KR102391160B1 - Naphthyridine-substituted anthracene derivative and organic electroluminescent device - Google Patents

Abstract

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여기에서, A¹과 A²가 N이고, A³이 C이거나 또는 A²와 A³이 N이고 A¹이 C이며; L와 L'는 화학결합, 치환 또는 미치환의 C₆~C₁₂의 아릴렌 또는 서브 축합고리계 방향족 탄화수소 라디칼, 치환 또는 미치환의 C₃~C₁₂의 서브 헤테로아릴기 또는 서브 축합헤테르고리계 방향족 탄화수소 라디칼로부터 선택하며; Ar¹, Ar², Ar⁴와 Ar⁵는 각각 독자적으로 치환 또는 비(非)치환의 C₆~C₃₀의 아릴기 또는 축합고리계 방향족 탄화수소 라디칼, 치환 또는 비치환의 C₃~C₃₀의 헤테로아릴기 또는 축합헤테르고리계 방향족 탄화수소 라디칼로부터 선택하며; R¹, R², R³, R^3', R⁴, R⁸과 R⁹는 각각 독자적으로 수소, C₁~C₁₀의 알킬기, 할로겐, 시아노, 니트로기, 치환 또는 미치환의 C₆~C₃₀의 아릴기 또는 축합고리계 방향족 탄화수소 라디칼, 치환 또는 미치환의 C₃~C₃₀의 헤테로아릴기 또는 축합헤테르고리계 방향족 탄화수소 라디칼로부터 선택하며; R⁶과 R⁷은 각각 수소 또는 C₁~C₁₀의 알킬기로부터 선택하고, 여기에서, R⁶과 R⁷은 동시에 수소가 아닌 것을 특징으로 한다.The present invention relates to a naphthyridine-substituted anthracene derivative, and specifically, has a structure indicated by Formula (I) or Formula (II) below;

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wherein A ¹ and A ² are N and A ³ is C or A ² and A ³ are N and A ¹ is C; L and L' are a chemical bond, a substituted or unsubstituted C ₆ -C ₁₂ arylene or sub-condensed ring-based aromatic hydrocarbon radical, a substituted or unsubstituted C ₃ -C ₁₂ sub-heteroaryl group, or a sub-condensed hetero selected from cyclic aromatic hydrocarbon radicals; Ar ¹ , Ar ² , Ar ⁴ and Ar ⁵ are each independently a substituted or unsubstituted C ₆ ~ C ₃₀ aryl group or a condensed cyclic aromatic hydrocarbon radical, or a substituted or unsubstituted C ₃ ~ C ₃₀ hetero selected from an aryl group or a condensed heterocyclic aromatic hydrocarbon radical; R ¹ , R ² , R ³ , R ^{3 '} , R ⁴ , R ⁸ and R ⁹ are each independently hydrogen, a C ₁ -C ₁₀ alkyl group, halogen, cyano, nitro group, substituted or unsubstituted C ₆ -C ₃₀ selected from an aryl group or a condensed ring-based aromatic hydrocarbon radical, a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group or a condensed heterocyclic aromatic hydrocarbon radical; R ⁶ and R ⁷ are each selected from hydrogen or a C ₁ ~ C ₁₀ alkyl group, wherein R ⁶ and R ⁷ are not hydrogen at the same time.

Description

Naphthyridine-substituted anthracene derivative and organic electroluminescent device

FIELD OF THE INVENTION The present invention relates to the field of organic optoelectronic materials, and more particularly, to a kind of naphthyridine-substituted anthracene derivative and an organic electroluminescent device.

This application is a Chinese patent application filed with the Chinese Patent Office on July 12, 2017 with the application number 201710565557.3 and the invention titled "New organic electroluminescent device", and an application filed with the Chinese Patent Office on December 8, 2017 The Chinese patent application number 201711297038.X and the invention title is "Naphthyridine-substituted anthracene derivative and organic electroluminescent device", and the application number 201711312321.5 filed with the Chinese Patent Office on December 8, 2017, the invention title is "quinoc" Priority is claimed on the Chinese patent application "Saline-substituted anthracene derivative and organic electroluminescent device", the entire contents of which are incorporated herein by reference.

As OLED technology continues to advance in the two fields of lighting and display, people are paying more attention to research on high-efficiency organic materials that affect the performance of OLED devices. OLED devices with excellent efficiency and long lifespan are usually the result of optimally matching the device structure with various organic materials. The most common OLED device structure typically includes organic materials such as hole injection material, hole hole transport material, electron transport material, and light emitting material of various colors (pigment or mixed object material) and corresponding body material.

Among the electroluminescent devices, the conventionally used electron transport material is Alq ₃ (tri(8-hydroxyquinoline)aluminum), but Alq ₃ has a relatively low electron mobility (about 10-6 cm ² /Vs). In order to improve the electron transport performance of the electroluminescent device, researchers have been conducting numerous exploratory research work. However, there is still a pedant that cannot consider luminous efficiency and OLED device lifetime at the same time.

In a first aspect, some embodiments of the present invention provide a naphthyridine-substituted anthracene derivative having a structure represented by Formula (I) below.

From here,

A ¹ and A ² are N and A ³ is C, or A ² and A ³ are N and A ¹ is C;

L is a chemical bond, a substituted or unsubstituted C ₆ to C ₁₂ arylene or sub-condensed ring-based aromatic hydrocarbon radical, a substituted or unsubstituted C ₃ to C ₁₂ sub-heteroaryl group or a sub-condensed heterocyclic aromatic hydrocarbon radicals;

Ar ¹ and Ar ² are each independently a substituted or unsubstituted C ₆ ~ C ₃₀ aryl group or a condensed ring-based aromatic hydrocarbon radical, a substituted or unsubstituted C ₃ ~ C ₃₀ heteroaryl group or a condensed heterocyclic aromatic hydrocarbon radicals;

R ¹ , R ² , R ³ , R ^{3 '} and R ⁴ are each independently hydrogen, a C ₁ -C ₁₀ alkyl group, halogen, cyano, a nitro group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group or a condensed ring-based aromatic hydrocarbon radical, a substituted or unsubstituted C ₃ to C ₃₀ heteroaryl group, or a condensed heterocyclic aromatic hydrocarbon radical.

In a second aspect, some embodiments of the present invention provide a naphthyridine-substituted anthracene derivative having a structure represented by Formula (II) below.

Here, L' is a chemical bond, a substituted or unsubstituted C ₆ ~ C ₁₂ arylene or sub-condensed ring-based aromatic hydrocarbon radical, a substituted or unsubstituted C ₃ ~ C ₁₂ sub-heteroaryl group, or a sub-condensed heteroaryl group tercyclic aromatic hydrocarbon radicals;

Ar ⁴ and Ar ⁵ are each independently selected from a substituted or unsubstituted C ₆ ~ C ₃₀ aryl group or a condensed ring aromatic hydrocarbon radical, a substituted or unsubstituted C ₃ ~ C ₃₀ heteroaryl group or a condensed heterocyclic aromatic hydrocarbon radical;

R ⁶ and R ⁷ are each selected from hydrogen or a C ₁ -C ₁₀ alkyl group, wherein R ⁶ and R ⁷ are not hydrogen at the same time;

R ⁸ and R ⁹ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a halogen, cyano, nitro group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group or a condensed ring-based aromatic hydrocarbon radical, a substituted or It is selected from an unsubstituted C ₃ -C ₃₀ heteroaryl group or a condensed heterocyclic aromatic hydrocarbon radical.

In a third aspect, some embodiments of the present invention include an electron transport layer and use, as an electron transport material, one of the naphthyridine-substituted anthracene derivatives provided in the first and second aspects in the electron transport layer. An organic electroluminescent device is provided.

Hereinafter, some embodiments of the present invention will be described in detail in conjunction with the drawings, wherein:
1 shows the Highest Occupied Molecular Orbital (HOMO) of Compound A8 provided by some examples;
2 shows the lowest unoccupied molecular orbital (LUMO) of compound A8 provided by some examples;
3 depicts the HOMO of Compound A17 provided by some examples;
4 depicts the LUMO of Compound A17 provided by some examples;
5 depicts the HOMO of compound B1 provided by some examples;
6 depicts the LUMO of compound B1 provided by some examples;
7 depicts the HOMO of compound B5 provided by some examples;
8 depicts the LUMO of compound B5 provided by some examples;
9 depicts the HOMO of compound E10 provided in some examples;
10 depicts the LUMO of compound E10 provided by some examples.

Some embodiments according to the present invention provide a naphthyridine-substituted anthracene derivative having a structure indicated by Formula (I) below.

From here,

A ¹ and A ² are N and A ³ is C, or A ² and A ³ are N and A ¹ is C;

L is a chemical bond, a substituted or unsubstituted C ₆ to C ₁₂ arylene or sub-condensed ring-based aromatic hydrocarbon radical, a substituted or unsubstituted C ₃ to C ₁₂ sub-heteroaryl group or a sub-condensed heterocyclic aromatic hydrocarbon radicals;

Ar ¹ and Ar ² are each independently a substituted or unsubstituted C ₆ ~ C ₃₀ aryl group or a condensed ring-based aromatic hydrocarbon radical, a substituted or unsubstituted C ₃ ~ C ₃₀ heteroaryl group or a condensed heterocyclic aromatic hydrocarbon radicals;

R ¹ , R ² , R ³ , R ^{3 '} and R ⁴ are each independently hydrogen, a C ₁ -C ₁₀ alkyl group, halogen, cyano, a nitro group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group or a condensed ring-based aromatic hydrocarbon radical, a substituted or unsubstituted C ₃ to C ₃₀ heteroaryl group, or a condensed heterocyclic aromatic hydrocarbon radical.

For example, defining that Ar ¹ and Ar ² are independently selected from aryl groups independently from R ¹ , R ² , R ³ , R ^{3 '} , and R ⁴ means that a certain number of aromatics of carbon atoms having a cyclic matrix It refers to a ring system, and includes a monocyclic structure-substituted radical (eg, a phenyl group, etc.), and also includes an aromatic ring-substituted radical (eg, biphenyl, tri-biphenyl, etc.) of a covalently linked structure.

For example, defining that R ¹ , Ar ¹ and Ar ² are independently selected from condensed cyclic aromatic hydrocarbon radicals independently from R ² , R ³ , R ^{3 '} and R ⁴ means having a certain number of cyclic matrices Refers to an aromatic ring system of carbon atoms, including a fused-ring structural-substituted radical (eg, naphthyl, anthracene, etc.), and a structural radical (for example, For example, benzene binaphthyl, naphthalene biphenyl, bibenzene bianthracene, etc.), and a condensed aromatic ring-substituted radical of a covalently linked structure (eg, dinaphthyl, etc.) is also included.

For example, defining that Ar ¹ and Ar ² are independently selected from a heteroaryl group or a condensed heterocyclic aromatic hydrocarbon radical independently from R ¹ , R ² , R ³ , R ^{3 '} , R ⁴ is B, Monocyclic or condensed ring aryl groups having one or more ring carbon atoms selected from heteroatoms of N, O, S, P(=O), Si and P and having ring carbon atoms are also included.

The naphthyridine-substituted anthracene derivative of formula (I) provided in some embodiments of the present invention has the following advantages.

Since the matrix structure has very good coplanarity, the operating voltage of the device using the material is significantly lowered by allowing the derivative to have a relatively high carrier transport property. The two positions of the naphthyridine and anthracene rings are linked to each other, and such a design can protect the active site of the parent nucleus, which is beneficial to the stability of the compound. We can ensure that the distributions are consistent with each other.

Since the parent structure has a relatively deep LUMO, it not only realizes excellent electron transport performance, but also maintains the coplanar structure, which is advantageous for the film-forming properties of molecules; Changes in the energy level of the substituent and the electronic properties can significantly improve the luminous efficiency of the device by fine-tuning the energy level and transmission performance of the final target compound and using the compound as the material for the electron transport layer.

The high mobility of the compound also makes it possible to control the thickness of the material within a wider adjustment range, and when used as an electron transport layer material, by thickening the film thickness of the material, so as not to significantly affect the operating voltage of the device. can do.

In some embodiments, L is selected from a substituted C ₆ -C ₁₂ arylene or sub-condensed ring-based aromatic hydrocarbon radical, a C ₃ -C ₁₂ sub-heteroaryl group, or a sub-condensed heterocyclic aromatic hydrocarbon radical, aryl Ren, sub-condensed cyclic aromatic hydrocarbon radical, sub-heteroaryl group or sub-condensed heterocyclic aromatic hydrocarbon radical is independently halogen, cyano, nitro group, C ₁ to C ₁₀ alkyl group, cyclic alkyl group, Alkylene, C ₁ ~ C ₆ An alkoxy group or thioalkoxy group radical, C ₆ ~ C ₃₀ A monocyclic aromatic hydrocarbon or condensed ring aromatic hydrocarbon radical, and C containing a hetero atom selected from N, O, S, Si ₆ ~ C ₃₀ A monocyclic aromatic hydrocarbon or condensed ring aromatic hydrocarbon radical and Si(R ⁵ ) ₃ It is selected from the group consisting of. Here, R ⁵ is selected from a C ₁ ~ C ₆ alkyl group.

In some embodiments, A ¹ and A ² are N, A ³ is C, and R ^3′ is hydrogen. In some of these examples, a naphthyridine-substituted anthracene derivative having the structure indicated by Formula (I-1) is provided.

In some embodiments, R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen, C ₁ -C ₅ alkyl group, halogen, cyano, nitro group, C ₆ -C ₁₅ substituted or unsubstituted aryl It is selected from a group or condensed ring-based aromatic hydrocarbon radical, a C ₃ to C ₁₅ substituted or unsubstituted heteroaryl group, or a condensed heterocyclic aromatic hydrocarbon radical.

R ¹ , R ² , R ³ and R ⁴ are each independently a substituted C ₆ ~ C ₃₀ aryl group or a condensed cyclic aromatic hydrocarbon radical, a C ₃ ~ C ₃₀ heteroaryl group or a condensed heterocyclic aromatic hydrocarbon In some embodiments selected from radicals, the substituted radicals in the aryl group, the condensed ring aromatic hydrocarbon radical, the heteroaryl group or the condensed heterocyclic aromatic hydrocarbon radical are independently halogen, cyano, nitro group, C ₁ ~ C ₁₀ alkyl group, cyclic alkyl group, alkylene, C ₁ ~ C ₆ alkoxy group or thioalkoxy group radical, C ₆ ~ C ₃₀ monocyclic aromatic hydrocarbon or condensed cyclic aromatic hydrocarbon radical, and N, O, S, from Si It is selected from the group consisting of a C ₆ -C ₃₀ monocyclic aromatic hydrocarbon or condensed ring aromatic hydrocarbon radical containing a selected hetero atom and Si(R ⁵ ) ₃ . Here, R ⁵ is selected from a C ₁ ~ C ₆ alkyl group. Furthermore, in some embodiments, the substituted radicals are independently F, cyano, C ₁ -C ₅ alkyl group, cyclic alkyl group, alkylene, Si(CH ₃ ) ₃ , C ₂ -C ₅ alkoxy group, or thio alkoxy group radicals.

