. More specifically, 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl group, 2-pyridinyl group, 2-pyrimidinyl group, 4-pyrimidinyl group, 5-pyrimidinyl group, 6- Pyrimidinyl, 1,2,3-triazin-4-yl, 1,2,4-triazin-3-yl, 1,3,5-triazin-2-yl, 1-imidazolyl, 2-imidazolyl group, 1-pyrazolyl group, 1-indolidinyl group, 2-indolidinyl group, 3-indolidinyl group, 5-indolidinyl group, 6-indolidinyl group, 7-indolidinyl group, 8 -Indolidinyl group, 2-imidazopyridinyl group, 3-imidazopyridinyl group, 5-imidazopyridinyl group, 6-imidazopyridinyl group, 7-imidazopyridinyl group, 8-imidazopi Ridinyl group, 3-pyridinyl group, 4-pyridinyl group, 1-indolyl group, 2-indolyl group, 3-indolyl group, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindolyl group, 2-isoindolyl group, 3-isoindolyl group, 4-isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2 -Fu Group, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group, 7-benzofuranyl group, 1-isobenzofuranyl group, 3-isobenzofuranyl group, 4-isobenzofuranyl group, 5-isobenzofuranyl group, 6-isobenzofuranyl group, 7-isobenzofuranyl group, 2-quinolyl group, 3-quinolyl group, 4-qui Tealyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5- Isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxalinyl group, 5-quinoxalinyl group, 6-quinoxalinyl group, 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-carbazolyl group, azacarbazolyl-1-yl group, azacarbazolyl-2-yl group, azacarbazolyl-3-yl group, azakaba Azocarbazolyl-9-, Azocarbazolyl-5-, Azacarbazolyl-6-, Azacarbazolyl-7-, Azacarbazolyl-8-, Group, 1-phenantridinyl group, 2-phenantridinyl group, 3-phenantridinyl group, 4-phenantridinyl group, 6-phenantridinyl group, 7-phenantridinyl group, 8-phenantridinyl group , 9-phenantridinyl group, 10-phenantridinyl group, 1-acridinyl group, 2-acridinyl group, 3-acridinyl group, 4-acridinyl group, 9-acridinyl group, 2-oxazolyl group , 4-oxazolyl group, 5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group, 3-thienyl group, 2-methylpyrrole-1- Diary, 2-methylpyrrole-3-yl group, 2-methylpyrrole-4-yl group, 2-methylpyrrole-5-yl group, 3-methylpyrrole-1-yl group, 3-methylpyrrole-2-yl group, 3-methyl Pyrrole-4-yl group, 3-methylpyrrole-5-yl group, 2-t-butylpyrrole-4-yl group, 3- (2-phenylpropyl) pyrrole-1-yl group, 2-methyl-1-indolyl group, 4 -Methyl-1-indolyl group, 2-methyl-3-indolyl group, 4-methyl-3-indolyl group, 2-t-butyl-1-indolyl group, 4-t-butyl-1-indolyl group, 2- t-butyl-3-indolyl group, 4-t-butyl-3-indolyl group, 1-dibenzofuranyl group, 2 -Dibenzofuranyl group, 3-dibenzofuranyl group, 4-dibenzofuranyl group, 1-dibenzothiophenyl group, 2-dibenzothiophenyl group, 3-dibenzothiophenyl group, 4-dibenzothiophenyl group, 1- Silafluorenyl, 2-silafluorenyl, 3-silafluorenyl, 4-silafluorenyl, 1-germafluorenyl, 2-germafluorenyl, 3-germafluorenyl, 4-germafluorenyl group is mentioned. "Halogen" herein includes F, Cl, Br and I atoms.

In addition, in the description of "substituted or unsubstituted" as described herein, "substituted" means that a hydrogen atom is replaced by another atom or another functional group (ie a substituent) in a certain functional group. Substituted (C1-C30) alkyl (lene), substituted (C6-C30) aryl (ene), substituted (3- to 30-membered) heteroaryl (ene), substituted (C3-C30) in the formulas herein Cycloalkyl (ene), substituted (C1-C30) alkoxy, substituted tri (C1-C30) alkylsilyl, substituted di (C1-C30) alkyl (C6-C30) arylsilyl, substituted (C1-C30) Alkyldi (C6-C30) arylsilyl, substituted tri (C6-C30) arylsilyl, substituted mono- or di- (C1-C30) alkylamino, substituted mono- or di- (C6-C30) arylamino And the substituents of substituted (C1-C30) alkyl (C6-C30) arylamino are each independently deuterium, halogen, cyano, carboxyl, nitro, hydroxy, (C1-C30) alkyl, halo (C1-C30) ) Alkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C1-C30) alkoxy, (C1-C30) alkylthio, (C3-C30) cycloalkyl, (C3-C30) cycloalkenyl (3-30 membered) heteroaryl unsubstituted or substituted with (3-7 membered) heterocycloalkyl, (C6-C30) aryloxy, (C6-C30) arylthio, (C6-C30) aryl, and (3 Heteroaryloxy Or unsubstituted (C6-C30) aryl, tri (C1-C30) alkylsilyl, tri (C6-C30) arylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, (C1-C30) alkyl Mono (or di- (C6-C30) arylamino, unsubstituted or substituted with di (C6-C30) arylsilyl, amino, mono- or di- (C1-C30) alkylamino, (C1-C30) alkyl, ( C1-C30) alkyl (C6-C30) arylamino, (C1-C30) alkylcarbonyl, (C1-C30) alkoxycarbonyl, (C6-C30) arylcarbonyl, di (C6-C30) arylboroyl , Di (C1-C30) alkylboronyl, (C1-C30) alkyl (C6-C30) arylboronyl, (C6-C30) ar (C1-C30) alkyl, and (C1-C30) alkyl (C6 -C30) aryl may be one or more selected from the group consisting of (C1-C20) alkyl, unsubstituted (C6-C25) aryl, and (C6-C25) aryl substituted or unsubstituted (5 -25 membered) at least one selected from the group consisting of heteroaryl, and more preferably (5- substituted with (C1-C10) alkyl, unsubstituted (C6-C18) aryl, and (C6-C18) aryl Heteroaryl At least one selected from the group consisting of, for example, may be at least one selected from the group consisting of methyl, phenyl, diphenyltriazinyl and phenylquinoxalinyl.

In the general formula of the present application, when connected to an adjacent substituent to form a ring or when two adjacent substituents are connected to each other to form a ring, the ring is substituted or unsubstituted (3- to 30-membered) monocyclic or polycyclic alicyclic ring, Aromatic or combinations thereof. In addition, the ring formed may comprise one or more heteroatoms selected from nitrogen, oxygen and sulfur. For example, the fused ring may be substituted or unsubstituted dibenzothiophene ring, substituted or unsubstituted dibenzofuran ring, substituted or unsubstituted naphthalene ring, substituted or unsubstituted phenanthrene ring, substituted or acyclic Fluorene ring, substituted or unsubstituted benzothiophene ring, substituted or unsubstituted benzofuran ring, substituted or unsubstituted indole ring, substituted or unsubstituted indene ring, substituted or unsubstituted benzene ring or substituted or It may be in the form of an unsubstituted carbazole ring.

In the formulas herein, heteroaryl or heteroarylene may each independently comprise one or more heteroatoms selected from B, N, O, S, Si and P. Further, the heteroatom may be hydrogen, deuterium, halogen, cyano, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (5- to 30-membered) Heteroaryl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted tri (C1-C30) alkylsilyl, substituted or unsubstituted di (C1) -C30) alkyl (C6-C30) arylsilyl, substituted or unsubstituted (C1-C30) alkyldi (C6-C30) arylsilyl, substituted or unsubstituted tri (C6-C30) arylsilyl, substituted or unsubstituted Mono- or di- (C1-C30) alkylamino, substituted or unsubstituted mono- or di- (C6-C30) arylamino, and substituted or unsubstituted (C1-C30) alkyl (C6-C30) aryl One or more selected from the group consisting of amino may be bonded.

, O 또는 S이다.In Formula 1, M is

, O or S.

In Formula 1, X ₁ to X ₁₂ are each independently N or CR ₁ . According to an aspect of the present disclosure, X ₁ to X ₁₂ may all be CR ₁ , and according to another aspect of the present disclosure, any one of X ₁ to X ₁₂ may be N, and according to another aspect of the present disclosure , X ₂ to X ₁₂ may be N.

In Formula 1, La is a single bond, substituted or unsubstituted (C1-C30) alkylene, substituted or unsubstituted (C6-C30) arylene, substituted or unsubstituted (3- to 30-membered) heteroarylene Or substituted or unsubstituted (C3-C30) cycloalkylene, preferably a single bond, substituted or unsubstituted (C6-C25) arylene, or substituted or unsubstituted (5- to 25-membered) heteroaryl Ren, more preferably a single bond, unsubstituted (C6-C18) arylene, or unsubstituted (5- to 18-membered) heteroarylene. The heteroarylene may include one or more of nitrogen, oxygen and sulfur, and preferably may include one or more of nitrogen and sulfur. According to an aspect of the present application, La is a single bond, phenylene, naphthylene, biphenylene, pyridylene, pyrimidinylene, triazinylene, isoquinolinylene, quinazolinylene, naphthyridinylene, quinoxalinylene, Benzoquinoxalinylene, indoloquinoxalinylene, benzothienopyrimidinylene, or benzoquinazolinylene.

