KR102382431B1 - Compound and organic electroluminescent device using same - Google Patents

Abstract

여기서, X는 CR₄ 또는 N에서 선택되고; R₁ 내지 R₄은 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, 히드록시기, 실라닐기, 치환 또는 비치환된 C1~C12의 알킬기, C1~C12 알콕시기, 치환 또는 비치환된 C5~C60의 아릴기 또는 헤테로아릴기에서 선택되고; R₃의 수량은 0~4개이고, R₃의 수량이 2개 이상인 경우, R₃은 동일하거나 상이하다; L₁ 및 L₂는 각각 독립적으로 단일 결합, -O-, -S-, -NR^a-, C1~C5의 알킬렌기, (C1~C3 알킬렌기)-O-(C1~C3 알킬렌기), C6~C30의 아릴렌기, C3~C30의 헤테로아릴렌기에서 선택되고; 화학식 (II)에서의 점선과 Cy는 피리미딘 고리와 축합된 5원 또는 6원의 방향족 고리 또는 헤테로 방향족 고리를 나타낸다. 상기 화합물은 호스트 재료 또는 전자 수송 재료로서, 유기 전계 발광소자에 사용될 수 있다. 본 발명은 상기 화합물을 포함하는 유기전계 발광소자를 추가로 제공한다.The present invention provides a compound represented by the following formula (I) or (II).

wherein X is selected from CR ₄ or N; R ₁ to R ₄ is each independently hydrogen, deuterium, halogen, cyano group, nitro group, hydroxyl group, silanyl group, substituted or unsubstituted C1~ C12 alkyl group, C1~ C12 alkoxy group, substituted or unsubstituted C5~ C60 aryl selected from a group or a heteroaryl group; The quantity of R ₃ is 0-4, and when the quantity of R ₃ is 2 or more, R ₃ is the same or different; L ₁ and L ₂ are each independently a single bond, -O-, -S-, -NR ^a -, C1-C5 alkylene group, (C1-C3 alkylene group)-O-(C1-C3 alkylene group), C6~ C30 arylene group, C3~ C30 heteroarylene group; A dotted line and Cy in the formula (II) represent a 5- or 6-membered aromatic ring or heteroaromatic ring condensed with a pyrimidine ring. The compound may be used in an organic electroluminescent device as a host material or an electron transport material. The present invention further provides an organic electroluminescent device comprising the compound.

Description

Compound and organic electroluminescent device using same

The present invention relates to an organic compound and an organic electroluminescent device using the same.

Recently, as OLED technology continues to develop in both lighting and display fields, people have become more interested in research on its core materials. An organic electroluminescent device with good efficiency and a long lifespan is generally the result of optimally matching the device structure and various organic materials. Common functionalized organic materials include a hole injection material, a hole transport material, an electron injection material, an electron transport material, a light emitting host material, and a light emitting guest (dye). In order to manufacture a light emitting device with better performance, the industry has continuously developed new organic electroluminescent materials to further increase the luminous efficiency and lifespan of the device.

In a typical phosphorescent OLED device, a phosphorescent dye is generally not used alone as a light-emitting layer, but is doped into a suitable host material to form a host-guest light-emitting system, thereby weakening the high-concentration quenching reaction of triplet excitons. In order to realize effective energy transfer, in general, the energy gap of the host material is required to be larger than that of the dye, and the triplet energy level (ET) must be higher than the triplet energy level (ET) of the dye molecule. Only in this way can high-efficiency phosphorescence emission be realized as the energy of the T1 state is smoothly transferred from the host material to the phosphorescent dye or triplet excitons are restricted to the dye molecule. In addition, the glass transition temperature (Tg) of the host material is related to the film formability and thermal stability of the material. Materials with a low Tg temperature have poor thermal stability and are easily crystallized or agglomerated, which greatly reduces the lifetime of the device and seriously reduces the efficiency.

CBP is a widely used phosphorescent host material, and there have been reports that high-efficiency OLED devices were obtained using CBP as a host material and BCP and BAlq as hole blocking materials. It has been reported that a high-efficiency OLED device has been secured by using a derivative as a host material.

Patent Document 1 discloses a compound having a condensed bicyclic group as a skeleton structure, and Patent Document 2 and Patent Document 3 disclose nitrogen-containing heteroaryl in which, for example, triazine is bonded to a dibenzocarbazole nitrogen atom as an organic electroluminescent compound. A group compound is disclosed, and Patent Document 4 discloses a nitrogen-containing heteroaryl group compound in which, for example, triazine is bonded to a nitrogen atom of benzocarbazole as an organic electroluminescent compound. Patent Document 5 discloses a nitrogen-containing heteroaryl group compound in which, for example, quinazoline is bonded to a nitrogen atom of a carbazole derivative as an organic electroluminescent compound. However, in the above-mentioned references, an organic electroluminescent compound that introduces a compound represented by Formula (1) or (2), which will be described later, into a structure of a host material as an electron-deficient group has not been specifically disclosed.

On the other hand, most electron transport materials have a relatively high electron affinity, so their ability to accept electrons is relatively strong, but the electron mobility of common electron transport materials such as AlQ ₃ (8-Hydroxyquinoline aluminum salt) is Since the hole mobility of the hole transport material is much lower than that of the hole transport material, on the one hand, the imbalance between the injection and transport of carriers is caused, and the recombination probability of holes and electrons is lowered, so that the luminous efficiency of the device is lowered, and on the other hand, electron transport is caused. An electron transporting material with a relatively low degree of energy is disadvantageous in energy saving because it increases the driving voltage of the device and affects the efficiency of power.

At present, OLED screen manufacturers have widely used technical means of doping LiQ into the ET material layer to realize the low voltage and high efficiency of the device. LiQ mainly works to greatly improve the electron injection effect, and on the other hand, lithium ions can improve the electron mobility of the ET material, so that the LiQ-doped ET device has a low driving voltage and high luminous efficiency. have

prior art literature

Patent Literature

Patent Document 1: International Patent Publication No. WO2006/049013

Patent Document 2: US Patent No. 8,227,798

Patent Document 3: Korean Patent Application No. 10-2010-0108924

Patent Document 4: Korean Patent No. 10-1074193

Patent Document 5: International Patent Publication No. WO2012/121561

Non-patent literature

Non-Patent Document 1: J. Appl. Phys, 2001, 90:5048-5051, Appl. Phys. Lett., 2002, 80: 2308-2310.

Although the above-described traditional host materials have relatively good photoelectric properties, their glass transition temperature is relatively low and thermal stability is poor, which leads to deterioration of device performance during use. In addition, when BAlq, CBP or similar materials are used as phosphorescent host materials, the power efficiency of these OLED devices was not significantly improved due to the high driving voltage, and the lifespan was short. As described above, there are still insufficient parts in the existing materials, and the development of a new host material having high thermal stability and high photoelectric performance has very important practical application value.

In consideration of this, an object of the present invention is to provide a condensed heterocyclic derivative having a high glass transition temperature and melting point, and furthermore, a condensed heterocyclic compound having a high glass transition temperature and melting point and high carrier transport and luminescence efficiency. To provide a ring derivative. Another object of the present invention is to obtain an organic electroluminescent device with high thermal stability and long lifespan by applying such a derivative as a host material for the light emitting layer to the light emitting functional layer, and furthermore, an organic electroluminescent device with a low driving voltage and high luminous efficiency. to obtain a light emitting device.

On the other hand, there are still problems in the technical method of combining ET and LiQ commonly used in the industry. On one side, LiQ is sensitive to water and the environment, so the complexity of the process increases, which is not advantageous for lowering the design and manufacturing cost of equipment. In order to solve the above problems, to further meet the need for continuous improvement of the photoelectric performance of OLED devices and the demand for energy saving of mobile electronic devices, new high-efficiency OLED materials, especially new electron transport with high mobility Material development is required.

In consideration of this, another object of the present invention is to provide a condensed heterocyclic derivative having excellent electron transport performance and a low driving voltage and high luminous efficiency as an organic electroluminescent device using such a compound compared to the prior art.

The inventors of the present invention, through in-depth research, propose a new compound that can be used in an organic electroluminescent device and a device using the present compound, and the present compound introduces a structure of Formula (I) or (II) to obtain a high glass transition temperature and melting point and at the same time have excellent electron transport performance, thereby solving the above-mentioned problems existing in the prior art. Specifically, the compound of the present invention is represented by the following formula (I) or (II):

wherein X is selected from CR ₄ or N;

R ₁ to R ₄ is each independently hydrogen, deuterium, halogen, cyano group, nitro group, hydroxyl group, silanyl group, substituted or unsubstituted C1~ C12 alkyl group, C1~ C12 alkoxy group, substituted or unsubstituted C5~ C60 aryl is selected from a group or heteroaryl group, and the substituent of the C5~ C60 aryl group or heteroaryl group is deuterium, halogen, cyano group, nitro group, hydroxy group, silane group, amino group, substituted or unsubstituted C1~ C12 alkyl group, C1~ C12 alkoxy group, C6~ C30 substituted or unsubstituted aryl group, C10~ C30 substituted or unsubstituted heteroaryl group, C6~ C30 substituted or unsubstituted arylamino group, C3~ C30 substituted or unsubstituted Selected from a cyclic heteroarylamino group, the substituents of the C6~ C30 substituted or unsubstituted aryl group and the C10~ C30 substituted or unsubstituted heteroaryl group are a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenane is selected from phenanthryl; The quantity of R ₃ is 0-4, and when the quantity of R ₃ is 2 or more, R ₃ is the same or different; L ₁ and L ₂ are each independently a single bond, -O-, -S-, -NR ^a -, C1-C5 alkylene group, (C1-C3 alkylene group)-O-(C1-C3 alkylene group), C6~ C30 arylene group, C3~ C30 heteroarylene group; A dotted line and Cy in the formula (II) represent a 5- or 6-membered aromatic ring or heteroaromatic ring condensed with a pyrimidine ring.

상호 작용을 충분히 발생시킬 수 있고, 재료 분자들 사이에서 전자의 수송에 유리하기 때문에 이러한 화합물이 포함되는 재료는 매우 높은 전자 이동도를 갖게 된다. 따라서 OLED 소자에 본 유형의 재료를 적용하면 소자의 구동 전압을 낮추고 소자의 발광 효율을 향상시키는데 유리하다. The inventors of the present invention have found that a compound satisfying the above limitations has a high glass transition temperature and a high melting point, and at the same time has excellent electron transport performance. Although the principle is not clear, it is assumed as follows: In the above compound of the present invention, a pyrimidotriazole group (when X is N) or a pyrimidoimidazole group (when X is CR ₄ ) as the parent nucleus is relatively large It has a conjugated structure, greatly improves the glass transition temperature (Tg) of the compound, and since the organic electroluminescent material containing this compound has high thermal and chemical stability, the lifespan is longer than that of the organic electroluminescent material of the prior art; On the other hand, the compound of the present invention has an excellent coplanar conjugated structure, so that in the solid state, the molecule is

A material containing such a compound has very high electron mobility because it can sufficiently generate an interaction and is advantageous for electron transport between material molecules. Therefore, application of this type of material to an OLED device is advantageous for lowering the driving voltage of the device and improving the luminous efficiency of the device.

The part to be explained here is that the expression in which the substitution bond of R ₃ in the structural formula is directed toward the center of the ring indicates that the substitution position may be any possible position of the ring. The meanings of substitution bonds in the structural formulas are all similar. The expression method of Ca~Cb means that the number of carbon atoms in the group is a to b, and unless otherwise specified, in general, the number of carbon atoms does not include the number of carbon atoms in the substituent.

In the present specification, the alkyl group may be linear or branched, and unless otherwise specified, examples of the C1-C12 alkyl group include a methyl group, an ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group , iso-butyl group, tert-butyl group, pentyl group, iso-pentyl, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group (undecyl), dodecyl group, etc., among which methyl group , preferably an ethyl group, an n-propyl group, or an iso-propyl group, and even more preferably a methyl group; Examples of the C1-C12 alkoxy group include a group obtained by linking the examples of the C1-C12 alkyl group with -O-, for example, a methoxy group, an ethoxy group, a propoxy group, a butyloxy group, a pentyloxy group, and a hexyl group. A siloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, a dodecyloxy group, etc., among them, preferably a methoxy group, an ethoxy group, or a propoxy group, more preferably a methoxy group Do; Examples of the C5-C60 aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a fluorenyl group, and the like, and among them, a phenyl group or a naphthyl group is preferable, and a phenyl group is more desirable. The C5-C60 heteroaryl group may be a nitrogen-containing heteroaryl group, an oxygen-containing heteroaryl group, or a sulfur-containing heteroaryl group, and specific examples include a pyridine group, a pyrimidine group, a pyrazine group, and a pyridine group. Minced group, triazine group, quinoline group, isoquinoline group, naphthyridine group, phthalazine group, quinoxaline group, quinazoline group, phenanthridine group, acridine group, phenanthroline group, pyrrole group, imidazole group, pyrazole group , triazole group, tetrazole group, indole group, benzimidazole group, indazole group, imidazolepyridine group, benzotriazole group, carbazole group, furan group, thiophene group, oxazole group, thiazole group, isoxazole group, isothiazole group , oxadiazole group, thiadiazole group, benzofuran group, benzothiophene group, benzoxazole group, benzothiazole group, benzoisooxazole group, benzoisothiazole group, benzoxadiazole group, benzothiadiazole group, dibenzofuran group , dibenzothiophene group, piperidine group, pyrrolidine group, piperazine group, morpholine group, phenazine group, phenothiazine group, phenoxazine group, etc., among them, pyridine group, quinoline group, dibenzofuran group, preferably a dibenzothiophene group, and even more preferably a pyridine group.

In the present specification, unless otherwise specified, an aryl group, an arylene group, a heteroaryl group, a heteroarylene group, and the like all include the case of a single ring as well as the case of a condensed ring. Heteroatom generally refers to an atom or group of atoms selected from B, N, O, S, P, P(=O), Si and Se.

In the present specification, unless otherwise specified, the expression "substituted or unsubstituted" means one or more substituents selected from halogen, cyano group, hydroxy group, alkoxy group, alkyl group, aryl group, heteroaryl group. preferably, fluorine, cyano group, methoxy group, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, phenyl group, biphenyl group, naphthyl group , a phenanthryl group, a fluorene group, a dibenzofuran group, a dibenzothiophene group, a pyridine group, a quinoline group, a phenylpyridine group, a pyridylphenyl group, and the like; Or it means that there is no substituent.

The inventors of the present invention have found that by appropriately defining the groups of the compound of the present invention, a host material or an electron transporting material having better performance in either aspect can be obtained. A detailed description is as follows.

A first preferred embodiment of the compound of the present invention relates to a compound represented by the following formula (I) or (II), which can be used as a host material:

wherein X is selected from CR ₄ or N; R ₁ to R ₄ are each independently selected from hydrogen, a C1 to C10 alkyl group, a substituted or unsubstituted C5 to C60 aryl group or a heteroaryl group, and the substituent of the aryl group or heteroaryl group is deuterium, fluorine, A methyl group, a methoxy group, a cyano group, a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a pyridine group, a furan group, a thiophene group, an indene group, a benzofuran group, a benzothiophene group, a substituted or unsubstituted indole group; It is selected from a dibenzofuran group, a dibenzothiophene group, a substituted or unsubstituted carbazole group, a benzocarbazole group, and a dibenzocarbazole group, and the substituents of the indole group and the carbazole group include a phenyl group, a biphenyl group, a naphthyl group, and a phenanthryl group. is selected from the group; The quantity of R ₃ is 1, and L ₁ and L ₂ are a single bond; A dotted line and Cy in the formula (II) represent a 5- or 6-membered aromatic ring or heteroaromatic ring condensed with a pyrimidine ring.

In the compound provided by the present invention, as a parent nucleus, a pyrimidotriazole group (when X is N) or a pyrimidoimidazole group (when X is CR ₄ ) has a relatively large conjugated structure, and the glass transition temperature of the compound (Tg) is greatly improved, and since the organic electroluminescent material containing such a compound has high thermal and chemical stability, the lifespan is longer than that of the organic electroluminescent material of the prior art.

In the above compound, the 5- or 6-membered aromatic ring or heteroaromatic ring in the formula (I) or (II) is preferably selected from a benzene ring, a pyridine ring, a furan ring, and a thiophene ring.

In the compound, R ₁ in the formula (I) or (II) is preferably a structure represented by the following formula (III).

Here, L ₃ is independently a single bond, -O-, -S-, C1~ C5 alkylene group, (C1~ C3 alkylene group)-O-(C1~ C3 alkylene group), C6~ C30 arylene group, It is selected from a C3~ C30 heteroarylene group; R ₅ and R ₆ are independently H, D, a substituted or unsubstituted C1-C12 alkyl group, a C1-C12 alkoxy group, a halogen, a cyano group, a nitro group, a hydroxyl group, a silanyl group, a C6-C30 substituted or unsubstituted It is selected from an aryl group, a C10~ C30 substituted or unsubstituted heteroaryl group; the quantity of R ₅ and R ₆ is 0-4, respectively, and when the quantity of R ₅ or R ₆ is 2 or more, R ₅ is the same or different, and R ₆ is the same or different; or R ₅ and R ₆ are independently condensed with a benzene ring connected to each other to form a C9~ C12 aryl group or heteroaryl group, and the formed aryl group or heteroaryl group is independently a substituted or unsubstituted C1~ C12 alkyl group, optionally substituted with 0-5 substituents selected from halogen, cyano group, nitro group, hydroxy group, silane group, C6-C30 substituted or unsubstituted aryl group, C3-C30 substituted or unsubstituted heteroaryl group; Y is C(R ₇ ) ₂ , NR ₈ , O, S; n is 0 or 1, and when n is 0, it indicates that the two carbon atoms connected to Y are directly connected; R ₇ and R ₈ are independently selected from hydrogen, a C1-C5 alkyl group, a phenyl group, a halogen, a cyano group, a nitro group, and a hydroxy group, and two R ₇ are the same or different.

By setting R ₁ in the formula (I) or (II) to the structure represented by the formula (III), a dibenzo nitrogen-containing heterocyclic group capable of acting as an electron donor can be introduced into the molecule, and the carrier's The transport is balanced, so that the performance of the organic electroluminescent device in which the compound is used as a host material is improved, and has high luminance, high efficiency and low driving voltage.

In the above compound, n in formula (III) is preferably 0. By setting n to 0, the compounds represented by formulas (I) and (II) having electron-deficient properties are linked with a carbazole derivative group that can be an electron donor, so that an acceptor-donor-type molecule is formed, and the energy of the molecule By improving the energy level of the gap and triplet, it is possible to secure a bipolar phosphorescent host material with excellent performance, which makes carrier transport in molecules more balanced, thereby improving the luminance and efficiency of the organic electroluminescent device in which the present compound is used do. In addition, the organic functional layer using a bipolar material can simplify the structure of the device.

In the above compound, L ₃ in formula (III) is preferably a single bond or a phenylene group. Preferably, by setting L ₃ as a single bond or a phenylene group, the compound represented by the formulas (I) and (II) having electron deficient properties is a carbazole derivative group that can be used as an electron donor directly or via a benzene ring. When connected to each other, the function as a bipolar host material is further improved.

In the compound, preferably R ₅ and R ₆ in Formula (III) are independently hydrogen, a substituted or unsubstituted C1-C4 alkyl group, a phenyl group, a naphthyl group, a furan group, a thiophene group, a pyrrole group, a pyridine group , biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, indene group, fluorenyl group and derivatives thereof, fluoranthenyl group, triphenylene group, pyrene group, perylene group, chrysene group, tetracene group, tri an arylamine group, a 9,9-dimethylfluorenyl group, a distyrenylphenyl, a benzofluorenyl group, an indenofluorenyl group or an indene group, or a dibenzoheteroaryl group as shown in formula (V); or R ₅ and R ₆ are independently condensed with a benzene ring connected thereto to form a naphthyl group, an anthryl group, a phenanthryl group, an indene group, a fluorenyl group, a benzofuran group, a benzothiophene group, a benzopyridine group, a benzopyr a roll group, or a dibenzoheteroaryl group as shown in formula (V):

Here, the linking moiety is located on N or the benzene ring in the formula (V), and when the linking site is positioned on the benzene ring of (V), N is connected to each other with H, a phenyl group and a C1-C4 alkyl group; X' is C(R ₉ ) ₂ , NR ₁₀ , O, S; m is 0 or 1, and when m is 0, it indicates that the two carbon atoms linked to X' are directly linked; R _a , R _b , R ₉ and R ₁₀ are independently selected from hydrogen, a C1-C5 alkyl group, a C1-C5 alkoxy group, a halogen, a cyano group, a nitro group, a hydroxyl group, and a phenyl group, and two R ₉ are the same or different and; X' is the same as or different from Y.

In the above compound, in formula (I) or (II), R ₂ to R ₄ are each independently selected from the following groups:

In the above compound, in formula (I) or (II), R ₁ is preferably one of the following groups:

When a compound in which R ₁ is one of the above groups is used as a bipolar host material of a doped light emitting device, a balance is made in carrier transport, so that excitons are uniformly distributed, recombination of carriers at the interface is prevented, and high At exciton concentrations, triplet-triplet extinction is reduced. An organic electroluminescent device in which a compound in which R ₁ is one of the above groups is used has high luminance, high efficiency and low driving voltage.

In the above compound, it is more preferred that in formula (I) or (II), R ₁ is one of the following groups:

When R ₁ is one of the above groups, the performance of the compound as a bipolar host material of a doped light emitting device can be further improved, and further, the balance in carrier transport is more properly made, so that triplet-triplet disappearance at high exciton concentration This is reduced. An organic electroluminescent device in which a compound in which R ₁ is one of the above groups is used has higher luminance, efficiency and lower driving voltage.

In the above compound, in formulas (I) and (II), when X is CR ₄ , R ₂ is preferably hydrogen, and more preferably, formulas (I) and (II) are one selected from the following structures. .

By setting the formulas (I) and (II) to one of the above structures, it is possible to obtain a parent nucleus with a further improved structure, so that the glass transition temperature (Tg) of the compound is greatly improved, and the organic electroluminescent material in which the present compound is used The thermal and chemical stability of the organic electroluminescent material is improved, and the lifetime of the organic electroluminescent material is improved.

In the compound, R ₁ to R ₄ are more preferably a combination selected from Table 1 below. Here, to describe R ₂ (R ₄ ) in the second column of Table 1, since Formulas (I) and (II) are one selected from the above structures, when X is N, R ₄ is not present, and X is _In the case of CR ₄ , R ₂ is hydrogen, so one _of R _{2 and} R ₄ must be already determined _. denote the other with

Table 1

By setting R ₁ to R ₄ in the compound as a combination of one of the tables above, the performance of the organic electroluminescent device including the compound can be greatly improved, and has high luminance, high efficiency, low driving voltage and long life.

The condensed heterocyclic derivative of the first preferred embodiment of the present invention has one, two or both of the following advantages:

1. The condensed heterocyclic derivative provided in this embodiment is an acceptor-donor type molecule by linking a compound represented by formulas (I) and (II) having electron deficient properties with a carbazole derivative group that can be an electron donor , and by improving the molecular energy gap and triplet energy level, a bipolar phosphorescent host material with excellent performance can be obtained. In addition, the pyrimidotriazole group or quinazotriazole group as the parent nucleus has a relatively large conjugated structure, greatly improves the glass transition temperature (Tg) of the compound, and this organic electroluminescent material has relatively high thermal and chemical stability. have

2. When the compound of this embodiment is used as a bipolar host material of a doped light emitting device, a balance is made in carrier transport, so that excitons are uniformly distributed, recombination of carriers at the interface is prevented, and high exciton concentration At triplet-triplet extinction is reduced. An organic functional layer using a bipolar material can simplify the structure of the device.

3. When the compound represented by the formulas (I) and (II) prepared in this embodiment is used as a host material of the red phosphorescent light emitting layer, the performance of the organic electroluminescent device can be greatly improved, and high luminance, high efficiency, low It has a driving voltage and a long life.

A second preferred embodiment of the compound of the present invention relates to a compound represented by the following formula (II), which can be used as a host material:

wherein Cy is a benzene ring, X is N; L ₁ and L ₂ are each independently a single bond, -O-, -S-, -NR ^a -, C1-C5 alkylene group, (C1-C3 alkylene group)-O-(C1-C3 alkylene group), C6~ C30 arylene group, C3~ C30 heteroarylene group; R ₁ is represented by the following formula (IV), R ₂ , and R ₃ are each independently hydrogen, deuterium, C1-C12 alkyl group, C1-C12 alkoxy group, halogen, cyano group, nitro group, hydroxyl group, silanyl group, It is selected from a C6~ C30 substituted or unsubstituted aryl group, a C3~ C30 substituted or unsubstituted heteroaryl group; The quantity of R ₃ is each 0-4, and when the quantity is 2 or more, R ₃ is the same or different;

Here, R ₅ and R ₆ are independently H, D, C1-C12 alkyl group, C1-C12 alkoxy group, halogen, cyano group, nitro group, hydroxyl group, silanyl group, amino group, C6-C30 substituted or unsubstituted aryl an amino group, a C3~ C30 substituted or unsubstituted heteroarylamine group, a C6~ C30 substituted or unsubstituted aryl group, and a C3~ C30 substituted or unsubstituted heteroaryl group; the quantity of R ₅ and R ₆ is 0-4, respectively, and when the quantity of R ₅ or R ₆ is 2 or more, R ₅ is the same or different, and R ₆ is the same or different; Or R ₅ and R ₆ are independently condensed with a benzene ring connected to each other to form a C9~ C30 aryl group or heteroaryl group, and the formed aryl group or heteroaryl group is independently a C1~ C12 alkyl group, halogen, cyano group, optionally substituted with 0-5 substituents selected from a nitro group, a hydroxyl group, a silanyl group, a C6-C30 substituted or unsubstituted aryl group, and a C3-C30 substituted or unsubstituted heteroaryl group; Y is C(R ₇ ) ₂ , NR ₈ , O, S; n is 0 or 1, and when n is 0, it indicates that the two carbon atoms connected to Y are directly connected; R ₇ and R ₈ are independently selected from hydrogen, a C1-C5 alkyl group, a phenyl group, a halogen, a cyano group, a nitro group, and a hydroxy group, and two R ₇ are the same or different.

In the above compound, n is preferably 0.

In the above compound, preferably L ₂ is a single bond, L ₁ is a single bond, benzene or naphthalene.

In the compound, preferably R ₅ and R ₆ are independently hydrogen, a substituted or unsubstituted C1-C4 alkyl group, a phenyl group, a naphthyl group, a furan group, a thiophene group, a pyrrole group, a pyridine group, a biphenyl group , terphenyl group, naphthyl group, anthryl group, phenanthryl group, indene group, fluorenyl group and derivatives thereof, fluorantenyl group, triphenylene group, pyrene group, perylene group, chrysene group, tetracene group, triarylamine group , 9,9-dimethylfluorenyl group, distyrenylphenyl, benzofluorenyl group, indenofluorenyl group or indene group, or a dibenzoheteroaryl group as shown in formula (V); or R ₁ and R ₂ are independently condensed with a benzene ring connected thereto to form a naphthyl group, an anthryl group, a phenanthryl group, an indene group, a fluorenyl group, a benzofuran group, a benzothiophene group, a benzopyridine group, or a benzopyr A roll group, or a dibenzoheteroaryl group as shown in formula (V), is formed:

Here, the linking moiety is located on N or the benzene ring in the formula (V), and when the linking site is positioned on the benzene ring of (V), N is connected to each other with H, a phenyl group and a C1-C4 alkyl group; X' is C(R ₉ ) ₂ , NR ₁₀ , O, S; m is 0 or 1, when m is 0, it indicates that two carbon atoms connected to X' are directly connected, and R _a , R _b , R ₉ and R ₁₀ are independently hydrogen, C1-C5 alkyl group, C1- selected from a C5 alkoxy group, a halogen, a cyano group, a nitro group, a hydroxy group, and a phenyl group, and two R ₉ are the same or different; X' is the same as or different from Y.