In some embodiments, R ¹ , R ² , R ³ and R ⁴ are each independently selected from a substituted or unsubstituted heteroaryl group or a condensed heterocyclic aromatic hydrocarbon radical, a heteroaryl group or a condensed heterocyclic aromatic hydrocarbon A heteroatom in the radical is one or more O, S and/or N.

In some embodiments, Ar ¹ and Ar ² are independently a C ₆ -C ₂₀ substituted or unsubstituted aryl group or condensed ring-based aromatic hydrocarbon radical, a C ₅ -C ₂₀ substituted or unsubstituted heteroaryl group or condensed hetero selected from cyclic aromatic hydrocarbon radicals.

In some embodiments in which Ar ¹ and Ar ² independently select a substituted or unsubstituted C ₃ to C ₃₀ heteroaryl group or a condensed heterocyclic aromatic hydrocarbon radical, a heteroaryl group or a condensed heterocyclic aromatic hydrocarbon radical The hetero atom in is one or more O, S and/or N.

In some embodiments, Ar ¹ and Ar ² are each independently selected from a substituted C ₆ -C ₃₀ aryl group or a condensed ring aromatic hydrocarbon radical, a C ₃ -C ₃₀ aryl group, or a condensed ring aromatic hydrocarbon radical, aryl Substitution radicals in the group, condensed ring aromatic hydrocarbon radical, heteroaryl group or condensed heterocyclic aromatic hydrocarbon radical are independently halogen, cyano, nitro group, C ₁ to C ₁₀ alkyl group, cyclic alkyl group, alkylene, C ₁ ~ C ₆ Alkoxy group or thioalkoxy group radical, C ₆ ~ C ₃₀ Monocyclic aromatic hydrocarbon or condensed ring aromatic hydrocarbon radical, and N, O, S, C ₆ ~ C containing a hetero atom selected from Si ₃₀ is selected from the group consisting of monocyclic aromatic hydrocarbon or condensed ring aromatic hydrocarbon radicals and Si(R ⁵ ) ₃ . Here, the R ⁵ is selected from a C ₁ ~ C ₆ alkyl group. Further, in some embodiments, the substituents are independently F, cyano, C ₁ -C ₅ alkyl group, cyclic alkyl group, alkylene, Si(CH ₃ ) ₃ , C ₁ -C ₅ alkoxy group or thioalkoxy A group consisting of a group radical, a C ₆ -C ₁₅ monocyclic aromatic hydrocarbon or condensed ring aromatic hydrocarbon radical, and a C ₆ -C ₁₅ monocyclic aromatic hydrocarbon or condensed ring aromatic hydrocarbon radical containing a hetero atom selected from N or O can be selected from

In some embodiments, Ar ¹ and Ar ² are each independently a phenyl group, biphenyl, tribiphenyl, naphthyl, anthracene, phenanthryl, indenyl, fluoroanthracene, fluorenyl, indenofluorene, triphenylene, Phenyl group substituted by pyrenyl, perylenyl, chrysene group, tetracene and furyl, thienyl, pyrrolyl and/or pyridyl, benzene binaphthyl, 4-naphthylphenyl group, 6-phenyl groupnaphthyl, 7-phenyl group may be selected from the group consisting of the phenanthryl radical. The biphenyl is selected from the group consisting of 2-biphenyl, 3-biphenyl, and 4-biphenyl.

In some embodiments, the tribiphenyl is bis-tribiphenyl-4-YL, bis-tribiphenyl-3-YL, bis-tribiphenyl-2-YL, m-tribiphenyl-4-YL, m-tribiphenyl-3-YL and m-tribiphenyl-2-YL radicals. In some embodiments, the naphthyl is selected from the group consisting of 1-naphthyl and 2-naphthyl. In some embodiments, the anthracene is selected from the group consisting of 1-anthracene, 2-anthracene and 9-anthracene. In some embodiments, the fluorenyl is selected from the group consisting of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl. In some embodiments, the fluorenyl derivative is selected from the group consisting of 9,9'-dimethylfluorene, 9,9'-spirobifluorene and benzofluorene. In some embodiments, the pyrenyl is selected from the group consisting of 1-pyrenyl, 2-pyrenyl and 4-pyrenyl. In some embodiments, the tetracene is selected from the group consisting of 1-tetracene, 2-tetracene and 9-tetracene.

In some embodiments, Ar ¹ and Ar ² are independently furyl, phenyl furyl, thienyl, phenyl thienyl, pyrrolyl, phenyl pyrrolyl, pyridyl, phenyl pyridyl, naphthyridine, quinoline, triazinyl, benzofuryl, Benzothienyl, benzotrizine, benzonaphthyridine, isobenzofuryl, indolyl, benzoquinoline, dibenzofuryl, dibenzothienyl, dibenzopyrrolyl, carbazole group and its derivatives, phenyl group-substituted diazole, pyrine group, pyrine thiazyl and benzodioxole alkylene radicals.

In some embodiments, the carbazole derivative is selected from the group consisting of 9-phenyl carbazole, 9-naphthyl carbazole benzo carbazole, dibenzo carbazole and indole carbazole.

In some embodiments, Ar ¹ and Ar ² are each independently a phenyl group, biphenyl, naphthyl, pyridyl substituted phenyl group, phenyl group pyridyl, anthracene, phenanthryl, furyl, phenyl group furyl, thienyl, phenyl group thienyl, pyrrolyl , phenyl group pyrrolyl or pyridyl.

In some embodiments, R ¹ , R ⁴ , R ³ and R ² are each independently a methyl group, ethyl group, propyl group, isopropyl group, tertbutyl, cyclopentyl, cyclohexyl, cyano, nitro group, phenyl group, naph group tyl, triphenylene, 9,9 dimethyl fluorene, spirobifluorene, furyl, phenyl furyl, thienyl, phenyl group thienyl, pyrrolyl, phenyl group pyrrolyl, pyridyl, phenyl group pyridyl, naphthyridine, fluorenyl , indenofluorene, quinoline, triazinyl, benzofuryl, benzothienyl, benzotriazine, benzonaphthyridine, isobenzofuryl, indolyl, benzoquinoline, dibenzofuryl, dibenzothienyl, dibenzopyrrolyl, It is selected from the group consisting of a carbazole group and its derivatives, a phenyl group-substituted diazole, a pyrine group, a pyrine thiazyl, and a benzodioxole alkylene radical.

In some embodiments, the carbazole derivative is selected from the group consisting of 9-phenyl carbazole, 9-naphthyl carbazole benzo carbazole, dibenzo carbazole and indole carbazole.

In some embodiments, R ¹ , R ⁴ , R ³ and R ² are each independently a methyl group, ethyl group, propyl group, isopropyl group, tertbutyl, phenyl group, naphthyl, pyridyl, phenyl group pyridyl, dibenzofuryl or biphenyl.

In some embodiments, A ² and A ³ are N and A ¹ is C. These examples provide naphthyridine-substituted anthracene derivatives having the structure indicated by (I-2).

From here,

R ¹ is selected from a substituted or unsubstituted C ₆ -C ₃₀ aryl group or a condensed ring-based aromatic hydrocarbon radical, a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group or a condensed heterocyclic aromatic hydrocarbon radical;

R ³ and R ^3′ may be connected to each other to form a cyclic structure.

For example, when it is defined that R ³ and R ^3' may be connected to each other to form a cyclic structure, such a cyclic structure may be an aliphatic monocyclic or polycyclic aromatic monocyclic or condensed ring system. Such a ring may include a hetero atom. In the example of an aliphatic monocyclic ring (for example, an aliphatic 5-membered ring or 6-membered ring formed by connecting two optionally adjacent radicals among R ³ and R ^3' ), the constituent atoms of the ring have a heteroatom in addition to a carbon atom may be present, the ring may have a substituent, and carbon atoms constituting the ring may also form a ketone group. Among the examples of the rings, carbon atoms in the cyclopentane ring, cyclohexane ring, dicyclopentene ring, tetrahydropyrrole ring, tetrahydrofuran ring, piperizine ring, cyclopentane ring and cyclopentane ring are substituted by a ketone group. The ester ring obtained by substitution, etc. are mentioned as an example. Among the examples of the aromatic monocyclic or condensed ring system, for example, a C ₆ to C ₃₀ monocyclic or condensed ring system such as a benzene ring or a naphthalene ring may be selected. Among monocyclic or polycyclic examples including hetero atoms, a pyrrole ring, a benzopyrrole ring, a pyridine ring, an indole ring, an N-phenyl group-substituted indole ring, a thiophene ring, a benzothiophene ring, a furan ring, a benzofuran ring, etc. may be selected. can

In some embodiments, in Formula (I-2), R ¹ , Ar ¹ and Ar ² are each independently a C ₆ -C ₂₀ substituted aryl group or a condensed ring-based aromatic hydrocarbon radical, and a C ₅ -C ₂₀ limit or an unsubstituted heteroaryl group or a condensed heterocyclic aromatic hydrocarbon radical.

In some embodiments, R ¹ , Ar ¹ and Ar ² are each independently selected from a substituted aryl group, a condensed ring aromatic hydrocarbon radical, a heteroaryl group, or a condensed heterocyclic aromatic hydrocarbon radical, an aryl group, a condensed ring system Substitution radicals in the aromatic hydrocarbon radical, heteroaryl group or condensed heterocyclic aromatic hydrocarbon radical are independently halogen, cyano, nitro group, C ₁ to C ₁₀ alkyl group, cyclic alkyl group, alkylene, C ₁ to C ₆ selected from the group consisting of an alkoxy group or a thioalkoxy group radical of Si(R ⁵ ) ₃ . The R ⁵ is selected from a C ₁ ~ C ₆ alkyl group. Furthermore, in some embodiments, the substituted radical is independently a group consisting of F, cyano, a C ₁ -C ₅ alkyl group, a cyclic alkyl group, an alkylene, an alkoxy group or a thioalkoxy group radical and Si(CH ₃ ) ₃ . Choose from

In some embodiments, each of R ¹ , Ar ¹ and Ar ² is independently selected from a substituted or unsubstituted heteroaryl group or a condensed heterocyclic aromatic hydrocarbon radical, the hetero atom is one or more O, S and/or N am.

In some embodiments, R ¹ , Ar ¹ and Ar ² in Formula (I-2) may be the same or different. Optionally, R ¹ , Ar ¹ and Ar ² are different.

In some embodiments wherein R ¹ , Ar ¹ and Ar ² are each independently selected from an aryl group condensed ring-based aryl group radical, the corresponding aryl group or condensed ring-based aryl group radical is a phenyl group, biphenyl, tribiphenyl, naphthyl , anthracene, phenanthryl, indenyl, fluoroanthracene, triphenylene, fluorenyl, indenofluorene, pyrenyl, perylenyl, chrysene group or tetracene and furyl, thienyl, pyrrolyl and/or pyridyl A phenyl group substituted with, 2-biphenyl, 3-biphenyl, 4-biphenyl, bis-tribiphenyl-4-YL, bis-tribiphenyl-3-YL, bis-tribiphenyl-2-YL, m-tribiphenyl-4-YL, m-tribiphenyl-3-YL, m-tribiphenyl-2-YL, benzene binaphthyl, 4-naphthylphenyl group, 6-phenyl group naphthyl, 7-phenyl group phenanthryl radicals.

In some embodiments, the naphthyl is selected from the group consisting of 1-naphthyl and 2-naphthyl. In some embodiments, the anthracene is selected from the group consisting of 1-anthracene, 2-anthracene and 9-anthracene. In some embodiments, the fluorenyl is selected from the group consisting of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl. In some embodiments, the fluorenyl derivative is selected from the group consisting of 9,9'-dimethylfluorene, 9,9'-spirobifluorene and benzofluorene. In some embodiments, the pyrenyl is selected from the group consisting of 1-pyrenyl, 2-pyrenyl and 4-pyrenyl. In some embodiments, the tetracene is selected from the group consisting of 1-tetracene, 2-tetracene and 9-tetracene.

In some embodiments where R ¹ , Ar ¹ and Ar ² are each independently selected from a heteroaryl group radical, the heteroaryl group radical is furyl, phenyl furyl, thienyl, phenyl thienyl, pyrrolyl, phenyl pyrrolyl, pyri Dill, phenyl group pyridyl, pyrazine group, quinoline, triazinyl, benzofuryl, benzothienyl, benzotriazine, quinoxaline, isobenzofuryl, indolyl, benzoquinoline, dibenzofuryl, dibenzothienyl, dibenzopyr Royl, a carbazole group and its derivatives, a diazole substituted with a phenyl group, a pyrine group, a pyrine thiazyl and a benzodioxole alkylene radical. The carbazole group derivative includes, but is not limited to, 9-phenyl carbazole, 9-naphthyl carbazole benzocarbazole, dibenzo carbazole and indole carbazole.

In some embodiments, R ² , R ⁴ , R ³ and R ^3' are each independently hydrogen, a C ₁ -C ₅ subalkyl group, halogen, cyano, nitro group, C ₆ -C ₁₅ substituted or unsubstituted of an aryl group or a condensed ring-based aromatic hydrocarbon radical, a C ₃ ~ C ₁₅ substituted or unsubstituted heteroaryl group, or a condensed heterocyclic aromatic hydrocarbon radical.

In some embodiments, R ² , R ³ , R ^{3 '} and R ⁴ are each independently selected from a substituted aryl group, a condensed ring aromatic hydrocarbon radical, a heteroaryl group, or a condensed heterocyclic aromatic hydrocarbon radical, an aryl group , A substituted radical in a condensed ring aromatic hydrocarbon radical, a heteroaryl group or a condensed heterocyclic aromatic hydrocarbon radical is independently halogen, cyano, nitro group, C ₁ to C ₃₀ alkyl group, cyclic alkyl group, alkylene, C ₁ ~ C ₆ An alkoxy group or a thioalkoxy group radical and Si(R ⁵ ) ₃ It is selected from the group consisting of. The R ⁵ is selected from a C ₁ ~ C ₆ alkyl group. Furthermore, in some embodiments, the substituted radical is independently a group consisting of F, cyano, a C ₁ -C ₅ alkyl group, a cyclic alkyl group, an alkylene, an alkoxy group, a thioalkoxy radical and a Si(CH ₃ ) ₃ group. Choose from

In some embodiments, in which R ² , R ³ , R ^{3 '} and R ⁴ are each independently selected from a substituted or unsubstituted heteroaryl group or a condensed heterocyclic aromatic hydrocarbon radical, the hetero atom is one or a plurality of O, S and/or N.

In some embodiments, in Formula (I-2), R ² , R ³ , R ^{3 '} and R ⁴ are each independently a methyl group, an ethyl group, an isopropyl group, tertbutyl, cyclopentyl, cyclohexyl, cyano, Nitro group, phenyl group, naphthyl, triphenylene, 9,9 dimethyl fluorene, spirobifluorene, furyl, phenyl group furyl, thienyl, phenyl group thienyl, pyrrolyl, phenyl group pyrrolyl, pyridyl, phenyl group pyridyl, Pyrazine group, fluorenyl, indenofluorene, quinoline, triazinyl, benzofuryl, benzothienyl, benzotriazine, quinoxaline, isobenzofuryl, indolyl, benzoquinoline, dibenzofuryl, dibenzothienyl, dibenzopyrrolyl, a carbazole group and its derivatives, a phenyl group substituted diazole, a pyrine group, a pyrine thiazyl, and a benzodioxole alkylene radical. Here, the carbazole group derivative includes, but is not limited to, 9-phenyl carbazole, 9-naphthyl carbazole benzocarbazole, dibenzo carbazole, and indole carbazole.

