CN114685484B

CN114685484B - Organic electroluminescent compound and organic electroluminescent device comprising same

Info

Publication number: CN114685484B
Application number: CN202011597216.2A
Authority: CN
Inventors: 李祥智; 蔡烨; 丁欢达; 魏定纬; 陈志宽
Original assignee: Ningbo Lumilan Advanced Materials Co Ltd
Current assignee: Ningbo Lumilan Advanced Materials Co Ltd
Priority date: 2020-12-28
Filing date: 2020-12-28
Publication date: 2023-09-01
Anticipated expiration: 2040-12-28
Also published as: CN114685484A

Abstract

The invention provides an organic electroluminescent compound and an organic electroluminescent device containing the same, wherein the organic electroluminescent compound has a structure shown in a formula I, and the organic electroluminescent compound is used as a luminescent layer material, a hole transport layer or an electron blocking layer material, so that the luminescent efficiency of the device can be improved, and the service life of the device can be prolonged.

Description

Organic electroluminescent compound and organic electroluminescent device comprising same

Technical Field

The invention belongs to the technical field of organic electroluminescent materials, and relates to an organic electroluminescent compound and an organic electroluminescent device containing the same.

Background

The organic electroluminescent display (OLED) has the advantages of self-luminescence, low voltage DC drive, full solidification, wide viewing angle, light weight, simple composition and process, and the like, compared with the liquid crystal display, the organic electroluminescent display does not need a backlight source, has large viewing angle and low power, has response speed which can be 1000 times that of the liquid crystal display, and has lower manufacturing cost than that of the liquid crystal display with the same resolution, so the organic electroluminescent device has wide application prospect.

With the continuous advancement of OLED technology in illumination and display fields, people pay more attention to research on efficient organic materials affecting the performance of OLED devices, and an organic electroluminescent device with good efficiency and long service life is usually the result of optimized collocation of device structures and various organic materials. In the most common OLED device structures, the following classes of organic materials are typically included: a hole injection material, a hole transport material, an electron transport material, a light emitting material (dye or doped guest material) of each color, a corresponding host material, and the like. Phosphorescent host materials currently in use tend to have a single carrier transport capability, such as hole-type transport hosts as well as electron-type transport hosts. The single carrier transport capability can cause electron and hole mismatch in the light emitting layer, resulting in severe efficiency roll-off and reduced lifetime.

However, the materials used for organic electroluminescent devices have room for improvement, and organic electroluminescent materials having better light-emitting properties, longer lifetime and higher efficiency have been desired in the industry. At present, in the use process of a phosphorescence main body, the problem of unbalance of carriers of a single main body material is solved through research of the main body material, but the performance is not satisfactory, and a new luminescent main body material still needs to be developed.

Disclosure of Invention

In view of the shortcomings of the prior art, the invention aims to provide an organic electroluminescent compound and an organic electroluminescent device comprising the same.

To achieve the purpose, the invention adopts the following technical scheme:

in one aspect, the present invention provides an organic electroluminescent compound having a structure according to formula I:

wherein X is ¹ 、X ² Each independently is N or CR ²⁵ ，

R ¹ 、R ² 、R ²⁵ Each independently selected from the group consisting of hydrogen, deuterium, tritium, cyano, nitro, halogen, substituted or unsubstituted C1-C10 straight chain alkyl, substituted or unsubstituted C3-C10 branched alkyl, substituted or unsubstituted C1-C10 cycloalkyl, substituted or unsubstituted C2-C10 alkylene, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl,The dotted line represents the attachment site of the group,

substituent R ¹ 、R ² 2 substituents which are not linked to each other or are adjacent or spaced apart by 1 to 3 carbon atoms are linked to form a ring A by chemical bonds,

the ring A is selected from a substituted or unsubstituted C5-C30 unsaturated carbocycle, a substituted or unsubstituted C3-C30 unsaturated heteroaryl ring,

n, m is selected from integers from 0 to 5 (e.g., 0, 1, 2, 3, 4, or 5);

d is selected from integers from 0-3 (e.g., 0, 1, 2, 3); preferably an integer of 1 to 2;

R ²³ 、R ²⁴ a C1-C10 linear alkyl group which is substituted or unsubstituted, a C3-C10 branched alkyl group which is substituted or unsubstituted, a C6-C15 aryl group which is substituted or unsubstituted, a C3-C15 heteroaryl group which is substituted or unsubstituted,

L、L ¹ each independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene, a substituted or unsubstituted C3-C30 heteroarylene,

ar is selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, -NAr ¹ Ar ² ，

Ar ¹ 、Ar ² Each independently selected from substituted or unsubstituted C6-C30 aryl, substitutedOr unsubstituted C3-C30 heteroaryl.

Preferably, the organic electroluminescent compound is a compound having a structure represented by the following formula II or III:

wherein R is ¹ 、R ² The definitions of L and Ar and m and n are the same as in formula I.

Preferably, the organic electroluminescent compound has a structure represented by the following formula IV or formula V:

wherein R is ¹ 、R ² L and Ar and m and n are as defined for formula I, T ^a 、T ^b Each independently selected from single bond, O, S, -NR ²⁷ or-CR ²⁸ R ²⁹ ，

R ²⁷ Selected from the group consisting of substituted or unsubstituted C1-C4 straight or branched alkyl groups, substituted or unsubstituted C6-C60 aryl groups, substituted or unsubstituted C3-C60 heteroaryl groups,

R ²⁸ -R ²⁹ Each independently selected from the group consisting of substituted or unsubstituted C1-C4 straight or branched alkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl,

R ²⁸ -R ²⁹ independently or linked to form a ring M selected from substituted or unsubstituted fluorene rings,

R ²² selected from deuterium, tritium, cyano, nitro, halogen, substituted or unsubstituted C1-C10 straight chain alkyl, substituted or unsubstituted C3-C10 branched alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl,The dotted line represents the attachment site of the group; k is an integer from 0 to 4 (e.g., 0, 1, 2, 3, or 4);