In the above compound, R ₂ is H, D, a substituted or unsubstituted C1-C4 alkyl group, a phenyl group, or a phenyl group substituted with a furan group, a thiophene group, a pyrrole group and/or a pyridine group, a biphenyl group, a terphenyl group, naph Tyl group, anthryl group, phenanthryl group, indene group, fluorenyl group and derivatives thereof, fluoranthenyl group, triphenylene group, pyrene group, perylene group, chrysene group, tetracene group, furan group, phenylfuran group, thiophene group, phenylthiophene group, pyrrole group, phenylpyrrole group, pyridine group, phenylpyridine group, pyrazine group, fluorenyl group, indenofluorenyl group, quinoline group, triazine group, benzofuran group, benzothiophene group, benzo Triazine, benzopyrazine, isobenzofuran group, indole group, benzoquinoline, dibenzofuran group, dibenzothiophene group, dibenzopyrrole group, triarylamine group, 9,9-dimethylfluorenyl group, distyrenylphenyl group , a benzofluorenyl group, an indenofluorenyl group or an indene group, a carbazole group, a carbazole group and derivatives thereof, a diazole substituted with phenyl, a phenanthroline group, a phenanthrolinothiazole group and a benzom-dioxocyclopentenyl group. It is preferred that at least one is selected.

In the above compound, when R ₅ and/or R ₆ is condensed with a benzene ring connected thereto, the group connected to L ₁ is one selected from the following formula, where * represents a connection site with L ₁ :

In the above compound, -L ₂ -R ₂ is preferably one selected from the following formula:

The C1-C12 alkyl group is more preferably a C1-C4 alkyl group, preferably a methyl group, an ethyl group, an isopropyl group, or a cyclohexyl group; The C1-C12 alkoxy group is more preferably a C1-C4 alkoxy group, and specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.

The quinazotriazole derivative containing a substituted or unsubstituted arylamino group proposed in this embodiment is a bipolar phosphorescent host material. Theoretically, the bipolar material is an ideal host material, because the organic functional layer based on the bipolar material not only simplifies the device structure, but also can properly balance the transport of carriers, so that the excitons are uniformly distributed, and the recombination of carriers at the interface This is prevented, because at high exciton concentrations it can reduce triplet-triplet extinction. In molecular design, electron-deficient acceptor groups are linked with electron-rich donor groups to form acceptor-donor-type molecules, thus increasing the energy gap and triplet energy level of the molecule, resulting in higher triplet and wider energy gaps. of excellent bipolar phosphorescent host material can be obtained.

In this embodiment, based on the above concept, a quinazotriazole group having an electron-deficient property is connected to a carbazole derivative group that can be an electron donor. These compounds have a relatively large spatial structure, which can prevent the doped guest from being deposited and annihilated during energy transport, while at the same time greatly increasing the glass transition temperature (Tg) of the material, and these materials also have high thermal and chemical stability. and can be used as a bipolar host material of a dopant-type light emitting device in an organic electroluminescent device.

In order to more clearly explain the contents of the present embodiment, preferred structures of the compounds related to the present embodiment will be described in detail below:

The condensed heterocyclic derivative provided in this embodiment has a high glass transition temperature and a high melting point, and at the same time has high carrier transport and luminous efficiency. By applying these derivatives to the organic light-emitting functional layer as a host material for the light-emitting layer, an organic electroluminescent device having a low driving voltage and high light-emitting efficiency can be obtained. Specifically, the fused heterocyclic derivative of the present invention has one, two or both of the following advantages:

1. In the condensed heterocyclic derivative provided in this embodiment, an acceptor-donor molecule is formed by linking a quinazotriazole group having electron-deficient properties with a carbazole derivative group that can be an electron donor, and the energy gap and triplet of the molecule By improving the energy level of the term, it is possible to obtain a bipolar phosphorescent host material with excellent performance. In addition, the quinazotriazole group as the parent nucleus has a relatively large conjugated structure, greatly improves the glass transition temperature (Tg) of the compound, and this organic electroluminescent material has relatively high thermal and chemical stability.

2. When the compound of the present invention is used as a bipolar host material for a doped light emitting device, a balance is made in carrier transport, so that excitons are uniformly distributed, recombination of carriers at the interface is prevented, and at high exciton concentrations Triplet-triplet extinction is reduced. An organic functional layer using a bipolar material can simplify the structure of the device.

3. When the compound represented by the formula (I) prepared in the present invention is used as a host material for the red phosphorescent light emitting layer, the performance of the organic electroluminescent device can be greatly improved, and high luminance, high efficiency, low driving voltage and long lifespan will have The compounds of the present invention can also be used in combination with conventionally known light emitting layer host materials.

A third preferred embodiment of the compound of the present invention relates to a compound which can be used as an electron transport material and is represented by the following formula (I) or (II):

wherein X is selected from CR ₄ or N; R ₁ to R ₄ are each independently selected from hydrogen, a C1 to C10 alkyl group, a substituted or unsubstituted C5 to C60 aryl group or a heteroaryl group, and the substituent of the aryl group or heteroaryl group is deuterium, fluorine, a methyl group, a methoxy group, a cyano group, a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a substituted or unsubstituted anthryl group, and the substituent of the anthryl group is a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, phenanthryl group; The quantity of R ₃ is 1, and L ₁ and L ₂ are a single bond; A dotted line and Cy in formula (II) represent a 5- or 6-membered aromatic ring or heteroaromatic ring condensed with a pyrimidine ring.

상호 작용을 충분히 발생시킬 수 있고, 재료 분자들 사이에서 전자의 수송에 유리하기 때문에 이러한 화합물이 포함되는 재료는 매우 높은 전자 이동도를 갖게 된다. 따라서 OLED 소자에 본 유형의 재료를 적용하면 소자의 구동 전압을 낮추고 소자의 발광 효율을 향상시키는데 유리하다.In order to improve the electron injection and transport performance of the material, it is necessary to select a group having a relatively strong electron affinity, and the group of the commonly used electron transport material includes groups such as pyridine, quinoline, o-phenanthroline and triazine. The compound of this embodiment employs a new type of group with strong electron affinity, and the LUMO of the compound of the present invention calculated by Gaussian calculation is about -1.651 eV, which is a commonly used electron withdrawing group such as pyridine (-0.61 eV). , significantly lower than the LUMO energy levels of quinoline (-1.38 eV) and o-phenanthroline (-1.41 eV), so that the compounds of formulas (I) and (II) have high electron affinity and are of this type as excellent electron withdrawing groups. A compound having a substituent indicates that it has excellent electron injection properties. The mechanism by which the compound of this embodiment has the above excellent properties is not yet orthodoxy, but according to inference, the compounds of formulas (I) and (II) have excellent coplanar conjugated structures, so that molecules having the above substituents in the solid state are between groups

A material containing such a compound has very high electron mobility because it can sufficiently generate an interaction and is advantageous for electron transport between material molecules. Therefore, when this type of material is applied to an OLED device, it is advantageous to lower the driving voltage of the device and improve the luminous efficiency of the device.

In the above compounds, in formulas (I) and (II), when X is CR ₄ , R ₂ is preferably hydrogen, and more preferably, formulas (I) and (II) are one selected from the following structures. Do:

In the above compound, at least one of R ₁ to R ₄ preferably includes an anthracene ring structure, and at least one of R ₁ to R ₄ is more preferably a structure represented by the following formula (VI):

-L-B (VI)

Here, B is a substituted or unsubstituted anthryl group, and the substituent of the anthryl group is selected from a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, and a phenanthryl group. L is a single bond, a monocyclic arylene group or monocyclic heteroarylene group having 5 to 10 carbon atoms, preferably a single bond, a monocyclic arylene group or monocyclic heteroarylene group having 5 to 6 carbon atoms, even more preferably is a single bond, a phenylene group, or a pyridylene group.

By setting at least one of R ₁ to R ₄ to the above structure, it is possible to better utilize the conjugated structure and strong electron affinity of the anthracene ring, thereby improving the electron transport performance of the compound.

In addition, among R ₁ to R ₄ , groups not having a structure represented by the formula (VI) are each independently selected from the following groups:

In the above compound, the structure represented by the formula (VI) is one selected from the following groups.

More preferably, the structure represented by the formula (VI) is one selected from the following groups:

By setting the structure represented by the formula (VI) to one of the above groups, the electron transfer efficiency between material molecules can be improved so that the compound has a higher electron mobility.

In the compound, R ₁ to R ₄ are more preferably a combination selected from Table 2 below. Here, to describe R ₂ (R ₄ ) in the second column of Table 2, Formulas (I) and (II) are one selected from the above structures, so when X is N, R ₄ is not present, and X is _In the case of CR ₄ , R ₂ is hydrogen, so one _of R _{2 and} R ₄ must be already determined _. indicate the other with

Table 2

By setting R ₁ to R ₄ as a combination of one of the above tables, the conjugated structure of the anthracene ring can be more fully utilized, so that the LUMO of the compound is further reduced, and the electron affinity of the compound is improved, so that the compound has excellent electron injection performance.

The compound of this embodiment, on the one hand, is closer to the work function of the cathode material due to the high electron affinity peculiar to the parent structure, so that the material can easily obtain electrons from the cathode, so that it has a strong electron injection property; On the other hand, it has a very high electron mobility. Combining the above two, when the material of this embodiment is used alone, the technical effect realized by matching the ET commonly used in the industry to LiQ can be achieved, and LiQ, which is sensitive to water and the environment, can be applied to the conventional ET material. By avoiding mixing and using, on the one hand, the type of material used in the screen mass production line is reduced, which is advantageous for material cost reduction, and on the other hand, it is possible to reduce the number of evaporation sources of the mass production equipment, the equipment The design manufacturing cost and process complexity are reduced, which is of great significance.

A fourth preferred embodiment of the compound of the present invention relates to a compound which can be used as an electron transport material and is represented by the following formula (II):

wherein Cy is a benzene ring, X is N; L ₁ and L ₂ are each independently a single bond, -O-, -S-, -NR ^a -, C1-C5 alkylene group, (C1-C3 alkylene group)-O-(C1-C3 alkylene group), C6~ C30 arylene group, C3~ C30 heteroarylene group; R ₁ , R ₂ , and R ₃ are each independently hydrogen, a substituted or unsubstituted C1-C12 alkyl group, a C1-C12 alkoxy group, a halogen, a cyano group, a nitro group, a hydroxyl group, a silanyl group, a C6-C30 substituted or unsubstituted It is selected from a cyclic aryl group, a C3~ C30 substituted or unsubstituted heteroaryl group, and the quantity of R ₃ is 1 to 4, and when the quantity is 2 or more, R ₃ is the same or different, and R ₁ and R At least one of ₂ is a substituted or unsubstituted condensed aryl group, and the condensed aryl group includes a condensed ring in which two or more benzene rings are formed, or R ₁ , R ₂ and R ₃ are all phenyl groups.

결합을 형성하며, 상기 공액

결합에는 적어도 4개의 벤젠 고리를 포함하거나, 또는 상기 축합 아릴기는 자체에 형성된 공액

결합에 적어도 3개의 벤젠 고리를 포함한다. In the compound, preferably, at least one of R ₁ and R ₂ is a substituted or unsubstituted condensed aryl group, and the condensed aryl group includes a condensed ring having two or more benzene rings formed thereon; In addition, the condensed aryl group is conjugated with a substituent on it or L ₁ or L ₂ connected thereto

form a bond, wherein the conjugation

The bond contains at least 4 benzene rings, or the fused aryl group is a conjugated aryl group formed therein.

contain at least three benzene rings in the bond.

In the compound, at least one of R ₁ and R ₂ is a substituted or unsubstituted naphthyl group, an anthryl group, a fluorantenyl group, a fluorenyl group, a phenanthryl group, a pyrene group, a benzoanthryl group, a benzopyrene group is preferably selected; The substituents are independently hydrogen, a substituted or unsubstituted C1-C12 alkyl group, a C1-C12 alkoxy group, a halogen, a cyano group, a nitro group, a hydroxy group, a silanyl group, a C6-C18 substituted or unsubstituted aryl group, C3- 1 to 4 are selected from the C11 substituted or unsubstituted heteroaryl group, and the substituents are the same or different.

In the compound, at least one of R ₁ and R ₂ is preferably a naphthyl group or a group represented by Formula (VII), where * represents a linking site, and Formula (VII) is independently H, substituted or unsubstituted optionally substituted with 1 to 4 substituents selected from a C1 to C12 alkyl group, a C1 to C12 alkoxy group, a phenyl group, a halogen, a cyano group, a nitro group, and a hydroxy group, wherein the substituents are the same or different; Here, Ar ₃ is H, a substituted or unsubstituted C1-C12 alkyl group, a C1-C12 alkoxy group, a halogen, a cyano group, a nitro group, a hydroxy group, a C6-C12 substituted or unsubstituted aryl group, a C3-C11 substitution or an unsubstituted heteroaryl group; When two Ar ₃ are present in formula (VII), the two Ar ₃ are the same or different;

Formula (VII)

In the compound, L ₁ and L ₂ are preferably a single bond, a phenyl group, a furan group, a thiophene group, a pyrrole group, a pyridine group, a biphenyl group, a terphenyl group or a naphthyl group independently.

In the compound, Ar ₃ is independently hydrogen, a phenyl group, a naphthyl group, a furan group, a thiophene group, a pyrrole group, a pyridine group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indene group, Fluorenyl group and derivatives thereof, fluoranthenyl group, triphenylene group, pyrene group, perylene group, chrysen group, tetracene group, triarylamine group, 9,9-dimethylfluorenyl group, distyrenylphenyl group, benzofluorenyl group , it is preferably selected from an indenofluorenyl group or an indene group.

In the compound, when one of R ₁ and R ₂ is a naphthyl group or a group represented by Formula (VII), the other is hydrogen, a phenyl group, a naphthyl group, a furan group, a thiophene group, a pyrrole group, a pyridine group, Biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, indene group, fluorenyl group and derivatives thereof, fluoranthenyl group, triphenylene group, pyrene group, perylene group, chrysene group, tetracene group, triaryl group It is preferably selected from an amine group, a 9,9-dimethylfluorenyl group, a distyrenylphenyl group, a benzofluorenyl group, an indenofluorenyl group, or an indene group.

Preferred structures of the compounds according to the present embodiment may be enumerated as follows, but are not limited to these compounds.

상호 작용을 충분히 발생시킬 수 있고, 재료 분자들 사이에서 전자의 수송에 유리하기 때문에 이러한 화합물이 포함되는 재료는 매우 높은 전자 이동도를 갖게 된다. 따라서 OLED 소자에 본 유형의 재료를 적용하면 소자의 구동 전압을 낮추고 소자의 발광 효율을 향상시키는데 유리하다.In order to improve the electron injection and transport performance of a material, a group having a relatively strong electron affinity should be selected, and the group of the electron transport material commonly used includes groups such as pyridine, quinoline, o-phenanthroline and triazine. The compound of this embodiment employs a new type of group having strong electron affinity, quinazotriazole, and the LUMO of the quinazotriazole parent compound calculated by Gaussian calculation is about -1.651 eV, which is a commonly used electron withdrawing group. For example, significantly lower than the LUMO energy level of pyridine (-0.61 eV), quinoline (-1.38 eV) and o-phenanthroline (-1.41 eV), the quinazotriazole group has a high electron affinity, and such an excellent electron withdrawing group It has been shown that compounds with tangible substituents have good electron injection properties. In addition, quinazotriazole has an excellent coplanar conjugated structure, so the compound molecule having such a substituent is intergroup in the solid state.

A material containing such a compound has very high electron mobility because it can sufficiently generate an interaction and is advantageous for electron transport between material molecules. Therefore, when this type of material is applied to an OLED device, it is advantageous to lower the driving voltage of the device and improve the luminous efficiency of the device.

The compound of this embodiment, on the one hand, is closer to the work function of the cathode material due to the high electron affinity peculiar to the parent structure, so that the material can easily obtain electrons from the cathode, so that it has a strong electron injection property; On the other hand, it has a very high electron mobility. Combining the above two, when the material of this embodiment is used alone, the technical effect realized by matching the ET commonly used in the industry to LiQ can be achieved, and LiQ, which is sensitive to water and the environment, can be applied to the conventional ET material. By avoiding mixing and using, on the one hand, the type of material used in the screen mass production line is reduced, which is advantageous for material cost reduction, and on the other hand, it is possible to reduce the number of evaporation sources of the mass production equipment, the equipment The design manufacturing cost and process complexity are reduced, which is of great significance.

In addition, the inventors added that when the quinazotriazole compound is substituted with an anthryl group, it has very suitable HOMO and LUMO energy levels, so that the resulting compound is suitable for electron and hole transport channels and also has a relatively high charge transport performance. was found with This may be related to the distribution of both HOMO and LUMO to the anthryl functional group, and the anthryl functional group can impart reversible electrochemical redox properties to the compound, so that the compound of the present invention containing the anthryl functional group It has excellent electron transport properties, and is therefore desirable as an electron transport material for devices.

The present invention further provides that the compound is applied to an organic electroluminescent device. Here, the compound may be used as an electron transport material or a light emitting layer host material, but is not limited thereto.

The present invention provides an organic electroluminescent device comprising a first electrode, a second electrode, and at least one organic layer positioned between the first electrode and the second electrode, wherein the organic layer comprises at least one of the compounds provides more The organic layer between the first electrode and the second electrode generally includes organic layers such as an electron injection layer, an electron transport layer, a light emitting layer, a hole transport layer, and a hole injection layer.

In the organic electroluminescent device, preferably, the organic layer includes a hole transport layer, an organic light emitting layer and an electron transport layer, the organic light emitting layer includes a host material and a dopant dye, and the host material of the organic light emitting layer is selected from the above compounds do. More preferably, the dopant material is a red phosphorescent dye.

In the organic electroluminescent device, preferably, the organic layer includes an electron injection layer, and the electron injection layer includes the compound; Also preferably, the organic layer includes an electron transport layer, and the electron transport layer includes the compound.

The compounds of this embodiment are organic electroluminescent devices, lighting devices, organic thin film transistors, organic field effect transistors, organic thin film solar cells, information labels, electronic artificial skin sheets, large sensors such as sheet type scanners, electronic paper and organic EL panels, etc. It can be applied to organic electronic devices such as In addition, the organic functional layer based on the bipolar material can simplify the device structure.

specific implementation

The organic electroluminescent device substrate of this embodiment, for example, may use a substrate of a conventional organic light emitting device such as glass or plastic, preferably a glass substrate.

For the anode material, a transparent and highly conductive material such as Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin oxide (SnO2), or zinc oxide (ZnO) may be employed. The device of the present invention preferably uses ITO as the anode material.

In the device of the present invention, the thickness of the hole transport layer is generally 5 nm-5 μm, and the hole transport layer is N,N'-bis(3-tolyl group)-N,N'-diphenyl group-[1,1-biphenyl group ]-4,4'-diamine (TPD) or N,N'-diphenyl group-N,N'-bis (1-naphthyl group)-(1,1'-biphenyl group)-4,4'-diamine ( A triarylamine type material such as NPB) may be employed. The device structure may be a single-layer or multi-layer light emitting layer structure; Each light emitting layer may be a single light emitting material structure or a doped structure; The luminescent dopant may be selected from a phosphorescent material; The emission color may be red, yellow, indigo, green, or the like, but is not limited thereto.

The cathode may adopt an electron injection layer/metal layer structure such as, for example, a structure of a metal and a mixture thereof such as Mg:Ag, Ca:Ag, or a common cathode structure such as, for example, LiF/Al, Li ₂ O/Al, etc. there is. Here, the electron injection layer may be a single, compound, or mixture of alkali metals, alkaline earth metals, and transition metals, and may also have a composite cathode structure composed of a multilayer material.

In general, an organic electroluminescent device includes a plurality of organic functional layers including a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer interposed between a cathode and an anode. In addition to the contents listed in the following general description and examples, other technical contents related to organic electroluminescent devices already known to those skilled in the art, such as manufacturing methods and general components, may also be applied to the present invention.

Hereinafter, a method for preparing a representative compound of the present invention will be described with reference to the following Examples. Since the compounds of the present invention have the same skeleton, those skilled in the art can easily synthesize other compounds of the present invention through known functional group conversion methods based on these preparation methods. Hereinafter, a method for manufacturing a light emitting device including the compound and measurement of light emitting characteristics are further provided. Unless otherwise specified, the raw materials and intermediates used in the present invention are all commercially available products; In the present invention, the mass spectrum was measured using a ZAB-HS type mass spectrometer (manufactured by Micromass, UK).

The method for preparing the intermediate according to the first preferred embodiment and the third preferred embodiment of the present application is largely divided into two types, one is pyrimidine (derivative) triazole type intermediate M1, and the other is pyrimidine ( derivative) of the imidazole type intermediate M2. The preparation method is as follows:

Preparation of Intermediate M1:

2,4-dichloropyrimidine (or a derivative thereof) as a starting material, first reacted with hydrazine hydrate, and an intermediate by substituting a chlorine atom at position 4 with a relatively high activity of 2,4-dichloropyrimidine (or a derivative thereof) create A. Intermediate A is further subjected to a condensation reaction with an aldehyde to remove one molecule of water and produce Intermediate B. Intermediate B is again subjected to oxidative cyclization with iodosobenzene diacetate to produce intermediate M1 of the first type.

Preparation of Intermediate M2:

-브로모(헤테로)아릴 또는 알킬에틸케톤(Alkyl ethyl ketone)과 추가로 반응시켜, 제 2유형의 중간체 M2를 생성한다. Intermediate C is obtained by first reacting 2,4-dichloropyrimidine (or a derivative thereof) with ammonia water as a starting material, and substituting a chlorine atom at position 4 with high activity of 2,4-dichloropyrimidine (or a derivative thereof) create Intermediate C

- Further reaction with bromo(hetero)aryl or Alkyl ethyl ketone gives intermediate M2 of the second type.

Synthesis examples of specific compounds of the first preferred embodiment of the present application are as follows:

Example A1: Preparation of compound 1I-12

Preparation of compound 1-1

After dissolving 2,4-dichloropyrimidine (2,4-Dichloropyrimidine, 500 g, 3.38 mol) in 10 L ethanol in a flask, hydrazine hydrate (634 g, 10.14 mol, 80% aqueous solution) was added dropwise at 5° C. under stirring, During the dropping process, the temperature was maintained below 10°C. After completion of the dropwise addition, the temperature was naturally raised to room temperature and reacted for 1 hour, and then the precipitated solid was filtered off with suction, washed with water and ethanol, respectively, and dried, as white solid Compound 1-1 (389 g, 80%) ) was obtained.

Preparation of compound 1-2

Compound 1-1 (144 g, 1 mol) was added to a flask containing 1.5 L of ethanol, and benzaldehyde (138 g, 1.3 mol) was added dropwise at room temperature under stirring, and after completion of the dropping, stirring reaction was continued for 30 minutes. Then, the solid obtained by filtration was washed with ethanol and n-hexane, respectively, and dried to obtain a yellow solid compound 1-2 (151 g, 65%).

Preparation of compound 1-3

Compound 1-2 (151 g, 0.65 mol) was added to a flask containing 3 L of ethanol, and iodobenzene diacetate (251 g, 0.78 mol) was added portionwise under stirring at room temperature, and after completion of the addition, continued for 1.5 hours After the reaction was stirred, TLC showed that the reaction was complete. The obtained solid was filtered with suction, washed with n-hexane, and dried to obtain a pale yellowish-brown solid compound 1-3 (109 g, 73%).

Preparation of compound 1-4

In a flask containing toluene: ethanol: water (3L: 1L: 1L), N-phenylcarbazole-3-boronic acid ((9-Phenyl-9H-carbazol-3-yl)boronic acid, 500 g, 1.742 mol), After dissolving 3-bromocarbazole (3-Bromo-9H-carbazole, 412 g, 1.584 mol) and potassium carbonate (656 g, 4.752 mol) at room temperature under stirring and nitrogen substitution, tetrakis (triphenylphosphine) Palladium (Tetrakis (triphenylphosphine) palladium, 18.3 g, 0.016 mol) was added. After the addition was completed, the reaction was stirred and refluxed for 6 hours, and the reaction endpoint was monitored by TLC. The precipitated solid was filtered off. The liquid layer was separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The crude solids were combined and purified by column chromatography (eluent: petroleum ether: methylene chloride = 10:1) to obtain compound 1-4 (543 g, yield 81%).

Preparation of compound 1I-12

Compound 1-3 (5.44 g, 23.64 mmol), compound 1-4 (10 g, 23.64 mmol), potassium carbonate (10 g, 72.46 mmol) were added to a flask containing 200 mL of acetonitrile, and under a nitrogen atmosphere, 12 hours After heating to reflux under stirring for a while, TLC showed that the reaction was complete. 200 mL of water was added, and the pale yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a white solid compound 1I-12 (12.1 g, yield 85%). Calculated molecular weight: 602.22, found m/Z: 602.2.

Example A2: Preparation of compound 1II-12

Preparation of compound 2-1

In a flask containing 1,4-dioxane/water (300mL/100mL), p-chlorophenylboronic acid (4-Chlorophenylboronic acid, 7.8g, 50mmol), compound 1-3 (11.5g, 50mmol), potassium carbonate (20.7 g, 150mmol), and after nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (578 mg, 0.5 mmol) was added. After completion of the addition, the reaction was stirred at 80° C. for 8 hours, and the reaction endpoint was monitored by TLC. The layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 2-1 (10.7 g, yield 70%).

Preparation of compound 1II-12

In a flask containing 200 mL of xylene, compound 2-1 (6.12 g, 20 mmol), compound 1-4 (8.46 g, 20 mmol), and sodium tert-butoxide (Sodium tert-butoxide, 5.8 g, 60 mmol) were added. and under a nitrogen atmosphere, Pd ₂ (dba) ₃ (183 mg, 0.2 mmol) and tri-tert-butylphosphine (Tri-tert-butylphosphine, 50% xylene solution, 242 mg, 0.6 mmol) were added under stirring, After the addition was completed, the reaction was heated to reflux for 15 hours, and then TLC showed that the reaction was complete. The solvent was rotary evaporated under reduced pressure, dissolved with methylene chloride, washed with water, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a white solid compound 1II-12 (11.2 g, yield 81%). Calculated molecular weight: 694.28, found m/Z: 694.3.0

Example A3: Preparation of compound 1II-63

Preparation of compound 3-1

In a flask containing 1,4-dioxane / water (1.5L / 0.5L), dibenzofuran-4-boronic acid (4-Dibenzofuranboronic acid, 116.6 g, 0.55 mmol), compound 1-3 (100.5 g, 0.5 mol) ), potassium carbonate (207 g, 1.5 mol) was added, nitrogen was substituted under stirring at room temperature, and then Pd(PPh ₃ ) ₄ (5.78 g, 5 mmol) was added. After completion of the addition, the reaction was heated to reflux under stirring for 8 hours, and the reaction endpoint was monitored by TLC. The layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 3-1 (130 g, yield 90%).

Preparation of compound 3-2

Compound 3-1 (130g, 0.45mol), PPh ₃ (295g, 1.13mol) was added to a flask containing o-dichlorobenzene (1,2-dichlorobenzene, 1.5L), and stirred under a nitrogen atmosphere for 36 hours The reaction was carried out under reflux under heating, and the reaction endpoint was monitored by TLC. The solvent was removed by rotary evaporation under reduced pressure, and separated and purified by column chromatography to obtain compound 3-2 (105 g, yield 91%).

Preparation of compound 1II-63

In a flask containing 200 mL of xylene, compound 2-1 (6.12 g, 20 mmol), compound 3-2 (5.14 g, 20 mmol), sodium tert-butoxide (5.8 g, 60 mmol) were added, and under a nitrogen atmosphere, Pd ₂ (dba) ₃ (183 mg, 0.2 mmol) and tri-tert-butylphosphine (50% xylene solution, 242 mg, 0.6 mmol) were added under stirring, and after completion of the addition, the reaction was heated to reflux for 15 hours, TLC indicated reaction completion. The solvent was rotary evaporated under reduced pressure, dissolved with methylene chloride, washed with water, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a white solid compound 1II-63 (9.2 g, yield 85%). Calculated molecular weight: 543.21, found m/Z: 543.2.