In some embodiments according to the present invention, the molecular weight of the naphthyridine-substituted anthracene derivative of formula (I) is 1000 or less. In some embodiments, the molecular weight is 450-900. Furthermore, in some embodiments, the molecular weight is 600-800. Based on the setting of the molecular weight, an appropriate substitution radical can be selected.

Since the molecular weight has an appropriate size, synthesis, dissolution, and deposition of the compound are all relatively convenient, and the luminescence property is improved.

Controlling the molecular weight with the naphthyridine-substituted anthracene derivative of formula (I) within the above range ensures that the molecular weight is sufficiently large to have a relatively high Tg (vitrification temperature), thereby providing excellent thermal stability; In addition, since the molecular weight is not too large, it is advantageous for film formation and material stability due to vacuum deposition, and it is possible to implement material purification and device manufacturing under a relatively low temperature.

For example, the naphthyridine-substituted anthracene derivative of formula (I) may be selected from the group consisting of compounds having structural formulas A1-A21 and B1-B27 as shown below.

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In some embodiments of the present invention, another naphthyridine-substituted anthracene derivative having a structure indicated by the following formula (II) is provided.

That is, the naphthyridine is quinoxaline,

From here,

L' is a chemical bond, a substituted or unsubstituted C ₆ -C ₁₂ arylene or sub-condensed ring-based aromatic hydrocarbon radical, a substituted or unsubstituted C ₃ -C ₁₂ sub-heteroaryl group or a sub-condensed heterocyclic group aromatic hydrocarbon radicals;

Ar ⁴ and Ar ⁵ are each independently a substituted or unsubstituted C ₆ ~ C ₃₀ aryl group or a condensed ring-based aromatic hydrocarbon radical, a substituted or unsubstituted C ₃ ~ C ₃₀ heteroaryl group or a condensed heterocyclic aromatic hydrocarbon radicals; Ar ⁴ and Ar ⁵ may be the same or different;

R ⁶ and R ⁷ are each selected from hydrogen or a C ₁ to C ₁₀ alkyl group; wherein R ⁶ and R ⁷ are not hydrogen at the same time; That is, at least one C ₁ -C ₁₀ lower alkyl group is substituted in the quinoxaline radical;

R ⁸ and R ⁹ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a halogen, cyano, nitro group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group or a condensed ring-based aromatic hydrocarbon radical, a substituted or It is selected from an unsubstituted C ₃ -C ₃₀ heteroaryl group or a condensed heterocyclic aromatic hydrocarbon radical.

For example, the definition that Ar ⁴ , Ar ⁵ , R ⁸ and R ⁹ are each independently selected from an aryl group refers to an aromatic ring system of carbon atoms having a certain number of cyclic matrices, monocyclic structure-substituted radicals (eg, a phenyl group, etc.), and also includes an aromatic ring-substituted radical (eg, biphenyl, tribiphenyl, etc.) of a covalently linked structure.

In some embodiments, R ⁶ and R ⁷ are independently selected from a C ₁ -C ₁₀ alkyl group. That is, one alkyl group is connected to each of the benzene ring and the pyrazine ring of the quinoxaline radical.

In some embodiments, at least one of R ⁶ and R ⁷ is a methyl group or an ethyl group. profiler. isopropyl group, tert-butyl, cyclopentyl or cyclohexyl.

In some embodiments, L' is a substituted C ₆ -C ₁₂ arylene or sub-condensed ring-based aromatic hydrocarbon radical, a C ₃ to C ₁₂ sub-heteroaryl group or a sub-condensed heterocyclic aromatic hydrocarbon radical. , aryl group, sub-condensed ring-based aromatic hydrocarbon radical, sub-heteroaryl group or sub-condensed heterocyclic aromatic hydrocarbon radical substituted radical is independently halogen, cyano, nitro group, C ₁ ~ C ₁₀ alkyl group, ring Alkyl group, alkylene, C ₁ ~ C ₆ alkoxy group or thioalkoxy group radical, C ₆ ~ C ₃₀ monocyclic aromatic hydrocarbon or condensed cyclic aromatic hydrocarbon radical and a hetero atom selected from N, O, S, Si A C ₆ ~ C ₃₀ monocyclic aromatic hydrocarbon or condensed ring aromatic hydrocarbon radical and Si(R ¹⁰ ) ₃ It is selected from the group consisting of. Here, R ¹⁰ is selected from a C ₁ ~ C ₆ alkyl group.

In some embodiments, R ⁸ and R ⁹ are each independently hydrogen, C ₁ -C ₅ alkyl group, halogen, cyano, nitro group, substituted or unsubstituted C ₆ -C ₁₅ aryl group, or condensed ring aromatic It is selected from a hydrocarbon radical, a substituted or unsubstituted C ₃ -C ₁₅ heteroaryl group, or a condensed heterocyclic aromatic hydrocarbon radical.

In some embodiments, R ⁸ and R ⁹ are each independently selected from a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group or a condensed heterocyclic aromatic hydrocarbon radical. Optionally, the heteroatoms therein are one or more O, S and/or N.

R ⁸ and R ⁹ are independently selected from a substituted C ₆ ~ C ₃₀ aryl group or a condensed ring aromatic hydrocarbon radical, a C ₃ ~ C ₃₀ heteroaryl group or a condensed heterocyclic aromatic hydrocarbon radical In, the substituted radicals therein are independently halogen, cyano, nitro group, C ₁ -C ₁₀ alkyl group, cyclic alkyl group, alkylene, C ₁ -C ₆ alkoxy group or thioalkoxy group radical, C ₆ -C _{30 monocyclic} aromatic hydrocarbon or condensed _- cyclic aromatic hydrocarbon radical and N, O, S, and Si (R ¹⁰ ) You can choose from a group consisting of ₃ . Here, R ¹⁰ is selected from a C ₁ ~ C ₆ alkyl group. Furthermore, the substituted radicals are independently F, cyano, a C ₁ -C ₅ alkyl group, a cyclic alkyl group, alkylene, Si(CH ₃ ) _{3 ,} a C ₁ -C ₅ alkoxy group or a thioalkoxy group radical, C It can be selected from the group consisting of ₆ ~ C ₁₅ monocyclic aromatic hydrocarbon or condensed ring aromatic hydrocarbon radical, C ₆ ~ C ₁₅ monocyclic aromatic hydrocarbon or condensed ring aromatic hydrocarbon radical containing a hetero atom selected from N or O.

In some embodiments, R ⁸ and R ⁹ are each independently a methyl group, ethyl group, propyl group, isopropyl group, tertbutyl, cyclopentyl, cyclohexyl, cyano, nitro group, phenyl group, naphthyl, triphenylene, 9,9 dimethyl fluorene, spirobifluorene, furyl, phenyl group furyl, thienyl, phenyl group thienyl, pyrrolyl, phenyl group pyrrolyl, pyridyl, phenyl group pyridyl, pyrazine group, fluorenyl, indenofluorene, quinoline, triazinyl, benzofuryl, benzothienyl, benzotriazine, quinoxaline, isobenzofuryl, indolyl, benzoquinoline, dibenzofuryl, dibenzothienyl, dibenzopyrrolyl, carbazole group and derivatives thereof; It is selected from the group consisting of phenyl-substituted diazole, pyrine, pyrine thiazyl and benzodioxole alkylene radicals.

In some embodiments, the carbazole derivative is selected from 9-phenyl carbazole, 9-naphthyl carbazole benzocarbazole, dibenzo carbazole or indole carbazole.

Furthermore, in some embodiments, R ⁸ and R ⁹ are each independently a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl, a phenyl group, a naphthyl, a pyridyl, a phenyl group pyridyl, dibenzofuryl, biphenyl selected from the group consisting of radicals.

In some embodiments, Ar ⁴ and Ar ⁵ are each independently a C ₆ -C ₂₀ substituted or unsubstituted aryl group or a condensed ring-based aromatic hydrocarbon radical, a C ₅ -C ₂₀ substituted or unsubstituted heteroaryl group or a condensed heteroaryl group tercyclic aromatic hydrocarbon radicals.

In some embodiments, each of Ar ⁴ and Ar ⁵ is independently selected from a substituted or unsubstituted C ₃ to C ₃₀ heteroaryl group or a condensed heterocyclic aromatic hydrocarbon radical, a heteroaryl group or a condensed heterocyclic aromatic hydrocarbon The heteroatoms in the radical are optionally one or more O, S and/or N.

Ar ⁴ and Ar ⁵ are each independently selected from a substituted C ₆ ~ C ₃₀ aryl group or a condensed ring aromatic hydrocarbon radical, a C ₃ ~ C ₃₀ heteroaryl group or a condensed heterocyclic aromatic hydrocarbon radical In an example, the substituted radical in the aryl group, the condensed ring aromatic hydrocarbon radical, the heteroaryl group or the condensed heterocyclic aromatic hydrocarbon radical is independently halogen, cyano, nitro group, C ₁ to C ₁₀ alkyl group, cyclic alkyl group , alkylene, C ₁ ~ C ₆ alkoxy group or thioalkoxy group radical, C ₆ ~ C ₃₀ monocyclic aromatic hydrocarbon or condensed ring aromatic hydrocarbon radical, N, O, S, containing a hetero atom selected from Si It may be selected from the group consisting of C ₃ ~ C ₃₀ monocyclic aromatic hydrocarbon or condensed cyclic aromatic hydrocarbon radical and Si(R ¹⁰ ) ₃ . Here, R ¹⁰ is selected from a C ₁ ~ C ₆ alkyl group. Furthermore, the substituted radicals are independently F, cyano, C ₁ -C ₅ alkyl group, cyclic alkyl group, alkylene, C ₁ -C ₅ alkoxy group or thioalkoxy group radical, Si(CH ₃ ) ₃ , C It can be selected from the group consisting of a ₆ to C ₁₅ monocyclic aromatic hydrocarbon or condensed cyclic aromatic hydrocarbon radical and a C ₅ to C ₁₅ monocyclic aromatic hydrocarbon or condensed cyclic aromatic hydrocarbon radical containing a hetero atom selected from N or O. .

In some embodiments, Ar ⁴ and Ar ⁵ are each independently a phenyl group, biphenyl, tribiphenyl, naphthyl, anthracene, phenanthryl, fluorenyl, fluorenyl derivative, indenyl, fluoroanthracene, triphenylene, Phenyl group substituted by pyrenyl, perylenyl, chrysene group, tetracenewa, furyl, thienyl, pyrrolyl and/or pyridyl, benzene binaphthyl, 4-naphthyl phenyl group, 6-phenyl group naphthyl, 7-phenyl group may be selected from the group consisting of phenanthryl.

In some embodiments, the biphenyl is selected from the group consisting of 2-biphenyl, 3-biphenyl and 4-biphenyl. In some embodiments, the tribiphenyl is bis-tribiphenyl-4-YL, bis-tribiphenyl-3-YL, bis-tribiphenyl-2-YL, m-tribiphenyl-4-YL, m-tribiphenyl-3-YL and m-tribiphenyl-2-YL. In some embodiments, the naphthyl is selected from the group consisting of 1-naphthyl and 2-naphthyl. In some embodiments, the anthracene is selected from the group consisting of 1-anthracene, 2-anthracene and 9-anthracene. In some embodiments, the fluorenyl is selected from the group consisting of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl. In some embodiments, the fluorenyl derivative is selected from the group consisting of 9,9'-dimethylfluorene, 9,9'-spirobifluorene and benzofluorene. In some embodiments, the pyrenyl is selected from the group consisting of 1-pyrenyl, 2-pyrenyl and 4-pyrenyl. In some embodiments, the tetracene is selected from the group consisting of 1-tetracene, 2-tetracene and 9-tetracene.

In some embodiments, Ar ⁴ and Ar ⁵ are each independently furyl, phenyl furyl, thienyl, phenyl thienyl, pyrrolyl, phenyl pyrrolyl, pyridyl, phenyl pyridyl, pyrazine group, quinoline, triazinyl, benzofuryl , benzothienyl, benzotriazine, quinoxaline, isobenzofuryl, indolyl, benzoquinoline, dibenzofuryl, dibenzothienyl, dibenzopyrrolyl, carbazole group and its derivatives, phenyl group-substituted diazole, pyrine group, pyrine thiazyl, benzodioxole alkylene radicals.

In some embodiments, the carbazole derivative is selected from 9-phenyl carbazole, 9-naphthyl carbazole benzocarbazole, dibenzo carbazole or indole carbazole.

In some embodiments, Ar ⁴ and Ar ⁵ are each independently a phenyl group, biphenyl, naphthyl, pyridyl-substituted phenyl group, phenyl group pyridyl, anthracene, phenanthryl, furyl, phenyl group furyl, thienyl, phenyl group thienyl, p It is selected from the group consisting of rollyl, phenyl group pyrrolyl, and pyridyl radicals.

In anthracene derivatives, when the two-position substituted radical of anthracene is a strong electroadsorption radical, the strong electroadsorption radical can interact with electron transfer of the anthracene ring, resulting in relatively high compound mobility. When an alkyl group substituent is present in the electrosorption radical, it is possible to lower the degree of densification of intermolecular arrangement, reduce intermolecular interaction force, and lower the deposition temperature of the material in a situation where the molecular weight does not significantly increase.

The naphthyridine-substituted anthracene derivative of formula (II) provided by some examples according to the present invention has the following advantages.

Since the matrix structure has very good coplanarity, the operating voltage using the material can be significantly lowered by making the derivative have a relatively high carrier transport property. The structure using the alkyl group-substituted quinoxaline-substituted anthracene structure as the parent nucleus radical protects the active site of the parent nucleus, is beneficial to the stability of the compound, and ensures that the electron cloud is distributed in the parent nucleus, and the LUMO distribution is consistent with the electron cloud distribution. make it match The presence of the alkyl group substituent ensures that the molecular arrangement is not too dense, thereby forming a loose intermolecular interaction force and realizing material purification and device fabrication under a relatively low temperature, that is, the deposition temperature is relatively low, and the stability of the material. beneficial to In addition, the selected and used alkyl group is a lower alkyl group, and the molecular weight is relatively small, which does not significantly increase the molecular weight of the entire compound, guarantees a relatively low deposition temperature, and further extends the service life of the device using the material.

Since the parent structure has a relatively deep LUMO, it not only realizes excellent electron transport performance, but also maintains the coplanar structure, which is advantageous for the film-forming properties of molecules; Changes in the energy level of the substituent and the electronic properties can significantly improve the luminous efficiency of the device by fine-tuning the energy level and transmission performance of the final target compound and using the compound as the material for the electron transport layer.

The high mobility of the compound also makes it possible to control the thickness of the material within a wider adjustment range, and when used as an electron transport layer material, by thickening the film thickness of the material, so as not to significantly affect the operating voltage of the device. can do.