R ²² independently or adjacent to each other, form a ring F;

preferably, ring F is a benzene ring;

preferably, at least one of Ta and Tb is a single bond; more preferably, one of Ta and Tb is a single bond;

preferably Ar, R ²⁷ Independently selected from any one of the following groups

Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Y ⁷ 、Y ⁸ Each independently selected from N or C-R ^Y ；

T ¹ Selected from O, S, N-R ^T1 Or CR (CR) ^T2 R ^T3 ；

R ^Y 、R ^T1 、R ^T2 、R ^T3 、R ³ 、R ⁴ 、R ⁵ 、R ⁶ 、R ⁷ 、R ⁸ Each independently selected from hydrogen, deuterium, tritium, cyano, nitro, halogen, substituted or unsubstituted C1-C4 straight or branched alkyl, substituted or unsubstituted C1-C4 straight or branched alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;

Substituent R ^Y At least 2 substituents which are not linked to each other or adjacent to each other are linked by a chemical bond to form a ring B;

R ⁵ 、R ⁶ 、R ⁷ 、R ⁸ at least 2 substituents which are not linked to each other or adjacent to each other are linked by a chemical bond to form a ring C;

Z ¹ selected from O, S;

Ar ¹ 、Ar ² each independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;

ring B is preferably selected from phenyl, pyridinyl; more preferably from phenyl;

ring C is preferably selected from phenyl, naphthyl, pyridinyl; more preferably a naphthyl group;

preferably Ar, R ²⁷ Independently selected from the group consisting of

R ⁹ -R ²¹ 、R ²⁶ Each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C4 straight or branched alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;

R ¹⁷ -R ²⁰ independently or adjacent to each other, form a ring D;

ring D is preferably selected from benzene rings, naphthalene rings;

R ¹⁵ -R ¹⁶ independently or adjacent to each other, form a ring E;

ring E is preferably a fluorene ring.

Preferably, R ⁹ -R ²¹ 、R ²⁶ 、Ar ¹ 、Ar ² Independently selected from hydrogen, deuterium, halogen, cyano, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, or any one or a combination of at least two of the following groups substituted or unsubstituted by deuterium, halogen, cyano, methyl, ethyl, propyl, isopropyl, butyl, or t-butyl:

In the present invention, when the groups described above contain substituents, each of the substituents is independently selected from deuterium, halogen, cyano, unsubstituted or R ' substituted C1-C4 straight-chain or straight-chain alkyl, unsubstituted or R ' substituted C6-C18 aryl, unsubstituted or R ' substituted C3-C18 heteroaryl, C6-C18 arylamine;

r' is selected from deuterium, halogen or cyano.

Preferably L, L ¹ Each independently selected from the group consisting of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted nitrogenous dibenzofuranyl group, a substituted or unsubstituted nitrogenous dibenzothiophenyl group; the substituted substituent is selected from deuterium, halogen, cyano, C1-C4 straight-chain or branched alkyl.

Preferably, the organic electroluminescent compound is any one of the following compounds 1-1 to 1-200, 2-1 to 2-200 or 3-1 to 3-200:

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the alkyl group of the present invention may be any of straight chain and branched chain, and optionally includes, but is not limited to, methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, and tert-butyl.

Cycloalkyl groups of the present invention include, but are not limited to, cyclopropane, cyclobutane, cyclohexane.

Alkenyl according to the invention means a monovalent substituent derived from a straight-chain or branched unsaturated hydrocarbon having one or more carbon-carbon double bonds and having 2 to 40 carbon atoms. Examples include, but are not limited to, vinyl, allyl, isopropenyl, 2-butenyl, and the like.

Aryl groups according to the invention include monocyclic, polycyclic, fused ring-like aryl groups, which rings may be interrupted by short non-aromatic units (e.g. methylene). The aryl is selected from phenyl, biphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthryl, phenylphenanthryl, anthracenyl, indenyl, triphenylene, pyrenyl, tetracenyl, perylenyl, droyl, fused tetraphenyl, fluoranthryl or spirobifluorenyl.

Heteroaryl groups of the present invention include monocyclic, polycyclic, fused ring species, which rings may be interrupted by short non-aromatic units (e.g., methylene, O, S, N). The heteroaryl is selected from furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, or dihydroacridinyl.

In the present invention, the definition of a group defines a range of carbon atoms, the number of carbon atoms being any integer within the defined range, for example, a C6-C30 aryl group, and the number of carbon atoms representing the aryl group may be any integer within the range of 6-30, for example, 6, 8, 10, 15, 18, 20, 23, 25, 28, 30, or the like.

In another aspect, the present invention provides an organic electroluminescent composition comprising an organic electroluminescent compound as described above.

Preferably, the organic electroluminescent composition further comprises another compound W, which is an electron-transporting compound or a hole-transporting compound.

Preferably, the thermal decomposition temperature difference of the further compound W and the organic electroluminescent compound as described above is less than 20 degrees celsius. More preferably, the thermal decomposition temperature difference of the further compound W and the organic electroluminescent compound as described above is less than 10 degrees celsius; further preferably, the thermal decomposition temperature difference of the further compound W and the organic electroluminescent compound as described above is less than 5 degrees celsius.