Example A4: Preparation of compound 1II-327

Preparation of compound 1II-327

In a flask containing 200mL of xylene, compound 2-1 (6.12g, 20mmol), 7H-dibenzocarbazole (7H-Dibenzo[c,g]carbazole, 5.34g, 20mmol), sodium tert-butoxide (5.8g) , 60 mmol), and under a nitrogen atmosphere, Pd ₂ (dba) ₃ (183 mg, 0.2 mmol) and tri-tert-butylphosphine (50% xylene solution, 242 mg, 0.6 mmol) were added under stirring, and the addition was completed Then, after heating and refluxing for 15 hours, TLC showed that the reaction was complete. The solvent was rotary evaporated under reduced pressure, dissolved with methylene chloride, washed with water, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a white solid compound 1II-327 (9.1 g, yield 82%). Calculated molecular weight: 553.23, found m/Z: 553.2.

Example A5: Preparation of compound 2I-12

Preparation of compound 5-1

Compound 2-chloro-4-aminopyrimidine (2-CHLORO-4-AMINOPYRIMIDINE, 129 g, 1 mol) and bromoacetophenone (Bromoacetophenone, 218 g, 1.1 mol) were added to a flask containing 1.3 L of DMF and stirred After reacting for 20 hours by heating to 100° C., TLC showed that the reaction was complete. The temperature was lowered to room temperature, water was added to precipitate a solid, and the solid obtained by filtration was washed with ethanol, dried and subjected to column chromatography to obtain a pale yellowish-brown solid compound 5-1 (172 g, 75%).

Preparation of compound 2I-12

Compound 5-1 (4.58 g, 20 mmol), compound 1-4 (8.46 g, 20 mmol), potassium carbonate (8.3 g, 60 mmol) were added to a flask containing 200 mL of acetonitrile, and under a nitrogen atmosphere, for 15 hours After heating to reflux under stirring, TLC showed that the reaction was complete. 200 mL of water was added, and the obtained pale yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a white solid compound 2I-12 (10.6 g, yield 88%). Calculated molecular weight: 601.23, found m/Z: 601.2.

Example A6: Preparation of compound 2II-63

Preparation of compound 6-1

In a flask containing 1,4-dioxane/water (300 mL/100 mL), p-chlorophenylboronic acid (17.2 g, 0.11 mmol), compound 5-1 (22.9 g, 0.1 mol), potassium carbonate (41.4 g, 0.3 mol), and after nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (1.2 g, 1 mmol) was added. After completion of the addition, the reaction was stirred at 80° C. for 8 hours, and the reaction endpoint was monitored by TLC. The layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 6-1 (22.9 g, yield 75%).

Preparation of compound 2II-63

In a flask containing 200 mL of xylene, compound 6-1 (6.1 g, 20 mmol), compound 3-2 (5.14 g, 20 mmol), and sodium tert-butoxide (5.8 g, 60 mmol) were added, and under a nitrogen atmosphere, Pd ₂ (dba) ₃ (183mg, 0.2mmol) and tri-tert-butylphosphine (50% xylene solution, 242mg, 0.6mmol) were added under stirring, and after completion of the addition, after heating and refluxing for 15 hours, TLC indicated reaction completion. The solvent was rotary evaporated under reduced pressure, dissolved with methylene chloride, washed with water, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a white solid compound 2II-63 (9.4 g, yield 87%). Calculated molecular weight: 542.21, found m/Z: 542.2.

Example A7: Preparation of compound 2II-327

Preparation of compound 2II-327

Compound 6-1 (6.1 g, 20 mmol), 7H-dibenzocarbazole (5.34 g, 20 mmol), sodium tert-butoxide (5.8 g, 60 mmol) was added to a flask containing 200 mL of xylene, and under a nitrogen atmosphere , Pd ₂ (dba) ₃ (183 mg, 0.2 mmol) and tri-tert-butylphosphine (50% xylene solution, 242 mg, 0.6 mmol) were added under stirring, and after completion of the addition, the reaction was heated and refluxed for 15 hours. , TLC indicated reaction completion. The solvent was rotary evaporated under reduced pressure, dissolved with methylene chloride, washed with water, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a white solid compound 2II-327 (8.8 g, yield 80%). Calculated molecular weight: 552.23, found m/Z: 552.2.

Example A8: Preparation of compound 3I-12

Preparation of compound 8-1

2,4-dichloroquinazoline (2,4-dichloroquinazoline, 500 g, 2.5 mol) is dissolved in a flask containing 10 L of ethanol, and hydrazine hydrate (470 g, 7.5 mol, 80% aqueous solution ) is added dropwise at 5°C under stirring. and the temperature was maintained at less than 10 °C during the dropping process. After completion of the dropwise addition, the temperature was naturally raised to room temperature to react for 1 hour, and then the obtained solid was filtered with suction, washed with water and ethanol, respectively, dried and dried to obtain a white solid compound 8-1 (415 g, 86%).

Preparation of compound 8-2

Compound 8-1 (200 g, 1.03 mol) was added to a flask containing 2 L of ethanol, and benzaldehyde (120 g, 1.13 mol) was added dropwise at room temperature under stirring, and after completion of the dropping, stirring was continued for 30 minutes, followed by filtration. The obtained solid was rinsed with ethanol and n-hexane, respectively, and dried to obtain a yellow solid compound 8-2 (184 g, 63%).

Preparation of compound 8-3

Compound 8-2 (184 g, 652.4 mmol) was added to a flask containing 4 L of ethanol, and iodobenzene diacetate (252 g, 782.9 mmol) was added portionwise under stirring at room temperature, and after completion of the addition, continued for 1.5 hours After the reaction was stirred, TLC showed that the reaction was complete. After adding 4L of n-hexane and stirring for 5 minutes, the obtained solid was suction filtered, rinsed with n-hexane, and dried to obtain a pale yellowish-brown solid compound 8-3 (130 g, 71%).

Preparation of compound 3I-12

Compound 8-3 (7g, 25mmol), compound 1-4 (10g, 23.64mmol), potassium carbonate (10g, 72.46mmol) were added to a flask containing 200mL of acetonitrile, and stirred under a nitrogen atmosphere for 12 hours After heating under reflux, TLC showed that the reaction was complete. 200 mL of water was added, and the pale yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography (eluent: methylene chloride-ethyl acetate) to conduct white solid compound 3I-12 (11.5 g, yield) 75%) was obtained. Calculated molecular weight: 652.24, found m/Z: 652.2.

Example A9: Preparation of compound 3I-327

Preparation of compound 3I-327

Compound 8-3 (5.6g, 20mmol), 7H-dibenzocarbazole (5.34g, 20mmol), potassium carbonate (8.3g, 60mmol) were added to a flask containing 200mL of acetonitrile, and under a nitrogen atmosphere, 15 After heating to reflux for an hour, TLC indicated that the reaction was complete. 200 mL of water was added, and the pale yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a white solid compound 3I-327 (9.1 g, yield 89%). Calculated molecular weight: 511.18, found m/Z: 511.2.

Example A10: Preparation of compound 3II-327

Preparation of compound 10-1

In a flask containing 1,4-dioxane/water (900mL/300mL), p-chlorophenylboronic acid (31.2g, 0.2mol), compound 8-3 (56g, 0.2mmol), potassium carbonate (82.8g, 0.6mol) ) was added, and nitrogen was substituted under stirring at room temperature, followed by addition of Pd(PPh ₃ ) ₄ (2.31 g, 2 mmol). After completion of the addition, the reaction was stirred at 80° C. for 8 hours, and the reaction endpoint was monitored by TLC. The layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 10-1 (50.6 g, yield 71%).

Preparation of compound 3II-327

Compound 10-1 (7.1 g, 20 mmol), 7H-dibenzocarbazole (5.34 g, 20 mmol), sodium tert-butoxide (5.8 g, 60 mmol) was added to a flask containing 200 mL of xylene, and under a nitrogen atmosphere , Pd ₂ (dba) ₃ (183 mg, 0.2 mmol) and tri-tert-butylphosphine (50% xylene solution, 242 mg, 0.6 mmol) were added under stirring, and after the addition was completed, the mixture was heated and refluxed for 15 hours. , TLC showed reaction completion. The solvent was rotary evaporated under reduced pressure, dissolved with methylene chloride, washed with water, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a white solid compound 3II-327 (9.1 g, yield 89%). Calculated molecular weight: 511.18, found m/Z: 511.2.

Example A11: Preparation of compound 4I-12

Preparation of compound 11-1

The compound 2-chloro-4-aminoquinazoline (179 g, 1 mol) and bromoacetophenone (218 g, 1.1 mol) were added to a flask containing 1.3 L of DMF, and heated to 100° C. under stirring to react for 20 hours. After completion of the reaction, TLC showed that the reaction was complete. The temperature was lowered to room temperature, water was added to precipitate a solid, and the solid obtained by filtration was washed with ethanol, dried and subjected to column chromatography to obtain a pale yellowish-brown solid compound 11-1 (209 g, 75%).

Preparation of compound 4I-12

Compound 11-1 (5.58 g, 20 mmol), compound 1-4 (8.46 g, 20 mmol), potassium carbonate (8.3 g, 60 mmol) were added to a flask containing 200 mL of acetonitrile, and under a nitrogen atmosphere, for 15 hours After heating to reflux under stirring, TLC showed that the reaction was complete. 200 mL of water was added, and the pale yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a white solid compound 4I-12 (10.6 g, yield 88%). Calculated molecular weight: 601.23, found m/Z: 601.2.

Example A12: Preparation of compound 4II-327

Preparation of compound 12-1

In a flask containing 1,4-dioxane/water (900mL/300mL), p-chlorophenylboronic acid (31.2g, 0.2mol), compound 11-1 (55.8g, 0.2mmol), potassium carbonate (82.8g, 0.6 mol), and after nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (2.31 g, 2 mmol) was added. After completion of the addition, the reaction was stirred at 80° C. for 12 hours, and the end point of the reaction was monitored by TLC. The layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 12-1 (49 g, yield 69%).

Preparation of compound 4II-327

Compound 12-1 (7.1 g, 20 mmol), 7H-dibenzocarbazole (5.34 g, 20 mmol), sodium tert-butoxide (5.8 g, 60 mmol) was added to a flask containing 200 mL of xylene, and under a nitrogen atmosphere , Pd ₂ (dba) ₃ (183 mg, 0.2 mmol) and tri-tert-butylphosphine (50% xylene solution, 242 mg, 0.6 mmol) were added under stirring, and after the addition was completed, the mixture was heated and refluxed for 15 hours. , TLC showed reaction completion. The solvent was rotary evaporated under reduced pressure, dissolved with methylene chloride, washed with water, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a white solid compound 4II-327 (9.5 g, yield 79%). Calculated molecular weight: 602.25, found m/Z: 602.3.

Example A13: Preparation of compound 4I-63

Preparation of compound 4I-63

Compound 11-2 (5.6 g, 20 mmol), compound 3-2 (5.5 g, 20 mmol), potassium carbonate (8.3 g, 60 mmol) were added to a flask containing 200 mL of acetonitrile, and under a nitrogen atmosphere, for 12 hours After heating to reflux under stirring, TLC showed that the reaction was complete. 200 mL of water was added, and the obtained pale yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a white solid compound 4I-63 (8.8 g, yield 88%). Calculated molecular weight: 500.16, found m/Z: 50.2.

Example A14: Preparation of compound 5BII-327

Preparation of compound 14-1

After dissolving 2,4-dichloropyrido [3,4-d] pyrimidine (2,4-Dichloropyrido [3,4-d] pyrimidine, 497.5 g, 2.5 mol) in 10 L ethanol in a flask, 5 ° C. Hydrazine hydrate (470 g, 7.5 mol, 80% aqueous solution) was added dropwise under stirring, and the temperature was maintained below 10°C during the dropping process. After completion of the dropwise addition, the temperature was naturally raised to room temperature to react for 1 hour, and the precipitated solid was filtered off with suction, washed with water and ethanol, respectively, and dried to obtain a white solid compound 14-1 (370.5 g, 76%).

Preparation of compound 14-2

Compound 14-1 (195 g, 1 mol) was added to a flask containing 2 L of ethanol, and benzaldehyde (138 g, 1.3 mol) was added dropwise at room temperature while stirring, and after completion of the dropping, stirring was continued for 30 minutes, followed by filtration. The obtained solid was washed with ethanol and n-hexane, respectively, and dried to obtain a yellow solid compound 14-2 (184 g, 65%).

Preparation of compound 14-3

Compound 14-2 (184 g, 650 mmol) was added to a flask containing 4 L of ethanol, and iodobenzene diacetate (251 g, 780 mmol) was added in portions under stirring at room temperature. After the addition was completed, stirring was continued for 1.5 hours. After completion of the reaction, TLC showed that the reaction was complete. The precipitated solid was filtered with suction, washed with n-hexane, and dried to obtain a pale yellowish-brown solid compound 14-3 (128 g, 70%).

Preparation of compound 5BII-327

Compound 14-3 (7.14 g, 20 mmol), 7H-dibenzocarbazole (5.34 g, 20 mmol), sodium tert-butoxide (5.8 g, 60 mmol) was added to a flask containing 200 mL of xylene, and under a nitrogen atmosphere , Pd ₂ (dba) ₃ (183 mg, 0.2 mmol) and tri-tert-butylphosphine (50% xylene solution, 242 mg, 0.6 mmol) were added under stirring, and after the addition was completed, the mixture was heated and refluxed for 15 hours. , TLC showed reaction completion. The solvent was rotary evaporated under reduced pressure, dissolved with methylene chloride, washed with water, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a white solid compound 5BII-327 (9.1 g, yield 75%). Calculated molecular weight: 604.24, found m/Z: 604.2.

Example A15: Preparation of compound 6BI-12

Preparation of compound 15-1

2,4-dichloropyrido [3,4-d] pyrimidine (49.8 g, 250 mmol) and 28% ammonia water (94 g, 750 mmol) were added to a flask containing 500 mL of ethanol, and the reaction was stirred at room temperature for 48 hours. and the reaction endpoint was monitored by TLC. The solid precipitated by filtration was washed with ethanol and dried to obtain compound 15-1 (27 g, yield 60%).

Preparation of compound 15-2

Compound 15-1 (27 g, 0.15 mol) and bromoacetophenone (32.7 g, 0.165 mol) were added to a flask containing 400 mL of DMF, and heated to 100° C. under stirring to react for 20 hours, followed by TLC Reaction completion was indicated. The temperature was lowered to room temperature, water was added to precipitate a solid, and the solid obtained by filtration was washed with ethanol, dried and subjected to column chromatography to obtain pale yellowish-brown compound 15-2 (31.5 g, 75%).

Preparation of compound 6BI-12

Compound 15-2 (5.6 g, 20 mmol), compound 1-4 (8.46 g, 20 mmol), potassium carbonate (8.3 g, 60 mmol) were added to a flask containing 200 mL of acetonitrile, and under a nitrogen atmosphere, for 15 hours After heating to reflux under stirring, TLC showed that the reaction was complete. 200 mL of water was added, and the pale yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a white solid compound 6BI-12 (11.6 g, yield 89%). Calculated molecular weight: 652.24, found m/Z: 652.2.

Example A16: Preparation of compound 6BI-63

Compound 15-2 (5.6 g, 20 mmol), compound 3-2 (5.5 g, 20 mmol), potassium carbonate (8.3 g, 60 mmol) were added to a flask containing 200 mL of acetonitrile, and under a nitrogen atmosphere, for 12 hours After heating to reflux under stirring, TLC showed that the reaction was complete. 200 mL of water was added, and the obtained pale yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a white solid compound 6BI-63 (8.6 g, yield 86%). Calculated molecular weight: 501.16, found m/Z: 501.2.

Example A17: Preparation of compound 7AII-327

Preparation of compound 17-1

After dissolving 2,4-dichlorothieno[2,3-d]pyrimidine (2,4-Dichlorothieno[2,3-d]pyrimidine, 510g, 2.5mol) in 10L ethanol in a flask, Hydrazine hydrate (470 g, 7.5 mol, 80% aqueous solution) was added dropwise under stirring, and the temperature was maintained below 10°C during the dropping process. After completion of the dropwise addition, the temperature was naturally raised to room temperature to react for 1 hour, and then the precipitated solid was suction filtered, washed with water and ethanol, respectively, dried and dried to obtain a white solid compound 17-1 (375 g, 75%). .

Preparation of compound 17-2

Compound 17-1 (375 g, 1.875 mol) was added to a flask containing 4 L of ethanol, and benzaldehyde (260 g, 2.45 mol) was added dropwise at room temperature under stirring, and after completion of the dropping, stirring was continued for 30 minutes, followed by filtration. The obtained solid was washed with ethanol and n-hexane, respectively, and dried to obtain a yellow solid compound 17-2 (351 g, 65%).

Preparation of compound 17-3

Compound 17-2 (351 g, 1.22 mol) was added to a flask containing 7 L of ethanol, and iodobenzene diacetate (471 g, 1.46 mol) was added portionwise under stirring at room temperature, after completion of the addition, continued for 1.5 hours After the reaction was stirred, TLC showed that the reaction was complete. The obtained solid was filtered with suction, washed with n-hexane, and dried to obtain a pale yellowish-brown solid compound 17-3 (251 g, 72%).

Preparation of compound 17-4

In a flask containing 1,4-dioxane/water (900mL/300mL), p-chlorophenylboronic acid (31.2g, 0.2mol), compound 17-3 (57.2g, 0.2mmol), potassium carbonate (82.8g, 0.6 mol), and after nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (2.31 g, 2 mmol) was added. After completion of the addition, the reaction was stirred at 80° C. for 12 hours, and the end point of the reaction was monitored by TLC. The obtained solid was filtered, dissolved with methylene chloride, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 17-4 (47 g, yield 65%).

Preparation of compound 7AII-327

Compound 17-4 (7.24 g, 20 mmol), 7H-dibenzocarbazole (5.34 g, 20 mmol), sodium tert-butoxide (5.8 g, 60 mmol) was added to a flask containing 200 mL of xylene, and under a nitrogen atmosphere , Pd ₂ (dba) ₃ (183 mg, 0.2 mmol) and tri-tert-butylphosphine (50% xylene solution, 242 mg, 0.6 mmol) were added under stirring, and after the addition was completed, the mixture was heated and refluxed for 15 hours. , TLC showed reaction completion. The solvent was rotary evaporated under reduced pressure, dissolved with methylene chloride, washed with water, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a white solid compound 7AII-327 (9 g, yield 76%). Calculated molecular weight: 593.17, found m/Z: 593.2.

Example A18: Preparation of compound 8AI-12

Preparation of compound 18-1

2,4-dichlorothieno[2,3-d]pyrimidine (51g, 250mmol) and 28% aqueous ammonia (94g, 750mmol) were added to a flask containing 500mL of ethanol, and the reaction was stirred at room temperature for 48 hours. , the reaction endpoints were monitored by TLC. The precipitated solid was filtered, washed with ethanol, and dried to obtain compound 18-1 (29 g, yield 63%).

Preparation of compound 18-2

Compound 18-1 (27.8 g, 0.15 mol) and bromoacetophenone (32.7 g, 0.165 mol) were added to a flask containing 400 mL of DMF, and heated to 100° C. under stirring to react for 20 hours, followed by TLC indicates the completion of the reaction. The temperature was lowered to room temperature, and water was added to precipitate a solid. The obtained solid was filtered, washed with ethanol, dried and subjected to column chromatography to obtain a pale yellowish-brown solid compound 18-2 (32.5 g, 76%).

Preparation of compound 8AI-12

Compound 18-2 (5.7 g, 20 mmol), compound 1-4 (8.46 g, 20 mmol), potassium carbonate (8.3 g, 60 mmol) were added to a flask containing 200 mL of acetonitrile, and under a nitrogen atmosphere, for 15 hours After heating to reflux under stirring, TLC showed that the reaction was complete. 200 mL of water was added, and the obtained pale yellow solid was filtered, dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a white solid compound 8AI-12 (11.2 g, yield 85%). Calculated molecular weight: 657.20, found m/Z: 657.2.

Example A19: Preparation of compound 9AII-327

Preparation of compound 19-1

After dissolving 2,4-dichlorothieno[3,2-d]pyrimidine (510g, 2.5mol) in 10L ethanol in a flask, hydrazine hydrate (470g, 7.5mol, 80% aqueous solution) was stirred at 5°C. was added, and the temperature was maintained at less than 10°C during the dropping process. After completion of the dropwise addition, the temperature was naturally raised to room temperature to react for 1 hour, and the precipitated solid was filtered off with suction, washed with water and ethanol, respectively, and dried to obtain a white solid compound 19-1 (365 g, 73%).

Preparation of compound 19-2

Compound 19-1 (365 g, 1.825 mol) was added to a flask containing 4 L of ethanol, and benzaldehyde (251 g, 2.37 mol) was added dropwise at room temperature under stirring, and after completion of the dropping, stirring reaction was continued for 30 minutes, The obtained solid was filtered, washed with ethanol and n-hexane, respectively, and dried to obtain a yellow solid compound 19-2 (347g, 66%).

Preparation of compound 19-3

Compound 19-2 (347 g, 1.2 mol) was added to a flask containing 7 L of ethanol, and iodobenzene diacetate (465 g, 1.44 mol) was added portionwise under stirring at room temperature, and after completion of the addition, continued for 1.5 hours After the reaction was stirred, TLC showed that the reaction was complete. The obtained solid was filtered with suction, washed with n-hexane, and dried to obtain a pale yellowish-brown solid compound 19-3 (240 g, 70%).

Preparation of compound 19-4

In a flask containing 1,4-dioxane/water (450 mL/150 mL), p-chlorophenylboronic acid (15.6 g, 0.1 mol), compound 19-3 (28.6 g, 0.1 mmol), potassium carbonate (41.4 g, 0.3 mol), and after nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (1.15 g, 1 mmol) was added. After completion of the addition, the reaction was stirred at 80° C. for 12 hours, and the reaction endpoint was monitored by TLC. The obtained solid was filtered, dissolved with methylene chloride, dried over anhydrous sodium sulfate, filtered, and the solvent was reduced and rotary evaporated. was removed with Separation and purification by column chromatography gave compound 19-4 (24.6 g, yield 68%).

Preparation of compound 9AII-327

Compound 19-4 (7.24 g, 20 mmol), 7H-dibenzocarbazole (5.34 g, 20 mmol), sodium tert-butoxide (5.8 g, 60 mmol) was added to a flask containing 200 mL of xylene, and under a nitrogen atmosphere , Pd ₂ (dba) ₃ (183 mg, 0.2 mmol) and tri-tert-butylphosphine (242 mg, 0.6 mmol) were added under stirring, and after the addition was completed, the reaction was heated to reflux for 15 hours, and then the reaction was completed in TLC has been displayed The solvent was rotary evaporated under reduced pressure, dissolved with methylene chloride, washed with water, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain white compound 9AII-327 (9.1 g, yield 75%). Calculated molecular weight: 609.20, found m/Z: 609.2.

Example A20: Preparation of compound 10AI-12

Preparation of compound 20-1

2,4-dichlorothieno[3,2-d]pyrimidine (51g, 250mmol) and 28% aqueous ammonia (94g, 750mmol) were added to a flask containing 500mL of ethanol, and the reaction was stirred at room temperature for 48 hours. , the reaction endpoints were monitored by TLC. The precipitated solid was filtered, washed with ethanol, and dried to obtain compound 20-1 (29.6 g, yield 64%).

Preparation of compound 20-2

Compound 20-1 (29.6 g, 0.16 mol) and bromoacetophenone (34.8 g, 0.176 mol) were added to a flask containing 400 mL of DMF, and heated to 100° C. under stirring to react for 20 hours, followed by TLC indicates the completion of the reaction. The temperature was lowered to room temperature, water was added to precipitate a solid, and the obtained solid was filtered, washed with ethanol, dried and subjected to column chromatography to obtain a pale yellowish-brown solid compound 20-2 (32.8 g, 72%).

Preparation of compound 10AI-12

In a flask containing 200 mL of acetonitrile, compound 20-2 (5.7 g, 20 mmol), compound 1-4 (8.46 g, 20 mmol), potassium carbonate (8.3 g, 60 mmol) were added, and under a nitrogen atmosphere, for 15 hours After heating to reflux under stirring, TLC showed that the reaction was complete. 200 mL of water was added, and the obtained pale yellow solid was filtered, dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a white solid compound 10AI-12 (11.4 g, yield 87%). Calculated molecular weight: 657.20, found m/Z: 657.2.

Synthesis examples of specific compounds of the second preferred embodiment of the present application are as follows:

Example C1: Preparation of compound C1

Preparation of compound 1-1

2,4-dichloroquinazoline (2,4-dichloroquinazoline, 500 g, 2.5 mol) is dissolved in a flask containing 10 L of ethanol, and hydrazine hydrate (470 g, 7.5 mol, 80% aqueous solution ) is added dropwise at 5°C under stirring. and the temperature was maintained at less than 10 °C during the dropping process. After completion of the dropwise addition, the temperature was naturally raised to room temperature to react for 1 hour, and the resulting solid was filtered with suction, washed with water and ethanol, respectively, and dried to obtain a white solid compound 1-1 (415 g, 86%).

Preparation of compound 1-2 (reference J. Heterocyclic chem. 27, 497, 1990)

Compound 1-1 (200 g, 1.03 mol) was added to a flask containing 2 L of ethanol, and benzaldehyde (120 g, 1.13 mol) was added dropwise at room temperature under stirring, and after completion of the dropping, stirring was continued for 30 minutes, and the obtained The solid was filtered, washed with ethanol and n-hexane, respectively, and dried to obtain a yellow solid compound 1-2 (184 g, 63%).

Preparation of compound 1-3

Compound 1-2 (184 g, 652.4 mmol) was added to a flask containing 4 L of ethanol, and iodobenzene diacetate (252 g, 782.9 mmol) was added portionwise under stirring at room temperature, after completion of the addition, continued for 1.5 hours After the reaction was stirred, TLC showed that the reaction was complete. After adding 4L of n-hexane and stirring for 5 minutes, the obtained solid was filtered with suction, washed with n-hexane, and dried to obtain a pale yellowish-brown solid compound 1-3 (130 g, 71%).

Preparation of compound 1-4

Toluene: ethanol: water (3L: 1L: 1L) in a flask containing N-phenylcarbazole-3-boronic acid (500 g, 1.742 mol), 3-bromocarbazole (412 g, 1.584 mol), potassium carbonate (656 g) , 4.752 mol) was dissolved and nitrogen was substituted at room temperature under stirring, followed by addition of tetrakis(triphenylphosphine)palladium (18.3 g, 0.016 mol). After completion of the addition, the reaction was stirred and refluxed for 6 hours, and the end point of the reaction was monitored by TLC. The precipitated solid was filtered to separate the liquid layer, the aqueous phase was extracted with methylene chloride, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The crude solids were combined and purified by column chromatography (eluent: petroleum ether: methylene chloride = 10:1) to obtain compound 1-4 (543 g, yield 81%).

Preparation of compound C1

Compound 1-3 (7g, 25mmol), compound 1-4 (10g, 23.64mmol), potassium carbonate (10g, 72.46mmol) were added to a flask containing 200mL of acetonitrile, and stirred under a nitrogen atmosphere for 12 hours After heating under reflux, TLC showed that the reaction was complete. 200 mL of water was added, and the obtained pale yellow solid was filtered, dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography (eluent: methylene chloride-ethyl acetate) as a white solid compound C1 (11.5 g, yield 75%). ) was obtained. Calculated molecular weight: 652.24, found m/Z: 652.2.

Example C2: Preparation of compound C2

Preparation of compound 2-1

Compound 1-1 (20 g, 103 mmol) was added to a flask containing 200 mL of ethanol, and p-methyl benzaldehyde (p-methyl benzaldehyde, 15 g, 125 mmol) was added dropwise under stirring at room temperature, after completion of the dropping, for 30 minutes After the stirring reaction was continued, the obtained solid was filtered, washed with ethanol and n-hexane, respectively, and dried to obtain a yellow solid compound 2-1 (19.8 g, 65%).

Preparation of compound 2-2

Compound 2-1 (19.8 g, 67 mmol) was added to a flask containing 200 L of ethanol, and iodobenzene diacetate (25.8 g, 80.1 mmol) was added in portions under stirring at room temperature. After the addition was completed, for 1.5 hours After the stirring reaction was continued, TLC showed that the reaction was complete. After adding 200 mL of n-hexane and stirring for 5 minutes, the obtained solid was filtered with suction, washed with n-hexane, and dried to obtain a pale yellowish-brown solid compound 2-2 (14.6 g, 74 %).