In one embodiment according to the present invention, the naphthyridine-substituted anthracene derivative of formula (II) has a molecular weight of 1000 or less. In some embodiments, the molecular weight is 450-900. Furthermore, in some embodiments, the molecular weight is 600-800. An appropriate substitution radical can be selected based on the setting of the molecular weight.

Controlling the molecular weight with the naphthyridine-substituted anthracene derivative of formula (II) within the above range ensures that the molecular weight is sufficiently large to have a relatively high Tg (vitrification temperature), thereby providing excellent thermal stability; In addition, the molecular weight is not too large, which is advantageous for film formation by vacuum deposition.

In some embodiments, the naphthyridine-substituted anthracene derivative of Formula (II) may be selected from the group consisting of compounds having the structure E1-E20 as follows.

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Corresponding to the naphthyridine-substituted anthracene derivative provided in the some embodiments of the present invention, some embodiments of the present invention further provide an organic electroluminescent device, wherein in the electron transport layer of the organic electroluminescent device, the naphthyridine At least one of the substituted anthracene derivatives is included.

In addition, the device may further include a first electrode, a second electrode, and one or more organic layers disposed between the first electrode and the second electrode. The organic layer includes the electron transport layer, and the electron transport layer includes at least one compound indicated by Formula (I) or Formula (II) provided in Examples according to the present invention.

The electron transport layer material of the organic electroluminescent device provided in some embodiments according to the present invention is by selecting and using a naphthyridine-substituted anthracene derivative indicated by Formula (I) or Formula (II), effectively lowering the device operating voltage, It is possible to improve the luminous efficiency and extend the service life of the device.

Furthermore, the OLED device provided by some embodiments according to the present invention has the following structure on a substrate.

(1) anode / hole injection layer (HIL) / hole transport layer (HTL) / light emitting layer (EML) / electron transport layer (ETL) / electron injection layer (EIL) / cathode;

(2) anode / hole transport layer (HTL) / light emitting layer (EML) / hole blocking layer (HBL) / electron transport layer (ETL) / electron injection layer (EIL) / cathode.

The "/" indicates that different functional layers are sequentially stacked.

In some embodiments, the substrate refers to the substrate used in OLED devices in the related art, for example glass or plastic. In some embodiments, the anode material uses a transparent, highly conductive material, such as, for example, indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO ₂ ), zinc oxide (ZnO), or the like. In some embodiments, a glass substrate is selected and used in manufacturing an OLED device, and ITO is selected and used as an anode material.

In some embodiments, the hole-injection material is selected from CuPc, TNATA, PEDT:PSS, and the like. In some embodiments, the hole injection layer uses 2-TNATA.

In some embodiments, the hole transport layer is N,N'-di(3-methylphenyl group)-N,N-diphenyl group-[1,1-biphenyl]-4,4'-diamine (TPD) or N, Triarylamine materials such as N'-diphenyl group-N,N'-di(1-naphthyl)-(1,1'-biphenyl)-4,4'-diamine (NPB) are used. In some embodiments, the air transport material selects and uses NPB.

The structure of the OLED device may be a single light-emitting layer or a multi-emission layer structure. In some embodiments, a structure of a single light emitting layer is used. The light emitting layer includes a light emitting body material and a light emitting pigment, wherein the mass ratio of the light emitting pigment and the light emitting body material is controlled by adjusting the deposition rate of both during the device manufacturing process. In some embodiments, controlling the deposition rate ratio of the luminescent pigment to the luminescent body material from 1% to 8%, for example, 1%, 2%, 3%, 3.5%, 4%, 4.5%, 5%, Controlled by 6%, 7%, 8%, etc., optionally, controlled by 3% to 5%.

In some embodiments, the luminescent pigment is selected from metallic iridium formulations Ir(ppy), FIrpic and small pure organic molecules, rubrene, DPP, DCJ, DCM, and the like. In some embodiments, the light emitting body material is selected from BAlq, AND, CBP, mCP, TBPe, and the like.

In the OLED device provided by some embodiments according to the present invention, the thickness of the light emitting layer is 5 nm-50 nm, for example, 5 nm, 6 nm, 8 nm, 10 nm, 12 nm, 15 nm, 20 nm, 25 nm, 28 nm, 30 nm, 35 nm, 38 nm , 40nm, 45nm, 50nm, etc. Optionally, the light emitting layer has a thickness of 10 nm-30 nm.

For the electron transport layer provided by some embodiments according to the present invention, the electron transport material provided by some embodiments according to the present invention may be used alone, and other types of electron transport material or other electronic transport materials provided by some embodiments according to the present invention It is also possible to use a combination of transmission materials. Other types of electronic transmission materials are selected from Alq ₃ , Bphen, BCP, PBD, and materials marked with CA, CC-1, CC-2, CC-3 in the drawing below. In some embodiments, the electron transport material provided in some embodiments according to the present invention is used in combination with 8-hydroxyl quinoline lithium.

The electron transport material provided in some embodiments according to the present invention is used in combination with another electron transport material provided in some embodiments according to the present invention, or other electron transport material (for example, 8-hydroxyl quinoline lithium) When used in combination with, in some embodiments, the weight ratio of both is 90:10-10:90, for example, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10.

In some embodiments, the thickness of the electron transport layer is 5-100 nm, for example, 5 nm, 6 nm, 8 nm, 10 nm, 12 nm, 15 nm, 20 nm, 30 nm, 35 nm, 38 nm, 40 nm, 50 nm, 60 nm, 80 nm, 90 nm, 95nm, 100nm, etc. Optionally, the thickness of the electron transport layer is 10-40 nm.

In some embodiments, as the electron injection layer/cathode material of the OLED device, LiF/Al is selected and used.

The concrete structures of some of the above materials are as follows.

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The organic electroluminescent device provided by some embodiments according to the present invention selects and uses the compounds indicated by the above formulas (I) and (II), and the compound is very excellently matched with the LUMO energy level of the light emitting layer body material By achieving this, the organic electroluminescent device has excellent photoelectric performance, has relatively low device light-up and operating voltage, and has relatively high luminous efficiency, and the service life of the device is relatively long. .

Hereinafter, in order to better explain the naphthyridine-substituted anthracene derivative and the OLED device provided by some examples according to the present invention, specific examples are given as examples.

Description: Various chemical agents used in the synthesis examples are all available for purchase in China's domestic chemical industry market. All of the compounds of the synthetic method not presented in the Examples according to the present invention are raw materials obtained through commercial routes. Intermediates and compounds in Examples according to the present invention were analyzed and tested using an AB SCIEX mass spectrometer (4000 QTRAP) and a Bruker magnetic resonance imaging (400M).

Synthesis Example 1.1: Synthesis of Compound A1

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Raw materials N1 (13.5 g, 0.01 mol) and N2 (19.9 g, 0.01 mol) are put in methylbenzene, a catalytic amount (3% eq) of para-toluenesulfonic acid is added, heated to reflux, fractionated, reacted for about 12 h, and reacted The liquid is concentrated, ethanol is added, and a yellow powder is precipitated and filtered to obtain an intermediate N3.

Intermediate N3 (22.1 g, 0.01 mol) is placed in dilute hydrochloric acid, hydrogen bromide (30 g, 0.012 mol) is added, mixed at room temperature for 12 h, the reaction solution is added to water to extract ethyl acetate, and the organic phase is concentrated and obtain an intermediate N4 by column chromatography separation method.

Under the protection of nitrogen, 2-bromine anthracene quinone M1 (26.5 g, 0.01 mol), pinacol boric acid ester (0.015 mol), Pd(dppf)Cl ₂ (1%) and potassium carbonate were mixed and dissolved in 500 ml methylbenzene. , heated to reflux, allowed to react overnight, and the reaction solution is concentrated using column chromatography and washed with boiling petroleum ether to obtain an intermediate M2 (20.1 g, yield 89.6%).

Under the protection of nitrogen, intermediate M2 (6.7 g, 22 mmol, 1.1 eq), intermediate N4 (1eq), potassium carbonate (5eq), Pd(Pph ₃ ) ₄ (2%), Methylbenzene 1000ml+ethanol 500ml+300ml water is added to start mixing, heated to reflux, and reacted for 8h. The organic phase is concentrated using silica gel column chromatography, and crystallized again using methylbenzene to obtain yellow powder M3 (9.0 g, 93.7%).

Under the protection of nitrogen, (25 mmol) 2-bromnaphthalene is dissolved in tetrahydrofuran, the ethanol is cooled to -78 ° C., n-butyllithium solution is added dropwise, and the low temperature condition is maintained, and the solution dripping is completed. When the temperature is controlled for 30 min, the intermediate M3 (4.8 g, 10 mmol) is dissolved in tetrahydrofuran and added dropwise into the reaction flask. When the dropping is completed, the temperature is naturally raised and the reaction is carried out for 8 h. Diluted hydrochloric acid is added to the reaction solution, extraction is performed with ethyl acetate, the organic phase is concentrated, and the solid is precipitated and filtered to obtain an intermediate M4 (4.8 g, 93.1%).

Intermediate M4 ((5.1 g, 10 mmol) is placed in a reaction flask, 100 ml of glacial acetic acid, potassium iodide (20 mmol) and sodium hypophosphite (20 mmol) are added, heated to reflux, and reacted for 5 h. Filtered water, ethanol was washed by eluting to obtain yellow powder A1 (5.3 g, 79.1%).

Nuclear magnetic spectrum data of compound A1:

1H NMR (400 MHz, CDCl ₃ ) δ8.79 (d, J = 12.0 Hz, 2H), 8.39 (d, J = 2.6 Hz, 2H), 8.31 (s, 1H), 8.20 (s, 2H), 8.16 - 8.04 (m, 5H), 7.99 (s, 2H), 7.63 (s, 2H), 7.60 - 7.51 (m, 6H), 7.39 (d, J = 12.0 Hz, 4H), 7.19 (s, 4H).

Synthesis Example 1.2: Synthesis of Compound A4

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Under the protection of nitrogen, Intermediate M (9.4 g, 22 mmol, 1.1 eq), Intermediate N4 (1eq), potassium carbonate (5eq), Pd(Pph ₃ ) ₄ (2%), Methylbenzene 1000ml+ethanol 500ml+300ml water is added to start mixing, heated to reflux, and reacted for 8h. The organic phase uses silica gel column chromatography method, is concentrated, and crystallizes again using methylbenzene to obtain yellow powder M1 (9.0 g, 93.7%).

Under the protection of nitrogen, the intermediate M1 (4.6g, 10mmol, 1eq) was dissolved in 100ml chloroform, 1.1eqNBS (N-bromosuccinimide) was added, mixed at room temperature for about 30min, and the reaction solution was water was added and mixed, the liquid was separated and the organic phase was concentrated to obtain an intermediate M2.

Intermediate M2 (10 mmol, 1eq), 1-naphthalene boric acid (1eq), potassium carbonate (5eq), Pd(Pph3)4 (2%), methylbenzene 1000ml+ in a three-neck flask equipped with a mechanical mixer under the protection of nitrogen Ethanol 500ml+300ml water is added to start mixing, heated to reflux, and reacted for 8h. The organic phase is concentrated using silica gel column chromatography, and crystallized again using methylbenzene to obtain yellow powder A4.

Nuclear magnetic spectrum data of compound A4:

¹ H NMR (400 MHz, CDCl ₃ ) δ8.91 (d, J = 8.0 Hz, 2H), 8.50 (s, 1H), 8.32 (d, J = 8.0 Hz, 3H), 8.20 (s, 2H), 8.15 - 8.02 (m, 4H), 8.00 (s, 2H), 7.92 (dd, J = 12.4, 6.8 Hz, 4H), 7.78 (d, J = 4.0 Hz, 2H), 7.63 (s, 1H), 7.60 - 7.46 (m, 6H), 7.43 - 7.31 (m, 3H).

Synthesis Example 1.3: Synthesis of compound A11

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Under the protection of nitrogen, intermediate N1 (28.7 g, 0.1 mol, 1eq), intermediate ethyl group boric acid (1eq), potassium carbonate (5eq), Pd(Pph ₃ ) ₄ (2%), methylbenzene 1000ml + ethanol 500ml in a 3-neck flask Add +300ml water to start mixing, heat to reflux, and react for 8h. The organic phase is concentrated using silica gel column chromatography, and then crystallized again using methylbenzene to obtain yellow powder N2 (25.8 g, 92.6%).

Intermediate N2 (0.1 mol, 1eq), 2-phenyl group-4-bromophenyl boric acid (leq), potassium carbonate (5eq), Pd(Pph ₃ ) ₄ (2%), methyl in a three-neck flask under the protection of nitrogen Benzene 1000ml+ethanol 500ml+300ml water is added to start mixing, heated to reflux, and reacted for 8h. The organic phase uses silica gel column chromatography method, is concentrated, and crystallizes again using methylbenzene to obtain yellow powder N3 (15.3 g, 75.1%).

Under the protection of nitrogen, 2-bromine anthracene quinone M1 (26.5 g, 0.01 mol), pinacol boric acid ester (.015 mol), d(dppf)Cl ₂ (1%) and potassium carbonate were mixed and dissolved in 500 ml methylbenzene. , heated to reflux, allowed to react overnight, and the reaction solution is concentrated using column chromatography and washed with boiling petroleum ether to obtain an intermediate M2 (20.1 g, yield 89.6%).

Under the protection of nitrogen, intermediate M2 (6.7 g, 22 mmol, 1.1 eq), intermediate N3 (1eq), potassium carbonate (5eq), Pd(Pph ₃ ) ₄ (2%), Methylbenzene 1000ml+ethanol 500ml+300ml water is added to start mixing, heated to reflux, and reacted for 8h. The organic phase is concentrated using silica gel column chromatography, and crystallized again using methylbenzene to obtain yellow powder M3 (9.0 g, 93.7%).

Under the protection of nitrogen, bromobenzene (25 mmol) is dissolved in tetrahydrofuran, the ethanol is cooled to -78°C, n-butyllithium solution is added dropwise, and the low temperature condition is maintained, and when the solution dripping is completed, The temperature is controlled for 30 min, the intermediate M3 (4.8 g, 10 mmol) is dissolved in tetrahydrofuran and added dropwise into the reaction flask, and when the dropping is completed, the temperature is naturally raised and the reaction is carried out for 8 h. Diluted hydrochloric acid is added to the reaction solution, extraction is performed with ethyl acetate, the organic phase is concentrated, and the solid is precipitated and filtered to obtain an intermediate M4 (4.8 g, 93.1%).

Intermediate M4 ((5.1 g, 10 mmol) is placed in a reaction flask, 100 ml of glacial acetic acid, potassium iodide (20 mmol) and sodium hypophosphite (20 mmol) are added, heated to reflux, and reacted for 5 h. Filtered water, ethanol eluted and washed to collect and obtain yellow powder A11 (5.3 g, 79.1%).

Nuclear magnetic spectrum data of compound A11:

1H NMR (400 MHz, CDCl ₃ ) δ8.99 (s, 2H), 8.54 (s, 2H), 8.37 (s, 2H), 8.24 (t, J = 22.0 Hz, 7H), 8.18 (d, J = 4.1 Hz, 1H), 8.11 (s, 2H), 7.79 (s, 4H), 7.63 (d, J = 14.4 Hz, 10H), 7.59 - 7.37 (m, 26H), 7.35 (s, 2H), 3.40 ( t, 4H), 1.30 (t, 6H).