In Formula 1, Ar and R ₁ are each independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted Substituted (3-30 membered) heteroaryl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted tri (C1-C30) alkylsilyl, substituted Or unsubstituted di (C1-C30) alkyl (C6-C30) arylsilyl, substituted or unsubstituted (C1-C30) alkyldi (C6-C30) arylsilyl, substituted or unsubstituted tri (C6-C30) Arylsilyl, substituted or unsubstituted mono- or di- (C1-C30) alkylamino, substituted or unsubstituted mono- or di- (C6-C30) arylamino, or substituted or unsubstituted (C1-C30) Alkyl (C6-C30) arylamino; Adjacent Ar may be connected to each other to form a ring, or adjacent R ₁ may be connected to each other to form a ring. When R ₁ is plural, each R ₁ may be the same or different from each other.

Ar may preferably be substituted or unsubstituted (C6-C25) aryl, substituted or unsubstituted (5- to 25-membered) heteroaryl, or substituted or unsubstituted di (C6-C25) arylamino, More preferably, (5- to 25-membered) heteroaryl unsubstituted or substituted with (C6-C18) aryl, (C1-C10) alkyl and / or (C6-C12) aryl, or (C1-C6) Di (C6-C25) arylamino unsubstituted or substituted with alkyl. According to an aspect of the present application, Ar is substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted fluorenyl, substituted Or unsubstituted fluoranthenyl, substituted or unsubstituted triazinyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted benzothienopyrimidinyl, substituted or unsubstituted Acenaphtopyrimidinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted benzoquinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted benzoquinoxalinyl, substituted or unsubstituted di Benzoquinoxalinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted benzoquinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted benzoisoquinolyl, substituted or unsubstituted benzothienoquinolyl , Chi Or unsubstituted benzofuroquinolyl, substituted or unsubstituted triazolyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted benzo Thiophenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzothiazolinyl, substituted or unsubstituted phenanthromimida Zolyl, substituted or unsubstituted diphenylamino, substituted or unsubstituted phenylbiphenylamino, substituted or unsubstituted fluorenylphenylamino, substituted or unsubstituted dibenzothiophenylphenylamino, or substituted or unsubstituted Dibenzofuranylphenylamino. According to another aspect of the present application, Ar is phenyl unsubstituted or substituted with one or more of deuterium and naphthyl; Unsubstituted naphthyl; Unsubstituted biphenyl; Fluorenyl substituted with one or more methyl; Unsubstituted fluoranthenyl; Triazinyl unsubstituted or substituted with one or more of phenyl and naphthyl; Pyridyl unsubstituted or substituted with one or more phenyl; Pyrimidinyl unsubstituted or substituted with one or more phenyl; Quinazolinyl substituted with one or more phenyl; Isoquinolyl substituted with one or more phenyl; Carbazolyl unsubstituted or substituted with one or more phenyl; Unsubstituted dibenzothiophenyl; Unsubstituted dibenzofuranyl; Naphthyridinyl substituted with one or more phenyl; Unsubstituted diphenylamino; Unsubstituted phenylbiphenylamino; Dimethylfluorenylphenylamino; Benzothienopyrimidinyl substituted with one or more phenyl; Unsubstituted benzothienoquinolyl; Unsubstituted benzofuroquinolyl; Benzoquinazolinyl substituted with one or more phenyl; Benzothiazolinyl substituted with one or more phenyl; Benzoquinoxalinyl substituted with one or more phenyl; Unsubstituted dibenzoquinoxalinyl; Phenanthroimidazolyl substituted with one or more phenyl; Unsubstituted dibenzothiophenylphenylamino; Unsubstituted dibenzofuranylphenylamino; Nitrogen-containing 17-membered heteroaryl substituted with one or more methyl; 25 membered heteroaryl containing nitrogen and oxygen; Or acenaphtopyrimidinyl substituted with one or more phenyl.

R ₁ is preferably substituted or unsubstituted (C6-C25) aryl, or substituted or unsubstituted (3- to 25-membered) heteroaryl; Adjacent R _{1 's may} be linked to each other to form a substituted or unsubstituted (3- to 25-membered) monocyclic or polycyclic alicyclic, aromatic, or combination ring thereof, and the alicyclic, aromatic, or combination thereof formed as described above. The carbon atoms of the ring of may be replaced with one or more heteroatoms selected from nitrogen, oxygen and sulfur, more preferably substituted or unsubstituted (C6-C18) aryl, or substituted or unsubstituted (5- to 18-membered) Heteroaryl; Adjacent R _{1 's may} be linked to each other to form a substituted or unsubstituted (3- to 18-membered) monocyclic or polycyclic aromatic ring, wherein the carbon atoms of the formed aromatic ring are at least one selected from nitrogen, oxygen and sulfur (5-6-membered) unsubstituted or substituted with (C6-C12) aryl, or (C6-C18) aryl unsubstituted or substituted with a (5- to 18-membered) heteroaryl, and more preferably Heteroaryl; Adjacent R _{1 's may} be linked to each other to form a substituted or unsubstituted (3-10 membered) monocyclic or polycyclic aromatic ring, wherein the carbon atoms of the formed aromatic ring are one or more selected from nitrogen, oxygen and sulfur It may be replaced with a heteroatom. According to an aspect of the present application, R ₁ is phenyl unsubstituted or substituted with diphenyltriazinyl, diphenyltriazinyl, quinazolinyl substituted with phenyl, or unsubstituted pyridyl, or adjacent R ₁ are connected to each other. Indene ring substituted with one or more of unsubstituted benzene rings, methyl and phenyl, unsubstituted pyridine ring, unsubstituted benzothiophene ring, unsubstituted benzofuran ring, or indole substituted with phenyl or phenylquinoxalinyl May form a ring.

According to an aspect of the present disclosure, in Formula 1, two adjacent X ₁ to X _{12 may be} CR ₁ , and two adjacent R ₁ may be connected to form a ring of any one of Formulas 2 to 6, wherein the ring One or more may be formed in one compound represented by the formula (1). For example, the ring may be a dibenzothiophene ring, a dibenzofuran ring, a naphthalene ring, a phenanthrene ring, or a substituted or unsubstituted carbazole ring.

[Formula 2] [Formula 3] [Formula 4] [Formula 5] [Formula 6]

는 CR₁에서의 C와 R₁의 연결 부위를 나타낸다. In Chemical Formulas 2 to 6,

Represents the joint of the C and R ₁ of the CR _1.

In Formula 4, X is N or CH. According to an aspect of the present disclosure, X may be all CH, and according to another aspect of the present disclosure, any one of X may be N.

In Formula 5, R ₂ is hydrogen, deuterium, halogen, cyano, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3-30 Heteroaryl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted tri (C1-C30) alkylsilyl, substituted or unsubstituted di (C1-C30) alkyl (C6-C30) arylsilyl, substituted or unsubstituted (C1-C30) alkyldi (C6-C30) arylsilyl, substituted or unsubstituted tri (C6-C30) arylsilyl, substituted or Unsubstituted mono- or di- (C1-C30) alkylamino, substituted or unsubstituted mono- or di- (C6-C30) arylamino, or substituted or unsubstituted (C1-C30) alkyl (C6-C30) ) Arylamino, preferably substituted or unsubstituted (C6-C25) aryl, or substituted or unsubstituted (5- to 25-membered) heteroaryl, more preferably unsubstituted (C6-C18) aryl, Or substituted with (C6-C18) aryl or Substituted (5-18 W) is heteroaryl. According to an aspect of the present application, R ₂ may be unsubstituted phenyl or quinoxalinyl substituted with phenyl.

In Formula 6, R ₁₁ and R ₁₂ are each independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted Substituted (3- to 30-membered) heteroaryl, or substituted or unsubstituted (C3-C30) cycloalkyl; May be linked to each other to form a ring, preferably R ₁₁ and R ₁₂ are each independently hydrogen, substituted or unsubstituted (C1-C6) alkyl, or substituted or unsubstituted (C6-C12) aryl; Connected to each other to form a substituted or unsubstituted (5- to 10-membered) monocyclic or polycyclic alicyclic, aromatic, or a combination thereof, and more preferably, each independently hydrogen, unsubstituted ( C1-C6) alkyl, or unsubstituted (C6-C12) aryl; They can be linked together to form a ring with a spy.

In Formula 1, a is an integer of 1 or 2, when a is 2, each Ar may be the same or different.

The compound of Formula 1 may be represented by at least one of the following Chemical Formulas 7 to 10.

