JP2014513083A - Novel compounds for organic electronic materials and organic electroluminescent devices using them - Google Patents

Abstract

The present invention relates to a novel compound and an organic electroluminescent device containing the compound. The compounds according to the invention have advantages in the production of organic electroluminescent devices with high luminous efficiency and long service life.
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Description

  The present invention relates to novel compounds for organic electronic materials and organic electroluminescent devices using them.

  Electroluminescent (EL) elements are self-luminous elements that have advantages over other types of display elements in that they provide a wider viewing angle, a greater contrast ratio, and a faster response speed. The organic EL element was originally developed by Eastman Kodak by using a low molecular weight aromatic diamine and an aluminum complex as a material for forming a light emitting layer [Appl. Phys. Lett. 51, 913, 1987].

The most important factor that determines the light emission efficiency in the organic EL element is a light emitting material. To date, fluorescent materials have been widely used as luminescent materials. However, considering the mechanism of electroluminescence, the phosphorescent material theoretically shows a luminous efficiency four times higher than the fluorescent material. Therefore, in recent years, phosphorescent materials have been studied. Iridium (III) complexes are widely known as phosphorescent materials, and these are bis (2- (2′-benzothienyl) -pyridinato-N, C3 ′) iridium (acetylacetonate) ((acac) Ir ( btp) ₂ ), tris (2-phenylpyridine) iridium (Ir (ppy) ₃ ) and bis (4,6-difluorophenylpyridinato-N, C2) picolinate iridium (Firpic), red, green and Including as blue material. Currently, 4,4′-N, N′-dicarbazole-biphenyl (CBP) is the most widely known host material for phosphors. Furthermore, Pioneer (Japan) et al. Developed a high performance organic EL device, which uses as a host material, butocuproin (BCP) and aluminum (III) bis (2), which are materials used for the hole blocking layer. -Methyl-8-quinolinate) (4-phenylphenolate) (BAlq) is used.

  Although these phosphorous host materials provide excellent luminescent characteristics, they have the following disadvantages: (1) The low glass transition temperature and low thermal stability of these phosphorous host materials make it possible for high temperature deposition processes under vacuum. In between, their decomposition can occur. (2) The power efficiency of the organic EL element is obtained by [(π / voltage) × current efficiency], and the power efficiency is inversely proportional to the voltage. Therefore, the power efficiency must be high to reduce power consumption. An organic EL device including a phosphorescent material provides higher current efficiency (cd / A) than an organic EL device including a fluorescent material. However, when an existing material such as BAlq or CBP is used as a phosphorescent host material, fluorescence A significantly higher driving voltage is required as compared with organic EL elements using materials. Therefore, there is no advantage with regard to power efficiency (lm / W). (3) Furthermore, the operating life of the organic EL element is short, and it is still necessary to improve the luminous efficiency.

  WO 2006/049013 discloses compounds for organic electroluminescent materials having fused bicyclic groups as the backbone structure. However, it contains a carbazole group substituted with an aromatic ring-fused cycloalkyl or heterocycloalkyl group, and an aromatic ring-fused heterocycloalkyl or cycloalkyl group at the nitrogen-containing fused bicyclic group, the 3-position and the 9-position, respectively. No compound is disclosed.

International Publication No. 2006/049013 Pamphlet

Appl. Phys. Lett. 51,913,1987

  The object of the present invention is to provide a device for organic electronic materials, which has excellent structure with high luminous efficiency and long service life and has accurate color adjustment, and high efficiency and long life using the compound It is providing the organic electroluminescent element which has these.

  The present inventors have found that the above object can be achieved by a compound represented by the following formula 1.

式中、
Ｌ_１およびＬ_２は、それぞれ独立して、単結合、置換もしくは非置換の５員から３０員のヘテロアリーレン基、置換もしくは非置換の（Ｃ６−Ｃ３０）アリーレン基または置換もしくは非置換の（Ｃ６−Ｃ３０）シクロアルキレン基を表し、
Ｘ_１はＣＨまたはＮを表し、
Ｙ_１およびＹ_２は、それぞれ独立して、−Ｏ−、−Ｓ−、−ＣＲ_８Ｒ_９−または−ＮＲ_１０−を表し、
Ｒ_１からＲ_１０は、それぞれ独立して、水素、重水素、ハロゲン、置換もしくは非置換の（Ｃ１−Ｃ３０）アルキル基、置換もしくは非置換の（Ｃ６−Ｃ３０）アリール基、置換もしくは非置換の３員から３０員のヘテロアリール基、置換もしくは非置換の（Ｃ３−Ｃ３０）シクロアルキル基、置換もしくは非置換の５員から７員のヘテロシクロアルキル基、置換もしくは非置換の（Ｃ６−Ｃ３０）アリール（Ｃ１−Ｃ３０）アルキル基、少なくとも１つの（Ｃ３−Ｃ３０）シクロアルキル基と縮合された置換もしくは非置換の（Ｃ６−Ｃ３０）アリール基、少なくとも１つの置換もしくは非置換の（Ｃ６−Ｃ３０）芳香環と縮合された５員から７員のヘテロシクロアルキル基、少なくとも１つの置換もしくは非置換の（Ｃ６−Ｃ３０）芳香環と縮合された（Ｃ３−Ｃ３０）シクロアルキル基、−ＮＲ_２１Ｒ_２２、−ＳｉＲ_２３Ｒ_２４Ｒ_２５、−ＳＲ_２６、−ＯＲ_２７、置換もしくは非置換の（Ｃ２−Ｃ３０）アルケニル基、置換もしくは非置換の（Ｃ２−Ｃ３０）アルキニル基、シアノ基、ニトロ基またはヒドロキシル基を表すか、または置換もしくは非置換の（Ｃ３−Ｃ３０）アルキレンもしくは（Ｃ３−Ｃ３０）アルケニレン基を介して隣の置換基に連結されて、単環式もしくは多環式の脂環式または芳香環を形成しており、前記環の１つまたは複数の炭素原子が、窒素、酸素および硫黄から選択される少なくとも１つのヘテロ原子で置き換えられていてよく、
Ｒ_２１からＲ_２７は、Ｒ_１からＲ_１０の定義と同じ定義を有し、
ａ、ｂ、ｅおよびｇは、それぞれ独立して１から４の整数を表し、ａ、ｂ、ｅまたはｇが２以上の整数である場合、個々のＲ_１、個々のＲ_２、個々のＲ_５または個々のＲ_７は、同じであるか、または異なり、
ｃ、ｄおよびｆは、それぞれ独立して１から３の整数を表し、ｃ、ｄまたはｆが２以上の整数である場合、個々のＲ_３、個々のＲ_４または個々のＲ_６は同じであるか、または異なり、並びに
前記ヘテロシクロアルキル基並びに前記ヘテロアリールおよびヘテロアリーレン基は、Ｂ、Ｎ、Ｏ、Ｓ、Ｐ（＝Ｏ）、ＳｉおよびＰから選択される少なくとも１つのヘテロ原子を含有する。