Preparation of compound C2

Compound 2-2 (7.35 g, 25 mmol), compound 1-4 (10 g, 23.64 mmol), potassium carbonate (10 g, 72.46 mmol) were added to a flask containing 200 mL of acetonitrile, and under a nitrogen atmosphere, for 15 hours After heating to reflux under stirring, TLC showed that the reaction was complete. 200 mL of water was added, and the obtained pale yellow solid was filtered, dissolved with methylene chloride, dried over anhydrous sodium sulfate, and column chromatography was performed (eluent: methylene chloride-ethyl acetate) as a white solid compound C2 (11.2 g, yield 71%). ) was obtained. Calculated molecular weight: 666.25, found m/Z: 666.2.

Example C3: Preparation of compound C6

Preparation of compound 3-1

Compound 1-1 (20 g, 103 mmol) was added to a flask containing 200 mL of ethanol, and 3-Pyridineformaldehyde (3-Pyridineformaldehyde, 13.3 g, 125 mmol) was added dropwise at room temperature under stirring, after completion of the dropping, 30 minutes After the stirring reaction was continued, the obtained solid was filtered, washed with ethanol and n-hexane, respectively, and dried to obtain a yellow solid compound 3-1 (16.3 g, 56%).

Preparation of compound 3-2

Compound 3-1 (16.3 g, 57.6 mmol) was added to a flask containing 200 L of ethanol, and iodobenzene diacetate (22.3 g, 69.1 mmol) was added in portions under stirring at room temperature, after completion of the addition, 1.5 hours After stirring for a while, TLC showed reaction completion. After adding 200 mL of n-hexane and stirring for 5 minutes, the obtained solid was filtered with suction, washed with n-hexane, and dried to obtain a pale yellowish-brown solid compound 3-2 (10 g, 70%).

Preparation of compound C6

Compound 2-2 (7.03 g, 25 mmol), compound 1-4 (10 g, 23.64 mmol), potassium carbonate (10 g, 72.46 mmol) were added to a flask containing 200 mL of acetonitrile, and under a nitrogen atmosphere, for 15 hours After heating to reflux under stirring, TLC showed that the reaction was complete. 200 mL of water was added, the obtained pale yellow solid was filtered, dissolved with methylene chloride, dried over anhydrous sodium sulfate, and column chromatography (eluent: methylene chloride ~ methylene chloride: methanol = 10:1) was performed to give a pale yellow solid compound C6 ( 10.6 g, yield 65%) was obtained. Calculated molecular weight: 653.23, found m/Z: 653.2.

Example C4: Preparation of compound C9

Preparation of compound 4-1

Compound 1-1 (20g, 103mmol) was added to a flask containing 200L of ethanol, and dibenzofuran-2-formaldehyde (DIBENZOFURAN-2-FORMALDEHYDE, 24.5g, 125mmol) was added under stirring at room temperature and added After completion, stirring was continued for 30 minutes, and then the obtained solid was filtered, washed with ethanol and n-hexane, respectively, and dried to obtain a yellow solid compound 4-1 (25.6 g, 67%).

Preparation of compound 4-2

Compound 4-1 (25.6 g, 69 mmol) was added to a flask containing 200 mL of ethanol, and iodobenzene diacetate (26.7 g, 82.8 mmol) was added in portions under stirring at room temperature. After completion of the addition, for 1.5 hours After the stirring reaction was continued, TLC showed that the reaction was complete. After adding 200 mL of n-hexane and stirring for 5 minutes, the obtained solid was filtered with suction, washed with n-hexane, and dried to obtain a yellowish-brown solid compound 4-2 (17.8 g, 70%).

Preparation of compound C9

Compound 4-2 (9.25 g, 25 mmol), compound 1-4 (10 g, 23.64 mmol), potassium carbonate (10 g, 72.46 mmol) were added to a flask containing 200 mL of acetonitrile, and under a nitrogen atmosphere, for 15 hours After heating to reflux under stirring, TLC showed that the reaction was complete. 200 mL of water was added, and the obtained pale yellow solid was filtered, dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography (eluent: methylene chloride-ethyl acetate) to obtain white solid compound C9 (12.8 g, yield 73). %) was obtained. Calculated molecular weight: 742.25, found m/Z: 742.2.

Example C5: Preparation of compound C12

Preparation of compound 5-1

Compound 1-1 (20 g, 103 mmol) was added to a flask containing 200 L of ethanol, and p-phenylbenzaldehyde (P-Phenylbenzaldehyde, 22.7 g, 125 mmol) was added dropwise under stirring at room temperature, after completion of the dropping, continued for 30 minutes After stirring and reacting, the solid obtained by filtration was washed with ethanol and n-hexane, respectively, and dried to obtain a pale yellow solid compound 5-1 (24.3 g, 66%).

Preparation of compound 5-2

Compound 5-1 (24.3 g, 69 mmol) was added to a flask containing 200 mL of ethanol, and iodobenzene diacetate (26.7 g, 82.8 mmol) was added portionwise under stirring at room temperature. After completion of the addition, for 1.5 hours After the stirring reaction was continued, TLC showed that the reaction was complete. After adding 200 mL of n-hexane and stirring for 5 minutes, the obtained solid was filtered with suction, washed with n-hexane, and dried to obtain a pale yellowish-brown solid compound 5-2 (18.1 g, 74 %).

Preparation of compound C12

Compound 5-2 (8.9 g, 25 mmol), compound 1-4 (10 g, 23.64 mmol), potassium carbonate (10 g, 72.46 mmol) were added to a flask containing 200 mL of acetonitrile, and under a nitrogen atmosphere, for 15 hours After heating to reflux under stirring, TLC showed that the reaction was complete. 200 mL of water was added, and the pale yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography (eluent: methylene chloride-ethyl acetate) as a white solid compound C12 (12 g, yield 70%). ) was obtained. Calculated molecular weight: 728.27, found m/Z: 728.2.

Example C6: Preparation of compound C13

Preparation of compound 6-1

In a flask containing 1,4-dioxane/water (0.3L/0.1L), p-bromobenzaldehyde (4-Bromobenzaldehyde, 18.4 g, 0.1 mol), 4-pyridylboronic acid (4-Pyridylboronic acid, 12.3 g, 0.1 mol) and potassium carbonate (41.4 g, 0.3 mol) were added, and nitrogen was substituted at room temperature under stirring, followed by addition of tetrakis(triphenylphosphine)palladium (1.15 g, 1 mmol). After completion of the addition, the reaction was stirred and refluxed for 6 hours, and the end point of the reaction was monitored by TLC. The layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The crude solids were combined and purified by column chromatography (eluent: petroleum ether-ethyl acetate=2:1) to obtain compound 6-1 (15 g, yield 82%).

Preparation of compound 6-2

Compound 1-1 (13.4 g, 69 mmol) was added to a flask containing 200 mL of ethanol, and 6-1 (15 g, 82 mmol) was added at room temperature under stirring, and after the addition was completed, stirring was continued for 30 minutes, and then, The solid obtained by filtration was washed with ethanol and n-hexane, respectively, and dried to obtain a yellow solid compound 6-2 (15.1 g, 61%).

Preparation of compound 2-2

Compound 2-1 (15.1 g, 42 mmol) was added to a flask containing 200 L of ethanol, and iodobenzene diacetate (16.1 g, 50 mmol) was added in portions under stirring at room temperature, after completion of the addition, continued for 1.5 hours After the reaction was stirred, TLC showed that the reaction was complete. After adding 200 mL of n-hexane and stirring for 5 minutes, the obtained solid was filtered with suction, washed with n-hexane, and dried to obtain a yellowish-brown solid compound 6-3 (10.5 g, 70%).

Preparation of compound C13

Compound 6-3 (8.93 g, 25 mmol), compound 1-4 (10 g, 23.64 mmol), potassium carbonate (10 g, 72.46 mmol) were added to a flask containing 200 mL of acetonitrile, and under a nitrogen atmosphere, for 15 hours After heating to reflux under stirring, TLC showed that the reaction was complete. 200 mL of water was added, and the pale yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography (eluent: methylene chloride to methylene chloride: methanol = 10: 1) to perform white solid compound C13 (11.2) g, yield 65%) was obtained. Calculated molecular weight: 729.26, found m/Z: 729.2.

Example C7: Preparation of compound C23

Preparation of compound 7-1

Dissolve 2,4-dichloro-7-bromoquinazoline (2,4-DICHLORO-7-BROMOQUINAZOLINE, 50 g, 0.181 mol) in a flask containing 1 L of ethanol, and hydrazine hydrate (34 g, 0.543 mol) at 5 ° C. , 80% aqueous solution ) was added dropwise under stirring, and the temperature was maintained at less than 10° C. during the dropping process. After completion of the dropwise addition, the temperature was naturally raised to room temperature to react for 1 hour, and then the obtained solid was filtered with suction, washed with water and ethanol, respectively, and dried to obtain a white solid compound 7-1 (39.4 g, 80%).

Preparation of compound 7-2

Compound 7-1 (39.4 g, 0.145 mol) was added to a flask containing 0.4 L of ethanol, and benzaldehyde (18.4 g, 0.174 mol) was added dropwise at room temperature under stirring, and after completion of the dropping, stirring reaction was continued for 30 minutes. Then, the solid obtained by filtration was washed with ethanol and n-hexane, respectively, and dried to obtain a pale yellow solid compound 7-2 (34 g, 65%).

Preparation of compound 7-3

Compound 7-2 (34 g, 94.3 mmol) was added to a flask containing 0.4 L of ethanol, and iodobenzene diacetate (36.4 g, 113.2 mmol) was added in portions under stirring at room temperature, 1.5 hours after completion of the addition After stirring was continued for a while, TLC showed that the reaction was complete. After adding 0.4 L of n-hexane and stirring for 5 minutes, the obtained solid was filtered with suction, washed with n-hexane, and dried to obtain a pale yellowish-brown solid compound 7-3 (23.6 g, 70%).

Preparation of compound 7-4

Compound 7-3 (7.5 g, 21 mmol), compound 1-4 (8.5 g, 20 mmol), potassium carbonate (8.3 g, 60 mmol) were added to a flask containing 200 mL of acetonitrile, and under a nitrogen atmosphere, for 12 hours After heating to reflux under stirring, TLC showed that the reaction was complete. 200 mL of water was added, and the pale yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography (eluent: methylene chloride-ethyl acetate) as a white solid compound 7-4 (11.1 g, Yield 76%) was obtained.

Preparation of compound C23

In a flask containing 1,4-dioxane/water (300 mL/100 mL), Phenylboronic Acid (1.85 g, 15.2 mmol), compound 7-4 (11.1 g, 15.2 mmol), potassium carbonate (6.3 g, 45.6) mmol) was added, and nitrogen was substituted at room temperature under stirring, followed by addition of tetrakis(triphenylphosphine)palladium (176 mg, 0.152 mmol). After completion of the addition, the reaction was stirred and refluxed for 8 hours, and the reaction endpoint was monitored by TLC. The precipitated solid was filtered. The liquid layer was separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The crude solids were combined and purified by column chromatography (eluent: petroleum ether: methylene chloride = 5:1) to obtain compound C23 (7.75 g, yield 70%). Calculated molecular weight: 728.27, found m/Z: 728.2.

Example C8: Preparation of compound C25

Preparation of compound 8-1

Compound 1-4 (12.69 g, 30 mmol), p-Bromoiodobenzene (13.4 g, 45 mmol), CuI (2.86 g, 15 mmol), ethylenediamine (Ethylenediamine, 1.8 g, 30 mmol) and potassium phosphate (19.1 g, 90 mmol) were added, and the reaction was heated to reflux under a nitrogen atmosphere for 20 hours, and the reaction endpoint was monitored by TLC. Water was added and stirred, the layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The crude solids were combined and purified by column chromatography (eluent: petroleum ether: methylene chloride = 10:1) to obtain compound 8-1 (13.7 g, yield 79%).

Preparation of compound 8-2

Compound 8-1 (13.7 g, 23.7 mmol), boronic acid pinacol ester, 9.04 g, 35.6 mmol), potassium acetate (7 g, 71.1 mmol) in a flask containing 300 mL of 1,4-dioxane was dissolved, nitrogen was substituted under stirring at room temperature, and Pd(dppf) ₂ Cl ₂ (196 mg, 0.24 mmol) was added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the reaction endpoint was monitored by TLC. The layers were separated by adding water, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The crude solids were combined and purified by column chromatography (eluent: petroleum ether: methylene chloride = 2:1) to obtain compound 8-1 (10.4 g, yield 70%).

Preparation of compound C25

In a flask containing 1,4-dioxane: water (210 mL: 70 mL), compound 8-2 (10.4 g, 16.6 mmol), compound 1-3 (4.88 g, 17.4 mmol), potassium carbonate (6.9 g, 49.8 mmol) was dissolved, nitrogen was substituted under stirring at room temperature, and Pd(PPh ₃ ) ₄ (196 mg, 0.17 mmol) was added. After completion of the addition, the reaction was stirred and refluxed for 8 hours, and the end point of the reaction was monitored by TLC. The layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The crude solids were combined and purified by column chromatography (eluent: petroleum ether: methylene chloride = 5:1) to obtain compound C25 (9 g, yield 75%). Calculated molecular weight: 728.27, found m/Z: 728.2.

Example C9: Preparation of compound C29

Preparation of compound 9-1

Compound 1-1 (20 g, 103 mmol) was added to a flask containing 200 mL of ethanol, and 3-Phenylbenzaldehyde (3-Phenylbenzaldehyde, 20.6 g, 113 mol) was added while stirring at room temperature. After the addition was completed, for 30 minutes After the stirring reaction was continued, the solid obtained by filtration was washed with ethanol and n-hexane, respectively, and dried to obtain a yellow solid compound 9-1 (22.9 g, 62%).

Preparation of compound 9-2

Compound 9-1 (22.9 g, 64 mmol) was added to a flask containing 400 mL of ethanol, and iodobenzene diacetate (24.7 g, 76.8 mmol) was added portionwise under stirring at room temperature, after completion of the addition, for 1.5 hours After the stirring reaction was continued, TLC showed that the reaction was complete. After adding 400 mL of n-hexane and stirring for 5 minutes, the obtained solid was filtered with suction, washed with n-hexane, and dried to obtain a pale yellowish-brown solid compound 9-2 (16.2 g, 71%).

Preparation of compound 9-3

Toluene: ethanol: water (300mL: 100mL: 100mL) in a flask containing dibenzofuran-2-boronic acid (Dibenzofuran-2-boronic acid, 50g, 0.236mol), 3-bromocarbazole (3-BROMOCARBAZOLE, 55.9 g, 0.215 mol) and potassium carbonate (89 g, 0.645 mol) were dissolved and nitrogen was substituted at room temperature under stirring, followed by addition of tetrakis(triphenylphosphine)palladium (2.5 g, 2.15 mmol). After completion of the addition, the reaction was stirred and refluxed for 8 hours, and the end point of the reaction was monitored by TLC. The precipitated solid was filtered. The liquid layer was separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The crude solids were combined and purified by column chromatography (eluent: petroleum ether: methylene chloride = 10:1) to obtain compound 9-3 (59.8 g, yield 80%).

Preparation of compound C29

In a flask containing 200 mL of acetonitrile, compound 9-2 (10.7 g, 30.2 mmol) and compound 9-3 (10 g, 28.7 mmol, potassium carbonate (11.9 g, 86.1 mmol) were added, and under a nitrogen atmosphere, 12 hours After heating to reflux under stirring for a while, TLC shows that the reaction is complete, 200 mL of water is added, and the pale yellow solid obtained by filtration is dissolved with methylene chloride, dried over anhydrous sodium sulfate, and column chromatography (eluent: methylene chloride) -ethyl acetate) to give a white solid compound C29 (13.7 g, yield 73%), calculated molecular weight: 653.22, found m/Z: 653.2.

Example C10: Preparation of compound C32

Preparation of compound 10-1

2,8-Dibromodibenzothiophene (2,8-Dibromodibenzothiophene, 20 g, 58.8 mmol), phenylboronic acid (7.2 g, 58.8 mmol) in a flask containing toluene: ethanol: water (300 mL: 100 mL: 100 mL) ), potassium carbonate (24.3 g, 176 mmol) was dissolved, nitrogen was substituted at room temperature under stirring, and then tetrakis(triphenylphosphine)palladium (693 mg, 0.6 mmol) was added. After completion of the addition, the reaction was stirred and refluxed for 6 hours, and the end point of the reaction was monitored by TLC. The layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography (eluent: petroleum ether: methylene chloride = 15:1) gave compound 10-1 (15.3 g, yield 77%).

Preparation of compound 10-2

Under a nitrogen atmosphere, compound 10-1 (15.3 g, 45.3 mmol) was added to a flask containing 200 mL of anhydrous tetrahydrofuran, and 2.5 M of n-butyllithium (n-Butyllithium, 20 mL) at -78 ° C. , 49.8 mmol) was added dropwise, and after completion of the dropping, the temperature was naturally raised to 0° C. and reacted for 30 minutes, and then the temperature was lowered to -78° C. and triisopropyl borate (12.8 g, 68 mmol) was added dropwise and dropped After completion, the temperature was naturally raised to room temperature and reacted for 2 hours, then 200 mL of 1M dilute hydrochloric acid was added dropwise and reacted for 1 hour. Ethyl acetate was added, the layers were separated, the aqueous phase was extracted with ethyl acetate, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. After washing with ethanol, compound 10-2 (11.2 g, yield 81%) was obtained.

Preparation of compound 10-3

Toluene: ethanol: water (150 mL: 50 mL: 50 mL) in a flask containing 3-bromocarbazole (8.2 g, 33.5 mmol), compound 10-2 (11.2 g, 36.8 mmol), potassium carbonate (13.8 g, 100 mmol) was dissolved, nitrogen was substituted at room temperature under stirring, and tetrakis(triphenylphosphine)palladium (393 mg, 0.34 mmol) was added. After the addition was completed, the reaction was stirred and refluxed for 6 hours, and the reaction endpoint was monitored by TLC. The precipitated solid was filtered off. The liquid layer was separated, the aqueous phase was extracted with methylene chloride, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The crude solids were combined and purified by column chromatography (eluent: petroleum ether: methylene chloride = 12:1) to obtain compound 10-3 (12 g, yield 84%).

Preparation of compound C32

Compound 10-3 (8 g, 18.8 mmol), compound 9-2 (7 g, 19.7 mmol), potassium carbonate (7.8 g, 56.4 mmol) were added to a flask containing 200 mL of acetonitrile, and under a nitrogen atmosphere, 15 hours After heating to reflux under stirring for a while, TLC showed that the reaction was complete. 200 mL of water was added, and the pale yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography (eluent: methylene chloride-ethyl acetate) as a white solid compound C32 (10 g, yield 71%) got Calculated molecular weight: 745.23, found m/Z: 745.2.

Example C11: Preparation of compound C33

Preparation of compound 11-1

Toluene: ethanol: water (150mL:50mL:50mL) in a flask containing 2-bromonitrobenzene (2-bromonitrobenzene, 10g, 49.75mmol), dibenzofuran-4-boronic acid (4-Dibenzofuranboronic acid, 111g, 52.2 mmol) and potassium carbonate (20.6 g, 149 mmol) were dissolved, nitrogen was substituted at room temperature under stirring, and then tetrakis(triphenylphosphine)palladium (578 mg, 0.5 mmol) was added. After completion of the addition, the reaction was stirred and refluxed for 6 hours, and the reaction endpoint was monitored by TLC. The layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography (eluent: petroleum ether: methylene chloride = 10:1) gave compound 11-1 (12.8 g, yield 89%).

Preparation of compound 11-2

Compound 11-1 (12.8 g, 44.3 mmol) and triphenylphosphine (29 g, 110.7 mmol) were added to a flask containing 300 mL of o-dichlorobenzene, and heated under a nitrogen atmosphere under stirring for 36 hours. After the reflux reaction, TLC indicated that the reaction was complete. The solvent was removed by rotary evaporation, dissolved with methylene chloride, and column chromatography (eluent: petroleum ether: methylene chloride = 5:1 to 1:1) was performed to perform white solid compound 11-2 (9.45 g, yield 83%). ) was obtained.

Preparation of compound C33

In a flask containing 300 mL of acetonitrile, compound 11-2 (8 g, 31.1 mmol), compound 5-2 (11.6 g, 32.7 mmol), potassium carbonate (12.9 g, 93.3 mmol) were added, and under a nitrogen atmosphere, 15 After heating to reflux under stirring for a while, TLC showed that the reaction was complete. 300 mL of water was added, and the pale yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography (eluent: methylene chloride-ethyl acetate) as a white solid compound C33 (14 g, yield 78%) got Calculated molecular weight: 577.19, found m/Z: 577.2.

Example C12: Preparation of compound C36

Preparation of compound 12-1

Compound 1-1 (20 g, 103 mmol) was added to a flask containing 200 L of ethanol, and 2-naphthaldehyde (2-Naphthaldehyde, 17.6 g, 113 mmol) was added dropwise at room temperature under stirring, after completion of the dropping, continued for 30 minutes After stirring and reaction, the solid obtained by filtration was washed with ethanol and n-hexane, respectively, and dried to obtain a yellow solid compound 12-1 (22.2 g, 65%).

Preparation of compound 12-2

Compound 12-1 (22.2 g, 67 mmol) was added to a flask containing 400 mL of ethanol, and iodobenzene diacetate (25.9 g, 80.4 mmol) was added in portions under stirring at room temperature. After the addition was completed, for 1.5 hours After the stirring reaction was continued, TLC showed that the reaction was complete. After adding 400 mL of n-hexane and stirring for 5 minutes, the obtained solid was filtered with suction, washed with n-hexane, and dried to obtain a pale yellowish-brown solid compound 12-2 (15.5 g, 70%).

Preparation of compound C36:

In a flask containing 300 mL of acetonitrile, compound 11-2 (10 g, 38.9 mmol), compound 12-2 (13.5 g, 40.9 mmol), potassium carbonate (16.1 g, 116.7 mmol) were added, and under a nitrogen atmosphere, 12 After heating to reflux under stirring for a while, TLC showed that the reaction was complete. 300 mL of water was added, and the pale yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography (eluent: methylene chloride-ethyl acetate) to perform white solid compound C36 (13 g, yield 61%) got Calculated molecular weight: 551.17, found m/Z: 551.2.

Example C13: Preparation of compound C41

Preparation of compound 13-2

In a flask containing 300 mL of toluene, compound 13-1 (10 g, 36.8 mmol), iodobenzene (12.1 g, 55.1 mmol), CuI (3.2 g, 16.8 mmol), ethylenediamine (2.2 g, 36.8 mmol), phosphoric acid Potassium phosphate (23.4 g, 110.4 mmol) was added, and the reaction was heated to reflux under a nitrogen atmosphere for 20 hours, and the reaction endpoint was monitored by TLC. Water was added, stirred, the layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography (eluent: petroleum ether: methylene chloride = 12:1) gave compound 13-2 (10.9 g, yield 85%).

Preparation of compound C41

In a flask containing 200 mL of acetonitrile, compound 13-2 (10.9 g, 31.3 mmol), compound 1-3 (9.2 g, 32.9 mmol), and potassium carbonate (13 g, 93.9 mmol) were added, and under a nitrogen atmosphere, 12 After heating to reflux under stirring for a while, TLC showed that the reaction was complete. 200 mL of water was added, and the pale yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography (eluent: methylene chloride-ethyl acetate) as a white solid compound C41 (14.5 g, yield 78%) ) was obtained. Calculated molecular weight: 592.24, found m/Z: 592.2.

Example C14: Preparation of compound C55

Preparation of compound 14-1

In a flask containing toluene: ethanol: water (300 mL: 100 mL: 100 mL), 2-nitrophenylboronic acid (15 g, 89.8 mmol), p-bromobenzaldehyde (4-Bromobenzaldehyde, 15.7 g, 85.5 mmol) ), potassium carbonate (35.4 g, 256.5 mmol) was dissolved, nitrogen was substituted at room temperature under stirring, and then tetrakis(triphenylphosphine)palladium (1.04 g, 0.9 mmol) was added. After completion of the addition, the reaction was stirred and refluxed for 6 hours, and the reaction endpoint was monitored by TLC. The layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography (eluent: petroleum ether: methylene chloride = 9:1) gave compound 14-1 (16.7 g, yield 86%).

Preparation of compound 14-2

Compound compound 14-1 (16.7 g, 73.5 mmol) and triphenylphosphine (48.2 g, 184 mmol) were added to a flask containing 300 mL of o-dichlorobenzene, and heated to reflux under nitrogen atmosphere under stirring for 36 hours. After completion of the reaction, TLC showed that the reaction was complete. The solvent was removed by rotary evaporation, dissolved with methylene chloride, and column chromatography (eluent: petroleum ether: methylene chloride = 20:1 to 10:1) was performed to perform white solid compound 14-2 (11.75 g, yield 82%). ) was obtained.

Preparation of compound 14-3

In a flask containing 300 mL of toluene, compound 14-2 (11.75 g, 60.3 mmol), iodobenzene (18.4 g, 90.4 mmol), CuI (5.7 g, 30 mmol), ethylenediamine (3.6 g, 60.3 mmol), Potassium phosphate (38.4 g, 181 mmol) was added, and the reaction was heated to reflux under a nitrogen atmosphere for 20 hours, and the reaction endpoint was monitored by TLC. Water was added, stirred, the layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography (eluent: petroleum ether: methylene chloride = 12:1) gave compound 14-3 (13.1 g, yield 80%).

Preparation of compound 14-4

Compound 1-1 (7.8 g, 40.3 mmol) was added to a flask containing 150 mL of ethanol, and 14-3 (13.1 g, 48.3 mmol) was added at room temperature under stirring, and after the addition was completed, stirring was continued for 30 minutes. Then, the solid obtained by filtration was washed with ethanol and n-hexane, respectively, and dried to obtain a yellow solid compound 14-4 (12.4 g, 69%).

Preparation of compound 14-5

Compound 14-4 (12.4 g, 27.8 mmol) was added to a flask containing 250 L of ethanol, and iodobenzene diacetate (10.7 g, 33.4 mmol) was added in portions under stirring at room temperature, after completion of the addition, 1.5 hours After stirring for a while, TLC showed reaction completion. After adding 250 mL of n-hexane and stirring for 5 minutes, the obtained solid was filtered with suction, washed with n-hexane, and dried to obtain a yellowish-brown solid compound 14-5 (8.9 g, 72%).

Preparation of compound C55

Compound 14-5 (8.9 g, 20 mmol), 7H-dibenzocarbazole (5.08 g, 19 mmol), potassium carbonate (7.9 g, 57 mmol) were added to a flask containing 150 mL of acetonitrile, and under a nitrogen atmosphere, 15 After heating to reflux under stirring for a while, TLC showed that the reaction was complete. 150 mL of water was added, and the pale yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography (eluent: methylene chloride to ethyl acetate) as a white solid compound C55 (9.9 g, yield 77%). ) was obtained. Calculated molecular weight: 676.24, found m/Z: 676.2.

Example C15: Preparation of compound C61

Preparation of compound C61

In a flask containing 300 mL of acetonitrile, 7H-dibenzocarbazole (10 g, 37.4 mmol), compound 9-2 (14 g, 39.3 mmol), potassium carbonate (15.5 g, 112.2 mmol) were added, and under a nitrogen atmosphere, After heating to reflux under stirring for 12 hours, TLC showed that the reaction was complete. 300 mL of water was added, and the pale yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography (eluent: methylene chloride-ethyl acetate) as a white solid compound C61 (15 g, yield 68%) got Calculated molecular weight: 587.21, found m/Z: 587.2.

Synthesis examples of specific compounds of the third preferred embodiment of the present application are as follows:

Example B1: Preparation of compound 1-121

2,4-Dichloropyrimidine (2,4-Dichloropyrimidine, 500 g, 3.38 mol) was dissolved in a flask containing 10 L of ethanol, and hydrazine hydrate (634 g, 10.14 mol, 80% aqueous solution) was added dropwise at 5 ° C. under stirring. and the temperature was maintained at less than 10 °C during the dropping process. After completion of the dropwise addition, the temperature was naturally raised to room temperature to react for 1 hour, and the precipitated solid was filtered with suction, washed with water and ethanol, respectively, and dried to obtain a white solid compound 1-1 (389 g, 80%).