Preferably, the hole transport compound is any one of A1, A2, A3;

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Wherein L is ² -L ⁴ Each independently selected from a single bond, a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted C3-C30 heteroaryl,

Ar ³ selected from the group consisting of substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, NR ³² R ³³ ，

d is an integer from 0 to 3, m1 is an integer from 0 to 4, m2 is an integer from 0 to 4, m3 is an integer from 0 to 4 (e.g., 0, 1, 2, 3, or 4), n1 is an integer from 1 to 2, and n2 is an integer from 1 to 2; n3 is an integer of 1 to 2,

L ³ is a single bond, n1 is 1; l (L) ⁴ Is a single bond, n2 is 1,

R ³⁰ -R ³¹ each independently selected from deuterium, halogen, cyano, substituted OR unsubstituted C1-C10 alkyl, substituted OR unsubstituted C1-C10 cycloalkyl, substituted OR unsubstituted C2-C10 alkenyl, substituted OR unsubstituted C6-C30 aryl, substituted OR unsubstituted C3-C30 heteroaryl, OR ³⁷ 、SR ³⁷ 、NR ³² R ³³ ，

n1×m1R ³⁰ Identical or different, n2 m 2R ³¹ The same or a different one of the above,

when m1 is greater than or equal to 2, R ³⁰ Either alone or in adjacent pairs, form a ring,

when m2 is greater than or equal to 2, R ³¹ Either alone or in adjacent pairs, form a ring,

Z ² -Z ³ each independently selected from O, S, NL ⁵ Ar ⁵ 、CR ³⁵ R ³⁶ ，

Ar ⁵ Selected from the group consisting of substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, NR ³² R ³³ ，

L ⁵ Selected from single bond, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl,

R ³⁵ -R ³⁷ each independently is hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl,

R ³⁵ 、R ³⁶ Alone, or joined to form a spiro ring,

R ³² 、R ³³ each independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted triphenylenyl substituted or unsubstituted pyridyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted benzonaphthofuryl, substituted or unsubstituted benzonaphthothienyl, substituted or unsubstituted benzonaphthocarbazolyl,Substituted or unsubstituted benzonaphthofluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted fluorenyl;

preferably Ar ³ 、Ar ⁵ Each independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted fluorenyl, NR ³² R ³³ Or a combination thereof.

Preferably, the hole transporting compound is any one of the following compounds I-1 to I-40:

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preferably, the electron transporting compound is a compound having an electron withdrawing group attached thereto, for example, a compound having a triazinyl group, a pyrimidinyl group, a quinoxalinyl group or a quinazolinyl group attached thereto,

the structural formula of the triazine compound is shown as the following B1:

wherein X is ⁸ -X ¹⁰ Each independently selected from the group consisting of N,

wherein L is ⁶ -L ⁸ Each independently selected from single bond, substituted or unsubstitutedC6-C30 aryl, ar ⁶ -Ar ⁸ Each independently selected from hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl,

adjacent substituents are not connected or connected to form a ring;

the ring is preferably a substituted or unsubstituted C6-C20 aromatic ring, a substituted or unsubstituted C3-C20 aromatic heterocyclic ring;

the ring is more preferably a self-substituted or unsubstituted group of: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, indene ring, indole ring, benzofuran ring, or benzothiophene ring;

when the number of rings is two or more, each ring is the same or different.

Preferably, the pyrimidine compound has the following structural formula:

wherein X is ⁸ -X ¹⁰ Each independently selected from N, CR ³⁸ Wherein two of the two are selected from N,

R ³⁸ Selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl,

L ⁶ -L ⁸ each independently selected from a single bond, a substituted or unsubstituted C6-C30 aryl,

Ar ⁶ -Ar ⁸ each independently selected from hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl,

adjacent substituents are not connected or connected to form a ring;

when the number of rings is two or more, each ring is the same or different.

Preferably, the quinoxaline compound has the following structure:

wherein X is ⁴ And X ⁷ Selected from N, X ⁵ And X ⁶ Selected from CR ³⁸ ，L ⁹ Each independently selected from single bond, substituted or unsubstituted C6-C30 aryl, R ³⁸ Selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl,

Ar ⁹ Each independently selected from hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl,

e is selected from integers of 1-2, and ring E is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 heteroaryl, and adjacent substituents are not connected or connected to form a ring;

when the number of rings is two or more, each ring is the same or different.

Preferably, the quinazoline compound has the following structure B4:

wherein X is ⁵ And X ⁷ Selected from N, X ⁴ And X ⁶ Selected from CR ³⁸ The method comprises the steps of carrying out a first treatment on the surface of the Or X ⁴ And X ⁶ Selected from N, X ⁵ And X ⁷ Selected from CR ³⁸ ；

L ⁹ Each independently selected from single bond, substituted or unsubstituted C6-C30 aryl, R ³⁸ Selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl,

when the number of rings is equal to or greater than two, each ring is the same or different;

preferably, ring E is a substituted or unsubstituted group of: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, indene ring, indole ring, benzofuran ring, or benzothiophene ring;

the definition of the substituent is the same as that above.

Preferably, the electron transporting compound is any one of the following compounds II-5 to II-56.

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In another aspect, the present invention provides an organic electroluminescent device comprising a first electrode, a second electrode, and an organic layer between the first electrode and the second electrode, the organic layer comprising any one or a combination of at least two of the organic electroluminescent compounds as described above.

In the present invention, the organic layer includes a light emitting layer including any one or a combination of at least two of the organic electroluminescent compounds as described above.

Preferably, the light emitting layer comprises a host material and a guest material, and the light emitting layer host material comprises any one or a combination of at least two of the organic electroluminescent compounds as described above or the organic electroluminescent composition as described above.

Preferably, the guest material comprises a phosphorescent dopant.

Preferably, the organic layer further includes any one or a combination of at least two of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

Preferably, the material of the hole transport layer comprises an organic electroluminescent compound as described above;

preferably, the material of the electron blocking layer comprises an organic electroluminescent compound as described above.

Compared with the prior art, the invention has the following beneficial effects:

the organic electroluminescent compound can be used as a luminescent layer material to improve the luminous efficiency of the device and prolong the service life, and the organic electroluminescent device using the organic electroluminescent compound as the luminescent layer material has lower driving voltage, higher current efficiency and prolonged service life.

Drawings

Fig. 1 is a schematic structural diagram of an organic electroluminescent device according to the present invention, wherein 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 is a light emitting layer, 6 is an electron transport layer, 7 is an electron injection layer, and 8 is a cathode.

Detailed Description

The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.