[Formula 7] [Formula 8]

[Formula 9] [Formula 10]

In Formulas 7 to 10, X ₁ to X ₁₂ , and M are as defined in formula (1).

According to one aspect of the present disclosure, at least one of X ₁ to X ₅ , at least one of X ₆ to X ₉ , and at least one of X ₁₀ to X ₁₂ are N or CR ₁ , wherein each R ₁ is independently substituted or Unsubstituted (C6-C25) aryl, or substituted or unsubstituted (3- to 25-membered) heteroaryl; Connected to an adjacent substituent to form a substituted or unsubstituted (3- to 25-membered) monocyclic or polycyclic alicyclic, aromatic, or combination thereof ring, wherein the alicyclic, aromatic, or combination thereof formed ring May be replaced with one or more heteroatoms selected from nitrogen, oxygen and sulfur.

According to an embodiment of the present disclosure, in Formula 1 of the first host compound, Ar is substituted or unsubstituted (3- to 30-membered) heteroaryl, and in Formula 1 of the second host compound, Ar is substituted or unsubstituted ( 3-30 membered) heteroaryl.

According to another embodiment of the present application, Ar in Formula 1 of the first host compound is substituted or unsubstituted (3- to 30-membered) heteroaryl, and Ar in Formula 1 of the second host compound is substituted or unsubstituted. (C6-C30) aryl, substituted or unsubstituted mono- or di- (C1-C30) alkylamino, substituted or unsubstituted mono- or di- (C6-C30) arylamino, or substituted or unsubstituted ( C1-C30) alkyl (C6-C30) arylamino.

The compound represented by Chemical Formula 1 may be exemplified more specifically as the following compound, but is not limited thereto.

Two or more of the compounds C-1 to C-449 may be used in combination in an organic electroluminescent device.

The compound of formula 1 according to the present invention may be prepared by synthetic methods known to those skilled in the art, for example, it may be prepared as shown in Schemes 1 to 7, but is not limited thereto.

Scheme 1

Scheme 2

Scheme 3

Scheme 4

Scheme 5

Scheme 6

Scheme 7

In Schemes 1 to 7, X ₁ to X ₁₂ , R ₁ , La, Ar, and a are the same as defined in Formula 1, R ₂ , R ₁₁ and R ₁₂ are the same as defined in Formulas 5 and 6, Z is as defined in R ₁ and OTf is trifluoromethanesulfonate.

The organic electroluminescent device according to the present invention comprises a first electrode; Second electrode; And at least one organic material layer interposed between the first electrode and the second electrode.

One of the first electrode and the second electrode may be an anode and the other may be a cathode. The organic layer includes a light emitting layer and is selected from a hole injection layer, a hole transport layer, a hole auxiliary layer, a light emission auxiliary layer, an electron transport layer, an electron buffer layer, an electron injection layer, an interlayer, a hole blocking layer and an electron blocking layer. It may further comprise one or more layers. Here, the second electrode may be a transflective electrode or a reflective electrode, and may be a top emission type, a bottom emission type, or a double emission type depending on the material. In addition, the hole injection layer may further dop the p- dopant, the electron injection layer may be further doped with the n- dopant.

The organic electroluminescent device according to the present invention includes an anode, a cathode, and at least one organic material layer between the anode and the cathode, wherein the organic material layer is represented by Chemical Formula 1 as the first organic electroluminescent material and the second organic electroluminescent material. It may include a plurality of types of organic electroluminescent materials including different compounds. The organic electroluminescent device according to the present application includes an anode, a cathode, and at least one light emitting layer between the anode and the cathode, and the light emitting layer may include two or more different compounds represented by Chemical Formula 1.

The emission layer may include a host and a dopant, and the host may include a plurality of host materials, and the compound represented by Formula 1 may be included as the first and second host compounds among the plurality of host materials. Wherein the weight ratio of the first host compound to the second host compound is from about 1:99 to about 99: 1, preferably from about 10:90 to about 90:10, more preferably from about 30:70 to about 70:30 , More preferably about 40:60 to about 60:40, even more preferably about 50:50.

The light emitting layer may be a single layer as a light emitting layer, and may be a plurality of layers in which two or more layers are stacked. In the plurality of types of host materials herein, both the first and second host materials may be included in one layer, and the first and second host materials may be included in different light emitting layers, respectively. According to one aspect of the present application, the doping concentration of the dopant compound with respect to the host compound of the light emitting layer may be less than 20% by weight.

The organic electroluminescent device of the present application is selected from a hole injection layer, a hole transport layer, a hole auxiliary layer, a light emitting auxiliary layer, an electron transport layer, an electron injection layer, an interlayer, an electron buffer layer, a hole blocking layer and an electron blocking layer It may further comprise one or more layers. According to an aspect of the present application, the organic electroluminescent device of the present application is a amine-based compound in addition to the plurality of host materials of the present application of the hole injection material, hole transport material, hole auxiliary material, light emitting material, light emission auxiliary material, and electron blocking material One or more may be included. In addition, according to an aspect of the present disclosure, the organic electroluminescent device of the present application may further include a azine compound as one or more of an electron transport material, an electron injection material, an electron buffer material, and a hole blocking material in addition to the plurality of host materials of the present application. Can be.

As the dopant included in the organic electroluminescent device of the present application, one or more phosphorescent or fluorescent dopants may be used, and a phosphorescent dopant is preferable. The phosphorescent dopant material applied to the organic electroluminescent device of the present application is not particularly limited, but may be a complex compound of a metal atom selected from iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt) , In some cases, preferably, ortho-metalized complex compounds of metal atoms selected from iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt), and more preferably in some cases, Ortho-metalized iridium complex compounds.

As a dopant included in the organic electroluminescent device of the present application, a compound represented by the following Formula 101 may be used, but is not limited thereto.

[Formula 101]

In Chemical Formula 101,

L is selected from structures 1 or 2 below;

[Structure 1] [Structure 2]

R ₁₀₀ to R ₁₀₃ are each independently hydrogen, deuterium, halogen, (C1-C30) alkyl substituted or unsubstituted, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C6- C30) aryl, cyano, substituted or unsubstituted (3- to 30-membered) heteroaryl, or substituted or unsubstituted (C1-C30) alkoxy; Can be linked to adjacent substituents to form a ring, for example substituted or unsubstituted quinoline with pyridine, substituted or unsubstituted benzofuropyridine, substituted or unsubstituted benzothienopyridine, substituted or unsubstituted benzo Thienoquinoline, or substituted or unsubstituted indenoquinoline formation is possible;

R ₁₀₄ to R ₁₀₇ are each independently hydrogen, deuterium, halogen, (C1-C30) alkyl substituted or unsubstituted, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C6- C30) aryl, substituted or unsubstituted (3- to 30-membered) heteroaryl, cyano, or substituted or unsubstituted (C1-C30) alkoxy; May be linked to adjacent substituents to form a ring, for example substituted or unsubstituted naphthyl, substituted or unsubstituted fluorene, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dialkyl with benzene Benzofuran, substituted or unsubstituted indenopyridine, substituted or unsubstituted benzofuropyridine, or substituted or unsubstituted benzothienopyridine is possible;

R ₂₀₁ to R ₂₁₁ are each independently hydrogen, deuterium, halogen, (C1-C30) alkyl unsubstituted or substituted with halogen, substituted or unsubstituted (C3-C30) cycloalkyl, or substituted or unsubstituted (C6 -C30) aryl; May be linked to an adjacent substituent to form a ring;

n is an integer of 1-3.

Specifically, specific examples of the dopant compound are as follows, but are not limited thereto.

In the organic electroluminescent device of the present application, a layer selected from a hole injection layer, a hole transport layer, an electron blocking layer, or a combination thereof may be used between the anode and the light emitting layer. As the hole injection layer, a plurality of layers may be used for the purpose of lowering the hole injection barrier (or hole injection voltage) from the anode to the hole transport layer or the electron blocking layer, and two layers may be used at the same time. A plurality of layers may also be used for the hole transport layer or the electron blocking layer.

In addition, a layer selected from an electron buffer layer, a hole blocking layer, an electron transport layer, or an electron injection layer or a combination thereof may be used between the light emitting layer and the cathode. As the electron buffer layer, a plurality of layers may be used for controlling electron injection and improving interface characteristics between the light emitting layer and the electron injection layer, and two layers may be used simultaneously for each layer. A plurality of layers may be used for the hole blocking layer or the electron transfer layer, and a plurality of compounds may be used for each layer.

In addition, the organic electroluminescent compound or a plurality of host materials according to the present application can also be used in organic electroluminescent devices including quantum dots (QD).

Each layer of the organic electroluminescent device of the present application is a dry film forming method such as vacuum deposition, sputtering, plasma, ion plating, ink jet printing, nozzle printing, slot coating, It may be formed by any one of wet film formation methods such as spin coating, dip coating, and flow coating.