Where
L ₁ and L ₂ are each independently a single bond, a substituted or unsubstituted 5- to 30-membered heteroarylene group, a substituted or unsubstituted (C6-C30) arylene group, or a substituted or unsubstituted (C6 -C30) represents a cycloalkylene group,
X ₁ represents CH or N;
Y ₁ and Y ₂ each independently represent —O—, —S—, —CR ₈ R ₉ — or —NR ₁₀ —.
R ₁ to R ₁₀ are each independently hydrogen, deuterium, halogen, a substituted or unsubstituted (C1-C30) alkyl group, a substituted or unsubstituted (C6-C30) aryl group, substituted or unsubstituted. 3- to 30-membered heteroaryl group, substituted or unsubstituted (C3-C30) cycloalkyl group, substituted or unsubstituted 5- to 7-membered heterocycloalkyl group, substituted or unsubstituted (C6-C30) An aryl (C1-C30) alkyl group, a substituted or unsubstituted (C6-C30) aryl group fused with at least one (C3-C30) cycloalkyl group, at least one substituted or unsubstituted (C6-C30) A 5- to 7-membered heterocycloalkyl group fused to an aromatic ring, at least one substituted or unsubstituted (C6-C30) aromatic Was engaged ring condensed (C3-C30) cycloalkyl _{group, -NR 21 R 22, -SiR 23} R 24 R 25, -SR 26, -OR 27, substituted or unsubstituted (C2-C30) alkenyl group, a substituted Or an unsubstituted (C2-C30) alkynyl group, a cyano group, a nitro group or a hydroxyl group, or an adjacent substitution via a substituted or unsubstituted (C3-C30) alkylene or (C3-C30) alkenylene group Linked to a group to form a monocyclic or polycyclic alicyclic or aromatic ring, wherein one or more carbon atoms of said ring is selected from nitrogen, oxygen and sulfur May be replaced by a heteroatom,
R ₂₁ to R ₂₇ have the same definition as defined for R ₁ to R ₁₀ ;
a, b, e, and g each independently represent an integer of 1 to 4, and when a, b, e, or g is an integer of 2 or more, R ₁ , R ₂ , R ₅ or individual R ₇ are the same or different,
c, d, and f each independently represent an integer of 1 to 3, and when c, d, or f is an integer of 2 or more, each R ₃ , each R _4, or each R ₆ is the same And the heterocycloalkyl group and the heteroaryl and heteroarylene group contain at least one heteroatom selected from B, N, O, S, P (═O), Si and P To do.

  The compounds for organic electronic materials according to the present invention can produce organic electroluminescent devices with high luminous efficiency and long operational lifetime.

  Hereinafter, the present invention will be described in detail. However, the following description is intended to illustrate the present invention, but is in no way meant to limit the scope of the invention.

  The present invention relates to a compound for an organic electronic material represented by the above formula 1 and an organic electroluminescent device containing the compound.

  In the present specification, “(C1-C30) alkyl and alkylene” means straight-chain or branched alkyl and alkylene having 1 to 30 carbon atoms, and the number of carbon atoms is preferably 1. To 20, more preferably 1 to 10, and include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc .; "(C2-C30) alkenyl and alkenylene" Means linear or branched alkenyl and alkenylene having 2 to 30 carbon atoms, the number of carbon atoms being preferably 2 to 20, more preferably 2 to 10 and Are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl “(C 2 -C 30) alkynyl” is a straight-chain or branched alkynyl having 2 to 30 carbon atoms, the number of carbon atoms is preferably 2 to 20 , More preferably 2 to 10, as well as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl and the like; "C1-C30) alkoxy" is a straight-chain or branched alkoxy having 1 to 30 carbon atoms, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, as well as Methoxy, ethoxy, propoxy, isopropoxy, 1-ethylpropoxy and the like; “(C3-C30) cycloalkyl” is 3 to 3 Monocyclic or polycyclic hydrocarbons having the number of carbon atoms, preferably 3 to 20, more preferably 3 to 7, as well as cyclopropyl, cyclobutyl, cyclopentyl "(C6-C30) cycloalkylene" is formed by removing hydrogen from a cycloalkyl having 6 to 30, preferably 6 to 20, more preferably 6 or 7 carbon atoms. “5- to 7-membered heterocycloalkyl” is at least one selected from B, N, O, S, P (═O), Si and P, preferably N, O and S Cycloalkyl having a heteroatom as well as 5 to 7 ring skeleton atoms, and includes tetrahydrofuran, pyrrolidine, thiolane, teto "(C6-C30) aryl or arylene" is a monocyclic or condensed ring derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, and the number of carbon atoms is preferably Is 6 to 20, more preferably 6 to 12, and includes phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl Etc. Further, “3- to 30-membered heteroaryl and heteroarylene” is selected from the group consisting of B, N, O, S, P (═O), Si and P, preferably from 1 Aryl having 4 heteroatoms as well as 3 to 30 ring skeleton atoms, which is a single ring or a fused ring fused with at least one benzene ring, which is preferably 5 to 21, more preferably Having from 5 to 12 ring skeleton atoms, which may be partially saturated, which is a heteroaryl group via at least one heteroaryl or aryl group and a single bond (s) And may be formed by concatenating and furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazo Monocyclic ring heteroaryls such as bis, isothiazolyl, isoxazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyradazinyl, and benzofuranyl, benzothiophenyl, Nyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl , Carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl and other condensed rings It includes heteroaryl. “Halogen” includes F, Cl, Br and I.

As used herein, “substituted” in the expression “substituted or unsubstituted” means that a hydrogen atom in a particular functional group is replaced with another atom or group, ie, a substituent. A substituted alkyl and alkylene group, a substituted alkenyl group, a substituted alkynyl group, a substituted cycloalkylene group, a substituted cycloalkyl group, a substituted heterocycloalkyl group in the L ₁ and L ₂ , R ₁ to R ₁₀ and R ₂₁ to R ₂₇ groups; Substituted aryl and arylene groups, substituted heteroaryl and heteroarylene groups and substituted aromatic ring substituents are each independently deuterium, halogen, halogen substituted or unsubstituted (C1-C30) alkyl, ( C6-C30) aryl, (C6-C30) aryl-substituted or unsubstituted 5- to 30-membered heteroaryl, (C3-C30) cycloalkyl group, 5- to 7-membered heterocycloalkyl group, (C1-C30) alkylsilyl group, (C6-C30) aryl group Ryl group, (C1-C30) alkyl (C6-C30) arylsilyl group, (C2-C30) alkenyl group, (C2-C30) alkynyl group, cyano group, carbazolyl group, (C1-C30) alkylamino group, C6-C30) arylamino group, (C1-C30) alkyl (C6-C30) arylamino group, (C6-C30) arylboronyl group, (C1-C30) alkylboronyl, (C1-C30) alkyl (C6 -C30) arylboronyl, (C6-C30) aryl (C1-C30) alkyl group, (C1-C30) alkyl (C6-C30) aryl group, carbonyl group, carboxyl group, nitro group and hydroxyl group At least one selected.

In Formula 1 above, L ₁ and L ₂ are each independently preferably a single bond, a substituted or unsubstituted 5- to 21-membered heteroarylene group, a substituted or unsubstituted (C6-C20) arylene group, or A substituted or unsubstituted (C6-C20) cycloarylene group, more preferably a single bond, phenylene, naphthylene, biphenylene, terphenylene, anthrylene, andenylene, fluorenylene, phenanthrylene, triphenylenylene, pyrenylene, phenylenylene, chrysenylene, Naphthacenylene, fluoranthenyl, furylene, thiophenylene, pyrrolylene, imidazolylene, pyrazolylene, thiazolylene, thiadiazolylene, isothiazolylene, isoxazolylene, oxazolylene, oxadiazolylene, triazini , Tetrazinylene, triazolylene, tetrazolylene, furazanylene, pyridylene, pyrazinylene, pyrimidinylene, pyridazinylene, benzofuranylene, benzothiophenylene, isobenzofuranylene, benzoimidazolylene, benzothiazolylene, benzoisothiazolylene, benzoisoxazolylene, benzo Consists of oxazolylene, isoindolylene, indoleylene, indazolylene, benzothiadiazolylene, quinolylene, isoquinolylene, cinnolinylene, quinazolinylene, quinoxalinylene, carbazolylene, phenanthridinylene, benzodioxorylene, dibenzofuranylene, and dibenzothiophenylene It is selected from the group.