Preparation of compound 1-2

Compound 1-1 (144 g, 1 mol) was added to a flask containing 1.5 L of ethanol, and benzaldehyde (138 g, 1.3 mol) was added dropwise at room temperature while stirring, and after completion of the dropping, stirring was continued for 30 minutes, followed by filtration. The obtained solid was washed with ethanol and n-hexane, respectively, and dried to obtain a yellow solid compound 1-2 (151 g, 65%).

Preparation of compound 1-3

Compound 1-2 (151 g, 0.65 mmol) was added to a flask containing 3 L of ethanol, and iodobenzene diacetate (251 g, 0.78 mol) was added portionwise under stirring at room temperature. After the addition was completed, for 1.5 hours After the stirring reaction was continued, TLC showed that the reaction was complete. The obtained solid was filtered with suction, washed with n-hexane, and dried to obtain a pale yellowish-brown solid compound 1-3 (109 g, 73%).

Preparation of compound 1-4

In a flask containing 1,4-dioxane (3L), 2-bromo-9,10-bis (2- naphthyl group) anthracene (2-Bromo-9,10-bis (2-naphthalenyl) anthracene, 508 g, 1 mol ), boronic acid pinacol ester (381 g, 1.5 mol), potassium acetate (Potassium Acetate, 294 g, 3 mol) were added, and nitrogen was substituted under stirring at room temperature, and then Pd (dppf ₂ )Cl ₂ (7.32 g, 0.01) mol) was added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the reaction endpoint was monitored by TLC. The solid precipitated after filtration was washed with water and dried to obtain compound 1-4 (500.4 g, yield 90%).

Preparation of compound 1-121

In a flask containing 1,4-dioxane: water (150 mL: 50 mL), compound 1-3 (5.75 g, 25 mmol), compound 1-4 (10 g, 18 mmol), potassium carbonate (7.45 g, 54 mmol) were added, After nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (208 mg, 0.18 mmol) was added. After completion of the addition, under nitrogen atmosphere, under stirring, the mixture was heated to 90° C. and reacted for 12 hours, and TLC indicated completion of the reaction. The precipitated yellow solid was filtered, dissolved with methylene chloride, dried over anhydrous sodium sulfate, and column Chromatography (eluent: methylene chloride) gave a yellow solid compound 1-121 (7.8 g, yield 70%). Calculated molecular weight: 624.23, found C/Z: 624.2.

Example B2: Preparation of compound 1-124

Preparation of compound 2-1

The compound 5-bromo-2,4-dichloropyrimidine (5-Bromo-2,4-dichloropyrimidine, 45.2 g, 200 mmol) was added to a flask containing 500 mL of ethanol, and hydrazine hydrate (37.5 g, 600 mol, 80% aqueous solution) was added dropwise under stirring, and the temperature was maintained at less than 10° C. during the dropping process. After completion of the dropwise addition, the temperature was naturally raised to room temperature to react for 1 hour, and the precipitated solid was filtered off with suction, washed with water and ethanol, respectively, and dried to obtain a white solid compound 2-1 (33.3 g, 75%).

Preparation of compound 2-2

Compound 2-1 (33.3 g, 0.15 mol) was added to a flask containing 350 mL of ethanol, and benzaldehyde (20.7 g, 0.2 mol) was added dropwise at room temperature under stirring, and after completion of the dropping, stirring was continued for 30 minutes. , the solid obtained by filtration was washed with ethanol and n-hexane, respectively, and dried to obtain a yellow solid compound 2-2 (28 g, 60%).

Preparation of compound 2-3

Compound 2-2 (28 g, 0.09 mol) was added to a flask containing 300 mL of ethanol, and iodobenzene diacetate (34.8 g, 0.11 mol) was added in portions under stirring at room temperature. After completion of the addition, for 1.5 hours After the stirring reaction was continued, TLC showed that the reaction was complete. The obtained solid was filtered with suction, washed with n-hexane, and dried to obtain a pale yellowish-brown solid compound 2-3 (19.7 g, 71%).

Preparation of compound 2-4

In a flask containing 1,4-dioxane: water (150 mL: 50 mL), compound 2-3 (7.7 g, 25 mmol), compound 1-4 (10 g, 18 mmol), potassium carbonate (7.45 g, 54 mmol) were added, After nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (208 mg, 0.18 mmol) was added. After completion of the addition, under a nitrogen atmosphere, under stirring, the reaction was heated to 90° C. for 12 hours, and then TLC showed that the reaction was complete. The precipitated yellow solid was filtered and dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography (eluent: methylene chloride) to obtain a yellow solid compound 2-4 (8.2 g, yield 65%).

Preparation of compound 1-124

In a flask containing 1,4-dioxane:water (150mL:50mL), compound 2-4 (8.2g, 11.7mmol), Pyridine-3-boronic Acid (1.73g, 14mmol), carbonic acid Potassium (4.84 g, 35.1 mmol) was added, and nitrogen was substituted at room temperature under stirring, followed by addition of Pd(PPh ₃ ) ₄ (139 mg, 0.12 mmol). After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain yellow solid compound 1-124 (6.8 g, yield 83%). Calculated molecular weight: 701.26, found C/Z: 701.3.

Example B3: Preparation of compound 1-321

Preparation of compound 3-1

In a flask containing 1,4-dioxane/water (300mL/100mL), p-chlorophenylboronic acid (4-Chlorophenylboronic acid, 7.8g, 50mmol), compound 1-3 (11.5g, 50mmol), potassium carbonate (20.7 g, 150mmol), and after nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (578 mg, 0.5 mmol) was added. After completion of the addition, the reaction was stirred at 80° C. for 8 hours, and the reaction endpoint was monitored by TLC. The layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 3-1 (10.7 g, yield 70%).

Preparation of compound 3-2

Compound 3-1 (10.7 g, 35 mmol), boronic acid pinacol ester (13.3 g, 52.5 mmol), potassium phosphate (14.5 g, 105 mmol) were added to a flask containing 1,4-dioxane (300 mL), and room temperature After replacing nitrogen under stirring, Pd ₂ (dba) ₃ (320 mg, 0.35 mmol) and Sphos (431 mg, 1.05 mmol) were added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the reaction endpoint was monitored by TLC. After washing with water, the layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 3-2 (15.1 g, yield 80%).

Preparation of compound 1-321

In a flask containing 1,4-dioxane:water (150mL:50mL), 9-bromo-10-naphthylanthracene (5.73g, 15mmol), compound 3-2 (5.97g, 15mmol), potassium carbonate (6.2g) , 45 mmol) was added, and nitrogen was substituted at room temperature under stirring, and then Pd(PPh ₃ ) ₄ (173 mg, 0.15 mmol) was added. After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved in methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain yellow solid compound 1-321 (4.3 g, yield 85%). Calculated molecular weight: 574.22, found C/Z: 574.2.

Example B4: Preparation of compound 2-121

Preparation of compound 4-1

The compound 2-chloro-4-aminopyrimidine (129 g, 1 mol) and bromoacetophenone (218 g, 1.1 mol) were added to a flask containing 1.3 L of DMF, and heated to 100° C. under stirring to react for 20 hours. and TLC showed reaction completion. The temperature was lowered to room temperature, water was added to precipitate a solid, and the solid obtained by filtration was washed with ethanol, dried and subjected to column chromatography to obtain a pale yellowish-brown solid compound 4-1 (172 g, 75%).

Preparation of compound 2-121

In a flask containing 1,4-dioxane: water (150 mL: 50 mL), compound 4-1 (4.1 g, 18 mmol), compound 1-4 (10 g, 18 mmol), potassium carbonate (7.45 g, 54 mmol) were added and , After nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (208 mg, 0.18 mmol) was added. After the addition was completed, the reaction was completed by heating to 80° C. under stirring under nitrogen atmosphere for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved in methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain yellow solid compound 2-121 (8.7 g, yield 78%). Calculated molecular weight: 623.24, found C/Z: 623.2.

Example B5: Preparation of compound 2-114

Preparation of compound 5-1

5-Bromo-2,4-dichloropyrimidine (5-Bromo-2,4-dichloropyrimidine, 56.5 g, 250 mmol) and 28% aqueous ammonia (94 g, 750 mmol) were added to a flask containing 500 mL of ethanol, and then at room temperature The reaction was stirred for 48 hours, and the reaction endpoint was monitored by TLC. The precipitated solid was filtered, washed with ethanol, and dried to obtain compound 5-1 (34 g, yield 66%).

Preparation of compound 5-2

Compound 5-1 (34 g, 165 mmol) and bromoacetophenone (36 g, 182 mmol) were added to a flask containing 600 mL of DMF, and heated to 100° C. under stirring to react for 20 hours, followed by TLC reaction completion was marked. The temperature was lowered to room temperature, water was added to precipitate a solid, and the solid obtained by filtration was washed with ethanol, dried and subjected to column chromatography to obtain yellowish-brown compound 5-2 (35.5 g, 70%).

Preparation of compound 5-3

In a flask containing 1,4-dioxane: water (150 mL: 50 mL), compound 5-2 (5.5 g, 18 mmol), compound 1-4 (10 g, 18 mmol), potassium carbonate (7.45 g, 54 mmol) were added, After nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (208 mg, 0.18 mmol) was added. After the addition was completed, the reaction was completed by heating to 80° C. under stirring under nitrogen atmosphere for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain yellow solid compound 5-3 (9 g, yield 71%).

Preparation of compound 2-114

In a flask containing 1,4-dioxane:water (150mL:50mL), compound 5-3 (9g, 12.8mmol), pyridine-3-boronic acid (1.73g, 14mmol), potassium carbonate (5.3g, 38.4mmol) was added, nitrogen was substituted at room temperature under stirring, and then Pd(PPh ₃ ) ₄ (150 mg, 0.13 mmol) was added. After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The solid obtained by filtration was dissolved in methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain yellow solid compound 2-114 (7.8 g, yield 87%). Calculated molecular weight: 700.26, found C/Z: 700.3.

Example B6: Preparation of compound 2-411

Preparation of compound 6-1

In a flask containing 700 mL of DMF, 2-chloro-4-aminopyrimidine (64.5 g, 0.5 mol) and bromoacetone (81.6 g, 0.6 mmol) were added, and heated to 100° C. under stirring to react for 15 hours. After completion of the reaction, TLC showed that the reaction was complete. The temperature was lowered to room temperature, water was added to precipitate a solid, and the solid obtained by filtration was washed with ethanol, dried and subjected to column chromatography to obtain a pale yellowish-brown solid compound 6-1 (58.7 g, 72%).

Preparation of compound 6-2

1,4-dioxane: p-chlorophenylboronic acid (34.3 g, 220 mmol), compound 6-1 (33.4 g, 200 mmol), potassium carbonate (82.8 g, 600 mmol) in a flask containing water (300 mL / 100 mL) After nitrogen was substituted at room temperature under stirring, Pd(PPh ₃ ) ₄ (2.3 g, 0.2 mmol) was added. After completion of the addition, the reaction was stirred at 80° C. for 8 hours, and the reaction endpoint was monitored by TLC. The layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 6-2 (35.9 g, yield 74%).

Preparation of compound 6-3

Compound 6-2 (24.3 g, 100 mmol), boronic acid pinacol ester (38.1 g, 150 mmol), potassium phosphate (41.4 g, 300 mmol) were added to a flask containing 1,4-dioxane (500 mL), and at room temperature After nitrogen substitution under stirring, Pd ₂ (dba) ₃ (1.15 g, 1 mmol) and Sphos (1.23 g, 3 mmol) were added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the reaction endpoint was monitored by TLC. After washing with water, the layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 6-3 (26.8 g, yield 80%).

Preparation of compound 2-411

In a flask containing 1,4-dioxane:water (150mL:50mL), 9-(4-biphenyl) -10-bromoanthracene (9-(4-Biphenylyl)-10-bromoanthracene, 6.12g, 15mmol), Compound 6-3 (5.03 g, 15 mmol) and potassium carbonate (6.2 g, 45 mmol) were added, and nitrogen was substituted at room temperature under stirring, followed by addition of Pd(PPh ₃ ) ₄ (173 mg, 0.15 mmol). After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved in methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a yellow solid compound 2-411 (6.9 g, yield 86%). Calculated molecular weight: 537.22, found C/Z: 537.2.

Example B7: Preparation of compound 3-121

Preparation of compound 7-1

2,4-dichloroquinazoline (500 g, 2.5 mol) was dissolved in a flask containing 10 L of ethanol, and hydrazine hydrate (470 g, 7.5 mol, 80% aqueous solution) was added dropwise under stirring at 5 ° C., and the temperature during the dropping process was kept below 10 °C. After completion of the dropwise addition, the temperature was naturally raised to room temperature to react for 1 hour, and then the obtained solid was filtered with suction, washed with water and ethanol, respectively, and dried to obtain a white solid compound 7-1 (415 g, 86%).

Preparation of compound 7-2

Compound 7-1 (200 g, 1.03 mol) was added to a flask containing 2 L of ethanol, and benzaldehyde (120 g, 1.13 mol) was added dropwise at room temperature under stirring, and after completion of the dropping, stirring was continued for 30 minutes, followed by filtration The obtained solid was washed with ethanol and n-hexane, respectively, and dried to obtain a yellow solid compound 7-2 (184 g, 63 %).

Preparation of compound 7-3

Compound 7-2 (184 g, 652.4 mmol) was added to a flask containing 4 L of ethanol, and iodobenzene diacetate (252 g, 782.9 mmol) was added portionwise under stirring at room temperature, after completion of the addition, continued for 1.5 hours After the reaction was stirred, TLC showed that the reaction was complete. After adding 4L of n-hexane and stirring for 5 minutes, the precipitated solid was suction filtered, washed with n-hexane, and dried to obtain a pale yellowish-brown solid compound 7-3 (130 g, 71%).

Preparation of compound 3-121

Compound 7-3 (5 g, 18 mmol), compound 1-4 (10 g, 18 mmol), potassium carbonate (7.45 g, 54 mmol) were added to a flask containing 1,4-dioxane: water (150 mL: 50 mL), and room temperature After replacing nitrogen under stirring, Pd(PPh ₃ ) ₄ (208 mg, 0.18 mmol) was added. After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The precipitated yellow solid was filtered. It was dissolved in methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a yellow solid compound 3-121 (8.5 g, yield 70%). Calculated molecular weight: 674.25, found C/Z: 674.2.

Example B8: Preparation of compound 3-321

Preparation of compound 8-1

In a flask containing 1,4-dioxane/water (900mL/300mL), p-chlorophenylboronic acid (31.2g, 0.2mol), compound 7-3 (56g, 0.2mmol), potassium carbonate (82.8g, 0.6mol) ) was added, and nitrogen was substituted under stirring at room temperature, followed by addition of Pd(PPh ₃ ) ₄ (2.31 g, 2 mmol). After completion of the addition, the reaction was stirred at 80° C. for 8 hours, and the reaction endpoint was monitored by TLC. The layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 8-1 (50.6 g, yield 71%).

Preparation of compound 8-2

Compound 8-1 (35.6 g, 0.1 mol), boronic acid pinacol ester (38.1 g, 0.15 mol), potassium phosphate (41.4 g, 0.3 mol) were added to a flask containing 1,4-dioxane (1 L) and , After nitrogen substitution at room temperature under stirring, Pd ₂ (dba) ₃ (916 mg, 1 mmol) and Sphos (1.23 g, 3 mmol) were added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the reaction endpoint was monitored by TLC. After washing with water, the layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 8-2 (31.4 g, yield 70%).

Preparation of compound 3-321

In a flask containing 1,4-dioxane:water (150mL:50mL), 9-bromo-10-naphthylanthracene (5.73g, 15mmol), compound 8-2 (6.72g, 15mmol), potassium carbonate (6.2g) , 45 mmol), and after nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (173 mg, 0.15 mmol) was added. After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The obtained yellow solid was filtered, dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a yellow solid compound 3-321 (7.5 g, yield 88%). Calculated molecular weight: 624.23, found C/Z: 624.2.

Example B9: Preparation of compound 3-401

Preparation of compound 9-1

Compound 7-1 (19.4 g, 0.1 mol) and trimethyl orthoformate (Trimethyl Orthoformate, 150 ml as a solvent) were added to a flask, and the reaction was heated to reflux under stirring for 3 hours, and the reaction endpoint was monitored by TLC. The solvent was removed by rotary evaporation under reduced pressure, washed by heating with ethanol, filtered with suction, and dried to obtain compound 9-1 (17.5 g, yield 86%).

Preparation of compound 9-2

In a flask containing 1,4-dioxane/water (300mL/100mL), p-chlorophenylboronic acid (14.8g, 94.6mmol), compound 9-1 (17.5g, 86mmol), potassium carbonate (35.6g, 258mmol) was added, and nitrogen was substituted under stirring at room temperature, and then Pd(PPh ₃ ) ₄ (1 g, 0.86 mmol) was added. After completion of the addition, the reaction was stirred at 80° C. for 8 hours, and the reaction endpoint was monitored by TLC. The layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 9-2 (16.9 g, yield 70%).

Preparation of compound 9-3

Compound 9-2 (16.8 g, 60 mmol), boronic acid pinacol ester (22.9 g, 90 mmol), potassium phosphate (38.2 g, 180 mmol) were added to a flask containing 1,4-dioxane (500 mL), and at room temperature After replacing nitrogen under stirring, Pd ₂ (dba) ₃ (550 mg, 0.6 mmol) and Sphos (738 mg, 1.8 mmol) were added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the reaction endpoint was monitored by TLC. After washing with water, the layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 9-3 (16.7 g, yield 75%).

Preparation of compound 3-401

In a flask containing 1,4-dioxane:water (150mL:50mL), 9-(4-biphenyl)-10- bromoanthracene (6.12g, 15mmol), compound 9-3 (5.58g, 15mmol), carbonic acid Potassium (6.2 g, 45 mmol) was added and nitrogen was substituted at room temperature under stirring, followed by addition of Pd(PPh ₃ ) ₄ (173 mg, 0.15 mmol). After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved in methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a yellow solid compound 3-401 (7.1 g, yield 83%). Calculated molecular weight: 574.22, found C/Z: 574.2.

Example B10: Preparation of compound 4-121

Preparation of compound 10-1

Compound 2-chloro-4-aminoquinazoline (179 g, 1 mol) and bromoacetophenone (218 g, 1.1 mol) were added to a flask containing 1.3 L of DMF, and heated to 100° C. under stirring to react for 20 hours. After completion of the reaction, TLC showed that the reaction was complete. The temperature was lowered to room temperature, water was added to precipitate a solid, and the solid obtained by filtration was washed with ethanol, dried and subjected to column chromatography to obtain a pale yellowish-brown solid compound 10-1 (209 g, 75%).

Preparation of compound 4-121

Compound 10-1 (5 g, 18 mmol), compound 1-4 (10 g, 18 mmol), potassium carbonate (7.45 g, 54 mmol) were added to a flask containing 1,4-dioxane: water (150 mL: 50 mL), and room temperature After replacing nitrogen under stirring, Pd(PPh ₃ ) ₄ (208 mg, 0.18 mmol) was added. After the addition was completed, the reaction was completed by heating to 80° C. under stirring under nitrogen atmosphere for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a yellow solid compound 4-121 (9.1 g, yield 75%). Calculated molecular weight: 673.25, found C/Z: 673.2.

Example B11: Preparation of compound 4-321

Preparation of compound 11-1

In a flask containing 1,4-dioxane/water (900mL/300mL), p-chlorophenylboronic acid (31.2g, 0.2mol), compound 10-1 (55.8g, 0.2mmol), potassium carbonate (82.8g, 0.6 mol), and after nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (2.31 g, 2 mmol) was added. After completion of the addition, the reaction was stirred at 80° C. for 12 hours, and the end point of the reaction was monitored by TLC. The layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 11-1 (49 g, yield 69%).

Preparation of compound 11-2

Compound 11-1 (35.5 g, 0.1 mol), boronic acid pinacol ester (38.1 g, 0.15 mol), potassium phosphate (41.4 g, 0.3 mol) were added to a flask containing 1,4-dioxane (1 L) and , After nitrogen substitution at room temperature under stirring, Pd ₂ (dba) ₃ (916 mg, 1 mmol) and Sphos (1.23 g, 3 mmol) were added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the reaction endpoint was monitored by TLC. After washing with water, the layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 11-2 (31.7 g, yield 71%).

Preparation of compound 4-321

In a flask containing 1,4-dioxane:water (150mL:50mL), 9-bromo-10-naphthylanthracene (5.73g, 15mmol), compound 11-2 (6.71g, 15mmol), potassium carbonate (6.2g) , 45 mmol), and after nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (173 mg, 0.15 mmol) was added. After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved in methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a yellow solid compound 4-321 (7.9 g, yield 85%). Calculated molecular weight: 623.24, found C/Z: 623.2.

Example B12: Preparation of compound 4-411

Preparation of compound 12-1

2-chloro-4-aminoquinazoline (89.5 g, 0.5 mol, bromoacetone (81.6 g, 0.6 mmol) was added to a flask containing 700 mL of DMF, and heated to 100 ° C. under stirring to react for 15 hours. After that, TLC showed that the reaction was completed.The temperature was lowered to room temperature, water was added to precipitate a solid, and the solid obtained by filtration was washed with ethanol, dried, and column chromatography was performed to perform column chromatography as a yellowish-brown solid compound 12-1 (79.2 g). , 73%) was obtained.

Preparation of compound 12-2

In a flask containing 1,4-dioxane / water (600mL / 200mL) p-chlorophenylboronic acid (34.3g, 220mmol), compound 12-1 (43.4g, 200mmol), potassium carbonate (82.8g, 600mmol) After nitrogen was substituted at room temperature under stirring, Pd(PPh ₃ ) ₄ (2.3 g, 0.2 mmol) was added. After completion of the addition, the reaction was stirred at 80° C. for 8 hours, and the reaction endpoint was monitored by TLC. The obtained solid was filtered with suction and purified by column chromatography to obtain compound 12-2 (43.9 g, yield 75%).

Preparation of compound 12-3

Compound 12-2 (29.3 g, 100 mmol), boronic acid pinacol ester (38.1 g, 150 mmol), potassium phosphate (41.4 g, 300 mmol) were added to a flask containing 1,4-dioxane (500 mL), and at room temperature After replacing nitrogen under stirring, Pd ₂ (dba) ₃ (1.15 g, 1 mmol) and Sphos (1.23 g, 3 mmol) were added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the reaction endpoint was monitored by TLC. Filtration and dissolving the solid with methylene chloride; The liquid layer was washed with water, the layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 12-3 (30.8 g, yield 80%).

Preparation of compound 4-411

In a flask containing 1,4-dioxane:water (150mL:50mL), 9-(4-biphenyl)-10-bromoanthracene (6.12 g, 15 mmol), compound 12-3 (5.78 g, 15 mmol) , potassium carbonate (6.2 g, 45 mmol) was added, and nitrogen was substituted at room temperature under stirring, followed by addition of Pd(PPh ₃ ) ₄ (173 mg, 0.15 mmol). After completion of the addition, the reaction was heated to reflux under stirring under nitrogen atmosphere for 12 hours, and TLC indicated completion of the reaction. The obtained yellow solid was filtered, dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain yellow color. of solid compound 4-411 (7.3 g, yield 83%) was obtained. Calculated molecular weight: 587.24, found C/Z: 587.2.

Example B13: Preparation of compound 5B-121

Preparation of compound 13-1

2,4-dichloropyrido [3,4-d] pyrimidine (497.5 g, 2.5 mol) was dissolved in a flask containing 10 L of ethanol, and hydrazine hydrate (470 g, 7.5 mol, 80% aqueous solution) at 5 ° C. was added dropwise under stirring, and the temperature was maintained below 10°C during the dropping process. After completion of the dropwise addition, the temperature was naturally raised to room temperature to react for 1 hour, and the precipitated solid was filtered off with suction, washed with water and ethanol, respectively, and dried to obtain a white solid compound 13-1 (370.5 g, 76%). .

Preparation of compound 13-2

Compound 13-1 (195 g, 1 mol) was added to a flask containing 2 L of ethanol, and benzaldehyde (138 g, 1.3 mol) was added dropwise at room temperature under stirring. After completion of the dropping, stirring was continued for 30 minutes, followed by filtration. The obtained solid was washed with ethanol and n-hexane, respectively, and dried to obtain a yellow solid compound 13-2 (184 g, 65%).

Preparation of compound 13-3

Compound 13-2 (184 g, 650 mmol) was added to a flask containing 4 L of ethanol, and iodobenzene diacetate (251 g, 780 mmol) was added in portions under stirring at room temperature. After the addition was completed, stirring was continued for 1.5 hours. After completion of the reaction, TLC showed that the reaction was complete. The precipitated solid was filtered with suction, washed with n-hexane, and dried to obtain a pale yellowish-brown solid compound 13-3 (128 g, 70%).

Preparation of compound 5B-121

In a flask containing 1,4-dioxane: water (150 mL: 50 mL), compound 13-3 (5.06 g, 18 mmol), compound 1-4 (10 g, 18 mmol), potassium carbonate (7.45 g, 54 mmol) were added, After nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (208 mg, 0.18 mmol) was added. After completion of the addition, the reaction was heated to reflux under stirring under nitrogen atmosphere for 12 hours, and TLC indicated that the reaction was complete. The precipitated yellow solid was filtered, dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain yellow color. A solid compound of 5B-121 (8.6 g, yield 71%) was obtained. Calculated molecular weight: 675.25, found C/Z: 675.2.

Example B14: Preparation of compound 5B-321

Preparation of compound 14-1

In a flask containing 1,4-dioxane/water (900mL/300mL), p-chlorophenylboronic acid (31.2g, 0.2mol), compound 13-3 (56.2g, 0.2mmol), potassium carbonate (82.8g, 0.6 mol), and after nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (2.31 g, 2 mmol) was added. After completion of the addition, the reaction was stirred at 80° C. for 12 hours, and the end point of the reaction was monitored by TLC. The solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 14-1 (46.4 g, yield 65%).

Preparation of compound 11-2

Compound 14-2 (35.7 g, 0.1 mol), boronic acid pinacol ester (38.1 g, 0.15 mol), potassium phosphate (41.4 g, 0.3 mol) were added to a flask containing 1,4-dioxane (1 L) and , After nitrogen substitution at room temperature under stirring, Pd ₂ (dba) ₃ (916 mg, 1 mmol) and Sphos (1.23 g, 3 mmol) were added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the reaction endpoint was monitored by TLC. The solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 14-2 (31.4 g, yield 70%).

Preparation of compound 5B-321

In a flask containing 1,4-dioxane: water (150 mL: 50 mL), 9-bromo-10-naphthylanthracene (5.73 g, 15 mmol), compound 14-2 (6.74 g, 15 mmol), potassium carbonate (6.2 g) , 45 mmol) was added, and nitrogen was substituted at room temperature under stirring, and then Pd(PPh ₃ ) ₄ (173 mg, 0.15 mmol) was added. After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The obtained yellow solid was filtered, dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a yellow solid compound 5B-321 (7.5 g, yield 80%). Calculated molecular weight: 625.23, found C/Z: 625.2.

Example B15: Preparation of compound 5B-401

Preparation of compound 15-1

Compound 13-1 (19.5 g, 0.1 mol) and trimethylorthoformate (150 ml as a solvent) were added to a flask, and the reaction was heated to reflux under stirring for 3 hours, and the reaction endpoint was monitored by TLC. The solvent was removed by rotary evaporation under reduced pressure, washed by heating with ethanol, and dried by suction filtration to obtain compound 15-1 (16.8 g, yield 82%).

Preparation of compound 15-2

In a flask containing 1,4-dioxane / water (300mL / 100mL) p-chlorophenylboronic acid (14g, 90.2mmol), compound 15-1 (16.8g, 82mmol), potassium carbonate (33.9g, 246mmol) After nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (947 mg, 0.82 mmol) was added. After completion of the addition, the reaction was stirred at 80° C. for 8 hours, and the reaction endpoint was monitored by TLC. filter with suction and dissolve the solid with methylene chloride; The liquid layer was separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 15-2 (16.1 g, yield 70%).