In the case of the wet film formation method, a thin film is formed by dissolving or dispersing the material forming each layer in a suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc., in which the solvent is dissolved or dispersed. As long as there is no problem in film-forming property, it may be any.

In addition, the first and second host compounds of the present application can be formed by the methods listed above, and can often be formed by a co-deposition or mixed deposition process. The co-deposition is a method in which two or more materials are put in each individual crucible source, and two cells are simultaneously applied to evaporate the material by evaporating the material, and the mixed deposition is one or more crucible sources before deposition. After mixing in, a current is applied to one cell to evaporate the material and vapor deposition. In addition, when the first and second host compounds are present in the same layer or in different layers in the organic electroluminescent device, the two host compounds may be deposited separately. For example, the second host compound may be deposited after the first host compound is deposited.

The present application may provide a display device using a plurality of types of host materials including two or more different compounds represented by Formula 1 above. In addition, it is possible to manufacture a display device or a lighting device using the organic electroluminescent element of the present application. Specifically, a display device, for example, a display device for a smartphone, a tablet, a notebook, a PC, a TV, or a vehicle, or a lighting device, for example, an outdoor or indoor lighting device, using the organic electroluminescent element of the present application. It is possible to manufacture.

In the following, for a detailed understanding of the present application, a representative compound of the present application will be described for the preparation method of the compound according to the present invention and its physical properties, and the characteristics of the OLED device comprising a plurality of host materials of the present application. However, the following examples merely illustrate the characteristics of an OLED device comprising a compound according to the present application and a plurality of host materials according to the present application for the detailed understanding of the present application, and the present application is not limited to the following examples.

[ Example  1] Preparation of Compound C-8

1) Synthesis of Compound 1

To the flask was dissolved 2-nitro-1-naphthol (70 g, 370 mmol), 4- (dimethylamino) pyridine (DMAP) (4.5 g, 37 mmol), and 1800 mL of methylene chloride (MC). Ethylamine (TEA) (62 mL, 444 mmol) is added dropwise at 0 ° C. and stirred for 20 minutes. Trifluoromethanesulfonic anhydride (125.3 g, 444 mmol) was slowly added dropwise to the reaction at the same temperature, followed by stirring for 1 hour. After the reaction, the organic layer was extracted with MC and residual moisture was removed using magnesium sulfate. Then dried and separated by column chromatography to give compound 1 (96.2 g, yield: 81%).

2) Synthesis of Compound 2

Flask compound 1 (96.2 g, 299 mmol), 2-bromophenylboronic acid (72.1 g, 359 mmol), tetrakis (triphenylphosphine) palladium (0) (17.3 g, 15 mmol), sodium carbonate (79.3 g, 749 mmol), 1400 mL of toluene, 350 mL of ethanol, and 350 mL of water were dissolved and refluxed for 1 hour. After the reaction, the organic layer was extracted with ethyl acetate, and residual moisture was removed using magnesium sulfate. Then dried and separated by column chromatography to give compound 2 (98 g, yield: 99%).

3) Synthesis of Compound 3

Flask compound 2 (98 g, 299 mmol), 2-aminophenylboronic acid pinacol ester (78.5 g, 358 mmol), tetrakis (triphenylphosphine) palladium (0) (17.2 g, 15 mmol), carbonic acid Potassium (103 g, 747 mmol), 1300 mL of toluene, 350 mL of ethanol and 350 mL of water were added thereto, and the mixture was refluxed for 20 hours. After the reaction, the organic layer was extracted with ethyl acetate, and residual moisture was removed using magnesium sulfate. Then dried and separated by column chromatography to give compound 3 (54 g, yield: 53%).

4) Synthesis of Compound 4

Compound 3 (25 g, 73 mmol), 250 mL of acetic acid and 25 mL of sulfuric acid were dissolved in the flask, and sodium nitrite (6.5 g, 95 mmol) was slowly added dropwise at 0 ° C., followed by stirring for 40 minutes. After the reaction, the reactants were added dropwise into water and filtered to remove moisture. Then dried and separated by column chromatography to give compound 4 (2 g, yield: 8.4%).

5) Synthesis of Compound 5

Compound 4 (4.7 g, 15 mmol), 48 mL of triethylphosphite and 48 mL of 1,2-dichlorobenzene were dissolved in the flask, and the mixture was refluxed for 3 hours. After the reaction, the organic layer was extracted with distillation under reduced pressure, and residual moisture was removed using magnesium sulfate. Then dried and separated by column chromatography to give compound 5 (2.7 g, yield: 63%).

6) Synthesis of Compound C-8

Flask compound 5 (2.1 g, 7 mmol), 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.1 g, 8 mmol), palladium (II) acetate (0.81 g, 0.36 mmol), 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl (S-Phos) (0.3 g, 0.7 mmol), sodium tert -butoxide (1.7 g, 18 mmol) ), And 72 mL of 1,2-xylene were dissolved and refluxed for 4 hours. After the reaction, the organic layer was extracted with distillation under reduced pressure, and residual moisture was removed using magnesium sulfate. Then dried and separated by column chromatography to give the compound C-8 (2.5 g, yield: 58%).

[ Example  2] Preparation of Compound C-301

In a flask, Compound 5 (5.0 g, 17 mmol), 2-([1,1'-biphenyl] -4-yl) -4-chloro-6-phenyl-1,3,5-triazine (7.08 g, 21 mmol), DMAP (105 mg, 0.858 mmol), potassium carbonate (7.1 g, 51 mmol), and dimethylformamide (DMF) (85 mL) were dissolved and refluxed for 3 hours. After the reaction, the organic layer was extracted with ethyl acetate after distillation under reduced pressure, and residual water was removed using magnesium sulfate. Then dried and separated by column chromatography to give the compound C-301 (4.8 g, yield: 47%).

[ Example  3] Preparation of Compound C-10

In a flask compound 5 (5.0 g, 17 mmol), 2- (4-bromonaphthalen-1-yl) -4,6-diphenyl-1,3,5-triazine) (11.28 g, 21 mmol), Tris (dibenzylideneacetone) dipalladium (0) (625 mg, 0.686 mmol), S-Phos (565 mg, 1 mmol), sodium tert -butoxide (4.9 g, 51 mmol) and o-xylene (100 mL) was dissolved and refluxed for 3 hours. After the reaction, the organic layer was extracted with ethyl acetate after distillation under reduced pressure, and residual water was removed using magnesium sulfate. Then dried and separated by column chromatography to give the compound C-10 (3.6 g, yield: 32%).

[ Example  4] Preparation of Compound C-7

Flask 5 (5 g, 17.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (5.5 g, 20.5 mmol), DMAP (0.1 g, 0.85 mmol), potassium carbonate (7.1 g, 51.4 mmol), and 85 mL of DMF were dissolved therein, followed by refluxing for 3 hours. After the reaction was cooled, the mixture was filtered with methanol and water. Then dried and separated by column chromatography to give the compound C-7 (4.4 g, yield: 49%).

[ Example  5] Preparation of Compound C-302

In a flask, Compound 5 (4.5 g, 15.4 mmol), 2-chloro-4- (naphthalen-2-yl) quinazolin (5.4 g, 18.5 mmol), DMAP (0.09 g, 0.7 mmol), potassium carbonate (6.4 g, 46.3 mmol), and 77 mL of DMF were dissolved and then refluxed for 1.5 hours. After the reaction was filtered, dried, and separated by column chromatography to give the compound C-302 (7.5 g, yield: 80%).

[ Example  6] Preparation of Compound C-9

Flask compound 5 (5.0 g, 17.16 mmol), 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (6.6 g, 17.16 mmol), tris (dibenzylidene Acetone) dipalladium (0) (0.6 g, 0.686 mmol), S-Phos (0.7 g, 1.176 mmol), sodium tert -butoxide (4.0 g, 42.9 mmol), and 90 mL of o-xylene were dissolved. Reflux for 4 hours. After the reaction, the organic layer was extracted with distillation under reduced pressure, and residual moisture was removed using magnesium sulfate. Then dried and separated by column chromatography to give the compound C-9 (6.2 g, yield: 62%).

[ Example  7] Preparation of Compound C-303

In a flask, Compound 5 (4.3 g, 14.83 mmol), 6-chloro-2,4-diphenylquinazoline (4.7 g, 14.83 mmol), Pd ₂ (dba) ₃ (0.5 g, 0.593 mmol), S-Phos ( 0.6 g, 1.483 mmol), sodium tert -butoxide (3.6 g, 37.07 mmol), and 80 mL of o-xylene were dissolved and refluxed for 4 hours. After the reaction, the organic layer was extracted with distillation under reduced pressure, and residual moisture was removed using magnesium sulfate. Then dried and separated by column chromatography to give the compound C-303 (1.8 g, yield: 21%).