In the above formula 1, Y ₁ and Y ₂ each independently represent —O—, —S—, —CR ₈ R ₉ — or —NR ₁₀ —, wherein R ₈ and R ₉ are preferably Each independently represents a substituted or unsubstituted (C1-C30) alkyl group or a substituted or unsubstituted (C6-C30) aryl group, or the adjacent substituent is substituted or unsubstituted (C3-C30). ) Alkylene or (C3-C30) alkenylene groups connected to form a monocyclic or polycyclic alicyclic or aromatic ring, more preferably each independently an unsubstituted (C1 -C10) represents an alkyl group or an unsubstituted (C6-C12) aryl group, or is linked to an adjacent substituent to form a monocyclic or polycyclic (C1-C10) alicyclic or (C6 -C 15) The aromatic ring is formed. R ₁₀ preferably represents a substituted or unsubstituted (C 6 -C 30) aryl group or a substituted or unsubstituted 3- to 30-membered heteroaryl group, more preferably deuterium, halogen, (C 1 A (C6-) alkyl or (C6-C12) aryl-substituted or unsubstituted (C6-C20) aryl group, or a (C6-C12) aryl-substituted 5- to 21-membered heteroaryl group Represent.

In Formula 1 above, R ₁ to R ₇ preferably each independently represent hydrogen, a substituted or unsubstituted (C 6 -C 30) aryl group or —SiR ₂₃ R ₂₄ R ₂₅ , or substituted or non-substituted Linked to an adjacent substituent through a substituted (C3-C30) alkylene or (C3-C30) alkenylene group to form a monocyclic or polycyclic alicyclic ring or aromatic ring, and more Preferably each independently represents hydrogen, an unsubstituted (C 6 -C 12) aryl group or —SiR ₂₃ R ₂₄ R ₂₅ , or linked to an adjacent substituent to form a monocyclic or polycyclic ( C6-C12) An aromatic ring is formed.

は、下記の構造から選択されるが、これらに限定されるものではない。 In Equation 1 above,

Is selected from the following structures, but is not limited thereto.

  Representative compounds of the present invention include the following compounds:

  Compounds for organic electronic materials according to the present invention can be prepared according to the following reaction scheme.

式中、Ｒ_１からＲ_７、Ｙ_１およびＹ_２、Ｘ_１、Ｌ_１およびＬ_２、ａ、ｂ、ｃ、ｄ、ｅ、ｆおよびｇは、上記の式１において定義した通りであり、Ｘはハロゲンを表す。

Wherein R ₁ to R ₇ , Y ₁ and Y ₂ , X ₁ , L ₁ and L ₂ , a, b, c, d, e, f and g are as defined in Formula 1 above, X represents a halogen.

  In addition, the present invention provides an organic electroluminescent device comprising a compound of Formula 1. The organic electroluminescent element includes a first electrode, a second electrode, and at least one organic layer between the first electrode and the second electrode. Said organic layer comprises at least one compound of formula 1 according to the invention. Further, the organic layer includes a light emitting layer containing the compound of Formula 1 as a host material.

  In addition, for organic electroluminescent devices, the phosphorescent dopant used with the host material according to the invention can be selected from the compounds represented by the following formula 2.

式中、Ｍ_１は、Ｉｒ、Ｐｔ、ＰｄおよびＯｓからなる群から選択され、Ｌ^１０１、Ｌ^１０２およびＬ^１０３はそれぞれ独立して、下記の構造から選択される。

Wherein M ₁ is selected from the group consisting of Ir, Pt, Pd and Os, and L ¹⁰¹ , L ¹⁰² and L ¹⁰³ are each independently selected from the following structures:

を表し、
Ｒ_２３１からＲ_２４２はそれぞれ独立して、水素、重水素、ハロゲン（１つまたは複数）で置換されているかもしくは置換されていない（Ｃ１−Ｃ３０）アルキル基、（Ｃ１−Ｃ３０）アルコキシ基、ハロゲン、置換もしくは非置換の（Ｃ６−Ｃ３０）アリール基、シアノ基または置換もしくは非置換の（Ｃ５−Ｃ３０）シクロアルキル基を表すか、またはＲ_２３１からＲ_２４２のそれぞれは、隣の置換基に、（Ｃ２−Ｃ３０）アルキレン基もしくは（Ｃ２−Ｃ３０）アルケニレン基を介して連結されて、スピロ環もしくは縮合環を形成していてもよく、またはＲ_２０７もしくはＲ_２０８に、（Ｃ２−Ｃ３０）アルキレン基もしくは（Ｃ２−Ｃ３０）アルケニレン基を介して連結されて、飽和もしくは不飽和の縮合環を形成していてもよい。 R ₂₀₁ to R ₂₀₃ are each independently a (C1-C30) alkyl group substituted with or not substituted with hydrogen, deuterium, halogen (s), or a (C1-C30) alkyl group ( One or more) substituted or unsubstituted (C6-C30) aryl groups, or halogen,
_R204 to _R219 each independently represents hydrogen, deuterium, a substituted or unsubstituted (C1-C30) alkyl group, a substituted or unsubstituted (C1-C30) alkoxy group, a substituted or unsubstituted (C3- C30) a cycloalkyl group, a substituted or unsubstituted (C2-C30) alkenyl group, a substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted mono- or di- (C1-C30) alkylamino group Substituted or unsubstituted mono- or di- (C6-C30) arylamino group, SF ₅ , substituted or unsubstituted tri (C1-C30) alkylsilyl group, substituted or unsubstituted di (C1-C30) alkyl (C6-C30) arylsilyl group, substituted or unsubstituted tri (C6-C30) arylsilyl group, cyano group, Represents halogen,
R ₂₂₀ to R ₂₂₃ are each independently a (C1-C30) alkyl group substituted with or not substituted with hydrogen, deuterium, halogen (s), or a (C1-C30) alkyl group ( One or more) represents a substituted or unsubstituted (C6-C30) aryl group,
R ₂₂₄ and R ₂₂₅ each independently represent hydrogen, deuterium, a substituted or unsubstituted (C 1 -C 30) alkyl group, a substituted or unsubstituted (C 6 -C 30) aryl group or halogen, or R ₂₂₄ And R ₂₂₅ are connected to each other via a (C3-C12) alkylene group or a (C3-C12) alkenylene group with or without a condensed ring to form a monocyclic or polycyclic alicyclic ring Or it may form an aromatic ring,
R ₂₂₆ represents a substituted or unsubstituted (C1-C30) alkyl group, a substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted 5-membered or 30-membered heteroaryl group or halogen;
R ₂₂₇ to R ₂₂₉ each independently represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30) alkyl group, a substituted or unsubstituted (C6-C30) aryl group, or halogen;
Q is

Represents
Each of R ₂₃₁ to R ₂₄₂ is independently a (C1-C30) alkyl group, (C1-C30) alkoxy group, halogen, substituted or unsubstituted with hydrogen, deuterium, halogen (s) Each represents a substituted or unsubstituted (C6-C30) aryl group, a cyano group or a substituted or unsubstituted (C5-C30) cycloalkyl group, or each of _R231 to _R242 is (C2-C30) is connected via an alkylene group or a (C2-C30) alkenylene group may form a spiro ring or a condensed or _{R 207} or _{R 208,} (C2-C30) alkylene group Alternatively, they may be linked via a (C2-C30) alkenylene group to form a saturated or unsaturated condensed ring. .

  The dopants of Formula 2 include, but are not limited to:

  The organic electroluminescent device according to the present invention may further include at least one compound selected from the group consisting of arylamine compounds and styrylarylamine compounds in addition to the compound represented by Formula 1. it can.