Synthesis Example 1.4: Synthesis of Compound A17

,

,

Under the protection of nitrogen, intermediate N1 (leq), 2-pyridine boric acid (leq), potassium carbonate (5eq), Pd(Pph ₃ ) ₄ (2%), methylbenzene 1000ml+ethanol in a three-necked flask equipped with a mechanical mixer Add 500ml + 300ml of water to start mixing, heat until refluxed, and react for 8h. The organic phase is concentrated using silica gel column chromatography, and crystallized again using methylbenzene to obtain yellow powder N2 (9.0 g, 93.7%).

Under the protection of nitrogen, N2 (26.5 g, 0.01 mol), pinacol boric acid ester (0.015 mol), Pd(dppf)Cl ₂ (1%) and potassium carbonate were mixed and dissolved in 500 ml methylbenzene, until refluxed. It is heated and allowed to react overnight, and the reaction solution is concentrated using column chromatography and washed with petroleum ether to obtain an intermediate N3 (20.1 g, yield 89.6%).

Under the protection of nitrogen, the intermediate 2-bromine anthracene quinone (leq), benzeneboric acid (leq), potassium carbonate 5eq, Pd(Pph ₃ ) ₄ (2%), methylbenzene 1000ml+ethanol in a three-necked flask equipped with a mechanical mixer under the protection of nitrogen Add 500ml + 300ml of water to start mixing, heat until refluxed, and react for 8h. The organic phase uses silica gel column chromatography method, is concentrated, and crystallizes again using methylbenzene to obtain yellow powder M1 (9.0 g, 93.7%).

Under the protection of nitrogen, the intermediate M1 (4.6g, 10mmol, 1eq) is dissolved in 100ml chloroform, 1.1eqNBS is added and mixed at room temperature, reacted for about 30min, water is added to the reaction solution, mixed, and the liquid is separated and the organic phase is concentrated to obtain an intermediate M2.

Under the protection of nitrogen, in a three-neck flask equipped with a mechanical mixer device, Intermediate M2 (leq), Intermediate N3 (leq), potassium carbonate (5eq), Pd(Pph ₃ ) ₄ (2%), methylbenzene 1000ml+ethanol 500ml+water Add 300 ml to start mixing, heat to reflux, and react for 8 h. The organic phase is concentrated using silica gel column chromatography, and crystallized again using methylbenzene to obtain yellow powder M3 (9.0 g, 93.7%).

Under the protection of nitrogen, 2-bromnaphthalene (25 mmol) is dissolved in tetrahydrofuran, the ethanol is cooled to -78°C, n-butyllithium solution is added dropwise, and the low temperature condition is maintained, and the solution dripping is complete When the temperature is controlled for 30 min, the intermediate M3 (4.8 g, 10 mmol) is dissolved in tetrahydrofuran and added dropwise into the reaction flask. When the dropping is completed, the temperature is naturally raised and the reaction is carried out for 8 h. Diluted hydrochloric acid is added to the reaction solution, extraction is performed with ethyl acetate, the organic phase is concentrated, and the solid is precipitated and filtered to obtain an intermediate M4 (4.8 g, 93.1%).

Intermediate M4 (5.1 g, 10 mmol) is placed in a reaction flask, 100 ml of glacial acetic acid, potassium iodide (20 mmol) and sodium hypophosphite (20 mmol) are added, heated to reflux, and reacted for 5 h. The yellow powder A17 (5.3 g, 79.1%) is collected and obtained by filtration, eluting water and ethanol, and washing|cleaning.

Nuclear magnetic spectrum data of compound A17:

1H NMR (400 MHz, CDCl ₃ ) δ9.15 (dd, J = 12.4, 8.0 Hz, 4H), 8.96 (s, 1H), 8.96 (s, 1H), 8.58 - 8.52 (m, 2H), 8.39 - 8.20 (m, 4H), 8.08 (d, J = 12.0 Hz, 4H), 7.99 (s, 3H), 7.77 - 7.69 (m, 3H), 7.67 - 7.57 (m, 5H), 7.52 (d, J = 24.0 Hz, 4H), 7.39 (d, J = 12.0 Hz, 3H), 7.23 (s, 1H).

Elemental analysis data of compounds A1-A21

The compounds of A1-A21 were synthesized using a synthesis method similar to the above synthesis method, and their elemental analysis and measurement data are as shown in Table 1-1 below.

[Table 1-1] Elemental analysis result of compound A1-A21

Synthesis Example 2.1: Synthesis of compound B1

,

,

Under the protection of nitrogen, 2-bromine anthracene quinone M11 (26.5 g, 0.01 mol), pinacol boric acid ester (0.015 mol), Pd(dppf)Cl2 (1%) and potassium carbonate were mixed and dissolved in 500 ml methylbenzene, The mixture is heated to reflux, allowed to react overnight, and the reaction solution is concentrated using column chromatography and washed with boiling petroleum ether to obtain an intermediate M12 (20.1 g, yield 89.6%).

Under the protection of nitrogen, mixed in the assembled machine, 4-phenyl group-2-chloropyrazine (leq.), potassium carbonate 5eq, Pd(Pph3)4 in a three-necked flask of intermediate M12 (6.7g, 22mmol, 1.1eq) (2%), methylbenzene 1000ml+ethanol 500ml+water 300ml is added to start mixing, heated to reflux, and reacted for 8h. The organic phase is concentrated using silica gel column chromatography, and crystallized again using methylbenzene to obtain yellow powder M13 (9.0 g, 93.7%).

Under the protection of nitrogen, (25mmol) 2-bromnaphthalene is dissolved in tetrahydrofuran, the ethanol is cooled to -78°C, n-butyllithium solution is added dropwise, and the low temperature condition is maintained, and the solution dripping is complete When the temperature is controlled for 30 min, the intermediate M13 (4.8 g, 10 mmol) is dissolved in tetrahydrofuran and added dropwise into the reaction flask. When the dropping is completed, the temperature is naturally raised and the reaction is carried out for 8 h. Diluted hydrochloric acid is added to the reaction solution, extraction is performed with ethyl acetate, the organic phase is concentrated, and the solid is precipitated and filtered to obtain an intermediate M14 (4.8 g, 93.1%).

Intermediate M14 (5.1 g, 10 mmol) is placed in a reaction flask, 100 ml of glacial acetic acid, potassium iodide (20 mmol) and sodium hypophosphite (20 mmol) are added, heated to reflux, and reacted for 5 h. By filtration and washing by eluting with water and ethanol, yellow powder B1 (5.3 g, 79.1%) was collected and obtained.

Nuclear magnetic spectrum data of compound B1:

1H NMR (400 MHz, Chloroform) δ 8.40 (s, 2H), 8.33 (s, 3H), 7.75 (s, 3H), 7.55 (s, 4H), 7.48 (t, J = 28.0 Hz, 10H), 7.24 (d, J = 4.0 Hz, 8H).

Synthesis Example 2.2: Synthesis of Compound B2

The synthesis step is the same as that of compound B1, with the difference being that the 4-phenyl group-2-chloropyrazine is replaced with the same equivalent of 4-(2-naphthyl)pyrazine,

After the reaction, it is separated to obtain 6.2 g of a white solid.

Nuclear magnetic spectrum data of compound B2:

1H NMR (400 MHz, Chloroform) δ 8.86 (s, 1H), 8.33 (d, J = 12.0 Hz, 2H), 8.20 (s, 1H), 8.08 (d, J = 12.0 Hz, 2H), 7.99 (s) , 1H), 7.63 (s, 1H), 7.57 (d, J= 12.0 Hz, 2H), 7.38 (s, 2H), 7.14 (s, 1H), 6.90 (s, 1H).

Synthesis Example 2.3: Synthesis of Compound B3

The synthesis step is the same as that of Compound B1, with the difference being that the 4-phenyl group-2-chloropyrazine is replaced with the same equivalent of the 2-phenyl group-4-chloropyrazine,

After the reaction, it is separated to obtain a white solid 6.4.

Nuclear magnetic spectrum data of compound B3:

¹ H NMR (400 MHz, Chloroform )δ 9.11 (s, 2H), 8.90 (s, 2H), 8.31 (d, J = 12.0 Hz, 50H), 7.86 (dd, J = 8.0, 59.0 Hz, 6H), 7.65 (s, 1H), 7.65 (s, 2H), 7.62 (s, 4H), 7.55 (s, 2H), 7.49 (s, 2H), 7.41 (s, 1H).

Synthesis Example 2.4: Synthesis of Compound B4

The synthesis steps are the same as those of compound B1, with the difference being that 4.6 g of intermediate M12B is obtained by substituting the same equivalent of 2,6-dibromine anthracene quinone for 2-bromine anthracene quinone.

Under the protection of nitrogen, mixed in an assembled machine, and in a 3-neck flask of intermediate M12B (6.7 g, 22 mmol, 1.1 eq) 4-phenyl group-2-chloropyrazine (leq.), potassium carbonate 5eq, Pd (Pph3)4 (2%), methylbenzene 1000ml+ethanol 500ml+300ml water is added to start mixing, heated to reflux, and reacted for 8h. The organic phase is concentrated using silica gel column chromatography, and crystallized again using methylbenzene to obtain yellow powder M13B (9.0 g, 93.7%).

Under the protection of nitrogen, mixed in an assembled machine and in a three-neck flask of intermediate M13B (6.7 g, 22 mmol, 1.1 eq) bromobenzene (leq), potassium carbonate 5eq, Pd(Pph3)4 (2%), methyl Benzene 1000ml+ethanol 500ml+300ml water is added to start mixing, heated to reflux, and reacted for 8h. The organic phase is concentrated using silica gel column chromatography, and crystallized again using methylbenzene to obtain yellow powder M14B.

Under the protection of nitrogen, (25mmol) 2-bromnaphthalene is dissolved in tetrahydrofuran, the ethanol is cooled to -78°C, n-butyllithium solution is added dropwise, and the low temperature condition is maintained, and the solution dripping is complete When the temperature is controlled for 30 min, the intermediate M14B (4.8 g, 10 mmol) is dissolved in tetrahydrofuran and added dropwise into the reaction flask. When the dropping is completed, the temperature is naturally increased and the reaction is carried out for 8 h. Diluted hydrochloric acid is added to the reaction solution, extraction is performed with ethyl acetate, the organic phase is concentrated, and the solid is precipitated and filtered to obtain an intermediate M15 (4.8 g, 93.1%).

Intermediate M15 (5.1 g, 10 mmol) is placed in a reaction flask, 100 ml of glacial acetic acid, potassium iodide (20 mmol) and sodium hypophosphite (20 mmol) are added, heated to reflux, and reacted for 5 h. By filtration, eluting with water and ethanol, and washing, yellow powder B4 (5.3 g, 79.1%) was collected and obtained.

Nuclear magnetic spectrum data of compound B4:

¹ H NMR (400 MHz, Chloroform ) δ 9.11 (s, 1H), 8.84 (s, 1H), 8.31 (d, J =10.0 Hz, 3H), 8.04 (dd, J = 10.0, 6.0 Hz, 4H), 7.96 - 7.96 (m, 2H), 7.85 (d, J= 8.0 Hz, 2H), 7.63 (s, 1H), 7.57 (d, J = 10.0 Hz, 3H), 7.49 (s, 1H), 7.38 (s) ,1H).

Synthesis Example 2.5: Synthesis of Compound B5

The synthetic steps are the same as for compound B4, the difference is that bromobenzene is replaced with an equivalent equivalent of 2-bromodibenzofuran,

After the reaction, it is separated to obtain 5.2 g of a white solid.

Nuclear magnetic spectrum data of compound B5:

1H NMR (400 MHz, Chloroform ) δ 8.97 (s, 1H), 8.56 (s, 2H), 8.35 (s, 1H), 8.28(s, 2H), 7.79 (t, J = 8.0 Hz, 4H), 7.65 (s, 2H), 7.63 - 7.47 (m, 4H), 7.41 (s, 1H), 7.28 (s, 1H).

Synthesis Example 2. 6: Synthesis of compound B6

Synthetic steps are the same as for compound B4, with the difference being that bromobenzene is replaced with an equivalent equivalent of 2-bromo triphenylene;

After the reaction, it is separated to obtain 5.1 g of the product.

Nuclear magnetic spectrum data of compound B6:

¹ H NMR (400 MHz, Chloroform ) δ 8.97 (s, 1H), 8.56 (s, 2H), 8.35 (s, 1H),

8.28 (s, 2H), 8.08 (d, J = 12.0 Hz, 2H), 7.99 (s, 1H), 7.79 (t, J = 8.0 Hz, 4H),15 7.63 (s, 1H), 7.60 - 7.47 ( m, 6H), 7.33 (d, J = 10.0 Hz, 3H), 7.24 (s, 2H).

Synthesis Example 2.7: Synthesis of Compound B7

Synthesis steps are the same as for compound B1, with the difference that 2-bromnaphthalene is replaced with an equivalent equivalent of 4-bromobibenzene,

After the reaction, it is separated to obtain 5.6 g.

Nuclear magnetic spectrum data of compound B7:

1H NMR (400 MHz, Chloroform )δ 8.97 (s, 2H), 8.56 (s, 3H), 8.35 (s, 1H),

20 7.88 (d, J = 10.0 Hz, 2H), 7.63 (d, J = 12.0 Hz, 4H), 7.60 - 7.44 (m, 6H), 7.39 (d, J = 12.0 Hz, 4H), 7.27 (d, J = 12.0 Hz, 2H).

Synthesis Example 2.8: Synthesis of compound B8

The synthesis steps are the same as those of compound B1, with the difference being that 2-bromnaphthalene is replaced with the same equivalent of 5-bromo-(2-phenyl group)pyridine boric acid,

After the reaction, it is separated to obtain 5.1 g of a white solid.

Nuclear magnetic spectrum data of compound B8:

1H NMR (400 MHz, Chloroform) 8.97 (t, J = 8.0 Hz, 1H), 8.56 (s, 10H), 8.54 (s,3H), 8.54 - 8.33 (m, 1H), 8.32 (s, 3H), 8.08 (d, J = 12.0 Hz, 1H), 8.33 - 7.86 (m, 3H), 7.83 - 7.74 (m, 2H), 7.67 - 7.52 (m, 3H), 7.52 (s, 2H), 7.52 - 7.34 ( m, 4H), 7.27 (d, J = 12.0 Hz, 2H).

Synthesis Example 2.9: Synthesis of compound B9

The synthetic steps are the same as those of compound B1, with the difference being that 2-bromnaphthalene is replaced with the same equivalent of 2-(4-phenyl group)-pyridine,

After the reaction, it is separated to obtain 5.2 g of a white solid.

Nuclear magnetic spectrum data of compound B9:

1H NMR (400 MHz, Chloroform ) δ 9.29 (s, 2H), 8.97 (s, 1H), 8.35 (s, 1H), 7.96 (s, 2H), 7.65 (s, 2H), 7.54 (d, J = 12.0 Hz, 4H), 7.41 (s, 2H), 7.25 (s, 2H).