[ Example  8] Preparation of Compound C-307

In a flask, Compound 5 (5.4 g, 18.53 mmol), 2-chloro-3-naphthylquinoxaline (4.5 g, 15.44 mmol), potassium carbonate (2.1 g, 15.44 mmol), DMAP (0.9 g, 7.72 mmol), and 80 mL of DMF was added to dissolve and refluxed for 4 hours. After the reaction was cooled to room temperature and distilled water was added. The organic layer was extracted with MC and dried over magnesium sulfate. Thereafter, the resulting mixture was distilled under reduced pressure and separated by column chromatography to obtain Compound C-307 (2.3 g, yield: 47%).

[ Example  9] Preparation of Compound C-13

Flask compound 5 (4.0 g, 13.73 mmol), 2-chloro-3-phenylquinoxaline (4.0 g, 16.47 mmol), potassium carbonate (3.8 g, 27.46 mmol), DMAP (0.84 g, 6.87 mmol), and DMF 68 mL was added to dissolve and refluxed for 18 hours. After the reaction was cooled to room temperature and distilled water was added. The organic layer was extracted with MC and dried over magnesium sulfate. Thereafter, the resulting mixture was distilled under reduced pressure and separated by column chromatography to obtain Compound C-13 (2.3 g, yield: 33.8%).

[ Example  10] Compound C- 304 of  Produce

1) Synthesis of Compound 10-1

Compound 5 (9 g, 30.89 mmol), 1-bromo-3-iodobenzene (10.6 g, 61.78 mmol), CuI (3 g, 15.44 mmol), EDA (1.8 g, 30.89 mmol), and K ₃ PO ₄ 155 mL of toluene was added to (16.4 g, 77.22 mmol), followed by stirring under reflux for one day. After the completion of the reaction, the mixture was cooled to room temperature, and the resulting solid was filtered under reduced pressure. CHCl ₃ solid Was dissolved in and separated by column chromatography with MC / Hex to obtain compound 10-1 (10 g, yield: 75%).

2) Synthesis of Compound C-304

Compound 10-1 (5.7 g, 12.77 mmol), Pd (PPh ₃ ) ₄ (0.73 g, 0.638 mmol), and K ₂ CO ₃ (3.5 g, 25.54 mmol) in 50 mL of toluene, 13 mL of EtOH, 13 mL of purified water After stirring, the mixture was stirred under reflux for 2 hours. After the completion of the reaction, the mixture was cooled to room temperature, and the resulting solid was filtered under reduced pressure. The solid was dissolved in CHCl ₃ and separated by column chromatography with MC / Hex to obtain compound C-304 (2.9 g, yield: 43%).

[ Example  11] Preparation of Compound C-306

Flask compound 10-1 (5.0 g, 11.2 mmol), N-phenyl- [1,1'-biphenyl] -4-amine (3.0 g, 12.3 mmol), Pd ₂ (dba) ₃ (0.51 g, 0.56 mmol), S-Phos (0.46 g, 1.12 mmol), sodium tert -butoxide (2.7 g, 28 mmol), and 60 mL of toluene were added and refluxed for 4 hours. After the reaction, the organic layer was extracted with ethyl acetate after distillation under reduced pressure, and residual water was removed using magnesium sulfate. Then dried and separated by column chromatography to give the compound C-306 (2.3 g, yield: 34%).

[ Example  12] Preparation of Compound C-333

Flask compound 12 (2.6 g, 7.6 mmol), 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (2.95 g, 7.6 mmol), tris (dibenzylidene Acetone) dipalladium (0) (0.27 g, 0.3 mmol), 2-dicyclo hexyl phosphino-2 ', 6'-dimethoxybiphenyl (0.3 g, 0.7 mmol), sodium tert -butoxide (1.8 g , 19 mmol), and 50 mL of 1,2-dimethylbenzene were dissolved and refluxed for 12 hours. After the reaction, the organic layer was extracted with distillation under reduced pressure, and residual moisture was removed using magnesium sulfate. Then dried and separated by column chromatography to give the compound C-333 (1.9 g, yield: 38%).

[ Example  13] Preparation of Compound C-372

1) Synthesis of Compound 13-1

Compound 5 (70 g, 240 mmol), N-bromosuccinimide (40.6 g, 255 mmol), and 1200 mL of dimethylformamide were dissolved in the flask, followed by stirring at 0 ° C. for 3 hours. After the reaction, the organic layer was extracted with ethyl acetate, and residual moisture was removed using magnesium sulfate. Then dried and separated by column chromatography to give compound 13-1 (68 g, yield: 76%).

2) Synthesis of Compound 13-2

Flask compound 13-1 (47.3 g, 127 mmol), bis (pinacolato) diboron (42 g, 166 mmol), bis (triphenylphosphine) palladium dichloride (II) (4.5 g, 6.4 mmol) , Potassium acetate (25 g, 255 mmol), and 635 mL of 1,4-dioxane were added to dissolve and refluxed for 4 hours. After the reaction, the organic layer was extracted with distillation under reduced pressure, and residual moisture was removed using magnesium sulfate. Then dried and separated by column chromatography to give compound 13-2 (31.5 g, yield: 59%).

3) Synthesis of Compound 13-3

In a flask, compound 13-2 (4.5 g, 10.7 mmol), 1-bromobenzene (1.9 g, 11.85 mmol), tetrakis (triphenylphosphine) palladium (0) (0.63 g, 0.54 mmol), potassium carbonate ( 3.7 g, 26.95 mmol), 54 mL of toluene, 13 mL of ethanol, and 13 mL of water were added thereto, and the mixture was refluxed for 12 hours. After the reaction, the organic layer was extracted with ethyl acetate, and residual moisture was removed using magnesium sulfate. Then dried and separated by column chromatography to give compound 13-3 (2.2 g, yield: 56%).

4) Synthesis of Compound C-372

In a flask, Compound 13-3 (2.2 g, 5.9 mmol), 2-chloro-3-phenylquinoxaline (1.58 g, 6.57 mmol), cesium carbonate (3.89 g, 11.96 mmol), 4-dimethylaminopyridine (0.36 g, 2.99 mmol), and 30 mL of dimethyl sulfur monoxide were dissolved and stirred at 100 ° C. for 4 hours. After the reaction was cooled to room temperature and distilled water was added. The organic layer was extracted with ethyl acetate and residual moisture was removed using magnesium sulfate. Then dried and separated by column chromatography to give the compound C-372 (2.9 g, yield: 85%).

[ Example  14] Preparation of Compound C-334

1) Synthesis of Compound 14-1

Flask compound 13-2 (27 g, 64.7 mmol), 1-bromo-2-nitrobenzene (14.4 g, 71.2 mmol), tetrakis (triphenylphosphine) palladium (0) (3.7 g, 3.2 mmol) , Potassium carbonate (22.4 g, 162 mmol), 320 mL of toluene, 80 mL of ethanol, and 80 mL of water were dissolved and refluxed for 12 hours. After the reaction, the organic layer was extracted with ethyl acetate, and residual moisture was removed using magnesium sulfate. Then dried and separated by column chromatography to give compound 14-1 (26.7 g, yield: 100%).

2) Synthesis of Compound 14-2

Flask compound 14-1 (26.7 g, 64.7 mmol), 1-iodobenzene (18 mL, 162 mmol), cuprous iodide (18.5 g, 97 mmol), ethylenediamine (13 mL, 194 mmol), phosphoric acid Potassium (27.4 g, 129 mmol), and 325 mL of toluene were added to dissolve and refluxed for 2 hours. After the reaction, the organic layer was extracted with ethyl acetate, and residual moisture was removed using magnesium sulfate. Then dried and separated by column chromatography to give compound 14-2 (15.7 g, yield: 49%).

3) Synthesis of Compound 14-3

To the flask was added Compound 14-2 (13.1 g, 26.8 mmol), 180 mL of triethylphosphite, and 180 mL of 1,2-dichlorobenzene, followed by stirring at 200 ° C. for 2 hours. After the reaction was completed by distillation under reduced pressure to remove the solvent, cooled to room temperature and hexane was added to obtain a solid. The resulting solid was removed by a solvent through a filter and then separated by column chromatography to obtain compound 14-3 (0.71 g, yield: 5.8%).

4) Compound C- 334 of  synthesis

In a flask, Compound 14-3 (0.71 g, 1.56 mmol), 2-chloro-3-phenylquinoxaline (0.45 g, 1.87 mmol), cesium carbonate (1.01 g, 3.12 mmol), 4-dimethylaminopyridine (0.095 g, 0.78 mmol), and 30 mL of dimethyl sulfur monoxide were dissolved and stirred at 100 ° C. for 4 hours. After the reaction was cooled to room temperature and distilled water and methanol was added. The resulting solid was removed through a filter and then separated by column chromatography to obtain a compound C-334 (0.50 g, yield: 49%).