  In the organic electroluminescent device according to the present invention, the organic layer includes a metal of Group 1 of the periodic table, a metal of Group 2, a transition metal of the fourth period, a transition metal of the fifth period, a lanthanide, and a d-transition. It may further comprise at least one metal selected from the group consisting of elemental organic metals, or at least one complex compound containing said metal. The organic layer can include a light emitting layer and a charge generation layer.

  The organic electroluminescent device according to the invention comprises at least one light emission comprising a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound in addition to the organic layer comprising a compound according to the invention. By further including a layer, white light can be emitted.

Preferably, in the organic electroluminescent device according to the present invention, at least one layer selected from a chalcogenide layer, a metal halide layer and a metal oxide layer (hereinafter referred to as “surface layer”) is one or both. On the inner surface (s) of the electrode (s). Specifically, a chalcogenide (including oxide) layer of silicon or aluminum is disposed on the anode surface of the electroluminescent medium layer, and a metal halide layer or metal oxide layer is disposed on the cathode surface of the electroluminescent medium layer. It is preferable. Such a surface layer provides operational stability for the organic electroluminescent device. Preferably, the chalcogenide includes SiO _X (1 ≦ X ≦ 2), AlO _X (1 ≦ X ≦ 1.5), SiON, SiAlON, etc., and the metal halide includes LiF, MgF ₂ , CaF ₂ , The rare earth metal fluoride is included, and the metal oxide includes Cs ₂ O, Li ₂ O, MgO, SrO, BaO, CaO and the like.

  Preferably, in the organic electroluminescent device according to the present invention, the mixed region of the electron transport compound and the reducing dopant or the mixed region of the hole transport compound and the oxidizing dopant is formed on at least one surface of the pair of electrodes. Can be arranged. In this case, the electron transport compound is reduced to an anion, thus making it easier to inject and transport electrons from the mixed region to the electroluminescent medium. Furthermore, the hole transport compound is oxidized to cations, thus making it easier to inject and transport holes from the mixed region to the electroluminescent medium. Preferably, the oxidizing dopant includes various Lewis acids and acceptor compounds, and the reducing dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare earth metals and mixtures thereof. By using the reducing dopant layer as a charge generation layer, an electroluminescent device having two or more electroluminescent layers and emitting white light can be prepared.

  Hereinafter, the luminescent properties of a compound containing an organic electronic material, a method for preparing the compound, and a device containing the compound of the present invention will be described in detail with reference to the following examples.

Preparation Example 1: Preparation of Compound C-2

Preparation of Compound C-1-1 9-phenyl-9H-carbazol-3-ylboronic acid (14 g, 48.76 mmol), 3-bromo-9H-carbazole (10 g, 40.63 mmol), K ₂ CO ₃ (13. 5 g, 97.52 mmol) and Pd (PPh ₃ ) ₄ (2.35 g, 2.03 mmol) were added to a mixture of 200 mL toluene, 50 mL EtOH and 50 mL purified water. After stirring the reaction mixture for 3 hours at 90-100 ° C., the mixture was cooled to room temperature. The aqueous layer was removed from the mixture by gravity separation. The resulting organic layer was concentrated, triturated with methylene chloride (MC), and then filtered to produce compound C-1-1 (12 g, 72%).

Preparation of Compound C-1-2 2,4-Dichloroquinazoline (30 g, 151 mmol), 9-phenyl-9H-carbazol-3-ylboronic acid (15.6 g, 75.3 mmol), Pd (PPh ₃ ) ₄ (2 0.6 g, 2.3 mmol) and Na ₂ CO ₃ (16 g, 150 mmol) were dissolved in a mixture of toluene (300 mL) and distilled water (75 mL), and then the reaction mixture was stirred at 90 ° C. for 2 hours. The resulting organic layer was distilled under reduced pressure and then triturated with MeOH. The resulting solid was dissolved in MC, filtered through silica, and then triturated with MC and hexane to yield compound C-1-2 (9.3 g, 51.4%).

Preparation of Compound C-2 Compound C-1-1 (5.3 g, 14.7 mmol) and Compound C-1-2 (6.4 g, 15.8 mmol) were suspended in 80 mL of dimethylformamide (DMF), 60% NaH (948 mg, 22 mmol) was added to the mixture at room temperature. The resulting reaction mixture was stirred for 12 hours. After adding purified water (1 L), the mixture was filtered under reduced pressure. The resulting solid was triturated with MeOH / ethyl acetate, dissolved in MC, filtered through silica, then triturated with MC / n-hexane to give compound C-2 (1.9 g, 16.8). %).
MS / FAB measured value 778; calculated value 777.91

Preparation Example 2: Preparation of compound C-13

Preparation of Compound C-2-1 2,4-Dichloroquinazoline (50 g, 251 mmol) and dibenzo [b, d] furan-4-ylboronic acid (53.2 g, 251 mmol) were added to toluene (1 L) and water (200 mL). After dissolution in the mixture, tetrakistriphenylphosphine palladium (14.5 g, 12.5 mmol) and sodium carbonate (80 g, 755 mmol) were added to the reaction mixture. The reaction mixture was stirred for 20 hours at 80 ° C. and cooled to room temperature. The reaction was terminated with 200 mL of aqueous ammonium chloride, and then the reaction mixture was extracted with 1 L of ethyl acetate, and the aqueous layer was further extracted with 1 L of dichloromethane. The organic layer was dried using anhydrous magnesium sulfate and removed under reduced pressure. The resulting solid was filtered through silica gel and the solution was removed under reduced pressure. The resulting solid was washed with 100 mL of ethyl acetate (EtOAc) to produce compound C-2-1 (50 g, 74%).

Preparation of Compound C-13 After dissolving Compound C-1-1 (50 g, 122 mmol) in DMF, 60% NaH (5.9 g, 148 mmol) was slowly added to the reaction mixture. After stirring the reaction mixture for 1 hour at room temperature, compound C-2-1 (51 g, 147 mmol) was added to the reaction mixture. The reaction mixture was stirred for 20 hours at room temperature. Ice water was slowly added to the reaction mixture to complete the reaction. Thereafter, the reaction mixture was filtered to obtain a produced solid. The resulting solid was washed with 1 L of water and then with 1 L of MeOH. The resulting solid was dried, dissolved in 4 L of CHCl ₃ and filtered through silica gel to remove inorganic material. The solvent in the obtained solution was removed to obtain a solid. The obtained solid was recrystallized in DMF to obtain compound C-13 (50 g, 58%).
MS / FAB measured value 703; calculated value 702.80

Preparation Example 3: Preparation of compound C-14

Preparation of Compound C-3-1 2,4-Dichloroquinazoline (50 g, 251 mmol) and dibenzo [b, d] thiophen-4-ylboronic acid (57.3 g, 251 mmol) were added to toluene (1 L) and water (200 mL). After dissolution in the mixture, tetrakistriphenylphosphine palladium (14.5 g, 12.5 mmol) and sodium carbonate (80 g, 755 mmol) were added to the reaction mixture. The reaction mixture was stirred for 20 hours at 80 ° C. and cooled to room temperature. The reaction was terminated with 200 mL of aqueous ammonium chloride, and then the reaction mixture was extracted with 1 L of ethyl acetate, and the aqueous layer was further extracted with 1 L of dichloromethane. The organic layer was dried using anhydrous magnesium sulfate and removed under reduced pressure. The resulting solid was filtered through silica gel and the solution was removed under reduced pressure. The resulting solid was washed with 100 mL of ethyl acetate (EtOAc) to produce compound C-3-1 (50 g, 60%).