Preparation of compound 15-3

Compound 15-2 (16.1 g, 57.4 mmol), boronic acid pinacol ester (21.9 g, 86.1 mmol), potassium phosphate (23.8 g, 172 mmol) was added to a flask containing 1,4-dioxane (500 mL), After nitrogen substitution at room temperature under stirring, Pd ₂ (dba) ₃ (550 mg, 0.6 mmol) and Sphos (738 mg, 1.8 mmol) were added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the reaction endpoint was monitored by TLC. filter with suction and dissolve the solid with methylene chloride; The liquid layer was washed with water to separate the layers, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 15-3 (19.1 g, yield 74%).

Preparation of compound 5B-401

In a flask containing 1,4-dioxane:water (150mL:50mL), 9-(4-biphenyl)-10- bromoanthracene (6.12g, 15mmol), compound 15-3 (6.74g, 15mmol), carbonic acid Potassium (6.2 g, 45 mmol) was added, and nitrogen was substituted under stirring at room temperature, followed by addition of Pd(PPh ₃ ) ₄ (173 mg, 0.15 mmol). After completion of the addition, the reaction was heated to reflux under stirring under nitrogen atmosphere for 12 hours, and TLC indicated completion of the reaction. The obtained yellow solid was filtered, dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain yellow color. of solid compound 5B-401 (7.1 g, yield 82%) was obtained. Calculated molecular weight: 575.21, found C/Z: 575.2.

Example B16: Preparation of compound 6B-121

Preparation of compound 16-1

2,4-dichloropyrido [3,4-d] pyrimidine (49.8 g, 250 mmol) and 28% aqueous ammonia (94 g, 750 mmol) were added to a flask containing ethanol (500 mL), and stirred at room temperature for 48 hours reacted, and the reaction endpoint was monitored by TLC. The precipitated solid was filtered, washed with ethanol, and dried to obtain compound 16-1 (27 g, yield 60%).

Preparation of compound 16-2

In a flask containing 400 mL of DMF, compound compound 16-1 (27 g, 0.15 mol) and bromoacetone (32.7 g, 0.165 mol) were added, heated to 100° C. under stirring, and reacted for 20 hours, followed by TLC Reaction completion was indicated. The temperature was lowered to room temperature, water was added to precipitate a solid, and the solid obtained by filtration was washed with ethanol, dried and subjected to column chromatography to obtain pale yellowish-brown compound 16-2 (31.5 g, 75%).

Preparation of compound 6B-121

In a flask containing 1,4-dioxane:water (150mL:50mL) were added compound 16-2 (5g, 18mmol), compound 1-4 (10g, 18mmol), potassium carbonate (7.45g, 54mmol), and room temperature After replacing nitrogen under stirring, Pd(PPh ₃ ) ₄ (208 mg, 0.18 mmol) was added. After completion of the addition, under a nitrogen atmosphere, under stirring, the reaction was heated to 80° C. for 12 hours, and TLC showed that the reaction was complete. The yellow solid obtained after filtration was dissolved in methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a yellow solid compound 6B-121 (9.3 g, yield 77%). Calculated molecular weight: 674.25, found C/Z: 674.2.

Example B17: Preparation of compound 6B-321

Preparation of compound 17-1

In a flask containing 1,4-dioxane/water (900mL/300mL), p-chlorophenylboronic acid (31.2g, 0.2mol), compound 16-2 (56g, 0.2mmol), potassium carbonate (82.8g, 0.6mol) ) was added, and nitrogen was substituted under stirring at room temperature, followed by addition of Pd(PPh ₃ ) ₄ (2.31 g, 2 mmol). After completion of the addition, the reaction was stirred at 80° C. for 12 hours, and the end point of the reaction was monitored by TLC. The solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 17-1 (47 g, yield 66%).

Preparation of compound 17-2

In a flask containing 1,4-dioxane (1L), compound 16-2 (35.6 g, 0.1 mol), boronic acid pinacol ester (38.1 g, 0.15 mol), potassium phosphate (41.4 g, 0.3 mol) was added and , After nitrogen substitution at room temperature under stirring, Pd ₂ (dba) ₃ (916 mg, 1 mmol) and Sphos (1.23 g, 3 mmol) were added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the reaction endpoint was monitored by TLC. The solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 17-2 (31.8 g, yield 71%).

Preparation of compound 6B-321

In a flask containing 1,4-dioxane:water (150mL:50mL), 9-bromo-10-naphthylanthracene (5.73g, 15mmol), compound 14-2 (6.73g, 15mmol), potassium carbonate (6.2g) , 45 mmol) was added, and nitrogen was substituted at room temperature under stirring, and then Pd(PPh ₃ ) ₄ (173 mg, 0.15 mmol) was added. After completion of the addition, the reaction was heated to reflux under stirring under nitrogen atmosphere for 12 hours, and TLC indicated completion of the reaction. The obtained yellow solid was filtered, dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain yellow color. A solid compound of 6B-321 (7.8 g, yield 83%) was obtained. Calculated molecular weight: 624.23, found C/Z: 624.2.

Example B18: Preparation of compound 6B-411

Preparation of compound 18-1

Compound 16-1 (90 g, 0.5 mol) and bromoacetone (Bromopropanone, 81.6 g, 0.6 mmol) were added to a flask containing 700 mL of DMF, and heated to 100° C. under stirring to react for 15 hours, then TLC indicates the completion of the reaction. The temperature was lowered to room temperature, water was added to precipitate a solid, and the solid obtained by filtration was washed with ethanol, dried and subjected to column chromatography to obtain a yellowish-brown solid compound 18-1 (76.3 g, 70%).

Preparation of compound 18-2

In a flask containing 1,4-dioxane / water (600mL / 200mL) p-chlorophenylboronic acid (34.3g, 220mmol), compound 18-1 (43.6g, 200mmol), potassium carbonate (82.8g, 600mmol) After nitrogen was substituted at room temperature under stirring, Pd(PPh ₃ ) ₄ (2.3 g, 0.2 mmol) was added. After completion of the addition, the reaction was stirred at 80° C. for 8 hours, and the reaction endpoint was monitored by TLC. The solid obtained by suction filtration was separated and purified by column chromatography to obtain 18-2 (45.3 g, yield 77%).

Preparation of compound 18-3

Compound 18-2 (29.4 g, 100 mmol), boronic acid pinacol ester (38.1 g, 150 mmol), potassium phosphate (41.4 g, 300 mmol) were added to a flask containing 1,4-dioxane (500 mL), and at room temperature After replacing nitrogen under stirring, Pd ₂ (dba) ₃ (1.15 g, 1 mmol) and Sphos (1.23 g, 3 mmol) were added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the reaction endpoint was monitored by TLC. filter with suction and dissolve the solid with methylene chloride; The liquid layer was washed with water to separate the layers, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 18-3 (30.9 g, yield 80%).

Preparation of compound 6B-411

In a flask containing 1,4-dioxane:water (150mL:50mL), 9-(4-biphenyl)-10-bromoanthracene (6.12g, 15mmol), compound 18-3 (5.79g, 15mmol), carbonic acid Potassium (6.2 g, 45 mmol) was added, and nitrogen was substituted under stirring at room temperature, followed by addition of Pd(PPh ₃ ) ₄ (173 mg, 0.15 mmol). After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved in methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a yellow solid compound 6B-411 (7.1 g, yield 81%). Calculated molecular weight: 588.23, found C/Z: 588.2.

Example B19: Preparation of compound 7A-121

Preparation of compound 19-1

After dissolving 2,4-dichlorothieno[2,3-d]pyrimidine (510g, 2.5mol) in 10L ethanol in a flask, hydrazine hydrate (470g, 7.5mol, 80% aqueous solution) was stirred at 5°C under stirring. It was dripped, and the temperature was maintained below 10 degreeC during the dripping process. After completion of the dropwise addition, the temperature was naturally raised to room temperature to react for 1 hour, and the precipitated solid was filtered off with suction, washed with water and ethanol, respectively, and dried to obtain a white solid compound 19-1 (375 g, 75%).

Preparation of compound 19-2

Compound 19-1 (375 g, 1.875 mol) was added to a flask containing 4 L of ethanol, and benzaldehyde (260 g, 2.45 mol) was added dropwise at room temperature under stirring, and after completion of the dropping, stirring was continued for 30 minutes, followed by filtration. The obtained solid was washed with ethanol and n-hexane, respectively, and dried to obtain a yellow solid compound 19-2 (351 g, 65%).

Preparation of compound 19-3

Compound 19-2 (351 g, 1.22 mol) was added to a flask containing 7 L of ethanol, and iodobenzene diacetate (471 g, 1.46 mol) was added portionwise under stirring at room temperature, and after completion of the addition, continued for 1.5 hours After the reaction was stirred, TLC showed that the reaction was complete. The precipitated solid was filtered with suction, washed with n-hexane, and dried to obtain a pale yellowish-brown solid compound 19-3 (251 g, 72%).

Preparation of compound 7A-121

In a flask containing 1,4-dioxane: water (150 mL: 50 mL), compound 19-3 (5.1 g, 18 mmol), compound 1-4 (10 g, 18 mmol), potassium carbonate (7.45 g, 54 mmol) were added, After nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (208 mg, 0.18 mmol) was added. After the addition was completed, the reaction was heated to reflux under stirring under nitrogen atmosphere for 12 hours, and TLC indicated completion of the reaction. The precipitated yellow solid was filtered and dissolved in methylene chloride, dried over anhydrous sodium sulfate, and column chromatography was performed. (Eluent: methylene chloride) A yellow solid compound 7A-121 (8.8 g, yield 72%) was obtained. Calculated molecular weight: 680.20, found C/Z: 680.2.

Example B20: Preparation of compound 7A-321

Preparation of compound 20-1

In a flask containing 1,4-dioxane/water (900mL/300mL), p-chlorophenylboronic acid (31.2g, 0.2mol), compound 19-3 (57.2g, 0.2mmol), potassium carbonate (82.8g, 0.6 mol), and after nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (2.31 g, 2 mmol) was added. After completion of the addition, the reaction was stirred at 80° C. for 12 hours, and the end point of the reaction was monitored by TLC. The solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 20-1 (47 g, yield 65%).

Preparation of compound 20-2

Compound 20-1 (36.2 g, 0.1 mol), boronic acid pinacol ester (38.1 g, 0.15 mol), potassium phosphate (41.4 g, 0.3 mol) were added to a flask containing 1,4-dioxane (1 L) and , After nitrogen substitution at room temperature under stirring, Pd ₂ (dba) ₃ (916 mg, 1 mmol) and Sphos (1.23 g, 3 mmol) were added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the reaction endpoint was monitored by TLC. The solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 20-2 (32.6 g, yield 72%).

Preparation of compound 7A-321

In a flask containing 1,4-dioxane:water (150mL:50mL), 9-bromo-10-naphthylanthracene (5.73g, 15mmol), compound 20-2 (6.81g, 15mmol), potassium carbonate (6.2g) , 45 mmol) was added, and nitrogen was substituted at room temperature under stirring, and then Pd(PPh ₃ ) ₄ (173 mg, 0.15 mmol) was added. After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved in methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a yellow solid compound 7A-321 (7.6 g, yield 81%). Calculated molecular weight: 630.19, found C/Z: 630.2.

Example B21: Preparation of compound 7A-401

Preparation of compound 21-1

Compound 19-2 (20.2 g, 0.1 mol) and trimethylorthoformate (150 ml as a solvent) were added to a flask, and the reaction was heated to reflux under stirring for 3 hours, and the reaction endpoint was monitored by TLC. The solvent was removed by rotary evaporation under reduced pressure, washed by heating with ethanol, and dried by suction filtration to obtain compound 21-1 (17.4 g, yield 83%).

Preparation of compound 21-2

In a flask containing 1,4-dioxane / water (300mL / 100mL) p-chlorophenylboronic acid (14g, 90.2mmol), compound 21-1 (17.2g, 82mmol), potassium carbonate (33.9g, 246mmol) After nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (947 mg, 0.82 mmol) was added. After completion of the addition, the reaction was stirred at 80° C. for 8 hours, and the reaction endpoint was monitored by TLC. filter with suction and dissolve the solid with methylene chloride; The liquid layer was separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 21-2 (16.9 g, yield 72%).

Preparation of compound 21-3

Compound 21-2 (16.9 g, 59 mmol), boronic acid pinacol ester (22.5 g, 88.6 mmol), potassium phosphate (24.4 g, 177 mmol) were added to a flask containing 1,4-dioxane (500 mL), and room temperature After replacing nitrogen under stirring, Pd ₂ (dba) ₃ (550 mg, 0.6 mmol) and Sphos (738 mg, 1.8 mmol) were added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the reaction endpoint was monitored by TLC. filter with suction and dissolve the solid with methylene chloride; The layers were separated by washing with water, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 21-3 (15.6 g, yield 70%).

Preparation of compound 7A-401

In a flask containing 1,4-dioxane:water (150mL:50mL), 9-(4-biphenyl)-10- bromoanthracene (6.12g, 15mmol), compound 15-3 (5.67g, 15mmol), carbonic acid Potassium (6.2 g, 45 mmol) was added, and nitrogen was substituted under stirring at room temperature, followed by addition of Pd(PPh ₃ ) ₄ (173 mg, 0.15 mmol). After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved in methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a yellow solid compound 7A-401 (7.4 g, yield 85%). Calculated molecular weight: 580.17, found C/Z: 580.2.

Example B22: Preparation of compound 8A-121

Preparation of compound 22-1

2,4-dichlorothieno[2,3-d]pyrimidine (51g, 250mmol) and 28% aqueous ammonia (94g, 750mmol) were added to a flask containing 500mL of ethanol, and the reaction was stirred at room temperature for 48 hours. , the reaction endpoints were monitored by TLC. The precipitated solid was filtered, washed with ethanol, and dried to obtain compound 22-1 (29 g, yield 63%).

Preparation of compound 22-2

Compound 22-1 (27.8 g, 0.15 mol) and bromoacetophenone (32.7 g, 0.165 mol) were added to a flask containing 400 mL of DMF, and heated to 100° C. under stirring to react for 20 hours, followed by TLC indicates the completion of the reaction. The temperature was lowered to room temperature, water was added to precipitate a solid, and the solid obtained by filtration was washed with ethanol, dried and subjected to column chromatography to obtain a pale yellowish-brown solid compound 22-2 (32.5 g, 76%).

Preparation of compound 8A-121

In a flask containing 1,4-dioxane: water (150 mL: 50 mL), compound 22-2 (5.1 g, 18 mmol), compound 1-4 (10 g, 18 mmol), potassium carbonate (7.45 g, 54 mmol) were added, After nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (208 mg, 0.18 mmol) was added. After the addition was completed, the reaction was completed by heating to 80° C. under stirring under nitrogen atmosphere for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved in methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a yellow solid compound 8A-121 (9.2 g, yield 75%). Calculated molecular weight: 679.21, found C/Z: 679.2.

Example B23: Preparation of compound 8A-321

Preparation of compound 23-1

In a flask containing 1,4-dioxane/water (450 mL/150 mL), p-chlorophenylboronic acid (15.6 g, 0.1 mol), compound 22-2 (28.5 g, 0.1 mmol), potassium carbonate (41.4 g, 0.3 mol), and after nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (1.15 g, 1 mmol) was added. After completion of the addition, the reaction was stirred at 80° C. for 12 hours, and the end point of the reaction was monitored by TLC. The solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 23-1 (24.2 g, yield 67%).

Preparation of compound 23-2

Compound 23-1 (23.2 g, 0.067 mol), boronic acid pinacol ester (25.4 g, 0.1 mol), potassium phosphate (27.7 g, 0.2 mol) was added to a flask containing 1,4-dioxane (500 mL) and , After nitrogen substitution at room temperature under stirring, Pd ₂ (dba) ₃ (641 mg, 0.7 mmol) and Sphos (861 mg, 2.1 mmol) were added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the end point of the reaction was monitored by TLC. The solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 23-2 (22.5 g, yield 74%).

Preparation of compound 8A-321

In a flask containing 1,4-dioxane:water (150mL:50mL), 9-bromo-10-naphthylanthracene (5.73g, 15mmol), compound 23-2 (6.8g, 15mmol), potassium carbonate (6.2g) , 45 mmol) was added, and nitrogen was substituted at room temperature under stirring, and then Pd(PPh ₃ ) ₄ (173 mg, 0.15 mmol) was added. After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved in methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a yellow solid compound 8A-321 (7.5 g, yield 80%). Calculated molecular weight: 629.19, found C/Z: 629.2.

Example B24: Preparation of compound 8A-411

Preparation of compound 24-1

Compound 22-1 (92.5 g, 0.5 mol) and bromoacetone (81.6 g, 0.6 mmol) were added to a flask containing 700 mL of DMF, and heated to 100° C. under stirring to react for 15 hours, followed by TLC Reaction completion was indicated. The temperature was lowered to room temperature, water was added to precipitate a solid, and the solid obtained by filtration was washed with ethanol, dried and subjected to column chromatography to obtain a yellowish-brown solid compound 24-1 (79.2 g, 71%).

Preparation of compound 24-2

In a flask containing 1,4-dioxane / water (600mL / 200mL) p-chlorophenylboronic acid (34.3g, 220mmol), compound 24-1 (44.6g, 200mmol), potassium carbonate (82.8g, 600mmol) After nitrogen was substituted at room temperature under stirring, Pd(PPh ₃ ) ₄ (2.3 g, 0.2 mmol) was added. After completion of the addition, the reaction was stirred at 80° C. for 8 hours, and the reaction endpoint was monitored by TLC. The solid obtained by suction filtration was separated and purified by column chromatography to obtain compound 24-2 (44.9 g, yield 75%).

Preparation of compound 24-3

Compound 24-2 (29.9 g, 100 mmol), boronic acid pinacol ester (38.1 g, 150 mmol), potassium phosphate (41.4 g, 300 mmol) were added to a flask containing 1,4-dioxane (500 mL), and at room temperature After replacing nitrogen under stirring, Pd ₂ (dba) ₃ (1.15 g, 1 mmol) and Sphos (1.23 g, 3 mmol) were added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the reaction endpoint was monitored by TLC. filter with suction and dissolve the solid with methylene chloride; The layers were separated by washing with water, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 24-3 (30.6 g, yield 77%).

Preparation of compound 8A-411

In a flask containing 1,4-dioxane:water (150mL:50mL), 9-(4-biphenyl)-10- bromoanthracene (6.12g, 15mmol), compound 24-3 (5.86g, 15mmol), carbonic acid Potassium (6.2 g, 45 mmol) was added, and nitrogen was substituted under stirring at room temperature, followed by addition of Pd(PPh ₃ ) ₄ (173 mg, 0.15 mmol). After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a yellow solid compound 8A-411 (7.3 g, yield 82%). Calculated molecular weight: 593.19, found C/Z: 593.2.

Example B25: Preparation of compound 9A-121

Preparation of compound 25-1

2,4-dichlorothieno[3,2-d]pyrimidine (510 g, 2.5 mol) was dissolved in a flask containing 10 L of ethanol, and hydrazine hydrate (470 g, 7.5 mol, 80% aqueous solution) was added at 5 ° C. It was dripped under stirring, and the temperature was maintained below 10 degreeC during the dripping process. After completion of the dropwise addition, the temperature was naturally raised to room temperature to react for 1 hour, and the precipitated solid was filtered with suction, washed with water and ethanol, respectively, and dried to obtain a white solid compound 25-1 (365 g, 73%).

Preparation of compound 25-2

Compound 25-1 (365 g, 1.825 mol) was added to a flask containing 4 L of ethanol, and benzaldehyde (251 g, 2.37 mol) was added dropwise at room temperature while stirring, and after completion of the dropping, stirring was continued for 30 minutes, followed by filtration. The obtained solid was washed with ethanol and n-hexane, respectively, and dried to obtain a yellow solid compound 25-2 (347g, 66%).

Preparation of compound 25-3

Compound 25-2 (347 g, 1.2 mol) was added to a flask containing 7 L of ethanol, and iodobenzene diacetate (465 g, 1.44 mol) was added portionwise under stirring at room temperature, after completion of the addition, continued for 1.5 hours After the reaction was stirred, TLC showed that the reaction was complete. The precipitated solid was filtered with suction, washed with n-hexane, and dried to obtain a pale yellowish-brown solid compound 25-3 (240 g, 70%).

Preparation of compound 9A-121

In a flask containing 1,4-dioxane: water (150 mL: 50 mL), compound 25-3 (5.1 g, 18 mmol), compound 1-4 (10 g, 18 mmol), potassium carbonate (7.45 g, 54 mmol) were added, After nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (208 mg, 0.18 mmol) was added. After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The precipitated yellow solid was filtered, dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography (eluent: methylene chloride) to obtain a yellow solid compound 9A-121 (9.1 g, yield 74%). Calculated molecular weight: 680.20, found C/Z: 680.2.

Example B26: Preparation of compound 9A-321

Preparation of compound 26-1

In a flask containing 1,4-dioxane/water (450 mL/150 mL), p-chlorophenylboronic acid (15.6 g, 0.1 mol), compound 25-3 (28.6 g, 0.1 mmol), potassium carbonate (41.4 g, 0.3 mol), and after nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (1.15 g, 1 mmol) was added. After completion of the addition, the reaction was stirred at 80° C. for 12 hours, and the end point of the reaction was monitored by TLC. The solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 26-1 (24.6 g, yield 68%).

Preparation of compound 26-2

Compound 26-1 (24.6 g, 0.067 mol), boronic acid pinacol ester (25.4 g, 0.1 mol), potassium phosphate (27.7 g, 0.2 mol) was added to a flask containing 1,4-dioxane (500 mL) and , After nitrogen substitution at room temperature under stirring, Pd ₂ (dba) ₃ (641 mg, 0.7 mmol) and Sphos (861 mg, 2.1 mmol) were added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the reaction endpoint was monitored by TLC. The solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 26-2 (21.3 g, yield 70%).

Preparation of compound 9A-321

In a flask containing 1,4-dioxane:water (150mL:50mL), 9-bromo-10-naphthylanthracene (5.73g, 15mmol), compound 26-2 (6.8g, 15mmol), potassium carbonate (6.2g) , 45 mmol) was added, and nitrogen was substituted at room temperature under stirring, and then Pd(PPh ₃ ) ₄ (173 mg, 0.15 mmol) was added. After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved in methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a yellow solid compound 9A-321 (8.5 g, yield 83%). Calculated molecular weight: 630.19, found C/Z: 630.2.

Example B27: Preparation of compound 9A-401

Preparation of compound 27-1

Compound 25-2 (20.2 g, 0.1 mol) and trimethylorthoformate (150 ml as a solvent) were added to a flask, and the reaction was heated to reflux under stirring for 3 hours, and the reaction endpoint was monitored by TLC. The solvent was removed by rotary evaporation under reduced pressure, washed by heating with ethanol, filtered with suction, and dried to obtain compound 27-1 (16.8 g, yield 80%).

Preparation of compound 27-2

In a flask containing 1,4-dioxane / water (300mL / 100mL) p-chlorophenylboronic acid (13.7g, 88mmol), compound 27-1 (16.8g, 80mmol), potassium carbonate (33.1g, 240mmol) After nitrogen was substituted at room temperature under stirring, Pd(PPh ₃ ) ₄ (924 mg, 0.8 mmol) was added. After completion of the addition, the reaction was stirred at 80° C. for 8 hours, and the reaction endpoint was monitored by TLC. filter with suction and dissolve the solid with methylene chloride; The layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 27-2 (16 g, yield 70%).

Preparation of compound 27-3

Compound 27-2 (16g, 56mmol), boronic acid pinacol ester (21.3g, 84mmol), potassium phosphate (23.2g, 168mmol) were added to a flask containing 1,4-dioxane (500mL), and stirred at room temperature. After replacing the nitrogen under the Pd ₂ (dba) ₃ (550mg, 0.6mmol) and Sphos (738mg, 1.8mmol) were added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the reaction endpoint was monitored by TLC. filter with suction and dissolve the solid with methylene chloride; The layers were separated by washing with water, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 27-3 (15.7 g, yield 74%).

Preparation of compound 9A-401

In a flask containing 1,4-dioxane:water (150mL:50mL), 9-(4-biphenyl)-10- bromoanthracene (6.12g, 15mmol), compound 27-3 (5.67g, 15mmol), carbonic acid Potassium (6.2 g, 45 mmol) was added, and nitrogen was substituted under stirring at room temperature, followed by addition of Pd(PPh ₃ ) ₄ (173 mg, 0.15 mmol). After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved in methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a yellow solid compound 9A-401 (7.7 g, yield 88%). Calculated molecular weight: 580.17, found C/Z: 580.2.

Example B28: Preparation of compound 10A-121

Preparation of compound 28-1

2,4-dichlorothieno[3,2-d]pyrimidine (51g, 250mmol) and 28% aqueous ammonia (94g, 750mmol) were added to a flask containing 500mL of ethanol, and the reaction was stirred at room temperature for 48 hours. , the reaction endpoints were monitored by TLC. The precipitated solid was filtered, washed with ethanol, and dried to obtain compound 28-1 (29.6 g, yield 64%).

Preparation of compound 28-2

Compound 28-1 (29.6 g, 0.16 mol) and bromoacetophenone (34.8 g, 0.176 mol) were added to a flask containing 400 mL of DMF, and heated to 100° C. under stirring to react for 20 hours, followed by TLC indicates the completion of the reaction. The temperature was lowered to room temperature, water was added to precipitate a solid, and the solid obtained by filtration was washed with ethanol, dried and subjected to column chromatography to obtain a pale yellowish-brown solid compound 28-2 (32.8 g, 72%).

Preparation of compound 10A-121

In a flask containing 1,4-dioxane: water (150 mL: 50 mL), compound 28-2 (5.1 g, 18 mmol), compound 1-4 (10 g, 18 mmol), potassium carbonate (7.45 g, 54 mmol) were added, After nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (208 mg, 0.18 mmol) was added. After the addition was completed, the reaction was completed by heating to 80° C. under stirring under nitrogen atmosphere for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved in methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a yellow solid compound 10A-121 (9.4 g, yield 77%). Calculated molecular weight: 679.21, found C/Z: 679.2

Example B29: Preparation of compound 10A-321

Preparation of compound 29-1

In a flask containing 1,4-dioxane/water (450 mL/150 mL), p-chlorophenylboronic acid (15.6 g, 0.1 mol), compound 28-2 (28.5 g, 0.1 mmol), potassium carbonate (41.4 g, 0.3 mol), and after nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (1.15 g, 1 mmol) was added. After completion of the addition, the reaction was stirred at 80° C. for 12 hours, and the end point of the reaction was monitored by TLC. The solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 29-1 (24.9 g, yield 69%).

Preparation of compound 29-2

Compound 29-1 (24.9 g, 0.069 mol), boronic acid pinacol ester (25.4 g, 0.1 mol), potassium phosphate (27.7 g, 0.2 mol) was added to a flask containing 1,4-dioxane (500 mL) and , After nitrogen substitution at room temperature under stirring, Pd ₂ (dba) ₃ (641 mg, 0.7 mmol) and Sphos (861 mg, 2.1 mmol) were added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the reaction endpoint was monitored by TLC. The solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 29-2 (23.4 g, yield 75%).

Preparation of compound 10A-321

In a flask containing 1,4-dioxane:water (150mL:50mL), 9-bromo-10-naphthylanthracene (5.73g, 15mmol), compound 29-2 (6.8g, 15mmol), potassium carbonate (6.2g) , 45 mmol) was added, and nitrogen was substituted at room temperature under stirring, and then Pd(PPh ₃ ) ₄ (173 mg, 0.15 mmol) was added. After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved in methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a yellow solid compound 10A-321 (7.6 g, yield 81%). Calculated molecular weight: 629.19, found C/Z: 629.2.