[ Example  15] Preparation of Compound C-197

1) Synthesis of Compound 15-1

Flask compound 13-1 (40 g, 108 mmol), (2-methylthiophenyl) boronic acid (25.4 g, 153.5 mmol), tetrakis (triphenylphosphine) palladium (O) (6.26 g, 5.40 mmol) , Potassium carbonate (26.3 g, 272.0 mmol), 536 mL of tetrahydrofuran, and 134 mL of distilled water were dissolved and refluxed at 100 ° C. for 18 hours. After the reaction, the organic layer was extracted with ethyl acetate, and residual moisture was removed using magnesium sulfate. Then dried and separated by column chromatography to give compound 15-1 (40 g, yield: 89%).

2) Synthesis of Compound 15-2

Compound 15-1 (40 g, 96.8 mmol), tetrahydrofuran 400 mL, acetic acid 200 mL and 34.5% hydrogen peroxide (12.6 mL, 145.2 mmol) were dissolved in the flask, followed by stirring at room temperature for 20 hours. After the reaction was completed, the mixture was concentrated, the organic layer was extracted with methylene chloride and aqueous sodium hydrogen carbonate solution, and residual water was removed using magnesium sulfate, followed by drying to obtain compound 15-2 (42 g, yield: 100%).

3) Synthesis of Compound 15-3

Compound 15-2 (42 g, 96.4 mmol) was dissolved in 190 mL of trifluoromethanesulfonic acid, followed by stirring at room temperature for 3 days. After the reaction, 50 mL of pyridine and 1M NaOH aqueous solution were added to the mixture at 0 ° C. to adjust the pH to 7 to 8, and the mixture was refluxed at 100 ° C. for 1 hour. The solvent was removed through a filter, and the resulting solid was separated by column chromatography to obtain compound 15-3 (9.1 g, yield: 24%).

4) Compound C- 197 of  synthesis

In a flask, Compound 15-3 (4 g, 10.1 mmol), 2-chloro-3-phenylquinoxaline (3 g, 12.1 mmol), cesium carbonate (6.6 g, 20.2 mmol), 4-dimethylaminopyridine (0.62 g, 5.1 mmol), and 50 mL of dimethyl sulfur monoxide were dissolved and stirred at 100 ° C. for 4 hours. After the reaction was cooled to room temperature and distilled water and methanol was added. The resulting solid was removed by a solvent through a filter and then separated by column chromatography to obtain a compound C-197 (4.8 g, yield: 79%).

[ Example  16] Preparation of Compound C-339

1) Synthesis of Compound 16-1

Compound 5 (15.6 g, 53.5 mmol), 2,3-dichlorobenzo [ f ] quinoxaline (20 g, 80.3 mmol), potassium carbonate (15 g, 107.0 mmol), N, N-dimethyl-4-pyridinamine ( 3.3 g, 26.7 mmol), and 270 mL of N, N-dimethylformamide were added, followed by stirring at 150 ° C. for 4 hours. After the reaction was cooled to room temperature and the solvent was removed by rotary evaporator. Then separated by column chromatography to give compound 16-1 (2.2 g, 8%).

2) Synthesis of Compound C-339

Compound 16-1 (2.2 g, 4.4 mmol), phenylboronic acid (800 mg, 6.6 mmol), tetrakis (triphenylphosphine) palladium (250 mg, 0.2 mmol), sodium carbonate (1.2 g, 10.9 mmol) in the reaction vessel ), 20 mL of toluene, and 5 mL of ethanol were added, followed by stirring at 130 ° C. for 3 hours. After the reaction was cooled to room temperature and the solvent was removed by rotary evaporator. Thereafter, the residue was separated by column chromatography, obtaining a compound C-339 (1.8 g, 76%).

[ Example  17] Preparation of Compound C-338

1) Synthesis of Compound 17-1

Compound 5 (15.6 g, 53.5 mmol), 2,3-dichlorobenzo [ f ] quinoxaline (20 g, 80.3 mmol), potassium carbonate (15 g, 107.0 mmol), N, N-dimethyl-4-pyridinamine ( 3.3 g, 26.7 mmol), and 270 mL of N, N-dimethylformamide were added and then stirred at 150 ° C. for 4 hours. After the reaction was cooled to room temperature and the solvent was removed by rotary evaporator. Thereafter, the residue was separated by column chromatography, obtaining a compound 17-1 (2.8 g, 10%).

2) Synthesis of Compound C-338

Compound 17-1 (2.7 g, 5.4 mmol), phenylboronic acid (1 g, 8.0 mmol), tetrakis (triphenylphosphine) palladium (310 mg, 0.3 mmol), sodium carbonate (1.4 g, 13.4 mmol) in the reaction vessel ), 28 mL of toluene, and 7 mL of ethanol were added and then stirred at 130 ° C. for 3 hours. After the reaction was cooled to room temperature and the solvent was removed by rotary evaporator. After separation by column chromatography to give the compound C-338 (2.5 g, 86%).

[ Example  18] Preparation of Compound C-379

Flask compound 5 (4.0 g, 13.73 mmol), 5-chloro-2,3-diphenylquinoxaline (5.2 g, 16.47 mmol), tris (dibenzylideneacetone) dipalladium (0) (0.629 g, 0.686 mmol ), 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl (0.564 mg, 1.0 mmol), sodium tert -butoxide (3.9 g, 41 mmol), and 1,2-dimethylbenzene 80 After adding mL to dissolve and reflux for 4 hours. After the reaction was cooled to room temperature and distilled water was added. The organic layer was extracted with MC and dried over magnesium sulfate. Distillation under reduced pressure and separation by column chromatography gave Compound C-379 (2.8 g, yield: 35.67%).

[ Example  19] Preparation of Compound C-389

Flask compound 5 (6.0 g, 21 mmol), 2-([1,1'-biphenyl] -3-yl) -3-chloroquinoxaline (7.8 g, 25 mmol), potassium carbonate (8.5 g, 62 mmol), 4-dimethylaminopyridine (0.126 g, 1 mmol), and 100 mL of dimethylformamide were added and dissolved at reflux for 4 hours. After the reaction was cooled to room temperature and distilled water was added. The organic layer was extracted with MC and dried over magnesium sulfate. Distillation under reduced pressure and separation by column chromatography gave Compound C-389 (8.8 g, yield: 74%).

[ Example  20] Preparation of Compound C-395

Flask compound 5 (7.9 g, 27 mmol), 2-chloro-3- (phenyl-D5) quinoxaline (7.9 g, 33 mmol), potassium carbonate (11.24 g, 81 mmol), 4-dimethylaminopyridine (0.166 g, 1 mmol), and 135 mL of dimethylformamide were dissolved and refluxed for 4 hours. After the reaction was cooled to room temperature and distilled water was added. The organic layer was extracted with MC and dried over magnesium sulfate. Distillation under reduced pressure and separation by column chromatography gave Compound C-395 (3.2 g, yield: 23.7%).

[ Example  21] Preparation of Compound C-380

In a flask, Compound 5 (10 g, 28.82 mmol), 2-chloro-3- (4- (naphthalen-2-yl) phenyl) quinoxaline (7.0 g, 24.02 mmol), 4- (dimethylamino) pyridine (1.5 g, 12.01 mmol), potassium carbonate (3.3 g, 24.02 mmol), and dimethylformamide (130 mL) were added thereto, and the mixture was refluxed for 3 hours. After the reaction, the organic layer was extracted with ethyl acetate after distillation under reduced pressure, and residual moisture was removed using magnesium sulfate. Then dried and separated by column chromatography to give compound C-380 (8.8 g, yield: 59%).

[ Example  22] Preparation of Compound C-394

Flask compound 5 (6 g, 20.59 mmol), 2- (3-chloroquinoxalin-2-yl) -9-phenyl-9H-carbazole (9.1 g, 22.65 mmol), 4- (dimethylamino) pyridine (1.2 g, 10.29 mmol), potassium carbonate (2.8 g, 20.59 mmol), and dimethylformamide (100 mL) were added thereto, and the mixture was refluxed for 3 hours. After the reaction, the organic layer was extracted with distillation under reduced pressure, and residual moisture was removed using magnesium sulfate. Then dried and separated by column chromatography to give compound C-394 (9.6 g, yield: 70%).

[ Example  23] Preparation of Compound C-346

Flask compound 5 (6.0 g, 20.59 mmol), 2- (2-chloroquinazolin-4-yl) -9-phenyl-9H-carbazole (9.1 g, 22.65 mmol), 4- (dimethylamino) pyridine (1.2 g, 10.29 mmol), potassium carbonate (2.8 g, 20.59 mmol), and dimethylformamide (100 mL) were added thereto, and the mixture was refluxed for 3 hours. After the reaction, the organic layer was extracted with distillation under reduced pressure, and residual moisture was removed using magnesium sulfate. Then dried and separated by column chromatography to give the compound C-346 (10 g, yield: 77%).

[ Example  24] Preparation of Compound C-388

Flask compound 5 (12 g, 41.1 mmol), 2- (4-bromophenyl) -4-phenylquinazoline (14.8 g, 41.1 mmol), tris (dibenzylideneacetone) dipalladium (0) (1.5 g , 1.6 mmol), 2-dicyclohexylphosphino-2'-6'-dimethoxybiphenyl (1.7 g, 4.1 mmol), sodium tert -butoxide (9.8 g, 102.9 mmol) and xylene (274 mL) Melted and refluxed for 4 hours. After the reaction was completed, the mixture was cooled and separated by column chromatography, obtaining a compound C-388 (1.1 g, yield: 4.7%).