Preparation of Compound C-14 After dissolving Compound C-1-1 (50 g, 122 mmol) in DMF, 60% NaH (5.9 g, 148 mmol) was slowly added to the reaction mixture. After stirring the reaction mixture for 1 hour at room temperature, compound C-3-1 (51 g, 147 mmol) was added to the reaction mixture. The reaction mixture was stirred for 20 hours at room temperature. Ice water was slowly added dropwise to the reaction mixture to complete the reaction. Thereafter, the reaction mixture was filtered to obtain a produced solid. The resulting solid was washed with 1 L of water and then with 1 L of MeOH. The resulting solid was dried, dissolved in 4 L of CHCl ₃ and filtered through silica gel to remove inorganic material. The solvent in the obtained solution was removed to obtain a solid. The obtained solid was recrystallized in DMF to obtain compound C-14 (50 g, 57%).
MS / FAB measured value 729; calculated value 718.87

Preparation Example 4: Preparation of compound C-20

Preparation of Compound C-4-1 Dibenzo [b, d] furan-4-ylboronic acid (19 g, 89.6 mmol), bromobenzene (18.4 ml, 138 mmol), Pd (PPh ₃ ) ₄ (2.9 g, 2 .5 mmol) and Na ₂ CO ₃ (23.2 g, 219 mmol) in a mixture of toluene (375 mL), EtOH (75 mL) and distilled water (75 mL), the reaction mixture was stirred at 90 ° C. for 4 h. did. The obtained organic layer was distilled under reduced pressure, and then filtered through a column using MC and hexane to obtain Compound C-4-1 (17 g, 77%).

Preparation of Compound C-4-2 After dissolving Compound C-4-1 (17 g, 65.3 mmol) in tetrahydrofuran (THF) (500 ml), 2.5M n-BuLi in hexane (52.2 ml, 130 mmol) was added. To the reaction mixture was added at −78 ° C. and the reaction mixture was stirred for 1 hour. The reaction mixture was stirred for 2 h while B (Oi-Pr) ₃ (21.8 ml, 195 mmol) was slowly added to the reaction mixture. After the reaction mixture was quenched by adding 2M HCl, the reaction mixture was extracted with distilled water and EA. The obtained solid was recrystallized from MC and hexane to obtain Compound C-4-2 (6.4 g, 33%).

Preparation of Compound C-4-3 Compound C-4-2 (4.9 g, 24.4 mmol), 2,4-dichloroquinazoline (6.4 g, 22.2 mmol), Pd (PPh ₃ ) ₄ (1.1 g , 2.5 mmol) and Na ₂ CO ₃ (7.1 g, 66.6 mmol) were dissolved in a mixture of toluene (300 mL) and distilled water (75 mL) and then the reaction mixture was stirred at 90 ° C. for 2 hours. . The resulting organic layer was distilled under reduced pressure and then triturated with MeOH. The obtained solid was dissolved in MC, filtered through silica gel, and then triturated with MC and hexane to obtain compound C-4-3 (4.1 g, 45%).

Preparation of Compound C-20 Compound C-4-3 (4.5 g, 10.9 mmol) and Compound C-1-1 (4.1 g, 9.9 mmol) were suspended in 80 mL of DMF, and then 60% NaH (594 mg). , 14.8 mmol) was added to the mixture at room temperature. The resulting reaction mixture was stirred for 12 hours. After adding purified water (1 L), the mixture was filtered under reduced pressure. The resulting solid was triturated with MeOH / ethyl acetate and DMF followed by EA / THF. The resulting solid was dissolved in MC, filtered through silica, and then triturated with MeOH / EA to give compound C-20 (3.4 g, 44%).
MS / FAB measured value 779; calculated value 778.90

Preparation Example 5: Preparation of compound C-21

Preparation of Compound C-5-1 Dibenzo [b, d] thiophen-4-ylboronic acid (20 g, 87.7 mmol), bromobenzene (18.4 ml, 175 mmol), Pd (PPh ₃ ) ₄ (2.9 g, 2 .5 mmol) and Na ₂ CO ₃ (23.2 g, 219 mmol) in a mixture of toluene (375 mL), EtOH (75 mL) and distilled water (75 mL), the reaction mixture was stirred at 90 ° C. for 4 h. did. The obtained organic layer was distilled under reduced pressure, and then filtered through a column using MC and hexane to obtain Compound C-5-1 (17 g, 75%).

Preparation of Compound C-5-2 Compound C-5-1 (17 g, 65.3 mmol) was dissolved in (THF (500 ml) and 2.5 M n-BuLi in hexane (52.2 ml, 130 mmol) was added to the solution. After addition to the reaction mixture at −78 ° C., the reaction mixture was stirred for 1 hour, the reaction mixture was slowly added B (Oi-Pr) ₃ (21.8 ml, 195 mmol) to the reaction mixture for 2 hours. After the reaction mixture was quenched by adding 2M HCl, the reaction mixture was extracted with distilled water and EA The resulting solid was recrystallized with MC and hexane, Compound C-5-2 (11.5 g, 60%) was obtained.

Preparation of Compound C-5-3 Compound C-5-2 (8.3 g, 41.5 mmol), 2,4-dichloroquinazoline (11.5 g, 37.8 mmol), Pd (PPh ₃ ) ₄ (2.2 g , 2.5 mmol) and Na ₂ CO ₃ (12 g, 113 mmol) were dissolved in a mixture of toluene (300 mL) and distilled water (75 mL) and the reaction mixture was stirred at 90 ° C. for 2 h. The resulting organic layer was distilled under reduced pressure and then triturated with MeOH. The obtained solid was dissolved in MC, filtered through silica gel, and then triturated with MC and hexane to obtain compound C-5-3 (10 g, 68%).

Preparation of Compound C-21 Compound C-5-3 (5 g, 11.8 mmol) and Compound C-1-1 (4.8 g, 11.8 mmol) were suspended in 80 mL of DMF, and then 60% NaH (881 mg, 22 mmol). ) Was added to the mixture at room temperature. The resulting reaction mixture was stirred for 12 hours. After adding purified water (1 L), the mixture was filtered under reduced pressure. The resulting solid was triturated with MeOH / ethyl acetate and with DMF followed by EA / THF. The resulting solid was dissolved in MC, filtered through silica and then triturated with MeOH / EA to give compound C-21 (4.8 g, 51%).
MS / FAB measured value 795; calculated value 794.96

Preparation Example 6: Preparation of compound C-33

Preparation of Compound C-6-1 Dibenzo [b, d] furan-4-ylboronic acid (20 g, 94.34 mmol), 1-bromo-4-iodo-benzene (53.4 ml, 188.68 mmol), Pd (PPh ₃ ) ₄ (5.45 g, 4.72 mmol) and K ₂ CO ₃ (39.1 g, 283.01 mmol) were dissolved in a mixture of toluene (900 mL), EtOH (200 mL) and distilled water (200 mL) The reaction mixture was stirred at 70-80 ° C. for 3 hours. After the reaction was complete, the aqueous layer was removed from the mixture by gravity separation. Then, the obtained organic layer was concentrated and purified through a column to obtain compound C-6-1 (17 g, 56%).

Preparation of Compound C-6-2 After dissolving Compound C-6-1 (17 g, 52.6 mmol) in THF (400 ml), 2.5M n-BuLi in hexane (31.5 ml, 78.9 mmol) was added to the compound C-6-2. To the reaction mixture was added at −78 ° C. and the reaction mixture was stirred for 1 hour. The reaction mixture was stirred for 12 h while B (Oi-Pr) ₃ (24.1 ml, 105.2 mmol) was slowly added to the reaction mixture. After the reaction was completed, 20 mL of purified water was slowly added dropwise to the reaction mixture. The reaction mixture was extracted with an EA / NH ₄ Cl aqueous solution. The obtained organic layer was concentrated, triturated with MC / hexane, and then filtered to obtain compound C-6-2 (14.5 g, 96%).