Synthetic examples

Synthesis example 1

In this example, compounds 2-31 were synthesized by the following routes:

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the preparation method comprises the following steps:

(1) Synthesis of intermediate 1-2-31: in a 100 ml three-necked flask, raw material 1 (3.49 g, 0.01 mol), raw material 2 (1.73 g, 0.01 mol), potassium carbonate (1.66 g, 0.012 mol), toluene (40 ml), water (5 ml), tetrakis (triphenylphosphine) palladium (0.58 g, 0.5 mmol) were charged under nitrogen protection, stirred for 6 hours at 100℃and cooled to room temperature after the reaction. Adding water into the reaction system, extracting by ethyl acetate, sequentially adding magnesium sulfate into the obtained extract, drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10, volume ratio) to give intermediate 1-2-31 (1.44 g, 44% yield).

(2) Synthesis of intermediate 2-2-31: a100 ml double neck round bottom flask was taken and put into a stirrer and an upper return tube, after drying, nitrogen was charged, and intermediate 1-2-31 (3.28 g, 0.01 mol), triphenylphosphine (0.02 mol) and 1, 2-dichlorobenzene (40 ml) were added respectively, the reaction was heated at 180℃for 8 hours, cooled to room temperature after completion of the reaction, the reaction system was concentrated, and the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10 (volume ratio)) to obtain intermediate 2-2-31 (2.52 g, yield 85%).

(3) Synthesis of intermediate 3-2-31: taking a 100 ml double-neck round bottom bottle, placing the bottle into a stirrer and an upper return pipe, drying, charging nitrogen, respectively adding 2-2-31 (0.01 mol) of intermediate,(0.01 mol), sodium bicarbonate (0.013 mol), palladium tetraphenylphosphine (0.5 mmol), tetrahydrofuran (60 ml) and water (30 ml), nitrogen was replaced three times. Under the protection of nitrogen, heating to 65 ℃ for reaction for 2 hours, extracting by ethyl acetate after the reaction is finished, and sequentially adding magnesium sulfate into the obtained extract for drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10, volume ratio) to give intermediate 3-2-31 (1.39 g, 43% yield).

(4) Synthesis of intermediate 4-2-31: a100 ml double neck round bottom flask was taken and placed in a stirrer and an upper return tube, after drying, nitrogen was charged, and intermediate 3-2-31 (0.01 mol), (methoxymethyl) triphenylphosphine chloride (0.015 mol) and tetrahydrofuran (40 ml) were added, respectively, and nitrogen was replaced three times. Under the protection of nitrogen, the temperature is reduced to-5 to-10 ℃, after the temperature is reached, a tetrahydrofuran (15 ml) solution of t-BuOK (0.015 mol) is slowly added into the reactor by a constant pressure dropping funnel, and the temperature is always kept below-5 ℃. After the completion of the dropwise addition, the reaction was carried out at this temperature for 20 minutes. Then slowly heating to room temperature, after the reaction liquid reaches the room temperature, continuing to react for 1h, adding water into the system after the reaction is finished, extracting by using dichloromethane, sequentially adding magnesium sulfate into the obtained extract liquid for drying, filtering and spin-drying; the crude product was purified by chromatography (dichloromethane/n-hexane, 1/10, volume ratio) to give intermediate 4-2-31 (2.70 g, 77% yield).

(5) Intermediate 5-2-31: a100 mL two-necked round bottom flask was taken and placed in a stirrer and upper return tube, and after drying, nitrogen was introduced, and intermediate 4-2-31 (0.01 mol) and hexafluoroisopropanol (14 mL) were added, respectively. Under the protection of nitrogen, the temperature is reduced to minus 5 ℃ to minus 10 ℃, after the temperature is reached, the trifluoro methanesulfonic acid (0.02 mol) is slowly added into the mixture by a constant pressure dropping funnel, and the temperature is always kept below minus 5 ℃. After the completion of the dropwise addition, the reaction was carried out at this temperature for 20 minutes. Then slowly heating to room temperature, after the reaction liquid reaches the room temperature, continuing to react for 1h, adding water into the system after the reaction is finished, extracting by using dichloromethane, sequentially adding magnesium sulfate into the obtained extract liquid for drying, filtering and spin-drying; the crude product was purified by chromatography (dichloromethane/n-hexane, 1/10, volume ratio) to give intermediate 5-2-31 (2.84 g, 89% yield).

(6) Synthesis of Compounds 2-31: a100 mL two-necked round bottom flask was taken and put in a stirrer and an upper reflux tube, after drying, nitrogen was charged, 5-2-31 (3.19 g, 0.01 mol) as an intermediate, 3 (3.16 g, 0.01 mol) as a starting material, cesium carbonate (0.015 mol), tris (dibenzylideneacetone) dipalladium (0.5 mmol) and 2-dicyclohexylphosphorus-2 ',4',6' -triisopropylbiphenyl (0.55 mmol) were added respectively, toluene was then added, the mixture was refluxed for 12 hours, cooled to room temperature after the reaction system was filtered, and concentrated, and the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10 (volume ratio)) to give compound 2-31 (4.85 g, yield 81%).

Elemental analysis: theoretical value of C42H25N 5: c,84.12, h,4.20, n,11.68, found: c,84.17, H,4.18, N,11.65, HRMS (ESI) M/z (M+): theoretical value: 599.2110, found: 599.2118.

synthesis example 2

In this example, compounds 2-13 were synthesized by the following routes:

the preparation method comprises the following steps:

(1) 2-13: the synthesis of 2-31 was repeated except that starting material 15 (0.01 mol) was used instead of starting material 3 to give compound 2-13 (5.46 g, 75% yield).