Example B30: Preparation of compound 10A-411

Preparation of compound 30-1

Compound 28-1 (92.5 g, 0.5 mol) and bromoacetone (81.6 g, 0.6 mmol) were added to a flask containing 700 mL of DMF, and heated to 100° C. under stirring to react for 15 hours, followed by TLC Reaction completion was indicated. The temperature was lowered to room temperature, water was added to precipitate a solid, and the solid obtained by filtration was washed with ethanol, dried and subjected to column chromatography to obtain a yellowish-brown solid compound 30-1 (78 g, 70%).

Preparation of compound 30-2

In a flask containing 1,4-dioxane / water (600mL / 200mL) p-chlorophenylboronic acid (34.3g, 220mmol), compound 30-1 (44.6g, 200mmol), potassium carbonate (82.8g, 600mmol) After nitrogen was substituted at room temperature under stirring, Pd(PPh ₃ ) ₄ (2.3 g, 0.2 mmol) was added. After completion of the addition, the reaction was stirred at 80° C. for 8 hours, and the reaction endpoint was monitored by TLC. The solid obtained by suction filtration was separated and purified by column chromatography to obtain compound 30-2 (44.9 g, yield 75%).

Preparation of compound 30-3

Compound 30-2 (29.9 g, 100 mmol), boronic acid pinacol ester (38.1 g, 150 mmol), potassium phosphate (41.4 g, 300 mmol) were added to a flask containing 1,4-dioxane (500 mL), and at room temperature After replacing nitrogen under stirring, Pd ₂ (dba) ₃ (1.15 g, 1 mmol) and Sphos (1.23 g, 3 mmol) were added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the reaction endpoint was monitored by TLC. filter with suction and dissolve the solid with methylene chloride; The layers were separated by washing with water, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography gave compound 30-3 (27.3 g, yield 70%).

Preparation of compound 10A-411

In a flask containing 1,4-dioxane:water (150mL:50mL), 9-(4-biphenyl)-10- bromoanthracene (6.12g, 15mmol), compound 30-3 (5.86g, 15mmol), carbonic acid Potassium (6.2 g, 45 mmol) was added, and nitrogen was substituted under stirring at room temperature, followed by addition of Pd(PPh ₃ ) ₄ (173 mg, 0.15 mmol). After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved in methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography to obtain a yellow solid compound 10A-411 (7.6 g, yield 85%). Calculated molecular weight: 593.19, found C/Z: 593.2.

Synthesis examples of specific compounds of the fourth preferred embodiment of the present application are as follows:

Example D1: Preparation of compound C2

Preparation of compound 1-1

2,4-dichloroquinazoline (500 g, 2.5 mol) was dissolved in a flask containing 10 L of ethanol, and hydrazine hydrate (470 g, 7.5 mol, 80% aqueous solution) was added dropwise under stirring at 5 ° C., and the temperature during the dropping process was kept below 10 °C. After completion of the dropwise addition, the temperature was naturally raised to room temperature to react for 1 hour, and the precipitated solid was filtered off with suction, washed with water and ethanol, respectively, and dried to obtain a white solid compound 1-1 (415 g, 86%).

Preparation of compound 1-2 (reference J. Heterocyclic chem. 27, 497, 1990)

Compound 1-1 (200 g, 1.03 mol) was added to a flask containing 2 L of ethanol, and benzaldehyde (120 g, 1.13 mol) was added dropwise at room temperature under stirring, and after completion of the dropping, stirring was continued for 30 minutes, followed by filtration. The obtained solid was washed with ethanol and n-hexane, respectively, and dried to obtain a yellow solid compound 1-2 (184 g, 63%).

Preparation of compound 1-3

Compound 1-2 (184 g, 652.4 mmol) was added to a flask containing 4 L of ethanol, and iodobenzene diacetate (252 g, 782.9 mmol) was added portionwise under stirring at room temperature, after completion of the addition, continued for 1.5 hours After the reaction was stirred, TLC showed that the reaction was complete. After adding 4L of n-hexane and stirring for 5 minutes, the precipitated solid was suction filtered, washed with n-hexane, and dried to obtain a pale yellowish-brown solid compound 1-3 (130 g, 71%).

Preparation of compound 1-4

In a flask containing 1,4-dioxane (3L), 2-bromo-9,10-bis (B-naphthyl group) anthracene (2-Bromo-9,10-bis (2-naphthalenyl) anthracene, 508 g, 1 mol ), boronic acid pinacol ester (381 g, 1.5 mol), potassium acetate (294 g, 3 mol) were added, and nitrogen was substituted under stirring at room temperature, and then Pd (dppf ₂ )Cl ₂ (7.32 g, 0.01 mol) was added. added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the reaction endpoint was monitored by TLC. The precipitated solid was filtered, washed with water, and dried to obtain compound 1-4 (500.4 g, yield 90%).

Preparation of compound C2

In a flask containing 1,4-dioxane: water (150 mL: 50 mL), compound 1-3 (5 g, 18 mmol), compound 1-4 (10 g, 18 mmol), potassium carbonate (7.45 g, 54 mmol) were added, and then at room temperature After replacing nitrogen under stirring, Pd(PPh ₃ ) ₄ (208 mg, 0.18 mmol) was added. After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography (eluent: methylene chloride) to obtain yellow solid compound C2 (8.5 g, yield 70%). Calculated molecular weight: 674.25, found C/Z: 674.2.

Example D2: Preparation of compound C14

Preparation of compound 2-1

Compound 1-1 (20g, 103mmol) was added to a flask containing 200L of ethanol, and dibenzofuran-2-formaldehyde (24.5g, 125mmol) was added under stirring at room temperature, after completion of the addition, continued for 30 minutes After stirring and reacting, the solid obtained by filtration was washed with ethanol and n-hexane, respectively, and dried to obtain a yellow solid compound 2-1 (25.6 g, 67%).

Preparation of compound 2-2

Compound 2-1 (25.6 g, 69 mmol) was added to a flask containing 200 mL of ethanol, and iodobenzene diacetate (26.7 g, 82.8 mmol) was added in portions under stirring at room temperature. After the addition was completed, for 1.5 hours After the stirring reaction was continued, TLC showed that the reaction was complete. After adding 200 mL of n-hexane and stirring for 5 minutes, the obtained solid was filtered with suction, washed with n-hexane, and dried to obtain a yellowish-brown solid compound 2-2 (17.8 g, 70%).

Preparation of compound C14

Compound 2-2 (6.66 g, 18 mmol), compound 1-4 (10 g, 18 mmol), potassium carbonate (7.45 g, 54 mmol) were added to a flask containing 1,4-dioxane: water (150 mL: 50 mL), After nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (208 mg, 0.18 mmol) was added. After completion of the addition, the reaction was heated to reflux under stirring under nitrogen atmosphere for 12 hours, and TLC indicated completion of the reaction. The obtained yellow solid was filtered, dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography (for Lyse: methylene chloride) to give a yellow solid compound C14 (10 g, yield 73%). Calculated molecular weight: 764.26, found C/Z: 764.3.

Example D3: Preparation of compound C26

Preparation of compound 3-1

2,4-dichloro-7-bromoquinazoline (50 g, 0.181 mol) was dissolved in a flask containing 1 L of ethanol, and hydrazine hydrate (34 g, 0.543 mol, 80% aqueous solution) was added dropwise at 5 ° C. under stirring. , the temperature was maintained below 10 °C during the dropping process. After completion of the dropwise addition, the temperature was naturally raised to room temperature to react for 1 hour, and then the obtained solid was filtered with suction, washed with water and ethanol, respectively, and dried to obtain a pale yellow solid compound 3-1 (39.4 g, 80%).

Preparation of compound 3-2

Compound 3-1 (39.4 g, 0.145 mol) was added to a flask containing 0.4 L of ethanol, and benzaldehyde (18.4 g, 0.174 mol) was added dropwise at room temperature under stirring, and after completion of the dropping, stirring reaction was continued for 30 minutes. Then, the solid obtained by filtration was washed with ethanol and n-hexane, respectively, and dried to obtain a pale yellow solid compound 3-2 (34 g, 65%).

Preparation of compound 3-3

Compound 3-2 (34 g, 94.3 mmol) was added to a flask containing 0.6 L of ethanol, and iodobenzene diacetate (36.4 g, 113.2 mmol) was added in portions under stirring at room temperature, after completion of the addition, 1.5 hours After stirring was continued for a while, TLC showed that the reaction was complete. After adding 0.6 L of n-hexane and stirring for 5 minutes, the obtained solid was filtered with suction, washed with n-hexane, and dried to obtain a pale yellow solid compound 3-3 (23.6 g, 70%).

Preparation of compound 3-4

In a flask containing 1,4-dioxane: water (150 mL: 50 mL), compound 3-3 (6.44 g, 18 mmol), compound 1-4 (10 g, 18 mmol), potassium carbonate (7.45 g, 54 mmol) were added and , after replacing nitrogen under stirring at room temperature, Pd(PPh ₃ ) ₄ (208 mg, 0.18 mmol) was added. After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography (eluent: methylene chloride) to obtain yellow solid compound 3-4 (10.2 g, yield 75%).

Preparation of compound C26

In a flask containing 1,4-dioxane/water (150mL/50mL), phenylboronic acid (1.65g, 13.56mmol), compound 3-4 (10.2g, 13.56mmol), potassium carbonate (5.6g, 40.7mmol) were added After nitrogen was substituted at room temperature under stirring, Pd(PPh ₃ ) ₄ (157 mg, 0.136 mmol) was added. After completion of the addition, the reaction was stirred and refluxed for 8 hours, and the end point of the reaction was monitored by TLC. The precipitated solid was filtered. The liquid layer was separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The crude solids were combined and purified by column chromatography (eluent: methylene chloride) to obtain compound C26 (7.1 g, yield 70%). Calculated molecular weight: 750.28, found C/Z: 750.3.

Example D4: Preparation of compound C32

Preparation of compound 4-1

Compound 1-1 (20 g, 0.103 mol) was added to a flask containing 0.4 L of ethanol, and 4-bromobenzaldehyde (22.8 g, 0.124 mol) was added under stirring at room temperature, after completion of addition, continued for 30 minutes After stirring and reacting, the solid obtained by filtration was washed with ethanol and n-hexane, respectively, and dried to obtain a pale yellow solid compound 4-1 (24.1 g, 65%).

Preparation of compound 4-2

Compound 4-1 (24.1 g, 66.9 mmol) was added to a flask containing 0.4 L of ethanol, and iodobenzene diacetate (225.9 g, 80.3 mmol) was added portionwise under stirring at room temperature, after completion of the addition, 1.5 After stirring and reacting for an hour, TLC showed that the reaction was complete. After adding 0.4 L of n-hexane and stirring for 5 minutes, the obtained solid was filtered with suction, washed with n-hexane, and dried to obtain a pale yellowish-brown solid compound 4-2 (16.8 g, 70%).

Preparation of compound 4-3

In a flask containing 1,4-dioxane: water (150 mL: 50 mL), phenylboronic acid (5.71 g, 46.83 mmol), compound 4-2 (16.8 g, 46.83 mmol), and potassium carbonate (19.4 g, 140.5 mmol) were added. After nitrogen was substituted at room temperature under stirring, Pd(PPh ₃ ) ₄ (541 mg, 0.468 mmol) was added. After completion of the addition, the reaction was stirred and refluxed for 8 hours, and the end point of the reaction was monitored by TLC. The layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography (eluent: petroleum ether: methylene chloride = 5:1 to 3:1) gave compound 4-3 (12.5 g, yield 67%).

Preparation of compound C32

In a flask containing 1,4-dioxane: water (150 mL: 50 mL), compound 4-3 (7.2 g, 18 mmol), compound 1-4 (10 g, 18 mmol), potassium carbonate (7.45 g, 54 mmol) were added, After nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (208 mg, 0.18 mmol) was added. After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography (eluent: methylene chloride) to obtain yellow solid compound C32 (10.8 g, yield 80%). Calculated molecular weight: 750.28, found C/Z: 750.3.

Example D5: Preparation of compound C43

Preparation of compound 5-1

In a flask containing 1,4-dioxane/water (300 mL/100 mL), p-chlorophenylboronic acid (8.36 g, 53.6 mmol), compound 1-3 (15 g, 53.6 mmol), potassium carbonate (22.2 g, 160.8 mmol) ) was added, and nitrogen was substituted at room temperature under stirring, and then Pd(PPh ₃ ) ₄ (619 mg, 0.536 mmol) was added. After completion of the addition, the reaction was stirred for 8 hours, and the reaction endpoint was monitored by TLC. The layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography (eluent: petroleum ether: methylene chloride = 5:1 to 2:1) gave compound 5-1 (14.1 g, yield 74%).

Preparation of compound 5-2

Compound 5-1 (14.1 g, 39.7 mmol), boronic acid pinacol ester (15.1 g, 59.5 mmol), potassium phosphate (25.2 g, 119.1 mmol) were added to a flask containing 1,4-dioxane (300 mL) and , after replacing nitrogen under stirring at room temperature, Pd ₂ (dba) ₃ (364 mg, 0.397 mmol) and Sphos (488 mg, 1.191 mmol) were added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the reaction endpoint was monitored by TLC. The layers were separated by washing with water, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separated and purified by column chromatography (eluent: petroleum ether: methylene chloride = 3:1) and dried to obtain compound 5-2 (15.1 g, yield 85%).

Preparation of compound C43

In a flask containing 1,4-dioxane:water (150mL:50mL), 9-bromo-10-naphthylanthracene (7.64g, 20mmol), compound 5-2 (8.96g, 20mmol), potassium carbonate (8.3g) , 60 mmol) was added, and nitrogen was substituted at room temperature under stirring, and then Pd(PPh ₃ ) ₄ (231 mg, 0.2 mmol) was added. After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography (eluent: methylene chloride) to obtain yellow solid compound C43 (10.2 g, yield 82%). Calculated molecular weight: 624.23, found C/Z: 624.2.

Example D6: Preparation of compound C53

Preparation of compound 6-1

Compound 4-3 (15 g, 37.5 mmol), boronic acid pinacol ester (14.3 g, 56.3 mmol), potassium acetate (11 g, 112.5 mmol) were added to a flask containing 1,4-dioxane (300 mL), and room temperature After replacing nitrogen under stirring, Pd(dppf ₂ )Cl ₂ (275 mg, 0.375 mmol) was added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the end point of the reaction was monitored by TLC. The precipitated solid was filtered and dissolved with methylene chloride, dried over anhydrous sodium sulfate, and column chromatography (eluent: petroleum ether: methylene chloride) = 2:1) and dried to obtain compound 6-1 (14.1 g, yield 84%).

Preparation of compound C53

In a flask containing 1,4-dioxane:water (150mL:50mL), 9-bromo-10-naphthylanthracene (7.64g, 20mmol), compound 6-1 (9g, 20mmol), potassium carbonate (8.3g, 60 mmol) was added, and nitrogen was substituted at room temperature under stirring, and then Pd(PPh ₃ ) ₄ (231 mg, 0.2 mmol) was added. After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography (eluent: methylene chloride) to obtain yellow solid compound C53 (10.7 g, yield 86%). Calculated molecular weight: 624.23, found C/Z: 624.2.

Example D7: Preparation of compound C63

Preparation of compound 7-1

In a flask containing 1,4-dioxane/water (150m/50mL), phenylboronic acid (3.66g, 30mmol), compound 3-3 (10.7g, 30mmol), potassium carbonate (12.4g, 90mmol) were added, After nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (347 mg, 0.3 mmol) was added. After completion of the addition, the reaction was stirred and refluxed for 8 hours, and the end point of the reaction was monitored by TLC. The layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography (eluent: petroleum ether: methylene chloride = 5:1) gave compound 7-1 (7.8 g, yield 65%).

Preparation of compound 7-2

Compound 7-1 (7.8 g, 19.5 mmol), boronic acid pinacol ester (7.44 g, 29.3 mmol), potassium acetate (5.7 g, 58.5 mol) were added to a flask containing 1,4-dioxane (200 mL) and , after replacing nitrogen under stirring at room temperature, Pd(dppf ₂ )Cl ₂ (143mg, 0.195mmol) was added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the reaction endpoint was monitored by TLC. The layers were separated by washing with water, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separated and purified by column chromatography (eluent: petroleum ether: methylene chloride = 3:1), and dried to obtain compound 7-2 (7.7 g, yield 88%).

Preparation of compound C63

In a flask containing 1,4-dioxane:water (150mL:50mL), 9-bromo-10-naphthylanthracene (6.57g, 17.2mmol), compound 6-1 (7.7g, 17.2mmol), potassium carbonate ( 7.1 g, 51.6 mmol) was added, and after nitrogen substitution at room temperature under stirring, Pd(PPh ₃ ) ₄ (200 mg, 0.17 mmol) was added. After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography (eluent: methylene chloride) to obtain yellow solid compound C63 (9.3 g, yield 87%). Calculated molecular weight: 624.23, found C/Z: 624.2.

Example D8: Preparation of compound C75

Preparation of compound 8-1

1,4-dioxane: Phenylboronic acid (3.66g, 30mmol), 2,7-Dibromophenanthrene (2,7-Dibromophenanthrene, 10g, 30mmol), potassium carbonate in a flask containing water (150m/50mL) (12.4 g, 90 mmol) was added, and nitrogen was substituted at room temperature under stirring, followed by addition of Pd(PPh ₃ ) ₄ (347 mg, 0.3 mmol). After completion of the addition, the reaction was stirred and refluxed for 8 hours, and the end point of the reaction was monitored by TLC. The layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography (eluent: petroleum ether: methylene chloride = 10:1) gave compound 8-1 (8.5 g, yield 85%).

Preparation of compound C75

In a flask containing 1,4-dioxane: water (150 mL: 50 mL), compound 8-1 (8.5 g, 25.5 mmol), compound 7-2 (11.4 g, 25.5 mmol), potassium carbonate (10.5 g, 76.5 mmol) was added, and nitrogen was substituted at room temperature under stirring, and then Pd(PPh ₃ ) ₄ (300 mg, 0.26 mmol) was added. After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography (eluent: methylene chloride) to obtain yellow solid compound C75 (12.9 g, yield 88%). Calculated molecular weight: 574.22, found C/Z: 574.2.

Example D9: Preparation of compound C89

Preparation of compound 9-1

Compound 8-1 (9.96 g, 30 mmol), boronic acid pinacol ester (11.43 g, 45 mmol), potassium acetate (8.82 g, 90 mol) were added to a flask containing 1,4-dioxane (200 mL), and at room temperature After replacing nitrogen under stirring, Pd(dppf ₂ )Cl ₂ (220 mg, 0.3 mmol) was added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the reaction endpoint was monitored by TLC. The layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separated and purified by column chromatography (eluent: petroleum ether: methylene chloride = 5:1), and dried to obtain compound 9-1 (9.12 g, yield 80%).

Preparation of compound C89

In a flask containing 1,4-dioxane: water (150 mL: 50 mL), compound 9-1 (9.12 g, 24 mmol), compound 1-3 (6.72 g, 24 mmol), potassium carbonate (9.94 g, 72 mmol) were added and , after replacing nitrogen under stirring at room temperature, Pd(PPh ₃ ) ₄ (277 mg, 0.24 mmol) was added. After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography (eluent: methylene chloride) to obtain yellow solid compound C89 (9.7 g, yield 81%). Calculated molecular weight: 498.18, found C/Z: 498.2.

Example D10: Preparation of compound C94

Preparation of compound 10-1

In a flask containing 1,4-dioxane:water (150mL:50mL), 4-Pyridineboronic acid (3.69g, 30mmol), 2,6-dibromopyrene (2,6-Dibromopyrene, 10.74) g, 30 mmol) and potassium carbonate (12.4 g, 90 mmol) were added, and nitrogen was substituted at room temperature under stirring, followed by addition of Pd(PPh ₃ ) ₄ (347 mg, 0.3 mmol). After completion of the addition, the reaction was stirred and refluxed for 8 hours, and the end point of the reaction was monitored by TLC. The layers were separated, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separation and purification by column chromatography (eluent: methylene chloride) gave compound 10-1 (8.57 g, yield 80%).

Preparation of compound 10-2

10-1 (8.57 g, 24 mmol), boronic acid pinacol ester (9.14 g, 36 mmol), potassium acetate (9.94 g, 72 mol) were added to a flask containing 1,4-dioxane (200 mL), and stirred at room temperature. After replacing nitrogen under the Pd(dppf ₂ )Cl ₂ (176mg, 0.24mmol) was added. After completion of the addition, the reaction was stirred and refluxed for 24 hours, and the reaction endpoint was monitored by TLC. The layers were separated by washing with water, the aqueous phase was extracted with methylene chloride, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Separated and purified by column chromatography (eluent: methylene chloride: methanol = 50: 1) and dried to obtain compound 10-2 (6.81 g, yield 70%).

Preparation of compound C94

In a flask containing 1,4-dioxane: water (150 mL: 50 mL), compound 10-2 (6.81 g, 16.8 mmol), compound 1-3 (4.7 g, 16.8 mmol), potassium carbonate (6.96 g, 50.4 mmol) was added, and nitrogen was substituted under stirring at room temperature, and then Pd(PPh ₃ ) ₄ (196 mg, 0.17 mmol) was added. After completion of the addition, the reaction was performed under nitrogen atmosphere under stirring under stirring under reflux for 12 hours, and then TLC showed that the reaction was complete. The yellow solid obtained by filtration was dissolved with methylene chloride, dried over anhydrous sodium sulfate, and subjected to column chromatography (eluent: methylene chloride: methanol = 30:1) to obtain a yellow solid compound C94 (7.3 g, yield 83%). . Calculated molecular weight: 523.18, found C/Z: 523.2.

Synthesis results for compounds C1 to C97 by mass spectrometry are shown, and the data are presented in Table 3.

Table 3. Synthesis Example compound result data

device embodiment

Device examples of specific compounds of the first preferred embodiment of the present application are as follows:

The evaluation of the OLED device was carried out by applying the following device structures: ITO (120nm) / HI-1 (80nm) / HI-2 (5nm) / HT-1 (10nm) / HT-2 (60nm) / Host : D-1 (97: 3,40 nm) / ET-1: EI-1 (50: 50, 40 nm) / EI-1 (2 nm) / Al (80 nm) (the above abbreviations are ITO anode / hole injection layer ( 1) / hole transporting layer (2) / hole transporting layer (1) / hole transporting layer (2) / light emitting layer / electron transporting layer / electron injection layer / corresponding to Al cathode, hereinafter the abbreviations have the same meaning), the following formula in the device The structural formula of the material used for each functional layer is shown:

All of the organic electroluminescent materials are materials that are commercially available in the art, and those skilled in the art may prepare themselves based on known methods or purchase them commercially.

Device Example 1-1. Using compound 1I-12 as host material

A glass substrate coated with a transparent conductive layer of ITO (120 nm) is sonicated with a commercial detergent, washed in deionized water, ultrasonically degreased with a mixed solvent of acetone: ethanol (volume ratio 1:1), and moisture is completely removed in a clean environment. Bake until removal, wash with ultraviolet and ozone, and bombard the surface with a low energy positive ion beam from Satella (ULVAC);

The glass substrate having the anode is placed in a vacuum chamber, evacuated to 1Х10 ^-5 to 9Х10 ^-3 Pa, and compound HI-1 is vacuum-deposited on the anode layer film to form a hole injection layer 1 having a thickness of 80 nm and; vacuum-depositing compound HI-2 on the hole injection layer (1) to form a hole injection layer (2) having a thickness of 5 nm; vacuum-depositing compound HT-1 on the hole injection layer (2) to form a hole transport layer (1) having a thickness of 10 nm; vacuum-depositing compound HT-2 on the hole transport layer (1) to form a hole transport layer (2) having a thickness of 80 nm; An electroluminescent layer was formed on the hole transport layer (2). The specific operation is as follows: Compound C1 as a light emitting layer host is placed in a unit of a vacuum deposition apparatus, and Compound D-1 as a dopant is placed in another unit of a vacuum deposition apparatus, so that both materials are evaporated simultaneously at different rates. The mass ratio of D-1 to the host material compound 1I-12 is 3:97, and the total thickness of the deposited film is 40 nm; Then, each of the compound ET-1 and the compound LiQ is put into two units of a vacuum deposition apparatus, evaporated at a ratio of 1:1, and deposited with a dopant amount of 50 Wt%, respectively, to form an electron transport layer with a thickness of 40 nm on the light emitting layer . Then, after depositing the compound LiQ as an electron injection layer with a thickness of 2 nm on the electron transport layer, an Al cathode with a thickness of 80 nm was deposited on the electron injection layer through another vacuum deposition apparatus. In this way, an OLED device was manufactured. Before use, all materials used for manufacturing OLED devices were purified through a vacuum sublimation purification apparatus under 10-6 torr.

Device Example 1-2

An organic electroluminescent device was prepared in the same manner as in Example 1-1, except that the host material compound 1I-12 was replaced with compound 1II-12.

Device Example 1-3

An organic electroluminescent device was prepared in the same manner as in Example 1-1, except that the host material compound 1I-12 was replaced with compound 1II-63.

Device Examples 1-4

An organic electroluminescent device was prepared in the same manner as in Example 1-1, except that the host material compound 1I-12 was replaced with compound 1II-327.

Device Examples 1-5

An organic electroluminescent device was prepared in the same manner as in Example 1-1, except that the host material compound 1I-12 was replaced with compound 2I-12.

Device Examples 1-6

An organic electroluminescent device was prepared in the same manner as in Example 1-1, except that the host material compound 1I-12 was replaced with compound 2II-63.

Device Examples 1-7

An organic electroluminescent device was manufactured in the same manner as in Example 1-1, except that the host material compound 1I-12 was replaced with compound 2II-327.

Device Examples 1-8

An organic electroluminescent device was prepared in the same manner as in Example 1-1, except that the host material compound 1I-12 was replaced with compound 3I-12.

Device Examples 1-9

An organic electroluminescent device was prepared in the same manner as in Example 1-1, except that the host material compound 1I-12 was replaced with compound 3I-327.

Device Examples 1-10

An organic electroluminescent device was prepared in the same manner as in Example 1-1, except that the host material compound 1I-12 was replaced with compound 3II-327.

Device Examples 1-11

An organic electroluminescent device was manufactured in the same manner as in Example 1-1, except that the host material compound 1I-12 was replaced with compound 4I-12.

Device Examples 1-12

An organic electroluminescent device was prepared in the same manner as in Example 1-1, except that the host material compound 1I-12 was replaced with compound 4II-327.

Device Examples 1-13

An organic electroluminescent device was prepared in the same manner as in Example 1-1, except that the host material compound 1I-12 was replaced with compound 4I-63.

Device Examples 1-14

An organic electroluminescent device was prepared in the same manner as in Example 1-1, except that the host material compound 1I-12 was replaced with compound 5BII-327.

Device Examples 1-15

An organic electroluminescent device was prepared in the same manner as in Example 1-1, except that the host material compound 1I-12 was replaced with compound 6BI-12.

Device Examples 1-16

An organic electroluminescent device was prepared in the same manner as in Example 1-1, except that the host material compound 1I-12 was replaced with compound 6BI-63.

Device Examples 1-17

An organic electroluminescent device was manufactured in the same manner as in Example 1-1, except that the host material compound 1I-12 was replaced with compound 7AII-327.

Device Examples 1-18

An organic electroluminescent device was prepared in the same manner as in Example 1-1, except that the host material compound 1I-12 was replaced with compound 8AI-12.

Device Examples 1-19.

An organic electroluminescent device was prepared in the same manner as in Example 1-1, except that the host material compound 1I-12 was replaced with compound 9AII-327.

Device Examples 1-20

An organic electroluminescent device was prepared in the same manner as in Example 1-1, except that the host material compound 1I-12 was replaced with compound 10AI-12.

Device Comparative Example 1-1

An organic electroluminescent device was manufactured in the same manner as in Example 1-1, except that the host material compound 1I-12 was replaced with the compound CBP.

Device Comparative Example 1-2

An organic electroluminescent device was manufactured in the same manner as in Example 1-1, except that the host material compound 1I-12 was replaced with the standard compound H-1 commercially available in the industry.