Preparation of Compound C-6-3 Compound C-6-2 (4.5 g, 50.33 mmol), 2,4-dichloroquinazoline (11.5 g, 50.33 mmol), Na ₂ CO ₃ (20.9 g, 150 .99 mmol) and Pd (PPh ₃ ) ₄ (2.9 g, 2.52 mmol) in a mixture of toluene (300 mL), EtOH (75 mL), and distilled water (75 mL), the reaction mixture was stirred for 12 hours. Stir at 75-80 ° C. After the reaction was complete, the reaction mixture was cooled to room temperature and the aqueous layer was removed from the mixture by gravity separation. The resulting organic layer was concentrated, triturated with THF / MeOH, filtered and then dried. The dried compound was dissolved in 3 L of chloroform and filtered through silica. The remaining solution was concentrated and triturated with EA to give compound C-6-3 (3.8 g, 19%).

Preparation of Compound C-33 Compound C-1-1 (3.8 g, 9.34 mmol) and Compound C-6-3 (3.8 g, 9.34 mmol) were suspended in 80 mL of DMF, and then 60% NaH (1 .12 g, 28.02 mL) was added to the mixture at room temperature. The resulting reaction mixture was stirred for 12 hours. After adding purified water (1 L), the mixture was filtered under reduced pressure. The resulting solid was triturated with MeOH / ethyl acetate and with DMF followed by EA / THF. The resulting solid was dissolved in MC, filtered through silica, then triturated with MeOH / EA to give compound C-33 (2.9 g, 40%).
MS / FAB measured value 779; calculated value 778.90

Preparation Example 7: Preparation of compound C-34

Preparation of Compound C-7-1 1-bromo-4-iodo-benzene (49.6 g, 0.17 mol), dibenzo [b, d] thiophen-4-ylboronic acid (20 g, 0.087 mol), Pd (PPh ₃ ) ₄ (5.0 g, 0.044 mol) and Na ₂ CO ₃ (18.5 g, 0.18 mol) are dissolved in a mixture of toluene (880 mL) and H ₂ O (200 mL) in a 2000 mL round bottom flask. The reaction mixture was subsequently stirred at 80 ° C. for 12 hours. After the reaction was complete, the reaction mixture was extracted with ethyl acetate. The resulting organic layer was then dried using MgSO ₄ and filtered. After removing the solvent from the organic layer under reduced pressure, the organic layer was filtered through an adsorption column to obtain Compound C-7-1 (21.2 g, 71%) as a white solid.

Preparation of Compound C-7-2 Compound C-7-1 (21.4 g, 0.06 mol) and dry THF (1000 ml) were placed in a 2000 mL round bottom flask under anhydrous conditions followed by n-in hexane. BuLi (37 ml, 2.25 M solution) was added slowly to the reaction mixture at −78 ° C. while stirring the mixture under nitrogen. The reaction mixture was stirred for 1 h at -78 ° C. B (Oi-Pr) ₃ (29 ml, 0.13 mol) was slowly added to the reaction mixture at −78 ° C., and then the reaction mixture was heated to room temperature and allowed to react for 12 hours. After the reaction was complete, the reaction mixture was extracted with ethyl acetate. The resulting organic layer was then dried using MgSO ₄ and filtered. After removing the solvent from the organic layer under reduced pressure, the organic layer was filtered through a column to obtain Compound C-7-2 (15.5 g, 81%) as a white solid.

Preparation of Compound C-7-3 Compound C-7-2 (15.5 g, 0.051 mol), 2,4-dichloroquinazoline (12.2 g, 0.06 mol), Na ₂ CO ₃ (16.2 g, 0 .153 mol) and Pd (PPh ₃ ) ₄ (2.94 g, 0.0025 mol) were added to a mixture of toluene (250 mL), EtOH (40 mL) and H ₂ O (70 mL) in a 250 mL round bottom flask. The reaction mixture was stirred at 80 ° C. for 12 hours. After the reaction was complete, the reaction mixture was extracted with ethyl acetate. The resulting organic layer was then dried using MgSO ₄ and filtered. After removing the solvent from the organic layer under reduced pressure, the obtained solid was recrystallized to obtain Compound C-7-3 (14 g, 65%).

Preparation of Compound C-34 NaH 60% (0.62 g, 0.0154 mol) and DMF (60 ml) were placed in a 250 mL round bottom flask under anhydrous conditions. Compound C-1-1 (4.83 g, 0.012 mol) was dissolved in DMF (30 ml), and the mixture was placed in a round bottom flask. The reaction mixture was stirred for 1 hour. Compound C-7-3 (5 g, 0.012 mol) was dissolved in DMF (30 ml), and the mixture was placed in a round bottom flask. After stirring the mixture for 12 hours, the yellow solid was filtered, washed with MeOH, triturated with THF, then triturated with DMF to give compound C-34 (4.2 g, 45%). Got.
MS / FAB measured value 795; calculated value 794.96

Preparation Example 8: Preparation of compound C-36

Preparation of Compound C-8-1 Dibenzo [b, d] furan-4-ylboronic acid (20 g, 94.34 mmol), 1,3-dibromobenzene (22.3 g, 94.34 mmol), Pd (PPh ₃ ) ₄ After dissolving (5.45 g, 4.72 mmol) and K ₂ CO ₃ (39.1 g, 283.01 mmol) in a mixture of toluene (800 mL), EtOH (200 mL) and distilled water (200 mL), the reaction mixture was Stir for 3 hours at 70-80 ° C. After the reaction was complete, the aqueous layer was removed from the mixture by gravity separation. The obtained organic layer was concentrated and purified through a silica column to obtain compound C-8-1 (13 g, 43%).

Preparation of Compound C-8-2 Compound C-8-1 (13 g, 40.23 mmol) was dissolved in THF (300 ml) and 2.5 M n-BuLi in hexane (19 ml, 48.27 mmol) was added to the reaction mixture. After addition at -78 ° C, the reaction mixture was stirred for 1 hour. The reaction mixture was stirred for 12 h while B (Oi-Pr) ₃ (13.9 ml, 60.34 mmol) was slowly added to the reaction mixture. After the reaction was completed, 20 mL of purified water was slowly added dropwise to the reaction mixture. The reaction mixture was extracted with an EA / NH ₄ Cl aqueous solution. The obtained organic layer was concentrated, triturated with MC / hexane, and then filtered to obtain compound C-8-2 (6.8 g, 58.7%).

Preparation of Compound C-8-3 Compound C-8-2 (6.8 g, 23.6 mmol), 2,4-dichloroquinazoline (5.38 g, 23.6 mmol), Na ₂ CO ₃ (9.8 g, 70 0.8 mmol) and Pd (PPh ₃ ) ₄ (1.36 g, 1.18 mmol) in a mixture of toluene (240 mL) and distilled water (50 mL), the reaction mixture was stirred at 90-100 ° C. for 12 hours. Stir. After the reaction was complete, the reaction mixture was cooled to room temperature and the aqueous layer was removed from the mixture by gravity separation. The resulting organic layer was concentrated, triturated with THF / MeOH, filtered and then dried. The dried compound was dissolved in 3 L of chloroform and filtered through silica. The remaining solution was concentrated and triturated with THF / MeOH to give compound C-8-3 (3.8 g, 40%).