Elemental analysis: theoretical value of C49H28N 8: c,80.75, h,3.87, n,15.38, found: c,80.79, H,3.86, N,15.35, HRMS (ESI) M/z (M+): theoretical value: 728.2437, found: 728.2443.

synthesis example 3

In this example, compounds 1-10 were synthesized by the following routes:

the preparation method comprises the following steps:

(1) Synthesis of intermediate 1-1-10: in a 100 mL three-necked flask, under nitrogen protection, raw material 4 (0.01 mol), palladium acetate (0.5 mmol), NBS (0.011 mol), toluene (40 ml) were added, the reaction was carried out at 110℃for 6 hours, the solvent was removed after the completion of the reaction, and the crude product was subjected to a column chromatography (ethyl acetate/n-hexane, 1/10 (volume ratio)) to obtain intermediate 1-1-10 (2.06 g, yield 80%).

(2) Synthesis of intermediate 2-1-10: in a 100 ml three-necked flask, 1-1-10 (0.01 mol) of intermediate, tetrahydrofuran (40 ml) and the reaction mixture were added, cooled to-78℃and n-butyllithium (0.01 mol) was slowly added, followed by 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborane (0.01 mol) and the reaction mixture was warmed to room temperature, stirred for 10 hours, after the reaction was completed, quenched with water, the product was washed with water and extracted 3 times with ethyl acetate, the organic layer was dried with anhydrous magnesium sulfate, the organic solvent was removed, and the crude product was separated by column chromatography (ethyl acetate/n-hexane, 1/10 (volume ratio)) to obtain intermediate 2-1-10 (yield 52%).

(3) Synthesis of intermediate 3-1-10: in a 100 mL three-necked flask, 2-1-10 (0.01 mol), 1-bromo-2-nitronaphthalene (0.01 mol), tetrakis (triphenylphosphine) palladium (0.5 mmol), tetrabutylammonium bromide (0.5 mmol), sodium carbonate (0.02 mol), toluene 30 mL, ethanol (5 mL), water (5 mL), the system was warmed to 80℃and reacted for 12 hours, after the reaction was completed, the system was cooled to room temperature, water was added, ethyl acetate was extracted, the organic layer was dried with anhydrous magnesium sulfate, the solvent was removed, and the crude product was separated by column chromatography (ethyl acetate/n-hexane, 1/10 (volume ratio)) to obtain 3-1-10 (yield 81%) as an intermediate.

(4) Synthesis of intermediate 4-1-10: the synthesis method was identical to that of intermediate 2-2-31, except that intermediate 3-1-10 (0.01 mol) was used instead of intermediate 1-2-31 to obtain intermediate 4-1-10 (2.48 g, 78% yield).

(5) 1-10: the synthesis of 2-31 was repeated except that intermediate 4-1-10 (0.01 mol) was used instead of intermediate 5-2-31, and starting material 5 (0.01 mol) was used instead of starting material 3 to give compound 1-10 (4.76 g, 89% yield).

Elemental analysis: theoretical value of C38H21N 3O: c,85.22, h,3.95, n,7.85, found: c,85.17, H,3.96, N,7.88, HRMS (ESI) M/z (M+): theoretical value: 535.1685, found: 535.1692.

synthesis example 4

In this example, compounds 1-28 were synthesized by the following routes:

the preparation method comprises the following steps:

(1) 1-28 synthesis: the synthesis of 2-31 was repeated except that intermediate 4-1-10 (0.01 mol) was used instead of intermediate 5-2-31, and starting material 6 (0.01 mol) was used instead of starting material 3 to give compound 1-28 (5.93 g, yield 83%).

Elemental analysis: theoretical value of C52H34N 4: c,87.37, h,4.79, n,7.84, found: c,87.34, H,4.79, N,7.87, HRMS (ESI) M/z (M+): theoretical value: 714.2783, found: 714.2788.

synthesis example 5

In this example, compounds 1-105 were synthesized by the following routes:

the preparation method comprises the following steps:

(1) Synthesis of intermediates 1-1-105: the synthesis of 2-31 was repeated except that intermediate 4-1-10 (0.01 mol) was used instead of intermediate 5-2-31 and bromobenzene (0.01 mol) was used instead of starting material 3 to give intermediate 1-1-105 (3.59 g, 91% yield).

(2) Synthesis of intermediate 2-1-105: a100 ml double neck round bottom flask was taken and placed in a stirrer and an upper return tube, after drying, nitrogen was charged, and intermediate 1-1-105 (3.94 g, 0.01 mol), N-bromosuccinimide (0.015 mol), 50 ml tetrahydrofuran was added, and stirred at room temperature for 12 hours. After the reaction is completed, water is added for quenching. Extracting the reaction system with dichloromethane for three times, sequentially adding magnesium sulfate into the obtained extract, drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/hexane, 1/10) to give intermediate 2-1-105 (1.94 g, 41% yield).

(3) Synthesis of Compounds 1-105: a100 ml two-necked round bottom flask was taken and put in a stirrer and an upper reflux tube, after drying, nitrogen was charged, intermediate 2-1-105 (4.72 g, 0.01 mol), diphenylamine (1.69 g, 0.01 mol), cesium carbonate (0.012 mol), tris (dibenzylideneacetone) dipalladium (Pd 2 (dba) 3,0.5 mmol) and 2-dicyclohexylphosphorus-2 ',4',6' -triisopropylbiphenyl (xphos, 0.55 mmol) were added respectively, then toluene was added, the mixture was refluxed for 24 hours, cooled to room temperature after the reaction system was filtered and concentrated, and the crude product was purified by chromatography (dichloromethane/n-hexane, 1/10 (volume ratio)) to give compound 1-105 (4.04 g, yield 72%).