Synthesis Example 2.10: Synthesis of compound B10

Synthesis steps are the same as in compound B1, with the difference that 2-bromo-benzofuran anthracene quinone is replaced with an equivalent equivalent of 2-bromo-benzofuran anthracene quinone, and 2-bromnaphthalene is replaced with an equivalent equivalent of bromobenzene,

After the reaction, it is separated to obtain 4.8 g of a white solid.

Nuclear magnetic spectrum data of compound B11:

1H NMR (400 MHz, Chloroform ) δ 8.97 (s, 2H), 8.69 (d, J = 8.0 Hz, 4H), 8.37 (d,J= 10.0 Hz, 3H), 8.07 (d, J = 10.0 Hz, 3H) ), 7.94 (s, 1H), 7.85 (s, 3H), 7.65 (s,10 3H), 7.54 (d, J = 12.0 Hz, 4H), 7.41 (s, 3H).

Synthesis Example 2.11: Synthesis of compound B11

Synthetic steps are the same as for compound B1, with the difference being that 2-bromo-benzothiophene anthracene quinone is replaced with an equivalent equivalent of 2-bromo-benzothiophene anthracene quinone,

After the reaction, it is separated to obtain 4.9 g of a white solid.

Nuclear magnetic spectrum data of compound B11:

1H NMR (400 MHz, Chloroform ) δ 9.57 (s, 2H), 9.09 (s, 4H), 8.97 (s, 2H),

15 8.35 (s, 2H), 7.65 (s, 4H), 7.54 (d, J = 12.0 Hz, 7H), 7.41 (s, 1H), 7.25 (s, 8H).

Synthesis Example 2.12: Synthesis of compound B12

The synthesis steps are the same as those of Compound B1, except that 2,6-dibromine anthracene quinone is replaced with the same equivalent of 9-bromo-5-phenyl carbazole naphthalenone to obtain 4.7 g of a pale yellow solid.

Nuclear magnetic spectrum data of compound B12:

¹ H NMR (400 MHz, Chloroform ) δ 9.13 (s, 2H), 8.97 (s, 3H), 8.92 (s, 1H), 8.28 (d, J = 10.0 Hz, 4H), 8.07 (s, 2H), 7.65 (s, 4H), 7.63 - 7.44 (m, 9H), 7.40 (d,J= 8.0 Hz, 3H), 7.25 (s, 8H).

Synthesis Example 2.13: Synthesis of compound B13

Synthesis steps are the same as for compound B1, with the difference that 4.6 g of a pale yellow solid is obtained by replacing 2-bromnaphthalene with an equivalent equivalent of 4-(2-naphthalene)-bromobenzene.

Nuclear magnetic spectrum data of compound B13:

1H NMR (400 MHz, Chloroform ) δ 9.68 (s, 4H), 8.97 (s, 2H), 8.35 (s, 2H), 7.65(s, 4H), 7.54 (d, J = 12.0 Hz, 7H), 7.41 (s, 1H), 7.25 (s, 8H).

Synthesis Example 2.14: Synthesis of compound B14

The synthesis steps are the same as those of Compound B1, except that the 4-phenyl group-2-chloropyrazine is replaced with the same equivalent of 4,7-diphenyl group-2-chloropyrazine, and 2-bromnaphthalene is replaced with the same equivalent of 4-bromine. Substitution with mobibenzene gives 6.6 g of a pale yellow solid.

Nuclear magnetic spectrum data of compound B14:

1H NMR (400 MHz, Chloroform) δ 8.41 (d, J = 12.0 Hz, 2H), 8.36 - 8.22 (m,4H), 8.12 - 7.67 (m, 6H), 7.80 (d, J = 12.0 Hz, 2H) , 7.75 (dd, J = 7.2, 12.4 Hz, 4H), 7.72 (d, J = 10.0 Hz, 2H), 7.70 (s, 1H), 7.71 - 7.46 (m, 6H), 7.34 (d, J= 10.0) Hz, 20H), 7.25 (d, J = 12.4 Hz, 6H), 7.14 (s, 1H), 1.69 (s, 12H).

Synthesis Example 2.15: Synthesis of compound B15

Synthesis steps are the same as those of compound B14, except that 4,7-diphenyl group-2-chloropyrazine is replaced with the same equivalent of 4-phenyl group-7-(2-pyridine)-2-chloropyrazine, and 5.8 g of a pale yellow solid will get

Nuclear magnetic spectrum data of compound B15:

1H NMR (400 MHz, Chloroform) δ 9.19 (s, 1H), 8.35 (dd, J = 28.0, 12.0 Hz, 6H), 7.92 (s, 3H), 7.67 (s, 4H), 7.55 (s, 3H) , 7.49 (s, 1H), 7.24 (d, J = 4.0 Hz, 6H).

Synthesis Example 2.16: Synthesis of compound B16

The synthesis steps are the same as those of compound B14, except that the 4-phenyl group-2-chloropyrazine is replaced with the same equivalent of the 4-phenyl group-2-(4-bromophenyl group)-2-pyrazine to obtain 5.8 g of a pale yellow solid. will be.

Nuclear magnetic spectrum data of compound B16:

1H NMR (400 MHz, Chloroform) δ 8.99 (s, 3H), 8.37 (s, 3H), 8.20 (s, 5H), 8.09 (t, J = 14.0 Hz, 15H), 7.93 (dd, J = 38.5, 37.5 Hz, 19H), 7.79 (s, 5H), 7.64 (d, J = 8.0 Hz, 14H), 7.60 - 7.46 (m, 22H), 7.45 - 7.09 (m, 15H).

Synthesis Example 2.17: Synthesis of compound B17

The synthesis steps are the same as those of Compound B14, except that the 4-phenyl group-2-chloropyrazine is replaced with the same equivalent of the 4-phenyl group-2-(6-bromonaphthyl)-2-pyrazine to obtain 5.8 g of a pale yellow solid. will be.

Nuclear magnetic spectrum data of compound B17:

1H NMR (400 MHz, Chloroform ) δ 9.15 (s, 1H), 8.99 (s, 1H), 8.51 (s, 1H), 8.37 (s, 1H), 8.37 (s, 1H), 8.49 - 8.01 (m, 8H), 8.49 - 7.88 (m, 6H), 7.80 (d, J = 12.0 Hz, 2H), 7.64 (d, J = 8.0 Hz, 4H), 7.60 - 7.46 (m, 5H), 7.40 (d, J ) = 12.0 Hz, 2H).

Synthesis Example 2.18: Synthesis of compound B18

Synthetic steps are the same as those of compound B1, with the difference being that 5.8 g of a pale yellow solid by substituting the same equivalent of 4-phenyl-2-(5-pyridine-2-bromine)-2-pyrazine for the 4-phenyl group-2-chloropyrazine will get

Nuclear magnetic spectrum data of compound B18:

1H NMR (400 MHz, Chloroform ) δ 9.16 (s, 1H), 8.88 (s, 1H), 8.35 (s, 2H), 8.32 - 8.18 (m, 4H), 8.10 (q, J = 12.0 Hz, 6H) , 8.04 - 7.94 (m, 4H), 7.79 (s, 1H), 7.63 (s, 2H), 7.60 - 7.48 (m, 10H), 7.38 (s, 2H).

Synthesis Example 2.19: Synthesis of compound B19

Synthesis steps are the same as B10, with the difference being that bromobenzene is replaced with an equivalent equivalent of 2-bromnaphthalene.

After the reaction, it is separated to obtain 5.2 g of a white solid.

Nuclear magnetic spectrum data of compound B19:

1H NMR (400 MHz, Chloroform ) δ9.53 (s, 2H), 9.24 (s, 2H), 8.70 (s, 3H), 8.49 - 8.49 (m, 4H), 8.49 (s, 1H), 8.49 - 7.90 (m, 20H), 7.71 (s, 2H), 7.64 (d, J = 8.0 Hz, 9H), 7.90 - 7.45 (m, 30H), 7.78 - 7.45 (m, 20H), 7.60 - 7.51 (m, 9H) ), 7.48 (d, J = 8.0 Hz, 3H), 7.38 (d, J = 4.0 Hz, 6H), 7.31 (s, 1H).

Synthesis Example 2.20: Synthesis of compound B20

Synthesis steps are the same as for compound B11, with the difference that 2-bromnaphthalene is replaced with an equivalent equivalent of bromobenzene.

After the reaction, it is separated to obtain 4.8 g of a white solid.

Nuclear magnetic spectrum data of compound B20:

1H NMR (400 MHz, Chloroform) δ8.54 - 8.42 (m, 4H), 8.31 (s, 1H), 8.25 (s, 1H), 8.12 (d, J = 4.0 Hz, 4H), 8.06 (d, J ) = 0.6 Hz, 3H), 7.99 (d, J = 8.0 Hz, 3H), 7.77 - 7.74 (m, 4H), 7.77 - 7.52 (m, 10H), 7.89 - 7.15 (m, 20H), 7.77 - 7.15 ( m, 20H), 7.41 (s, 1H), 7.31 (s, 1H).

Synthesis Example 2.21: Synthesis of compound B21

The synthesis steps are the same as those of Compound B12, with the difference being that the 4-phenyl group-2-chloropyrazine is replaced with the same equivalent of the 2-phenyl group-4-chloropyrazine.

After the reaction, it is separated to obtain 4.9 g of a white solid.

Nuclear magnetic spectrum data of compound B21:

1H NMR (400 MHz, Chloroform) δ8.61 (s, 11H), 8.49 (s, 11H), 8.39 (dd, J = 7.6, 3.1 Hz, 2H), 8.33 (d, J = 16.0 Hz, 33H), 8.40 - 8.04 (m, 116H), 8.03 (d, J = 7.8 Hz, 6H), 7.99 (s, 28H), 8.04 - 7.66 (m, 55H), 7.66 - 7.47 (m, 156H), 7.39 (d, J = 8.0 Hz, 33H), 7.19 (d, J = 8.0 Hz, 22H).

Synthesis Example 2.22: Synthesis of compound B22

The synthesis steps are the same as those of Compound B1, except that the 4-phenyl group-2-chloropyrazine is replaced with the same equivalent of 4-(4-(2-pyridyl)-phenyl group)-2-chloropyrazine, and 4.7 g of a pale yellow solid will get

Nuclear magnetic spectrum data of compound B22:

¹ H NMR (400 MHz, Chloroform ) δ8.69 (s, 2H), 8.49 (s, 1H), 8.20 (s, 2H), 8.11 (d, J = 16.0 Hz, 3H), 8.07 - 7.85 (m, 5H), 8.39 - 7.53 (m, 25H), 8.07 - 7.69 (m, 7H), 8.28 - 7.53 (m, 21H), 7.63 (s, 2H), 7.60 - 7.51 (m, 7H), 7.38 (s, 2H), 7.14 (s, 2H), 6.90 (s, 1H).

Synthesis Example 2.23: Synthesis of compound B23

The synthesis steps are the same as those of compound B21, except that 2-bromnaphthalene is replaced with the same equivalent of bromobenzene, and the 2-chlorine-4-phenyl group pyrazine is replaced with the same equivalent of 2-chlorine-4-(2-naphthyl). ) to obtain 4.6 g of a pale yellow solid by substituting with pyrazine.

Nuclear magnetic spectrum data of compound B23:

1H NMR (400 MHz, Chloroform) δ9.09 (s, 2H), 8.47 (d, J = 12.0 Hz, 4H), 8.32 (s, 1H), 8.31 - 8.04 (m, 11H), 8.06 (s, 4H) ), 8.06 (s, 4H), 8.04 - 7.89 (m, 6H), 7.79 (s, 2H), 7.71 (s, 2H), 7.69 - 7.44 (m, 32H), 7.40 (d, J = 4.0 Hz, 6H), 7.19 (d, J = 8.0 Hz, 4H).

Synthesis Example 2.24: Synthesis of compound B24

The synthesis steps are the same as those of compound B1, with the difference being that 6.6 g of a pale yellow solid is obtained by substituting the same equivalent of 4-biphenyl-2-chloropyrazine for 4-phenyl-2-chloropyrazine.

Nuclear magnetic spectrum data of compound B24:

1H NMR (400 MHz, Chloroform) δ8.95 (s, 1H), 8.49 (d, J = 4.0 Hz, 2H), 8.31 (d, J = 2.8 Hz, 2H), 8.20 (s, 2H), 8.09 ( t, J = 14.0 Hz, 3H), 7.97 (d, J = 12.0 Hz, 3H), 7.63 (s, 1H), 7.91 - 7.05 (m, 23H), 7.60 - 7.51 (m, 5H), 7.69 - 7.05 (m, 16H), 7.51 - 7.32 (m, 7H), 7.25 (s, 2H).

Synthesis Example 2.25: Synthesis of compound B25

The synthesis steps are the same as those of Compound B1, except that the 4-phenyl group-2-chloropyrazine is replaced with the same equivalent of 7-phenyl group-4-(4-phenyl group-pyridine-2)-2-chloropyrazine as a pale yellow solid 5.8 to get g.

Nuclear magnetic spectrum data of compound B25:

1H NMR (400 MHz, Chloroform) δ9.18 (s, 2H), 8.49 (s, 2H), 8.43 (d, J = 8.0 Hz, 4H), 8.34 - 7.83 (m, 23H), 8.01 (d, J = 16.7 Hz, 6H), 8.01 (d, J = 16.7 Hz, 6H), 7.73 (d, J = 16.0 Hz, 7H), 7.63 (s, 4H), 7.52 (dt, J = 20.0, 12.0 Hz, 25H) ), 7.39 (d, J = 12.0 Hz, 8H).

Synthesis Example 2.26: Synthesis of compound B26

The synthesis steps are the same as those of Compound B1, except that the 4-phenyl group-2-chloropyrazine is replaced with the same equivalent of 4-(1-naphthyl)-2-chloropyrazine, and 2-bromnaphthalene is replaced with the same equivalent of bromine. Substitution with parent benzene yields 5.8 g of a pale yellow solid.

Nuclear magnetic spectrum data of compound B26:

1H NMR (400 MHz, Chloroform) δ8.97 (s, 2H), 8.49 (s, 2H), 8.26 (d, J = 44.0 Hz, 5H), 8.19 - 8.15 (m, 1H), 8.13 (s, 2H) ), 8.00 (s, 2H), 7.94 (s, 2H), 7.82 (dd, J = 13.1, 5.8 Hz, 8H), 7.71 (s, 2H), 7.65 (s, 10H), 7.57 - 7.51 (m, 12H), 7.47 (s, 4H), 7.41 (s, 4H).

Synthesis Example 2.27: Synthesis of compound B27

The synthesis steps are the same as those of Compound B24, with the difference being that 5.8 g of a pale yellow solid was obtained by substituting the same equivalent of 2-phenyl group-7-(2-naphthyl)-4-chloropyrazine for 4-biphenyl-2-chloropyrazine. will get

Nuclear magnetic spectrum data of compound B27:

1H NMR (400 MHz, Chloroform ) δ9.35 (s, 1H), 8.95 (s, 1H), 8.49 (d, J = 4.0 Hz, 2H), 8.38 - 8.23 (m, 4H), 8.20 (s, 2H) ), 8.08 (d, J = 12.0 Hz, 4H), 7.99 (s, 2H), 7.89 (s, 3H), 7.88 - 7.74 (m, 3H), 7.62 (dd, J = 12.0, 8.0 Hz, 7H) , 7.57 (d, J = 12.0 Hz, 4H), 7.54 (dd, J = 10.0, 8.0 Hz, 8H), 7.43 - 7.32 (m, 4H).