Preparation of Compound C-36 Compound C-1-1 (3.8 g, 9.34 mmol) and Compound C-8-3 (3.8 g, 9.34 mmol) were suspended in 80 mL of DMF, and then 60% NaH (1. 12 g, 28.02 mL) was added to the mixture at room temperature. The resulting reaction mixture was stirred for 12 hours. After adding purified water (1 L), the mixture was filtered under reduced pressure. The resulting solid was triturated with MeOH / ethyl acetate, dissolved in MC, filtered through silica, then triturated with MC / n-hexane to give compound C-36 (1.6 g, 21% )
MS / FAB measured value 779; calculated value 778.90

Preparation Example 9: Preparation of compound C-37

Preparation of compound C-9-1 1,3-dibromobenzene (16.5 g, 0.2 mol), dibenzo [b, d] thiophen-4-ylboronic acid (15 g, 0.06 mol), Pd (PPh ₃ ) ₄ (3.8 g, 0.003 mol) and Na ₂ CO ₃ (14 g, 0.13 mol) dissolved in a mixture of toluene (330 mL) and H ₂ O (70 mL) in a 2000 mL round bottom flask, the reaction mixture Was stirred at 80 ° C. for 12 hours. After the reaction was complete, the reaction mixture was extracted with ethyl acetate. Thereafter, the obtained organic layer was dried using MgSO ₄ and filtered. After removing the solvent from the organic layer under reduced pressure, the organic layer was filtered through a column to obtain Compound C-9-1 (8.4 g, 40%) as a white solid.

Preparation of Compound C-9-2 Compound C-9-1 (8.4 g, 0.025 mol) and dry THF (200 ml) were placed in a 500 mL round bottom flask under anhydrous conditions followed by n-in hexane. BuLi (15 ml, 2.25 M solution) was added slowly to the reaction mixture at −78 ° C. while stirring the mixture under nitrogen. The reaction mixture was stirred for 1 h at -78 ° C. B (Oi-Pr) ₃ (11.4 ml, 0.05 mol) was slowly added to the reaction mixture at −78 ° C., and then the reaction mixture was heated to room temperature and reacted for 12 hours. After the reaction was complete, the reaction mixture was extracted with ethyl acetate. The resulting organic layer was then dried using MgSO ₄ and filtered. After removing the solvent from the organic layer under reduced pressure, the organic layer was filtered through a column to obtain Compound C-9-2 (6 g, 80%) as a white solid.

Preparation of Compound C-9-3 Compound C-9-2 (5.9 g, 0.02 mol), 2,4-dichloroquinazoline (4.6 g, 0.02 mol), Na ₂ CO ₃ (6.2 g, 0 0.058 mol) and Pd (PPh ₃ ) ₄ (1.1 g, 0.00097 mol) after being added to a mixture of toluene (100 mL), EtOH (14 mL) and H ₂ O (30 mL) in a 250 mL round bottom flask. The reaction mixture was stirred at 70 ° C. for 3 hours. After the reaction was complete, the reaction mixture was extracted with ethyl acetate. The resulting organic layer was then dried using MgSO ₄ and filtered. After the solvent was removed from the organic layer under reduced pressure, the organic layer was filtered through a column to obtain Compound C-9-3 (7.0 g, 85%).

Preparation of Compound C-37 NaH 60% (0.5 g, 0.013 mol) and DMF (40 ml) were placed in anhydrous conditions in a 250 mL round bottom flask. Compound C-1-1 (3.7 g, 0.009 mol) was dissolved in DMF (30 ml), and the mixture was placed in a round bottom flask. The reaction mixture was stirred for 1 hour. Compound C-9-3 (4 g, 0.0095 mol) was dissolved in DMF (30 ml), and the mixture was placed in a round bottom flask. After stirring the mixture for 12 hours, the yellow solid was filtered, washed with MeOH, triturated with THF, then triturated with DMF to give compound C-37 (1.7 g, 20%). Obtained.
MS / FAB measured value 795; calculated value 794.96

Preparation Example 10: Preparation of compound C-39

Preparation of Compound C-10-1 Compound C-1-1 (14 g, 34.3 mmol) and 1-bromo-4-iodobenzene (48.5 g, 171.4 mmol), CuI (3.3 g, 17.1 mmol) , K ₃ PO ₄ (21.8 g, 102.9 mmol) and ethylenediamine (EDA) (2.3 ml, 34.3 mmol) were placed in toluene (500 ml) and the reaction mixture was stirred at reflux for 1 day. did. The reaction mixture was extracted with EA, distilled under reduced pressure, then passed through a column and filtered with MC / hexane to give compound C-10-1 (15.5 g, 80.1%).

Preparation of Compound C-10-2 Compound C-10-1 (15.5 g, 27.5 mmol) was dissolved in THF (250 ml) and 2.5 M n-BuLi in hexane (17.6 ml, 44 mmol) was dissolved in the solution. After addition to the reaction mixture at −78 ° C., the reaction mixture was stirred for 1 hour. The reaction mixture was stirred for 2 h while B (Oi-Pr) ₃ (12.6 ml, 55 mmol) was slowly added to the reaction mixture. After the reaction mixture was quenched by adding 2M HCl, the reaction mixture was extracted with distilled water and EA. The obtained solid was recrystallized using MC and hexane to obtain Compound C-10-2 (8.7 g, 60%).

Preparation of Compound C-39 Compound C-3-1 (3.2 g, 9.2 mmol), Compound C-10-2 (4.9 g, 9.2 mmol), Pd (PPh ₃ ) ₄ (532 mg, 0.46 mmol) ) And Na ₂ CO ₃ (2.9 g, 27.6 mmol) in a mixture of toluene (55 ml), EtOH (14 ml) and distilled water (14 ml), then the reaction mixture is stirred for 2 hours at 90 ° C. did. The reaction mixture was extracted with distilled water and EA, then passed through a column and filtered using MC and hexane to give compound C-39 (5.5 g, 75%).
MS / FAB measured value 795; calculated value 794.96

Preparation Example 11: Preparation of compound C-40

Preparation of Compound C-40 Compound C-2-1 (3.2 g, 9.2 mmol), Compound C-10-2 (4.9 g, 9.2 mmol), Pd (PPh ₃ ) ₄ (532 mg, 0.46 mmol) ) And Na ₂ CO ₃ (2.9 g, 27.6 mmol) in a mixture of toluene (55 ml), EtOH (14 ml) and distilled water (14 ml), then the reaction mixture is stirred for 2 hours at 90 ° C. did. The reaction mixture was extracted with distilled water and EA, then passed through a column and filtered using MC and hexane to give compound C-40 (5.5 g, 75%).
MS / FAB measured value 779; calculated value 778.90

Example 1: Preparation of an OLED device using a compound according to the invention An OLED device was prepared using a compound according to the invention. A transparent electrode indium tin oxide (ITO) thin film (15 Ω / sq) on a glass substrate for an organic light emitting diode (OLED) device (Samsung Corning, Korea) was ultra-thin using trichloroethylene, acetone, ethanol and distilled water. Sequentially subjected to sonic cleaning and then stored in isopropanol. Thereafter, the ITO substrate was attached to a substrate holder of a vacuum deposition apparatus. N1- (naphthalen-2-yl) -N4, N4-bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N1-phenylbenzene-1,4-diamine was added to the cell of the vacuum deposition apparatus. After that, the pressure in the chamber of the apparatus was adjusted to 10 ⁻⁶ torr. Thereafter, an electric current was applied to the cell to evaporate the introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate. Thereafter, N, N′-di (4-biphenyl) -N, N′-di (4-biphenyl) -4,4′-diaminobiphenyl was introduced into another cell of the vacuum deposition apparatus, and current was supplied to the cell. To form a hole transport layer having a thickness of 20 nm on the hole injection layer. Thereafter, Compound C-2 was introduced as a host material into one cell of the vacuum deposition apparatus, and Compound D-11 was introduced as a dopant into another cell. The two materials were evaporated at different rates and evaporated at a doping amount of 4 to 20 wt% to form a light emitting layer having a thickness of 30 nm on the hole transport layer. Then, 9,10-di (1-naphthyl) -2- (4-phenyl-1-phenyl-1H-benzo [d] imidazole) anthracene is introduced into one cell and lithium quinophosphate is introduced into another cell. Introduced. The two materials were evaporated at different rates and deposited with a doping amount of 30 to 70 wt% to form an electron transport layer having a thickness of 30 nm on the light emitting layer. Thereafter, lithium quinolinate was deposited on the electron transport layer as an electron injection layer having a thickness of 1 to 2 nm, and then an Al cathode having a thickness of 150 nm was deposited on the electron injection layer by another vacuum deposition apparatus. . In this way, an OLED element was produced. All materials used to make OLED devices were materials purified by vacuum sublimation at 10 ⁻⁶ torr.
The fabricated OLED element showed red emission with a luminance of 1,020 cd / m ² and a current density of 14.0 mA / cm ² at a driving voltage of 4.0V. Further, the shortest time required for the luminance to drop to 90% at a luminance of 5,000 nits was 60 hours.