Elemental analysis: theoretical value of C41H27N 3: c,87.67, h,4.85, n,7.48, found: c,87.63, H,4.87, N,7.50, HRMS (ESI) M/z (M+): theoretical value: 561.2205, found: 561.2213.

synthesis example 6

In this example, compounds 3-12 were synthesized by the following routes:

the preparation method comprises the following steps:

(1) Synthesis of intermediates 1-3-12: in a 100 ml three-necked flask, intermediate 2-2-31 (0.01 mol), o-formaldehyde phenylboronic acid (0.01 mol), potassium carbonate (1.66 g, 0.012 mol), toluene (30 ml), water (6 ml), tetrakis (triphenylphosphine) palladium (0.58 g, 0.5 mmol) were added under nitrogen protection, stirred for 10 hours at 100℃and cooled to room temperature after the reaction. Adding water into the reaction system, extracting by ethyl acetate, sequentially adding magnesium sulfate into the obtained extract, drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to give intermediate 1-3-12 (yield 68%).

(2) Synthesis of intermediate 2-3-12: in a 100 ml three-necked flask, intermediate 2-2-31 (0.01 mol), (methoxymethyl) triphenylphosphine chloride (0.012 mol) and tetrahydrofuran (40 ml) were added, and nitrogen was substituted three times. Under the protection of nitrogen, the temperature is reduced to-5 to-10 ℃, after the temperature is reached, a tetrahydrofuran (15 ml) solution of t-BuOK (0.015 mol) is slowly added into the reactor by a constant pressure dropping funnel, and the temperature is always kept below-5 ℃. After the completion of the dropwise addition, the reaction was carried out at this temperature for 20 minutes. Then slowly heating to room temperature, and after the reaction liquid reaches the room temperature, continuing the reaction for 1h, and stopping the reaction. After the reaction was completed, 20 ml of water was slowly added, 100 ml of ethyl acetate was further added, and then the layers were separated by a separating funnel, the organic layer was left to stand, the aqueous layer was extracted once with dichloromethane, the organic phases were combined, and the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to give intermediate 2-3-12 (2.66 g, yield 76%).

(3) Synthesis of intermediate 3-3-12: in a 100 ml three-necked flask, intermediate 2-3-12 (0.01 mol) and hexafluoroisopropanol (25 ml) were added. Under the protection of nitrogen, the temperature is reduced to minus 5 ℃ to minus 10 ℃, after the temperature is reached, the trifluoro methanesulfonic acid (0.018 mol) is slowly added dropwise by a constant pressure dropping funnel, and the temperature is always kept below minus 5 ℃. After the completion of the dropwise addition, the reaction was carried out at this temperature for 20 minutes. Then slowly heating to room temperature, and after the reaction liquid reaches the room temperature, continuing the reaction for 1h, and stopping the reaction. After the reaction was completed, 20 ml of water was slowly added, extraction was performed three times with ethyl acetate, and the organic phases were combined, and the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to obtain intermediate 3-3-12 (2.51 g, yield 79%).

(4) 3-12, the same as 2-31 except that intermediate 3-3-12 (0.01 mol) was used instead of intermediate 5-2-31, and raw material 7 (0.01 mol) was used instead of raw material 3 to obtain compound 3-12 (6.23 g, yield 78%).

Elemental analysis: theoretical value of C60H37N 3: c,90.09, h,4.66, n,5.25, found: c,90.12, H,4.65, N,5.23, HRMS (ESI) M/z (M+): theoretical value: 799.2987, found: 799.2993.

synthesis example 7

In this example, compounds 3-33 were synthesized by the following routes:

The preparation method comprises the following steps:

(1) Synthesis of intermediates 1-3-33: taking a 100 ml double-neck round bottom bottle, placing the bottle into a stirrer and an upper return pipe, drying, filling nitrogen, adding 3-3-12 (0.01 mol) of an intermediate, and 50 ml of tetrahydrofuran, and stirring for 12 hours at room temperature; after the reaction is completed, adding water for quenching, extracting the reaction system by ethyl acetate for three times, sequentially adding magnesium sulfate into the obtained extract for drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to give intermediate 1-3-33 (yield 47%).

(2) Synthesis of intermediate 2-3-33: 100 ml of a three-necked flask was taken, and placed in a stirrer and an upper return pipe, nitrogen was charged, intermediate 1-3-33 (0.01 mol), phenylboronic acid (0.01 mol), potassium carbonate (0.015 mol), tetrakis (triphenylphosphine) palladium (0.5 mmol), toluene (30 ml), water (5 ml), under the protection of nitrogen, reaction at 60 ℃ for 10 hours, cooling to room temperature after completion of the reaction, adding 3 ml of ice water for quenching, ethyl acetate (3×20 ml) for extraction, the obtained extract was sequentially added with magnesium sulfate for drying, filtration and spin-drying, and the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10 (volume ratio)) to obtain intermediate 2-3-33 (yield 91%).

(3) 3-33: the synthesis of 2-31 was repeated except that intermediate 2-3-33 (0.01 mol) was used instead of intermediate 5-2-31, and starting material 8 (0.01 mol) was used instead of starting material 3 to give compound 3-33 (4.19 g, yield 64%).

Elemental analysis: theoretical value of C45H26N 4S: c,82.54, h,4.00, n,8.56, s,4.90, found: c,82.58, H,3.98, N,8.53, S,4.91, HRMS (ESI) M/z (M+): theoretical value: 654.1878, found: 654.1886.

synthesis example 8

In this example, compounds 3-106 were synthesized by the following routes:

the preparation method comprises the following steps:

(1) Synthesis of intermediates 1-3-106: the synthesis method of intermediate 2-3-33 was different in that pyridine-3-boric acid (0.01 mol) was used instead of phenylboronic acid, to obtain intermediate 1-3-106 (3.04 g, yield 77%).

(2) 3-106 synthesis: the synthesis of 2-31 was repeated except that intermediate 1-3-106 (0.01 mol) was used instead of intermediate 5-2-31, and starting material 9 (0.01 mol) was used instead of starting material 3 to give compound 3-106 (4.07 g, 82% yield).

Elemental analysis: theoretical value of C35H20N 4: c,84.66, h,4.06, n,11.28, found: c,84.61, H,4.08, N,11.31, HRMS (ESI) M/z (M+): theoretical value: 496.1688, found: 496.1679.