At the same luminance, the driving voltage, current efficiency and device lifetime of the organic electroluminescent devices prepared in Device Examples 1-1 to 1-20 and Device Comparative Examples 1-1 to 1-2 were measured using a digital source meter (Digital Source Table). ) and a luminance meter. Specifically, by increasing the voltage at a rate of 0.1V per second, the voltage when the luminance reached 1000cd/m ² , that is, the driving voltage, was measured, and the current density at the time was measured at the same time; The ratio of luminance and current density is the current efficiency; In the lifetime test of T95, a constant current was maintained at 5000 cd/m ² luminance using a luminance meter, and the time for the luminance to drop to 4750 cd/m ² was measured in hours h. The measurement results are shown in Table 4.

Table 4. Device measurement results when the compound of the first preferred embodiment is used as a host material

As can be seen from the figures in Table 4, when other materials are the same in the organic electroluminescent device structure, Device Examples 1-1 to 1-20 are compared with Comparative Example 1-1 of the device as a red light host material of this embodiment. There is a difference that CBP of Device Comparative Example 1-1 was replaced by employing a series of compounds. Since the material itself has both an electron donating group and an electron withdrawing group, it has a relatively good dual carrier transport performance and can effectively expand the recombination region of excitons, so that the annihilation between excitons in the triplet state is significantly reduced. Therefore, it is possible to effectively improve the luminous efficiency, and the data result of the device shows that when the material of this embodiment is used as the light emitting layer host material, the driving voltage of the device is lowered and the current efficiency is relatively high, so that the material of this embodiment is excellent. The carrier transport balance and energy level suitability are shown.

Compared with Device Comparative Example 1-1, the novel organic material of this embodiment is used in an organic electroluminescent device as a host material, reducing the voltage by 50% or more compared to the CBP host material, and at the same time, more improved voltage-current- It has luminescent properties and higher efficiency. In particular, the lifetime of the device was significantly improved compared to that of Comparative Example 1.

Compared with the device Comparative Example 1-2, the new organic material of this embodiment is used as a host material in the organic electroluminescent device, and the voltage is equal to or reduced compared to the case where the host material is H-1, and the efficiency and lifespan are also improved differently.

Device examples of specific compounds of the second preferred embodiment of the present application are as follows:

The evaluation of the OLED device was carried out by applying the following device structures: ITO (120nm) / HI-1 (80nm) / HI-2 (5nm) / HT-1 (10nm) / HT-2 (60nm) / Host : D-1 (97:3,40nm) / ET-1: EI-1 (50:50,40nm) / EI-1 (2nm) / Al (80nm) (the abbreviations are anode / first hole injection layer, respectively) / second hole injection layer / first hole transport layer / second hole transport layer / light emitting layer / electron transport layer / electron injection layer / corresponds to the cathode, the meaning of the above abbreviations is the same), the following formula is used for each functional layer in the device The structural formula of the material being made is:

All of the organic electroluminescent materials are materials that are commercially available in the art, and those skilled in the art may prepare themselves based on known methods or purchase them commercially.

Device Example 2-1. Using compound C1 as host material

A glass substrate coated with a transparent conductive layer of ITO (120 nm) is sonicated with a commercial detergent, washed in deionized water, ultrasonically degreased with a mixed solvent of acetone: ethanol (volume ratio 1:1), and moisture is completely removed in a clean environment. Bake until removal, wash with UV and ozone, and bombard the surface with a low-energy positive ion beam from Satella (ULVAC);

The glass substrate having the anode is placed in a vacuum chamber, evacuated to 1Х10 ^-5 to 9Х10 ^-3 Pa, and compound HI-1 is vacuum-deposited on the anode layer film to form a first hole injection layer having a thickness of 80 nm, ; vacuum-depositing compound HI-2 on the first hole injection layer to form a second hole injection layer having a thickness of 5 nm; vacuum-depositing compound HT-1 on the second hole injection layer to form a first hole transport layer having a thickness of 10 nm; vacuum-depositing compound HT-2 on the first hole transport layer to form a second hole transport layer having a thickness of 80 nm; An electroluminescent layer was formed on the second hole transport layer. The specific operation is as follows: Compound C1 as a light emitting layer host is placed in a unit of a vacuum deposition apparatus, and Compound D-1 as a dopant is placed in another unit of a vacuum deposition apparatus, so that both materials are evaporated simultaneously at different rates. The mass ratio of D-1 to the host material compound C1 is 3:97, and the total thickness of the deposited film is 40 nm; Then, compound ET-1 and compound EI-1 were respectively put in two units of a vacuum deposition apparatus, evaporated at a ratio of 1:1, and deposited with a dopant amount of 50 Wt%, respectively, to form an electron transport layer with a thickness of 40 nm on the light emitting layer. formed. Next, compound EI-1 was deposited on the electron hydrogen layer as an electron injection layer with a thickness of 2 nm, and then an Al cathode with a thickness of 80 nm was deposited on the electron injection layer through another vacuum deposition apparatus. In this way, an OLED device was manufactured. Before use, all materials used for manufacturing OLED devices were purified through a vacuum sublimation purification apparatus under 10 ^-6 torr.

Device Example 2-2

An organic electroluminescent device was manufactured in the same manner as in Example 2-1, except that the host material compound C1 was replaced with the compound C2.

Device Example 2-3

An organic electroluminescent device was prepared in the same manner as in Example 2-1, except that the host material compound C1 was replaced with the compound C12.

Device Example 2-4

An organic electroluminescent device was prepared in the same manner as in Example 2-1, except that the host material compound C1 was replaced with the compound C25.

Device Example 2-5

An organic electroluminescent device was manufactured in the same manner as in Example 2-1, except that the host material compound C1 was replaced with the compound C29.

Device Example 2-6

An organic electroluminescent device was prepared in the same manner as in Example 2-1, except that the host material compound C1 was replaced with the compound C32.

Device Example 2-7

An organic electroluminescent device was manufactured in the same manner as in Example 2-1, except that the host material compound C1 was replaced with the compound C33.

Device Examples 2-8

An organic electroluminescent device was prepared in the same manner as in Example 2-1, except that the host material compound C1 was replaced with the compound C36.

Device Examples 2-9

An organic electroluminescent device was manufactured in the same manner as in Example 2-1, except that the host material compound C1 was replaced with the compound C55.

Device Example 2-10

An organic electroluminescent device was prepared in the same manner as in Example 2-1, except that the host material compound C1 was replaced with the compound C61.

Device Comparative Example 2-1

An organic electroluminescent device was manufactured in the same manner as in Example 2-1, except that the host material compound C1 was replaced with the compound CBP.

Device Comparative Example 2-2

An organic electroluminescent device was manufactured in the same manner as in Example 2-1, except that the host material compound C1 was replaced with compound H-1.

Table 5. Device measurement results when the compound of the second preferred embodiment is used as a host material

As can be seen from the figures in Table 5, when other materials are the same in the structure of the organic electroluminescent device, Device Examples 2-1 to 2-10 are compared with Comparative Example 2-1 of the device as a red light host material of this embodiment. There is a difference that CBP of Device Comparative Example 2-1 was replaced by employing a series of compounds. Since the material itself has both an electron donating group and an electron withdrawing group, it has a relatively good dual carrier transport performance and can effectively expand the recombination region of excitons, so that the annihilation between excitons in the triplet state is significantly reduced. Therefore, the light emitting efficiency can be effectively improved, and the data result of the device shows that when the material of this embodiment is used as the light emitting layer host material, the driving voltage of the device is lowered and the device exhibits relatively high current efficiency, so that the material of this embodiment is excellent. The carrier transport balance and energy level suitability are shown.

Compared with Device Comparative Example 2-1, the novel organic material of this embodiment is used in an organic electroluminescent device as a host material, reducing the voltage by 50% or more compared to the CBP host material, and at the same time, more improved voltage-current- It has luminescent properties and higher efficiency. In particular, the lifetime of the device was significantly improved compared to that of Comparative Example 1.

Compared with the device Comparative Example 2-2, the new organic material of this embodiment is used as a host material in the organic electroluminescent device, and the voltage is equal to or reduced compared to the case where the host material is H-1, and the efficiency and lifespan are also improved differently.

Device examples of specific compounds of the third preferred embodiment of the present application are as follows:

The evaluation of the OLED device was carried out by applying the following device structure: ITO / HAT / HIL / HTL / EML / ETL / LiF / Al (the abbreviation is ITO anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / Electron injection layer / Corresponds to the cathodes of LiF and Al, and the abbreviations have the same meaning below), and the following formula shows the structural formula of the material used for each functional layer in the device (all materials were purchased from J&K Scientific). Purity > 99.9%):

Device Example 3-1: Using the compound of the present invention as an electron transport material

A glass substrate coated with a transparent conductive layer of ITO (150 nm) is sonicated with a commercial detergent, washed in deionized water, ultrasonically degreased with a mixed solvent of acetone: ethanol (volume ratio 1:1), and moisture is completely removed in a clean environment. Bake until removed, wash with UV and ozone, and bombard the surface with a low-energy positive ion beam;

putting the glass substrate having the anode into a vacuum chamber, evacuating the vacuum to 1Х10 ^-5 to 9Х10 ^-3 Pa, and vacuum-depositing HAT on the anode layer film to form a first hole injection layer having a thickness of 10 nm; 2-TNATA [4,4',4"-tris(N,N-(2-naphthyl group)-phenylamine group)triphenylamine] was vacuum-deposited on the first hole injection layer to form second holes having a thickness of 60 nm forming an injection layer: vacuum-depositing compound NPB on the second hole injection layer at a deposition rate of 0.1 nm/s to form a hole transport layer having a thickness of 20 nm;

An electroluminescent layer was formed on the hole transport layer, and the specific operation was as follows: Zn(Bzp) ₂ as a light emitting layer host was placed in one unit of a vacuum deposition apparatus, and (piq) ₂ Ir(acac)[bis-(1) as a dopant -Phenylisoquinoline group) Acetylacetoneiridium (III)] is placed in the other unit of the vacuum vapor deposition apparatus to evaporate both materials simultaneously at unequal rates. The concentration of (piq) ₂ Ir(acac) was 4%, and the total thickness of the deposited film was 30 nm;

On the light emitting layer, the compound 1-121 of the present invention was vacuum-deposited at a deposition rate of 0.1 nm/s to form an electron transport layer having a thickness of 20 nm;

On the electron transport layer, 0.5 nm LiF was vacuum-deposited as an electron injection layer, and an Al layer with a thickness of 150 nm was used as a cathode of the device.

Device Example 3-2. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 1-124.

Device Example 3-3. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 1-321.

Device Example 3-4. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 2-121.

Device Example 3-5. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 2-114.

Device Example 3-6. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 2-411.

Device Example 3-7. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 3-121.

Device Example 3-8. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 3-321.

Device Example 3-9. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that Compound 1-121 was replaced with 3-401.

Device Example 3-10. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 4-121.

Device Example 3-11. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 4-321.

Device Example 3-12. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 4-411.

Device Example 3-13. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 5B-121.

Device Example 3-14. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 5B-321.

Device Examples 3-15. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 5B-401.

Device Examples 3-16. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 6B-121.

Device Example 3-17. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 6B-321.

Device Example 3-18. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 6B-411.

Device Example 3-19. I used the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 7A-121.

Device Examples 3-20. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 7A-321.

Device Example 3-21. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 7A-401.

Device Example 3-22. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 8A-121.

Device Example 3-23. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 8A-321.

Device Example 3-24. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 8A-411.

Device Examples 3-25. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 9A-121.

Device Example 3-26. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 9A-321.

Device Example 3-27. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 9A-401.

Device Example 3-28. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 10A-121.

Device Example 3-29. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 10A-321.

Device Examples 3-30. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that compound 1-121 was replaced with 10A-411.

Device Comparative Example 3-1. Using Bphen as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 3-1, except that Compound 1-121 was replaced with Bphen.

Device Comparative Example 3-2. LG201:LiQ as electron transport material

An organic electroluminescent device was manufactured in the same manner as in Example 3-1, except that Compound 1-121 was replaced with 1:1 LG201:LiQ and a method of depositing two raw materials together was implemented.

At the same luminance, the driving voltage and current efficiency of the organic electroluminescent devices prepared in Device Examples 3-1 to 3-30 and Device Comparative Examples 3-1 to 3-2 were measured using a Keithley 2602 digital source meter luminance meter (Beijing Normal University). Photoelectric Instrument Factory) was used, and the results are shown in Table 6.

Table 6. Measurements of devices when the compound of the third preferred embodiment is used as an electron transport material

As can be seen from Table 6, when other materials are the same in the organic electroluminescent device structure, Device Examples 3-1 to 3-30 are compared with Device Comparative Example 3-1, a series of There is a difference in that the Bphen of Device Comparative Example 3-1 was replaced by employing a compound. Since the compound of the present invention uses a pyrimidine (derivative) triazole (imidazole) system that is more deficient in electrons, electron injection is more efficient, and at the same time, good electron mobility performance makes electron transport easier Thus, hole transport and balance can be realized more efficiently. Accordingly, the driving voltage of the device is effectively lowered, the current efficiency is improved, and the luminous efficiency of the light emitting device is improved under the same device structure.

When other materials are the same in the structure of the organic electroluminescent device, device Examples 3-1 to 3-30 are compared with Device Comparative Example 3-2, employing a series of compounds of this embodiment as an electron transporting material, The difference is that the combination of LG201 and LiQ, which is a commercialized electron transport material of 3-2, was replaced, and the voltage was lowered and the efficiency was slightly improved. However, compared to LG201, which must be used in combination with LiQ, which is relatively sensitive to water, the compound of the present invention efficiently realizes the effect of injecting electrons from the cathode into the light emitting layer even when LiQ is not used, thereby reducing the complexity of the process and at the same time Relatively high electron mobility is also advantageous in improving luminous efficiency and lowering the driving voltage. The above results indicate that the novel organic material of the present invention is an organic light emitting functional material with excellent performance as an electron transport material for organic electroluminescent devices, and is expected to be popularized for commercial use.

Device examples of specific compounds of the fourth preferred embodiment of the present application are as follows:

The evaluation of the OLED device was carried out by applying the following device structure: ITO / HAT / HIL / HTL / EML / ETL / LiF / Al (the abbreviation is ITO anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / Electron injection layer / Corresponds to the cathodes of LiF and Al, and the abbreviations are the same hereafter) .Purity > 99.9%):

Device Example 4-1: Using the compound of the present invention as an electron transport material

A glass substrate coated with a transparent conductive layer of ITO (150 nm) is sonicated with a commercial detergent, washed in deionized water, ultrasonically degreased with a mixed solvent of acetone: ethanol (volume ratio 1:1), and moisture is completely removed in a clean environment. Bake until removed, wash with UV and ozone, and bombard the surface with a low-energy positive ion beam;

putting the glass substrate having the anode into a vacuum chamber, evacuating the vacuum to 1Х10 ^-5 to 9Х10 ^-3 Pa, and vacuum-depositing HAT on the anode layer film to form a first hole injection layer having a thickness of 10 nm; 2-TNATA [4,4',4"-tris(N,N-(2-naphthyl group)-phenylamine group)triphenylamine] was vacuum deposited on the first hole injection layer to form second holes having a thickness of 60 nm forming an injection layer: vacuum-depositing compound NPB on the second hole injection layer at a deposition rate of 0.1 nm/s to form a hole transport layer having a thickness of 20 nm;

An electroluminescent layer was formed on the hole transport layer, and the specific operation was as follows: Zn(Bzp) ₂ as a light emitting layer host was placed in one unit of a vacuum deposition apparatus, and (piq) ₂ Ir(acac)[bis-(1) as a dopant -Phenylisoquinoline group) Acetylacetoneiridium (III)] is placed in the other unit of the vacuum vapor deposition apparatus to evaporate both materials simultaneously at unequal rates. The concentration of (piq) ₂ Ir(acac) was 4%, and the total thickness of the deposited film was 30 nm;

The compound C2 of the present invention was vacuum-deposited on the light emitting layer at a deposition rate of 0.1 nm/s to form an electron transport layer having a thickness of 20 nm;

On the electron transport layer, 0.5 nm LiF was vacuum-deposited as an electron injection layer, and an Al layer with a thickness of 150 nm was used as a cathode of the device.

Device Example 4-2. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 4-1, except that compound C2 was replaced with C14.

Device Example 4-3. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 4-1, except that compound C2 was replaced with C26.

Device Example 4-4. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 4-1, except that compound C2 was replaced with C32.

Device Example 4-5. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 4-1, except that compound C2 was replaced with C43.

Device Example 4-6. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 4-1, except that compound C2 was replaced with C53.

Device Example 4-7. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 4-1, except that compound C2 was replaced with C63.

Device Examples 4-8. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 4-1, except that compound C2 was replaced with C75.

Device Examples 4-9. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 4-1, except that compound C2 was replaced with C89.

Device Examples 4-10. Use of the material of the present invention as an electron transport material

An organic electroluminescent device was prepared in the same manner as in Example 4-1, except that compound C2 was replaced with C94.

Device Comparative Example 4-1. Using Bphen as an electron transport material

An organic electroluminescent device was manufactured in the same manner as in Example 4-1, except that compound C2 was replaced with Bphen.

Device Comparative Example 4-2. LG201:QLi as electron transport material

An organic electroluminescent device was manufactured in the same manner as in Example 4-1, except that compound C2 was replaced with 1:1 LG201:QLi and the two raw materials were deposited together.

At the same luminance, the driving voltage and current efficiency of the organic electroluminescent devices prepared in Device Examples 4-1 to 4-10 and Device Comparative Examples 4-1 to 4-2 were measured using a Keithley 2602 digital source meter luminance meter (Beijing Normal University). Photoelectric Instrument Factory), and the results are shown in Table 7.

Table 7. Measurement results of devices when the compound of the fourth preferred embodiment is used as an electron transport material

As can be seen from the figures in Table 7, when other materials are the same in the structure of the organic electroluminescent device, Device Examples 4-1 to 4-10 are compared with Comparative Example 4-1 of the device as an electron transport material of this embodiment. The difference is that Bphen in Device Comparative Example 3-1 was replaced by employing a series of compounds. Since the compound of the present invention uses a quinazotriazole system that is more deficient in electrons, electron injection is more efficient, and at the same time, good electron mobility performance makes the transport of electrons easier and more efficient hole transport. and balance can be achieved. Accordingly, the driving voltage of the device is effectively lowered, the current efficiency is improved, and the luminous efficiency of the light emitting device is improved under the same device structure.

Device Examples 4-1 to 4-10 and Device Comparative Example 4-2, when the other materials are the same in the organic electroluminescent device structure, a combination of the vaporized electron transport material LG201 and QLi of Device Comparative Example 4-2 Instead, a series of compounds of this embodiment were used as electron transport materials, and the voltage was basically identical and even lower, and the efficiency was slightly improved. However, compared to LG201, which must be used in combination with QLi, which is relatively sensitive to water, the compound of the present invention efficiently realizes the effect of injecting electrons from the cathode into the light emitting layer even when QLi is not used, thereby reducing the complexity of the process and at the same time Relatively high electron mobility is also advantageous in improving luminous efficiency and lowering the driving voltage. The above results indicate that the novel organic material of the present invention is an organic light emitting functional material with excellent performance as an electron transport material for organic electroluminescent devices, and is expected to be popularized for commercial use.

As mentioned above, although the preferred embodiment of the present invention has been described in detail, the present invention is not limited to the specific content of the embodiment, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical spirit of the present invention. and such simple modifications are all within the protection scope of the present invention.

In addition, it should be noted that each of the specific technical features described in the above specific embodiments may be combined in any suitable manner as long as they do not contradict each other. In order to avoid unnecessary repetition, the present invention is not described separately for various possible combinations.

In addition, as long as the spirit of the present invention is not violated, various implementations of the present invention may be arbitrarily combined, and the content disclosed by the present invention should be regarded as the same.

Claims (15)

A compound represented by the following formula (I) or (II).

In the above formula (I), X is selected from CR ₄ or N;
R ₂ to R ₄ is each independently hydrogen, deuterium, halogen, cyano group, nitro group, hydroxyl group, silanyl group, substituted or unsubstituted C1~ C12 alkyl group, C1~ C12 alkoxy group, substituted or unsubstituted C6~ C60 aryl group or C3~ C60 heteroaryl group, the C6~ C60 aryl group or C3~ C60 heteroaryl group substituent is deuterium, halogen, cyano group, nitro group, hydroxy group, silanyl group, amino group, substituted or Unsubstituted C1~ C12 alkyl group, C1~ C12 alkoxy group, C6~ C30 substituted or unsubstituted aryl group, C10~ C30 substituted or unsubstituted heteroaryl group, C6~ C30 substituted or unsubstituted arylamino group , C3~ C30 is selected from a substituted or unsubstituted heteroarylamino group, and the C6~ C30 substituted or unsubstituted aryl group and the C10~ C30 substituted or unsubstituted heteroaryl group are a phenyl group, a biphenyl group , a terphenyl group, a naphthyl group, and a phenanthryl group;
The quantity of R ₃ is 0-4, and when the quantity of R ₃ is 2 or more, R ₃ is the same or different;
L ₁ and L ₂ are each independently a single bond, -O-, -S-, -NR ^a -, C1-C5 alkylene group, (C1-C3 alkylene group)-O-(C1-C3 alkylene group), C6~ C30 aryl group, C3~ C30 heteroarylene group;
In formula (II),
The dotted line and Cy represent a benzene ring condensed with a pyrimidine ring,
X is N;
R ₂ is an unsubstituted or methyl group-substituted phenyl group; biphenyl group; a pyridyl group substituted with a phenyl group; a phenanthrenyl group substituted with a phenyl group; or a pyrene group substituted with a pyridyl group;
R ₃ is hydrogen; Or a phenanthrenyl group substituted with a phenyl group,
The quantity of R ₃ is 0-4, and when the quantity of R ₃ is 2 or more, R ₃ is the same or different;
L ₁ is a single bond or a phenylene group, L ₂ is a single bond,

In the above formulas (I) and (II), R ₁ is a structure represented by the following formula (III),

L ₃ is a single bond, -O-, -S-, C1 to C5 alkylene group, (C1 to C3 alkylene group)-O-(C1 to C3 alkylene group), C6 to C30 arylene group, C3 to C30 selected from heteroarylene groups; R ₅ and R ₆ are independently H, D, a substituted or unsubstituted C1-C12 alkyl group, a C1-C12 alkoxy group, a halogen, a cyano group, a nitro group, a hydroxyl group, a silanyl group, a C6-C30 substituted or unsubstituted It is selected from an aryl group, a C10~ C30 substituted or unsubstituted heteroaryl group; the quantity of R ₅ and R ₆ is each 0-4, and when the quantity of R ₅ or R ₆ is 2 or more, R ₅ is the same or different, and R ₆ is the same or different; Or R ₅ and R ₆ are independently condensed with a benzene ring connected to each other to form a C9~ C12 aryl group or heteroaryl group, and the formed aryl group or heteroaryl group is independently a substituted or unsubstituted C1~ C12 alkyl group, optionally substituted with 0-5 substituents selected from halogen, cyano group, nitro group, hydroxy group, silanyl group, C6-C30 substituted or unsubstituted aryl group, C3-C30 substituted or unsubstituted heteroaryl group; Y is C(R ₇ ) ₂ , NR ₈ , O, S ; n is 0 or 1, and when n is 0, it indicates that the two carbon atoms connected to Y are directly connected; R ₇ and R ₈ are independently selected from hydrogen, a C1-C5 alkyl group, a phenyl group, a halogen, a cyano group, a nitro group, and a hydroxy group, and two R ₇ are the same or different. According to claim 1, wherein in Formula (I) R ₂ To R ₄ are each independently selected from hydrogen, a C1 to C10 alkyl group, a substituted or unsubstituted C6 to C60 aryl group, or a C3 to C60 heteroaryl group and the substituents of the aryl group or heteroaryl group are deuterium, fluorine, methyl group, methoxy group, cyano group, phenyl group, biphenyl group, naphthyl group, phenanthryl group, pyridine group, furan group, thiophene group, indene group, benzo It is selected from a furan group, a benzothiophene group, a substituted or unsubstituted indole group, a dibenzofuran group, a dibenzothiophene group, a substituted or unsubstituted carbazole group, a benzocarbazole group, and a dibenzocarbazole group, and the indole group and a substituent of the carbazole group is selected from a phenyl group, a biphenyl group, a naphthyl group, and a phenanthryl group, the number of R ₃ is 1, and L ₁ and L ₂ are a single bond. delete The compound of claim 1 , wherein R ₁ is selected from the following groups.

A compound represented by the following formula (II).

Cy is a benzene ring, X is N, R ₁ is represented by the following formula (IV), R ₂ , and R ₃ are each independently hydrogen, deuterium, C1-C12 alkyl group, C1-C12 alkoxy group, halogen, a cyano group, a nitro group, a hydroxyl group, a silanyl group, a C6~ C30 substituted or unsubstituted aryl group, and a C3~ C30 substituted or unsubstituted heteroaryl group;

R ₅ and R ₆ are independently H, D, C1-C12 alkyl group, C1-C12 alkoxy group, halogen, cyano group, nitro group, hydroxyl group, silanyl group, amino group, C6-C30 substituted or unsubstituted arylamino group, It is selected from a C3~ C30 substituted or unsubstituted heteroarylamine group, a C6~ C30 substituted or unsubstituted aryl group, and a C3~ C30 substituted or unsubstituted heteroaryl group; the quantity of R ₅ and R ₆ is 0-4, respectively, and when the quantity of R ₅ or R ₆ is 2 or more, R ₅ is the same or different, and R ₆ is the same or different; or R ₅ and R ₆ are independently condensed with a benzene ring connected to each other to form a C9~ C30 aryl group or heteroaryl group, and the formed aryl group or heteroaryl group is independently a C1~ C12 alkyl group, halogen, cyano group, optionally substituted with 0-5 substituents selected from a nitro group, a hydroxyl group, a silanyl group, a C6~ C30 substituted or unsubstituted aryl group, and a C3~ C30 substituted or unsubstituted heteroaryl group; Y is C(R ₇ ) ₂ , NR ₈ , O, S; n is 0 or 1, and when n is 0, it indicates that the two carbon atoms connected to Y are directly connected; R ₇ and R ₈ are independently selected from hydrogen, a C1-C5 alkyl group, a phenyl group, a halogen, a cyano group, a nitro group, and a hydroxy group, and two R ₇ are the same or different. The method of claim 5, wherein R ₅ and R ₆ are independently hydrogen, a substituted or unsubstituted C1-C4 alkyl group, a phenyl group, a naphthyl group, a furan group, a thiophene group, a pyrrole group, a pyridine group, a biphenyl group, a terphenyl group , naphthyl group, anthryl group, phenanthryl group, indene group, fluorenyl group and derivatives thereof, fluoranthenyl group, triphenylene group, pyrene group, perylene group, chrysene group, tetracene group, triarylamine group, 9, 9-dimethylfluorenyl group, distyrenylphenyl, benzofluorenyl group, indenofluorenyl group or indene group, or a dibenzoheteroaryl group as shown in formula (V); or R ₁ and R ₂ are independently condensed with a benzene ring connected thereto to form a naphthyl group, an anthryl group, a phenanthryl group, an indene group, a fluorenyl group, a benzofuran group, a benzothiophene group, a benzopyridine group, and a benzopyr group. Forming a roll group, or a dibenzoheteroaryl group as shown in formula (V),

The linking moiety is located on N or the benzene ring in formula (V), and when the linking moiety is positioned on the benzene ring of (V), N is connected to each other with H, a phenyl group and a C1-C4 alkyl group; X' is C(R ₉ ) ₂ , NR ₁₀ , O, S; m is 0 or 1, and when m is 0, it indicates that the two carbon atoms linked to X' are directly linked; R _a , R _b , R ₉ and R ₁₀ are independently selected from hydrogen, a C1-C5 alkyl group, a C1-C5 alkoxy group, a halogen, a cyano group, a nitro group, a hydroxyl group, and a phenyl group, and two R ₉ are the same or different and; X' is the same as or different from Y. The compound according to claim 5, wherein -L ₂ -R ₂ is one selected from the following formula.

delete delete delete delete delete delete delete A first electrode, a second electrode, and one or more organic layers positioned between the first electrode and the second electrode,
The organic layer is an organic electroluminescent device, characterized in that it comprises at least one of the compound of any one of claims 1, 2, and 4 to 7.