Examples 2 to 11: Preparation of OLED devices using compounds according to the present invention OLED devices were used in the same manner as in Example 1 except that the OLED devices were used as host materials and dopants as shown in the table below. Produced.

Comparative Example 1: Production of an OLED element using an existing electroluminescent compound An OLED element was formed by using a light emitting layer having a thickness of 30 nm on a hole transport layer and 4,4′-N, N′-dicarbazole. -Deposited by using biphenyl (CBP) as the host material and using compound D-11 as a dopant, and a hole blocking layer having a thickness of 10 nm, aluminum (III) bis (2-methyl-8) -Quinolinato) Prepared in the same manner as in Example 1 except that it was deposited using 4-phenylphenolate.
The fabricated OLED element exhibited red emission having a luminance of 1,000 cd / m ² and a current density of 20.0 mA / cm ² at a driving voltage of 8.2V. Furthermore, the shortest time required for the luminance to decrease to 90% at a luminance of 5,000 nits was 10 hours.

  The results of Examples and Comparative Examples are shown in the following table.

  The compounds of the present invention have better luminescent properties than existing materials. Furthermore, a device using the compound according to the present invention as a host material brings about an increase in power efficiency due to a decrease in driving voltage, and thus it is possible to improve power consumption.

Claims (6)

Compound represented by Formula 1 below

(Where
L ₁ and L ₂ are each independently a single bond, a substituted or unsubstituted 5- to 30-membered heteroarylene group, a substituted or unsubstituted (C6-C30) arylene group, or a substituted or unsubstituted (C6 -C30) represents a cycloalkylene group,
X ₁ represents CH or N;
Y ₁ and Y ₂ each independently represent —O—, —S—, —CR ₈ R ₉ — or —NR ₁₀ —.
R ₁ to R ₁₀ are each independently hydrogen, deuterium, halogen, a substituted or unsubstituted (C1-C30) alkyl group, a substituted or unsubstituted (C6-C30) aryl group, substituted or unsubstituted. 3- to 30-membered heteroaryl group, substituted or unsubstituted (C3-C30) cycloalkyl group, substituted or unsubstituted 5- to 7-membered heterocycloalkyl group, substituted or unsubstituted (C6-C30) An aryl (C1-C30) alkyl group, a substituted or unsubstituted (C6-C30) aryl group fused with at least one (C3-C30) cycloalkyl group, at least one substituted or unsubstituted (C6-C30) A 5- to 7-membered heterocycloalkyl group fused to an aromatic ring, at least one substituted or unsubstituted (C6-C30) aromatic Was engaged ring condensed (C3-C30) cycloalkyl _{group, -NR 21 R 22, -SiR 23} R 24 R 25, -SR 26, -OR 27, substituted or unsubstituted (C2-C30) alkenyl group, a substituted Or an unsubstituted (C2-C30) alkynyl group, a cyano group, a nitro group or a hydroxyl group, or an adjacent substitution via a substituted or unsubstituted (C3-C30) alkylene or (C3-C30) alkenylene group Linked to a group to form a monocyclic or polycyclic alicyclic or aromatic ring, wherein one or more carbon atoms of said ring is selected from nitrogen, oxygen and sulfur May be replaced by a heteroatom,
R ₂₁ to R ₂₇ have the same definition as defined for R ₁ to R ₁₀ ;
a, b, e, and g each independently represent an integer of 1 to 4, and when a, b, e, or g is an integer of 2 or more, R ₁ , R ₂ , R ₅ or individual R ₇ are the same or different,
c, d, and f each independently represent an integer of 1 to 3, and when c, d, or f is an integer of 2 or more, each R ₃ , each R _4, or each R ₆ is the same And the heterocycloalkyl group and the heteroaryl and heteroarylene group contain at least one heteroatom selected from B, N, O, S, P (═O), Si and P To do). A substituted alkyl and alkylene group, a substituted alkenyl group, a substituted alkynyl group, a substituted cycloalkylene group, a substituted cycloalkyl group, a substituted heterocycloalkyl group in the L ₁ and L ₂ , R ₁ to R ₁₀ and R ₂₁ to R ₂₇ groups; Substituted aryl and arylene groups, substituted heteroaryl and heteroarylene groups, and substituted aromatic ring substituents are each independently substituted or unsubstituted (C1-C30) alkyl groups with deuterium, halogen, halogen. , (C6-C30) aryl group, (C6-C30) aryl-substituted or unsubstituted 5- to 30-membered heteroaryl group, (C3-C30) cycloalkyl group, 5- to 7-membered heteroaryl A cycloalkyl group, a (C1-C30) alkylsilyl group, a (C6-C30) a Lillesilyl group, (C1-C30) alkyl (C6-C30) arylsilyl group, (C2-C30) alkenyl group, (C2-C30) alkynyl group, cyano group, carbazolyl group, (C1-C30) alkylamino group, C6-C30) arylamino group, (C1-C30) alkyl (C6-C30) arylamino group, (C6-C30) arylboronyl group, (C1-C30) alkylboronyl, (C1-C30) alkyl (C6 The group consisting of -C30) aryl boronyl, (C6-C30) aryl (C1-C30) alkyl group, (C1-C30) alkyl (C6-C30) aryl group, carbonyl group, carboxyl group, nitro group, and hydroxyl group The compound according to claim 1, wherein the compound is at least one selected from: X ₁ represents CH or N, and L ₁ and L ₂ each independently represent a single bond, phenylene, naphthylene, biphenylene, terphenylene, anthrylene, andenylene, fluorenylene, phenanthrylene, triphenylenylene, pyrenylene, phenylenylene, chrysenylene. , Naphthacenylene, fluoranthenyl, furylene, thiophenylene, pyrrolylene, imidazolylene, pyrazolylene, thiazolylene, thiadiazolylene, isothiazolylene, isoxazolylene, oxazolylene, oxadiazolylene, triazinylene, tetrazinylene, triazorylene, tetrazolylene, pyrazolenylene, pyridylene, pyridylene, pyridylene, pyridylene, pyridylene, dizylene , Pyridazinylene, benzofuranylene, benzothiophenylene, isobenzofuranylene, benzo Imidazolylene, benzothiazolylene, benzoisothiazolylene, benzoisoxazolylene, benzoxazolylene, isoindoleylene, indolylene, indazolylene, benzothiadiazolylene, quinolylene, isoquinolylene, cinnolinylene, quinazolinylene, quinoxalinylene, carbazolylene, fe 2. A compound according to claim 1, characterized in that it is selected from the group consisting of nantridinylene, benzodioxorylene, dibenzofuranylene and dibenzothiophenylene. In Equation 1

But the following structure

The compound according to claim 1, characterized in that it is selected from: The compound represented by Formula 1 is

The compound according to claim 1, wherein the compound is selected from the group consisting of:   An organic electroluminescent device comprising the compound according to claim 1.