Elemental analysis data of compounds B1-B27

Elemental analysis data of the compound B1-B27 are as shown in Table 1-2 below.

[Table 1-2] Elemental analysis results of compounds B1-B27

Synthesis Example 3.1: Synthesis of compound E1

,

,

Synthetic intermediate N21:

Put 4-ethyl group phthaldiamine (13.6 g, 0.01 mol) and methyl glyoxylate (10 g, 0.011 mol) in methylbenzene, add a catalytic amount (3% eq) of para-toluenesulfonic acid, heat to reflux, and dissolve After reacting for 12 h, the reaction solution is concentrated, ethanol is added, and a yellow powder is precipitated and filtered to obtain an intermediate N20.

Intermediate N (17.4 g, 0.01 mol) is put in methylbenzene, and boron tribromide (30 g, 0.012 mol 0) is added, heated to reflux, and reacted for 12 h. The reaction solution is added to water to separate the liquid, and the organic phase is concentrated and separated by column chromatography to obtain an intermediate N21.

For the synthesis of compound E1 using intermediate N21:

Under the protection of nitrogen, 2-bromine anthracene quinone (M21) (26.5 g, 0.01 mol), pinacol boric acid ester (0.015 mol), Pd(dppf)Cl ₂ (1%) and potassium carbonate were mixed in 500 ml methylbenzene. Dissolve, heat to reflux, and allow to react overnight. The reaction solution is concentrated using column chromatography, and washed with petroleum ether to obtain an intermediate M22 (20.1 g, yield 89.6%).

Under the protection of nitrogen, intermediate M22 (6.7 g, 22 mmol, 1.1 eq), intermediate N21 (1eq), potassium carbonate (5eq), Pd(Pph ₃ ) ₄ (2%), Add 1000 ml of methylbenzene + 500 ml of ethanol + 300 ml of water to start mixing, heat to reflux, and react for 8 hours. The organic phase uses silica gel column chromatography method, is concentrated, and crystallizes again using methylbenzene to obtain yellow powder M23 (9.0 g, 93.7%).

Under the protection of nitrogen, 2-bromnaphthalene (25 mmol) is dissolved in tetrahydrofuran, the ethanol is cooled to -78°C, n-butyllithium solution is added dropwise, and the low temperature condition is maintained, and the solution dripping is complete When the temperature is controlled for 30 min, the intermediate M23 (4.8 g, 10 mmol) is dissolved in tetrahydrofuran and added dropwise into the reaction flask, and when the dropping is completed, the temperature is naturally raised and the reaction is carried out for 8 h. Diluted hydrochloric acid is added to the reaction solution, extracted with ethyl acetate, the organic phase is concentrated, and the solid is precipitated and filtered to obtain an intermediate M24 (4.8 g, 93.1%).

Intermediate M24 (5.1 g, 10 mmol) is placed in a reaction flask, 100 ml of glacial acetic acid, potassium iodide (20 mmol) and sodium hypophosphite (20 mmol) are added, heated to reflux, and reacted for 5 h. By filtration and washing by eluting with water and ethanol, yellow powder E1 (5.3 g, 79.1%) was collected and obtained.

Nuclear magnetic spectrum data of compound E1:

1H NMR (400 MHz, CDCl ₃ ) δ9.65 (s, 1H), 9.05 (s, 1H), 8.08 (d, J = 12.0 Hz, 4H), 8.50 - 7.64 (m, 7H), 8.17 - 7.64 ( m, 4H), 7.92 (d, J = 10.0 Hz, 2H), 7.70 - 7.51 (m, 5H), 7.38 (s, 1H), 2.72 (t, 2H), 1.18 (t, 3H).

Synthesis Example 3.2: Synthesis of compound E4

,

,

Intermediate N21 was synthesized using the same steps as in Synthesis Example 3.1.

Under the protection of nitrogen, a mechanical mixer apparatus was assembled and the intermediates N21 (leq), potassium carbonate (5eq), Pd(Pph ₃ ) ₄ (2%) in a three-necked flask containing the intermediate M200 (9.4 g, 22 mmol, 1.1 eq). , methylbenzene 1000ml+ethanol 500ml+300ml water is added to start mixing, heated to reflux, and reacted for 8h. The organic phase is concentrated using silica gel column chromatography, and again crystallized using methylbenzene to obtain yellow powder M201 (9.0 g, 93.7%).

Under the protection of nitrogen, the intermediate M201 (4.6g, 10mmol, 1eq) was dissolved in 100ml chloroform, 1.1eqNBS (N-bromosuccinimide) was added, mixed at room temperature for about 30min, and the reaction solution was water is added to the mixture, the liquid is separated, and the organic phase is concentrated to obtain an intermediate M202.

Under the protection of nitrogen, 1-naphthalene boric acid (1eq), potassium carbonate (5eq), Pd(Pph ₃ ) ₄ (2%), methylbenzene in intermediate M202 (10 mmol, 1eq) in a 3-neck flask equipped with a mechanical mixer device Add 1000ml+ethanol 500ml+300ml water to start mixing, heat to reflux, and react for 8h. The organic phase is concentrated using silica gel column chromatography, and crystallized again using methylbenzene to obtain yellow powder E4.

Nuclear magnetic spectrum data of compound E4:

1H NMR (400 MHz, CDCl ₃ )δ9.67 (s, 1H), 9.05 (s, 1H), 8.95 (s, 1H), 8.50 (s, 1H), 8.35 (s, 1H), 8.27 (s, 1H), 8.20 (s, 2H), 8.17 - 8.11 (m, 1H), 8.11 - 7.96 (m, 2H), 7.87 (d, J = 16.0 Hz, 2H), 7.78 (d, J = 4.0 Hz, 2H) ), 7.70 - 7.51 (m, 7H), 7.43 - 7.32 (m, 3H), 2.72 (t, 2H), 1.18 (t, 3H).

Synthesis Example 3.3: Synthesis of compound E11

,

,

For intermediate N213:

Put 4-ethyl group phthaldiamine (13.6 g, 0.01 mol) and malonaldehyde methyl ester (10 g, 0.011 mol) in methylbenzene, add a catalytic amount (3% eq) of para-toluenesulfonic acid, and heat to reflux and fractionate After reacting for 12 h, the reaction solution is concentrated, ethanol is added, and a yellow powder is precipitated and filtered to obtain an intermediate N211.

Intermediate N211 (17.4 g, 0.01 mol) is placed in methylbenzene, boron tribromide (30 g, 0.012 mol) is added, heated to reflux, reacted for 12 h, and the reaction solution is added to water to separate water. , the organic phase is concentrated, and an intermediate N212 is obtained by column chromatography separation.

Under the protection of nitrogen, intermediate N212 (leq), p-chlorobenzeneboric acid (leq), potassium carbonate (5eq), Pd (Pph ₃ ) ₄ (2%), methylbenzene 1000ml+ Add 500ml of ethanol + 300ml of water to start mixing, heat to reflux, and react for 8h. The organic phase uses silica gel column chromatography method, is concentrated, and crystallizes again using methylbenzene to obtain yellow powder N213 (9.0 g, 93.7%).

For the synthesis of compound E11 using intermediate N213:

Under the protection of nitrogen, 2-bromine anthracene quinone (M211) (26.5 g, 0.01 mol), pinacol boric acid ester (0.015 mol), Pd(dppf)Cl ₂ (1%) and potassium carbonate were mixed in 500 ml methylbenzene. Dissolve, heat to reflux, and allow to react overnight. The reaction solution is concentrated using column chromatography, and washed with petroleum ether to obtain an intermediate M212 (20.1 g, yield 89.6%).

Under the protection of nitrogen, Intermediate M212 (6.7g, 22mmol, 1.1eq), Intermediate N213 (1eq), Potassium carbonate (5eq), Pd(Pph ₃ ) ₄ (2%), Add 1000 ml of methylbenzene + 500 ml of ethanol + 300 ml of water to start mixing, heat to reflux, and react for 8 hours. The organic phase is concentrated using silica gel column chromatography, and crystallized again using methylbenzene to obtain yellow powder M213 (9.0 g, 93.7%).

Under the protection of nitrogen, bromobenzene (25 mmol) is dissolved in tetrahydrofuran, the ethanol is cooled to -78°C, n-butyllithium solution is added dropwise, and the low temperature condition is maintained, and when the solution dropwise is completed, The temperature is controlled for 30 min, the intermediate M213 (4.8 g, 10 mmol) is dissolved in tetrahydrofuran and added dropwise into the reaction flask, and when the dropping is completed, the temperature is naturally raised and the reaction is carried out for 8 h. Diluted hydrochloric acid is added to the reaction solution, extraction is performed with ethyl acetate, the organic phase is concentrated, and the solid is precipitated and filtered to obtain an intermediate M214 (4.8 g, 93.1%).

Intermediate M214 (5.1 g, 10 mmol) is placed in a reaction flask, 100 ml of glacial acetic acid, potassium iodide (20 mmol) and sodium hypophosphite (20 mmol) are added, heated to reflux, and reacted for 5 h. By filtration and washing by eluting with water and ethanol, yellow powder E11 (5.3 g, 79.1%) was collected and obtained.

Nuclear magnetic spectrum data of compound E11:

1H NMR (400 MHz, CDCl ₃ ) δ8.99 (s, 1H), 8.86 (s, 2H), 8.37 (s, 1H), 8.20 (s, 2H), 7.87 (d, J = 16.0 Hz, 3H) , 7.71 - 7.61 (m, 6H), 7.54 (d, J = 8.0 Hz, 6H), 7.41 (d, J = 4.0 Hz, 3H), 2.80 (s, 3H), 2.72 (t, 2H), 1.18 ( s, 3H).

Synthesis Example 3.4: Synthesis of compound E17

Under the protection of nitrogen, intermediate N221 (leq), propyl boric acid (leq), potassium carbonate (5eq), Pd(Pph ₃ ) ₄ (2%), methylbenzene 1000ml+ethanol 500ml+ Add 300 ml of water to start mixing, heat to reflux, and react for 8 h. The organic phase uses silica gel column chromatography method, is concentrated, and crystallizes again using methylbenzene to obtain yellow powder N222 (9.0 g, 93.7%).

Under the protection of nitrogen, N222 (26.5 g, 0.01 mol), pinacol boric acid ester (0.015 mol), Pd(dppf)Cl ₂ (1%) and potassium carbonate were mixed and dissolved in 500 ml methylbenzene, until refluxed. Heat and allow to react overnight. The reaction solution is concentrated using column chromatography, and washed with petroleum ether to obtain an intermediate N223 (20.1 g, yield 89.6%).

Intermediate 2-bromine anthracene quinone (leq), benzeneboric acid (leq), potassium carbonate (5eq), Pd(Pph ₃ ) ₄ (2%), methylbenzene in a three-necked flask equipped with a mechanical mixer under the protection of nitrogen Add 1000ml+ethanol 500ml+water300ml, start mixing, heat until reflux, and react for 8h. The organic phase is concentrated using silica gel column chromatography, and crystals are formed again using methylbenzene to obtain yellow powder M221 (9.0 g, 93.7%).

Under the protection of nitrogen, intermediate M221 (4.6g, 10mmol, 1eq) is dissolved in 100ml chloroform, 1.1eqNBS is added and mixed at room temperature, reacted for about 30min, water is added to the reaction solution, mixed, and the liquid is separated and concentrating the organic phase to obtain intermediate M222.

Under the protection of nitrogen, intermediate M222 (leq), intermediate N223 (leq), potassium carbonate (5eq), Pd(Pph ₃ ) ₄ (2%), methylbenzene 1000ml+ethanol 500ml+water in a three-necked flask equipped with a mechanical mixer device under the protection of nitrogen Add 300 ml to start mixing, heat to reflux, and react for 8 h. The organic phase is concentrated using silica gel column chromatography, and crystallized again using methylbenzene to obtain yellow powder M3 (9.0 g, 93.7%).

Under the protection of nitrogen, 2-bromnaphthalene (25 mmol) is dissolved in tetrahydrofuran, the ethanol is cooled to -78°C, n-butyllithium solution is added dropwise, and the low temperature condition is maintained, and the solution is added dropwise. Upon completion, the temperature is controlled for 30 min, the intermediate M223 ((4.8 g, 10 mmol) is dissolved in tetrahydrofuran, and added dropwise into the reaction flask. When the dropwise addition is completed, the temperature is naturally increased and the reaction is carried out for 8 h. Diluted hydrochloric acid is added, extraction is performed with ethyl acetate, the organic phase is concentrated, and the solid is precipitated and filtered to obtain an intermediate M224 (4.8 g, 93.1%).

Intermediate M224 (5.1 g, 10 mmol) is placed in a reaction flask, 100 ml of glacial acetic acid, potassium iodide (20 mmol) and sodium hypophosphite (20 mmol) are added, heated to reflux, and reacted for 5 h. By filtration and washing by eluting with water and ethanol, yellow powder E17 (5.3 g, 79.1%) was collected and obtained.

Intermediate M224 (5.1 g, 10 mmol) is placed in a reaction flask, 100 ml of glacial acetic acid, potassium iodide (20 mmol) and sodium hypophosphite (20 mmol) are added, heated to reflux, and reacted for 5 h. By filtration and washing by eluting with water and ethanol, yellow powder E17 (5.3 g, 79.1%) was collected and obtained.

Nuclear magnetic spectrum data of compound E17:

1H NMR (400 MHz, CDCl ₃ ) δ9.80 (s, 1H), 9.05 (s, 1H), 8.96 (s, 1H), 8.55 - 8.11 (m, 5H), 8.08 (d, J = 12.0 Hz, 3H), 7.99 (s, 2H), 7.80 (d, J = 10.0 Hz, 3H), 7.70 - 7.53 (m, 9H), 7.49 (s, 2H), 7.40 (d, J = 12.0 Hz, 2H), 2.61 (t, 2H), 1.64 (t, 2H), 0.94 (t, 3H).

Elemental analysis data of compounds E1-E20

The compounds of E1-E20 were synthesized using a synthesis method similar to the above synthesis method, and their elemental analysis and measurement data are as shown in Tables 1-3 below.

[Table 1-3] Elemental analysis results of compounds E1-E20

Device Example of OLED

In terms of structure, this OLED device embodiment 1.1-1.9, 2.1-2.9, 3.1-3.9 is "hole injection layer (HIL) / hole transport layer (HTL) / light emitting layer (EML) / electron transport layer (ETL) / electrons The injection layer (EIL)/cathode" is sequentially stacked. The material used by each layer is detailed, ITO/2-TNATA (30 nm)/NPB(20nm)/CBP: Ir(ppy) ₃ (5%) (20 nm)/electron transport material (50 nm)/LiF (1 nm)/Al.