[ Example  25] Preparation of Compound C-381

Flask compound 5 (5.7 g, 19.5 mmol), 2-chloro-3- (dibenzo [b, d] furan-1-yl) quinoxaline (7.7 g, 23.2 mmol), 4- (dimethylamino) pyridine (0.1 g, 0.9 mmol), potassium carbonate (8.1 g, 58.5 mmol), and 99 mL of dimethylformamide were added thereto, and the resulting mixture was refluxed for 3 hours 30 minutes. After the reaction was cooled, the mixture was filtered with methanol and water. Then dried and separated by column chromatography to give compound C-381 (6 g, yield: 52%).

[ Example  26] Preparation of Compound C-378

Flask compound 5 (3.8 g, 13 mmol), 2-([1,1'-biphenyl] -4-yl) -3-chloroquinoxaline (5.0 g, 16 mmol), DMAP (800 mg, 7 mmol ), Potassium carbonate (3.6 g, 26 mmol), and 55 mL of dimethylformamide were added thereto, and the mixture was refluxed for 18 hours. After the reaction, the organic layer was extracted with distillation under reduced pressure, and residual moisture was removed using magnesium sulfate. Then dried and separated by column chromatography to give compound C-378 (1.4 g, yield: 19%).

[ Example  27] Preparation of Compound C-386

Flask compound 5 (5.1 g, 17 mmol), 6-chloro-2,3-diphenylquinoxaline (5.0 g, 16 mmol), tris (dibenzylideneacetone) dipalladium (0) (578 mg, 0.631 mmol ), 2-dicyclohexylphosphino-2'-6'-dimethoxybiphenyl (648 mg, 2 mmol), sodium tert -butoxide (3.8 g, 39 mmol), and 100 mL of toluene were dissolved to dissolve 16 It was refluxed for hours. After the reaction, the organic layer was extracted with distillation under reduced pressure, and residual moisture was removed using magnesium sulfate. Then dried and separated by column chromatography to give the compound C-386 (7.6 g, yield: 84%).

[ Example  28] Compound C- Of 387  Produce

Compound 10-1 (6.6 g, 14.78 mmol), dibenzo [b, d] furan-1-yl-boronic acid (3.4 g, 16.24 mmol), tetrakis (triphenylphosphine) palladium (0) (0.85 g , 0.739 mmol), and potassium carbonate (4 g, 29.57 mmol) were added with 60 mL of toluene, 15 mL of ethanol, and 15 mL of purified water, followed by stirring under reflux for one day. After completion of the reaction, the mixture was cooled to room temperature, and the resulting solid was filtered under reduced pressure. CHCl ₃ solid Was dissolved in and separated by column chromatography with MC / Hex to obtain compound C-387 (3.5 g, yield: 45%).

[ Example  29] Preparation of Compound C-393

Flask compound 5 (4.4 g, 15.16 mmol), 9-chloro-6-phenyl-6H-indolo [2,3, b] quinoxaline (5.0 g, 15.16 mmol), tris (dibenzylideneacetone) dipalladium (0) (0.5 g, 0.606 mmol), 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl (0.6 g, 1.516 mmol), sodium tert -butoxide (12 g, 37.90 mmol) , And 100 mL of 1,2-dimethylbenzene were dissolved and refluxed for 4 hours. After the reaction, the organic layer was extracted with ethyl acetate after distillation under reduced pressure, and residual water was removed using magnesium sulfate. Then dried and separated by column chromatography to give compound C-393 (1.9 g, yield: 21%).

[ Example  30] Preparation of Compound C-447

1) Synthesis of Compound 30-1

Flask compound 13-1 (8.0 g, 21.6 mmol), 4-iodobiphenyl (12.1 g, 43.2 mmol), tris (dibenzylideneacetone) dipalladium (0) (1.0 g, 1.08 mmol), tri- tert Butyl phosphine (0.87 mL, 2.16 mmol 50% toluene solution), sodium tert -butoxide (5.2 g, 54.0 mmol), and 216 mL of toluene were added and refluxed for 18 hours. After the reaction, the reaction solution was cooled to room temperature and the solvent was removed by a rotary evaporator. Then separated by column chromatography to give compound 30-1 (7.5 g, 66%).

2) Synthesis of Compound 30-2

Flask compound 30-1 (7.5 g, 14.4 mmol), methyl 2- (4,4,5,5-tetramethyl-1,3,2-dioxylboren-2-yl) benzoate (4.5 g, 17.3 mmol), palladium acetate (Pd (OAc) ₂ ) (323 mg, 1.44 mmol), ligand (2-dicyclohexylphosphonium-2 ', 6'-dimethoxybiphenyl) (1.2 g, 2.88 mmol), carbonic acid Cesium (14 g, 43.2 mmol), 80 mL of xylene, 40 mL of ethanol and 40 mL of distilled water were added thereto, and the mixture was stirred under reflux for 18 hours. Cooled to room temperature and distilled water was added. The organic layer was extracted with MC and dried over magnesium sulfate. Distillation under reduced pressure and separation by column chromatography gave Compound 30-2 (2.2 g, yield: 27%).

3) Compound 30- 3 of  synthesis

To the flask was added Compound 30-2 (2.2 g, 3.8 mmol), 2 mL Eaton's reagent, and 13 mL benzene chloride, and the mixture was stirred under reflux for 18 hours. After cooling to room temperature, an aqueous sodium hydrogen carbonate solution was added. The organic layer was extracted with ethyl acetate (EA) and dried over magnesium sulfate. Distillation under reduced pressure and separation by column chromatography gave Compound 30-3 (1.5 g, yield: 71%).

4) Synthesis of Compound C-447

Iodine (244 mg, 0.96 mmol), hypophosphoric acid (0.48 mL, 4.4 mmol, 50% aqueous solution) and 14 mL of acetic acid were added to the flask, and the mixture was stirred at 80 ° C. for 30 minutes. Compound 30-3 (1.5 g, 2.75 mmol) was slowly added dropwise thereto, followed by stirring under reflux for 4 hours. The reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with a large amount of water and ethanol. The resulting solid removed solvent through a filter. Then separated by column chromatography to give the compound C-447 (270 mg, yield: 18%).

[ Comparative example  1] organic containing a conventional compound as a host Electric field  Manufacture of light emitting device

OLED devices using conventional compounds as host materials, not according to the present application, were prepared. First, the transparent electrode ITO thin film (10 μs / □) on a glass for OLED (Geomatec Co., Ltd.) substrate was subjected to ultrasonic cleaning using acetone and isopropyl alcohol sequentially, and then stored in isopropanol and used. Next, the ITO substrate is mounted on the substrate holder of the vacuum deposition apparatus, the compound HI-1 is put into the cell in the vacuum deposition apparatus, and evacuated until the vacuum in the chamber reaches 10 ^-7 torr, and then a current is applied to the cell. By evaporation to deposit an 80 nm thick first hole injection layer on the ITO substrate. Subsequently, compound HI-2 was placed in another cell in the vacuum deposition equipment, and a second hole injection layer having a thickness of 5 nm was deposited on the first hole injection layer by applying an electric current to the cell to evaporate. Subsequently, Compound HT-1 was placed in another cell in the vacuum deposition equipment, and a current was applied to the cell to evaporate to deposit a first hole transport layer having a thickness of 10 nm on the second hole injection layer. Subsequently, Compound HT-3 was placed in another cell in the vacuum deposition equipment, and a second hole transport layer having a thickness of 60 nm was deposited on the first hole transport layer by evaporation by applying a current to the cell. After the hole injection layer and the hole transport layer were formed, the light emitting layer was deposited thereon as follows. Place CBP as a host in one cell in the vacuum deposition equipment, compound D-39 as a dopant in another cell, and then evaporate the two materials at different rates to add 3 weights of dopant to the total amount of host and dopant. A 40 nm thick light emitting layer was deposited on the second hole transport layer by doping in an amount of%. Subsequently, 35 nm of a compound ETL- 1 : EIL- 1 was deposited at a weight ratio of 50:50 as an electron transporting material on the light emitting layer. Subsequently, the compound EIL- 1 was deposited to a thickness of 2 nm on the electron transport layer using an electron injection layer, and then an Al cathode was deposited to a thickness of 80 nm on the electron injection layer using another vacuum deposition equipment to manufacture an OLED device. . For each material, each compound was used by vacuum sublimation purification under 10 ⁻⁶ torr.