Synthesis example 9

In this example, compounds 1-96 were synthesized by the following routes:

the preparation method comprises the following steps:

(1) Synthesis of intermediates 1-1-96: the synthesis of 2-31 was different in that intermediate 4-1-10 (0.01 mol) was used instead of intermediate 5-2-31, and starting material 10 (0.01 mol) was used instead of starting material 3 to give intermediate 1-1-96 (5.31 g, yield 85%).

(2) Synthesis of intermediate 2-1-96: the synthesis of intermediate 1-3-33 was repeated except that intermediate 1-1-96 (0.01 mol) was used instead of intermediate 3-3-12 to obtain intermediate 2-1-96 (4.71 g, 67% yield).

(3) Synthesis of intermediate 3-1-96: the synthesis method of intermediate 2-3-33 was identical, except that intermediate 2-1-96 (0.01 mol) was used instead of intermediate 1-3-33 to give intermediate 3-1-96 (5.69 g, yield 81%).

(4) Synthesis of intermediate 4-1-96: the synthesis of intermediate 2-2-31 was distinguished by the fact that intermediate 3-1-96 (0.01 mol) was used instead of intermediate 1-2-31 to give intermediate 4-1-96 (5.00 g, 70% yield).

(5) Synthesis of Compounds 1-96: the synthesis of 2-31 was repeated except that intermediate 4-1-96 (0.01 mol) was used instead of intermediate 5-2-31 and bromobenzene (0.01 mol) was used instead of starting material 3 to give compound 1-96 (6.24 g, 79% yield).

Elemental analysis: theoretical value of C56H34N 6: c,85.04, h,4.33, n,10.63, found: c,85.09, H,4.31, N,10.60, HRMS (ESI) M/z (M+): theoretical value: 790.2845, found: 790.2853.

Synthesis example 10

In this example, compounds 1-60 were synthesized by the following routes:

the preparation method comprises the following steps:

(1) Synthesis of intermediate 1-1-60: in a 100 ml three-necked flask, intermediate 2-1-96 (0.01 mol), raw material 11 (0.01 mol), tetrakis (triphenylphosphine) palladium (0.58 g, 0.5 mmol), toluene (40 ml), an aqueous solution (5 ml) of potassium carbonate (0.012 mol) was added, heated to 100 degrees centigrade, reacted for 8 hours, after completion of the reaction, quenched with water, extracted three times with dichloromethane, the organic layer was dried over anhydrous magnesium sulfate, the organic solvent was removed, and the crude product was separated by column chromatography (dichloromethane/n-hexane, 1/10 (volume ratio)) to obtain intermediate 1-1-60 (yield 78%).

(2) Synthesis of Compounds 1-60: in a 100 ml three-necked flask, 1-1-60 (0.01 mol), glacial acetic acid (30 ml), silver acetate (0.02 mol), palladium dichloride (2.5 mmol), heating and refluxing were carried out, stirring was carried out for two hours, the solvent was removed under reduced pressure after the reaction was completed, and the crude product was separated by column chromatography (dichloromethane/n-hexane, 1/10 (volume ratio)) to obtain the compound 1-60 (yield 74%).

Elemental analysis: theoretical C50H29N 5S: c,82.06, h,3.99, n,9.57, s,4.38, found: c,82.01, H,4.00, N,9.60, S,4.39, HRMS (ESI) M/z (M+): theoretical value: 731.2144, found: 731.2149.

Synthesis example 11

In this example, compounds 1-82 were synthesized by the following routes:

the preparation method comprises the following steps:

(1) Synthesis of intermediate 1-1-82: the synthesis of 2-31 was carried out in the same manner as that of 2-31 except that intermediate 4-1-10 (0.01 mol) was used instead of intermediate 5-2-31, and raw material 12 (0.01 mol) was used instead of raw material 3, to obtain intermediate 1-1-82 (5.07 g, yield 84%).

(2) Synthesis of intermediate 2-1-82: the synthesis of intermediate 1-3-33 was repeated except that intermediate 1-1-82 (0.01 mol) was used instead of intermediate 3-3-12 to obtain intermediate 2-1-82 (4.29 g, 63% yield).

(3) Synthesis of intermediate 3-1-82: 50 ml of a three-necked flask was taken, and placed in a stirrer and an upper reflux tube, after drying, nitrogen was charged, intermediate 2-1-82 (0.1 mol), bis-pinacolatyldiboron (0.12 mol), dioxane (8 ml), potassium tert-butoxide (0.12 mol), [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride (5 mmol), heating at 70℃for 12 hours, after completion of the reaction, quenching with water, extraction with ethyl acetate (3X 20 ml), and the obtained extract was sequentially added with magnesium sulfate, dried, filtered and spin-dried, and the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10 (volume ratio)) to obtain intermediate 3-1-82 (yield 50%).

(4) Synthesis of intermediate 4-1-82: in a 100 ml three-necked flask, intermediate 2-1-96 (0.01 mol), raw material 11 (0.01 mol), tetrakis (triphenylphosphine) palladium (0.5 mmol), toluene (40 ml), sodium bicarbonate (0.012 mol) in water (5 ml) were added, heated to 100℃and reacted for 8 hours, after the end of the reaction, quenched with water, dichloromethane was extracted three times, the organic layer was dried over anhydrous magnesium sulfate, the organic solvent was removed, and the crude product was separated by column chromatography (dichloromethane/n-hexane, 1/10 (volume ratio)) to obtain intermediate 4-1-82 (4.84 g, yield 64%).

(5) Synthesis of intermediate 5-1-82: in a 100 ml three-necked flask, intermediate 4-1-82 (0.01 mol), anhydrous THF (30 ml) was added under nitrogen blanket, and the reaction was cooled to-78 ℃. N-butyllithium (4.4 ml,0.025 mol) was added with stirring and the reaction was carried out at this temperature for 1 hour. Acetone (0.01 mol) was dissolved in 10ml of anhydrous tetrahydrofuran and added dropwise to the reaction flask. After reacting for 1h at room temperature, adding water into a reaction system, extracting by methylene dichloride, sequentially adding magnesium sulfate into the obtained extract for drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to give intermediate 5-1-82 (yield 81%).