Here, as described in Tables 2-1, 2-2, and 2-3, the electron transport material is, for example, a compound provided in some embodiments according to the present invention, a compound provided in some embodiments according to the present invention, and Like a mixture of LiQ or a mixture of two compounds provided by some embodiments according to the present invention, only one or a plurality of electron transport materials provided by some embodiments according to the present invention can be selected and used, and some according to the present invention The electronic transport material provided in the embodiment and other types of electronic transport material may be mixed and used. The mixing ratio may be 10:90-90:10.

OLED device control example

As shown in Table 2-1, Table 2-2, and Table 2-3, in order to contrast with the device Examples 1.1-1.9, 2.1-2.9, and 3.1-3.9, respectively, Device Control Examples 1.1-1.4 and 2.1-2.2 , 3.1-3.5 were further provided. The structure of the device control example is the same as that of the embodiment, with the difference being that only other types of electron transport materials are selected and used.

The manufacturing process according to the OLED device embodiment and the device control example is as follows.

A glass substrate with an ITO transparent conductive thin film applied to the surface is cleaned with ultrasonic waves in a cleaning solution, treated with ultrasonic waves in deionized water, deoiled with ultrasonic waves in a mixed solution of ethanol and acetone, and dried in a clean environment until moisture is completely removed. Etching and ozone treatment with an ultraviolet lamp, and irradiating the surface using a low-energy positive ion beam.

As described above, a glass substrate having an anode is placed in a vacuum chamber, a vacuum state is formed until it reaches 1Х10 ^-5 to 9Х10 ^-3 Pa, and 2-TNATA vacuum deposition is performed on the anode layer film, and the deposition rate is 0.1 nm. /s, and a hole injection layer having a thickness of 30 nm is formed. The compound NPB is vacuum deposited on the hole injection layer to form a hole transport layer with a thickness of 20 nm, and the deposition rate is 0.1 nm/s. EML is vacuum deposited on the hole transport layer to be used as a light emitting layer of the device, and EML includes a body material and a pigment material. The deposition rate of Ir(ppy) ₃ is set according to the mixing ratio, and the total thickness of the deposited thin film is 20 nm.

Materials and methods for manufacturing the device electron transport layer are as described above, the deposition rate is 0.1 nm/s, and the total thickness of the deposited thin film is 50 nm.

In the electron transport layer (ETL), LiF having a vacuum deposition thickness of 1 nm is used as an electron injection layer, and an Al layer having a thickness of 150 nm is used as a cathode of the device.

For the obtained organic electroluminescent device, the driving voltage and current efficiency were measured at the same luminance (10000 cd/m ² ), and the performance is as described in Tables 2-1, 2-2, and 2-3.

[Table 2-1] Driving voltage, current efficiency and LT90 of Device Examples 1.1-1.9 and Device Control Example 1.1-1.4 at the same luminance

[Table 2-2] Driving voltage, current efficiency and LT90 of Device Examples 2.1-2.9 and Device Control Example 2.1-2.2 at the same luminance

As can be seen from Table 2-1 and Table 2-2, in the situation where the other materials in the structure of the OLED device are the same, the ETL materials in the device use different compounds, compared to Control Examples 1.1-1.4 and 2.1-2.2 , device Examples 1.1-1.9 and 2.1-1-9 respectively significantly lower the operating voltage of the device and significantly improve the device current efficiency, thereby improving the luminous efficiency of the device; By significantly lengthening LT90, which is the time consumed when the luminance of OLED is attenuated from 100% to 90%, that is, the lifetime of the OLED element layer is extended.

The relatively high performance of the device embodiment is derived from the characteristics of the electron transport layer material used therein. Preferably, the electronic transport material should have the following characteristics. First, HOMO and LUMO have appropriate energy levels and high electron mobility; Second, to ensure that the thermal stability is high and the required molecular weight is sufficiently large to have a relatively high Tg; Third, the film forming performance is excellent, that is, the molecular weight should not be too large in order to be advantageous for film formation by vacuum deposition.

First, compared to Alq ₃ and CA, the electron transport layer material provided in the above device embodiment has excellent coplanarity, and thus the electron transport rate is high. Next, in CC-1, the active position of the anthracene ring, the 2nd and 6th positions, does not constitute a substituent protection, so that the material is easily degraded under high temperature conditions, affecting the luminous efficiency and service life; The electron transport material provided by the above device embodiment has two positions or two and six positions of substituent protection activation sites to improve thermal stability, so that the luminous efficiency is relatively high and the lifespan is relatively long.

[Table 2-3] Driving voltage, current efficiency and LT90 at the same luminance and ETL deposition temperature of Device Examples 3.1-3.9 and Device Control Examples 3.2-3.5

As can be seen from Table 2-3, in the situation where the other materials in the structure of the OLED device are the same, the ETL materials in the device use different compounds, and compared to Device Control Examples 3.1-3.5, Device Example 3.1 according to the present invention -3.9 significantly lowers the operating voltage of the device and greatly improves the device current efficiency, thereby improving the luminous efficiency of the device; Compared to Alq ₃ , which has a relatively small molecular weight, the deposition temperature is not significantly improved, and compared to other electron transport layer materials with comparable molecular weights, it has a significantly lower deposition temperature; By significantly lengthening LT90, which is the time consumed when the luminance of OLED is attenuated from 100% to 90%, that is, the lifetime of the OLED element layer is extended.

The relatively high performance of the device embodiments 3.1-3.9 according to the present invention is derived from the characteristics of the electron transport layer material used therein. Preferably, the electronic transport material should have the following characteristics. Relative to Alq ₃ and CA, the electron transport layer material provided by some embodiments according to the present invention has excellent coplanarity, and thus the electron transport rate is high. Similarly, among compounds having an anthracene ring, when radicals at two positions of anthracene are substituted with strong electroadsorption radicals, electron mobility is relatively high because electron transfer interlocking between the electroadsorption radical and the anthracene ring exists in the molecule. However, in CC-3, the substituent quinoxaline connects the benzene ring and the anthracene ring, which have weak electron adsorption power, to each other, so that the electron mobility of the compound is relatively low, and the luminous efficiency is relatively low. Furthermore, when an alkyl group substituent exists in the electron radical connected to the anthracene ring, the electron arrangement lowers the density to lower the deposition temperature of the material, and at the same time, the alkyl group substituent having a relatively small number of carbon atoms does not expand the molecular weight too much. Guarantee the proof temperature. However, in CC-2, since radicals such as alkyl groups do not exist other than the conjugated aromatic system, the molecular arrangement becomes dense, the crystal performance is relatively weak, the lifetime is relatively short, and the deposition temperature is relatively high. Substituents in CA and CC-3 are both aromatic radicals, and at the same time have a relatively large molecular weight and a relatively dense arrangement, the deposition temperature is relatively high, and the service life is affected.

In addition, when the materials provided in some embodiments according to the present invention are mixed with each other or mixed with LiQ, under conditions of different mixing proportions, compared to the non-mixed embodiments, all of them secure a lower device voltage and at the same time , in a situation where it is possible to maintain the consistency of efficiency, the lifetime of the device is also significantly longer.

The above has only described the detailed implementation manner of the present invention, and the protection scope of the present invention is not limited thereto. Any person skilled in the art will be able to easily make changes or substitutions within the technical scope presented in the present invention, and all of them should also be included within the protection scope of the present invention. Accordingly, the protection scope of the present invention should be based on the protection scope of the claims.

Above all, various specific technical features described in the above specific embodiments can be combined in any suitable way in a non-contradictory situation, and in order to avoid unnecessary repetition, various possible combinations of the present invention will not be separately described again. . In addition, any combination may be formed between various embodiments according to the present invention, and it should also be considered to be included in the content disclosed by the present invention.

Claims (30)

It has the structure indicated by the formula (I-2) below,

(I-2),
From here,
L is a chemical bond, a substituted or unsubstituted C ₆ to C ₁₂ arylene or sub-condensed ring-based aromatic hydrocarbon radical, a substituted or unsubstituted C ₃ to C ₁₂ sub-heteroaryl group or a sub-condensed heterocyclic aromatic hydrocarbon radicals;
Ar ¹ and Ar ² are each independently a substituted or unsubstituted C ₆ ~ C ₃₀ aryl group or a condensed ring-based aromatic hydrocarbon radical, a substituted or unsubstituted C ₃ ~ C ₃₀ heteroaryl group or a condensed heterocyclic aromatic hydrocarbon radicals;
R ¹ is a substituted or unsubstituted C ₆ -C ₃₀ aryl group or a condensed ring aromatic hydrocarbon radical, a substituted or unsubstituted C ₃ ~ C ₃₀ heteroaryl group or a condensed heterocyclic aromatic hydrocarbon radical;
R ² , R ³ , R ^{3 '} and R ⁴ are each independently hydrogen, a C ₁ ~ C ₁₀ alkyl group, halogen, cyano, a nitro group, a substituted or unsubstituted C ₆ ~ C ₃₀ aryl group or a condensed ring selected from a system aromatic hydrocarbon radical, a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group, or a condensed heterocyclic aromatic hydrocarbon radical;
A naphthyridine-substituted anthracene derivative, characterized in that R ³ and R ^3' are connected to each other to form a cyclic structure. According to claim 1,
A naphthyridine-substituted anthracene derivative, characterized in that the molecular weight of the naphthyridine-substituted anthracene derivative is 1000 or less. 3. The method of claim 2,
A naphthyridine-substituted anthracene derivative, characterized in that the molecular weight of the naphthyridine-substituted anthracene derivative is 450 to 900. 4. The method of claim 3,
A naphthyridine-substituted anthracene derivative, characterized in that the molecular weight of the naphthyridine-substituted anthracene derivative is 600 to 800. According to claim 1,
Wherein L is a substituted C ₆ ~ C ₁₂ Arylene or sub-condensed ring-based aromatic hydrocarbon radical, C ₃ ~ C ₁₂ It is selected from a sub-heteroaryl group or a sub-condensed heterocyclic aromatic hydrocarbon radical,
Here, the substitution radical in the C ₆ ~ C ₁₂ arylene or sub-condensed ring-based aromatic hydrocarbon radical, C ₃ ~ C ₁₂ sub-heteroaryl group or sub-condensed heterocyclic aromatic hydrocarbon radical is independently halogen, Cyano, nitro group, C ₁ ~ C ₁₀ alkyl group, cyclic alkyl group, alkylene, C ₁ ~ C ₆ alkoxy group or thioalkoxy group radical, C ₆ ~ C ₃₀ monocyclic aromatic hydrocarbon or condensed cyclic aromatic hydrocarbon radical And, C ₆ ~ C ₃₀ containing a hetero atom selected from N, O, S, Si selected from the group consisting of a monocyclic aromatic hydrocarbon or condensed ring aromatic hydrocarbon radical and Si(R ⁵ ) ₃ ,
Here, R ⁵ is a naphthyridine-substituted anthracene derivative, characterized in that it is selected from a C ₁ ~ C ₆ alkyl group. The method of claim 1,
wherein R ¹ , Ar ¹ and Ar ² are different from each other. According to claim 1,
Wherein R ¹ , Ar ¹ and Ar ² are each independently a substituted C ₆ ~ C ₃₀ aryl group or a condensed ring-based aromatic hydrocarbon radical, a substituted C ₃ ~ C ₃₀ heteroaryl group or a condensed heterocyclic aromatic hydrocarbon selected from radicals,
From here,
The C ₆ ~ C ₃₀ aryl group or condensed ring aromatic hydrocarbon radical, C ₃ ~ C ₃₀ heteroaryl group or substituted radical in the condensed heterocyclic aromatic hydrocarbon radical is independently a halogen, cyano, nitro group, C ₁ ~ C ₁₀ Alkyl group, cyclic alkyl group, alkylene, C ₁ ~ C ₆ Alkoxy group and thioalkoxy group radical and Si(R ⁵ ) ₃ selected from the group consisting of,
Here, R ⁵ is a naphthyridine-substituted anthracene derivative, characterized in that it is selected from a C ₁ ~ C ₆ alkyl group. The method of claim 1,
R ² , and R ⁴ are each independently hydrogen, a C ₁ to C ₅ subalkyl group, a halogen, cyano, a nitro group, a C ₆ to C ₁₅ substituted or unsubstituted aryl group or a condensed ring-based aromatic hydrocarbon radical, C ₃ ~ C ₁₅ selected from a substituted or unsubstituted heteroaryl group or a condensed heterocyclic aromatic hydrocarbon radical; R ³ and R ^3' are each independently a C ₁ ~ C ₅ sub-alkyl group, a C ₆ ~ C ₁₅ substituted or unsubstituted aryl group or a condensed ring-based aromatic hydrocarbon radical, a C ₃ ~ C ₁₅ substituted or unsubstituted A naphthyridine-substituted anthracene derivative, characterized in that it is selected from a heteroaryl group or a condensed heterocyclic aromatic hydrocarbon radical. The method of claim 1,
A naphthyridine-substituted anthracene derivative, characterized in that it is selected from the group consisting of compounds having the following structural formula B1-B27.

,

,

,

,

,

,

,

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. A naphthyridine-substituted anthracene derivative, characterized in that it is selected from the group consisting of compounds having the following structural formulas A1-A21.

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. A naphthyridine-substituted anthracene derivative, characterized in that it is selected from the group consisting of compounds represented by the following structural formulas E1-E20.

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. It includes an electron transport layer,
An organic electroluminescent device comprising at least one of the naphthyridine-substituted anthracene derivatives according to any one of claims 1 to 10 in the electron transport layer and used as an electron transport material. 13. The method of claim 12,
Organic electric field, characterized in that two compounds are included in the electron transport layer, at least one of the two compounds is the naphthyridine-substituted anthracene derivative, and the mixing weight ratio of the two compounds is 90:10 to 10:90. light emitting element. 13. The method of claim 12,
The electron transport layer is an organic electroluminescent device, characterized in that it further comprises 8-hydroxyl quinoline lithium. 15. The method of claim 14,
An organic electroluminescent device, characterized in that the mixing weight ratio of the naphthyridine-substituted anthracene derivative and the 8-hydroxyl group quinoline lithium in the electron transport layer is 90:10-10:90. 13. The method of claim 12,
A first electrode, a second electrode, and one or more organic layers positioned between the first electrode and the second electrode, the organic layer comprising at least a light emitting layer and the electron transport layer among the organic layers, An organic electroluminescent device, characterized in that the thickness is 5-100 nm. 17. The method of claim 16,
An organic electroluminescent device, characterized in that the thickness of the electron transport layer is 10-40 nm. It includes an electron transport layer,
An organic electroluminescent device comprising at least one naphthyridine-substituted anthracene derivative according to claim 11 in the electron transport layer and used as an electron transport material. 19. The method of claim 18,
The electron transport layer is an organic electroluminescent device, characterized in that it further comprises 8-hydroxyl quinoline lithium. 20. The method of claim 19,
An organic electroluminescent device, characterized in that the mixing weight ratio of the naphthyridine-substituted anthracene derivative and the 8-hydroxyl group quinoline lithium in the electron transport layer is 90:10-10:90. delete delete delete delete delete delete delete delete delete delete

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