[device Production Example  1 to 5] organic comprising a plurality of host materials according to the present application Electric field  Manufacture of light emitting device

In device fabrication examples 1 to 5, the first host compound and the second host compound described in Table 1 were respectively put as two hosts in two cells of the light emitting layer in the vacuum deposition equipment, and then D-39 was placed in another cell. 40 nm thick over the second hole transport layer by evaporating the host material at a rate of 1: 1 and at the same time evaporating the dopant material at a different rate to dope the dopant in an amount of 3% by weight relative to the total amount of host and dopant. An OLED device was manufactured in the same manner as in Comparative Example 1, except that the light emitting layer was deposited.

The driving voltage, luminous efficiency, and time taken for the light intensity to fall from 100% to 98% of the organic electroluminescent devices of Comparative Example 1 and Device Preparation Examples 1 to 5 manufactured as described above (lifetime; T98) is shown in Table 1 below.

TABLE 1

[device Production Example  6] organic comprising a plurality of host materials according to the present application Electric field  Manufacture of light emitting device

In device fabrication example 6, the compound of the second hole transport layer instead of compound HT-3 The first host compound ( C-339 ) and the second host compound ( C-338 ) were used as the host in two cells of the compound HT-2 and the light emitting layer in the vacuum deposition equipment, and in another cell, D-39 And then evaporate the two host materials at a rate of 1: 1 and simultaneously evaporate the dopant material at a different rate to deliver the second hole by doping the dopant in an amount of 3% by weight relative to the total amount of host and dopant. An OLED device was manufactured in the same manner as in Comparative Example 1, except that a light emitting layer having a thickness of 40 nm was deposited on the layer.

The driving voltage was 2.8 V and the emission efficiency was 29.0 cd / A at 1,000 nit luminance of the organic electroluminescent device of Example 6 manufactured as described above, and the intensity of the light at 5,000 nit luminance was 100% to 98%. The time it took to fall to was 169.8 hours.

From the above Table 1 and Device Manufacturing Example 6, the organic electroluminescent device comprising a plurality of host materials of the present application has a lower driving voltage and a higher luminous efficiency than an organic electroluminescent device containing one conventional organic electroluminescent compound. And / or improved lifetime characteristics.

The compounds used in the device examples and comparative examples are shown in Table 2 below.

TABLE 2

Claims (9)

A plurality of types of host materials including a first host compound and a second host compound, wherein the first host compound and the second host compound are represented by the following Chemical Formula 1, and the first host compound and the second host compound are different from each other. And a plurality of host materials:
[Formula 1]

In Chemical Formula 1,
M is

, O or S;
X ₁ to X ₁₂ are each independently N or CR ₁ ;
La is a single bond, substituted or unsubstituted (C1-C30) alkylene, substituted or unsubstituted (C6-C30) arylene, substituted or unsubstituted (3- to 30-membered) heteroarylene, or substituted or unsubstituted Ring (C3-C30) cycloalkylene;
Ar and R ₁ are each independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3-30 Heteroaryl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted tri (C1-C30) alkylsilyl, substituted or unsubstituted di (C1-C30) alkyl (C6-C30) arylsilyl, substituted or unsubstituted (C1-C30) alkyldi (C6-C30) arylsilyl, substituted or unsubstituted tri (C6-C30) arylsilyl, substituted or Unsubstituted mono- or di- (C1-C30) alkylamino, substituted or unsubstituted mono- or di- (C6-C30) arylamino, or substituted or unsubstituted (C1-C30) alkyl (C6-C30) Arylamino; Adjacent Ar are connected to each other to form a ring, or may form a ring are connected to each other, the adjacent R _1, if R ₁ is plural, each of R ₁ are the same or may be different from one another, and;
a is an integer of 1 or 2, and when a is 2, each Ar may be the same or different. The substituted (C1-C30) alkyl (lene), substituted (C6-C30) aryl (lene), substituted (3- to 30-membered) heteroaryl (lene) of claim ₁ ), Substituted (C3-C30) cycloalkyl (ene), substituted (C1-C30) alkoxy, substituted tri (C1-C30) alkylsilyl, substituted di (C1-C30) alkyl (C6-C30) aryl Silyl, substituted (C1-C30) alkyldi (C6-C30) arylsilyl, substituted tri (C6-C30) arylsilyl, substituted mono- or di- (C1-C30) alkylamino, substituted mono- or Substituents of di- (C6-C30) arylamino and substituted (C1-C30) alkyl (C6-C30) arylamino are each independently deuterium, halogen, cyano, carboxyl, nitro, hydroxy, (C1-C30 ) Alkyl, halo (C1-C30) alkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C1-C30) alkoxy, (C1-C30) alkylthio, (C3-C30) cycloalkyl, (C3-C30) cycloalkenyl, (3- to 7-membered) heterocycloalkyl, (C6-C30) aryloxy, (C6-C30) arylthio, (C6-C30) aryl unsubstituted or substituted (3- Heteroaryl, (30-30 won) (C6-C30) aryl, tri (C1-C30) alkylsilyl, tri (C6-C30) arylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, unsubstituted or substituted with teraryl; -C30) alkyldi (C6-C30) arylsilyl, mono- or di- (C6-C30) unsubstituted or substituted with amino, mono- or di- (C1-C30) alkylamino, (C1-C30) alkyl Arylamino, (C1-C30) alkyl (C6-C30) arylamino, (C1-C30) alkylcarbonyl, (C1-C30) alkoxycarbonyl, (C6-C30) arylcarbonyl, di (C6-C30) Arylboronyl, di (C1-C30) alkylboronyl, (C1-C30) alkyl (C6-C30) arylboronyl, (C6-C30) ar (C1-C30) alkyl, and (C1-C30) At least one host material selected from the group consisting of: alkyl (C6-C30) aryl. The compound of claim 1, wherein Ar is substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted fluorenyl, substituted or Unsubstituted fluoranthenyl, substituted or unsubstituted triazinyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted benzothienopyrimidinyl, substituted or unsubstituted ace Naphthopyrimidinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted benzoquinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted benzoquinoxalinyl, substituted or unsubstituted dibenzo Quinoxalinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted benzoquinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted benzoisoquinolyl, substituted or unsubstituted benzothienoquinolyl, Substitution or ratio Substituted benzofuroquinolyl, substituted or unsubstituted triazolyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted benzothiophenyl , Substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzothiazolinyl, substituted or unsubstituted phenanthromidazolyl, substituted Or unsubstituted diphenylamino, substituted or unsubstituted phenylbiphenylamino, substituted or unsubstituted fluorenylphenylamino, substituted or unsubstituted dibenzothiophenylphenylamino, or substituted or unsubstituted dibenzo Two or more types of host materials which are furanyl phenylamino. 2. The compound of claim 1, wherein two adjacent X ₁ to X ₁₂ are CR ₁ , and two adjacent R ₁ are connected to each other to form a ring of Formula 2 to 6, wherein the ring is represented by Formula 1 Wherein at least one host material is formed from a compound of:
[Formula 2] [Formula 3] [Formula 4] [Formula 5] [Formula 6]

In Chemical Formulas 2 to 6,
R ₂ is hydrogen, deuterium, halogen, cyano, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3- to 30-membered) heteroaryl, Substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted tri (C1-C30) alkylsilyl, substituted or unsubstituted di (C1-C30) Alkyl (C6-C30) arylsilyl, substituted or unsubstituted (C1-C30) alkyldi (C6-C30) arylsilyl, substituted or unsubstituted tri (C6-C30) arylsilyl, substituted or unsubstituted mono- Or di- (C1-C30) alkylamino, substituted or unsubstituted mono- or di- (C6-C30) arylamino, or substituted or unsubstituted (C1-C30) alkyl (C6-C30) arylamino;
X is N or CH;
R ₁₁ and R ₁₂ are each independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3- 30 membered) heteroaryl or substituted or unsubstituted (C3-C30) cycloalkyl; Can be linked to each other to form a ring;

Represents the joint of the C and R ₁ of the CR _1. The host material of claim 1, wherein Formula 1 is represented by at least one of Formulas 7 to 10:
[Formula 7] [Formula 8]

[Formula 9] [Formula 10]

In Chemical Formulas 7 to 10,
X ₁ to X ₁₂ , and M are as defined in claim 1. The host material of claim 1, wherein the compound represented by Formula 1 is at least one selected from the following compounds.

The substituted or unsubstituted (3- to 30-membered) heteroaryl of the first host compound of Formula 1, wherein Ar is substituted or unsubstituted in Formula 1 of the second host compound (3). A plurality of host materials, which is heteroaryl. The substituted or unsubstituted (3- to 30-membered) heteroaryl of claim 1, wherein Ar in Formula 1 of the first host compound is substituted or unsubstituted (C6). -C30) aryl, substituted or unsubstituted mono- or di- (C1-C30) alkylamino, substituted or unsubstituted mono- or di- (C6-C30) arylamino, or substituted or unsubstituted (C1- C30) Alkyl (C6-C30) arylamino, Multiple types of host material. An organic electroluminescent element comprising an anode, a cathode, and at least one light emitting layer between the anode and the cathode, at least one of the light emitting layers comprising a plurality of types of host materials according to claim 1.