(6) 1-82: in a 100 ml three-necked flask, intermediate 5-1-82 (0.01 mol) was added, and the mixture was refluxed for 4 hours in 30 ml of acetic acid, washed with saturated sodium bicarbonate, and the organic layer was dried over anhydrous magnesium sulfate, the organic solvent was removed, and the crude product was purified with tetrahydrofuran: ethanol=1:4 recrystallisation gives compounds 1-82 (92% yield).

Elemental analysis: theoretical value of C52H29N4D 5: c,86.76, h,5.46, n,7.78, found: c,86.75, H,5.45, N,7.80, HRMS (ESI) M/z (M+): theoretical value: 719.3097, found: 719.3102.

synthesis example 12

In this example, compounds 1-89 were synthesized by the following routes:

the preparation method comprises the following steps:

(1) Synthesis of intermediate 1-1-89: the synthesis of intermediate 1-3-33 was repeated except that intermediate 3-3-12 was replaced with 1-10 (0.01 mol) to give intermediate 1-1-89 (3.80 g, 62% yield).

(2) Synthesis of intermediate 2-1-89: the synthesis of intermediate 3-1-82 was repeated except that intermediate 1-1-89 (0.01 mol) was used instead of intermediate 2-1-82 to give intermediate 2-1-89 (3.57 g, 54% yield).

(3) Synthesis of intermediate 3-1-89: the synthesis of intermediate 4-1-82 was repeated except that intermediate 2-1-89 (0.01 mol) was used instead of intermediate 3-1-82 to give intermediate 3-1-89 (4.20 g, 61% yield).

(4) Synthesis of intermediate 4-1-89: the synthesis of intermediate 5-1-82 was repeated except that intermediate 3-1-89 (0.01 mol) was used instead of intermediate 4-1-82, and starting material 13 was used instead of acetone to give intermediate 4-1-89 (6.01 g, 76% yield).

(5) Synthesis of Compounds 1-89: the synthesis of 1-82 was repeated except that intermediate 4-1-89 (0.01 mol) was used instead of intermediate 5-1-82 to give compound 1-89 (6.80 g, 88% yield).

Elemental analysis: theoretical C57H31N 3O: c,88.47, h,4.04, n,5.43, found: c,88.51, H,4.02, N,5.41, HRMS (ESI) M/z (M+): theoretical value: 773.2467, found: 773.2474.

synthesis example 13

In this example, compounds 1-92 were synthesized by the following routes:

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the preparation method comprises the following steps:

(1) Synthesis of intermediates 1-1-92: the synthesis of 2-31 was repeated except that intermediate 4-1-10 (0.01 mol) was used instead of intermediate 5-2-31, and starting material 14 (0.01 mol) was used instead of starting material 3 to give intermediate 1-1-92 (4.72 g, yield 84%).

(2) Synthesis of intermediate 2-1-92: the synthesis of intermediate 1-3-33 was repeated except that intermediate 1-1-92 (0.01 mol) was used instead of intermediate 3-3-12 to obtain intermediate 2-1-92 (3.65 g, 57% yield).

(3) Synthesis of intermediate 3-1-92: the synthesis of intermediate 3-1-82 was carried out in the same manner as described above except that intermediate 2-1-82 was replaced with intermediate 2-1-92 (0.01 mol) to give intermediate 3-1-92 (4.27, yield 62%).

(4) Synthesis of intermediate 4-1-92: the synthesis of intermediate 4-1-82 was repeated except that intermediate 3-1-82 was replaced with intermediate 3-1-92 (0.01 mol) to give intermediate 4-1-92 (4.37 g, 61% yield).

(5) Synthesis of intermediate 5-1-92: the synthesis of intermediate 5-1-82 was identical, except that intermediate 4-1-82 was replaced with intermediate 4-1-92 (0.01 mol), benzophenone was replaced with acetone, intermediate 5-1-92 (6.64 g, 81% yield).

(6) Synthesis of Compounds 1-92: the synthesis of 1-82 was repeated except that intermediate 5-1-82 (0.01 mol) was used instead of intermediate 5-1-82 to give compound 1-92 (6.82 g, 85% yield).

Elemental analysis: theoretical value of C58H34N 4O: c,86.76, h,4.27, n,6.98, found: c,86.79, H,4.28, N,6.95, HRMS (ESI) M/z (M+): theoretical value: 802.2733, found: 802.2737.

synthesis example 14

In this example, compounds 3-52 were synthesized by the following routes:

the preparation method comprises the following steps:

(1) Synthesis of intermediates 1-3-52: the synthesis of 2-31 was repeated except that intermediate 4-1-10 (0.01 mol) was used instead of intermediate 5-2-31, and starting material 14 (0.01 mol) was used instead of starting material 3 to give intermediate 1-3-52 (3.55 g, yield 90%).

(2) Synthesis of intermediate 2-3-52: the synthesis of intermediate 1-3-33 was repeated except that intermediate 1-3-52 (0.01 mol) was used instead of intermediate 3-3-12 to obtain intermediate 2-3-52 (2.88 g, 61% yield).

(3) Synthesis of intermediate 3-3-52: the synthesis of intermediate 3-1-82 was carried out in the same manner as in intermediate 2-3-52 (0.01 mol) except that intermediate 2-1-82 was replaced with intermediate 3-3-52 (3.38, yield 65%).

(4) Synthesis of intermediate 4-3-52: the synthesis of intermediate 4-1-82 was repeated except that intermediate 3-3-52 (0.01 mol) was used instead of intermediate 3-1-82 to give intermediate 4-3-52 (3.34 g, 61% yield).

(5) Synthesis of intermediate 5-3-52: the synthesis of intermediate 5-1-82 was identical, except that intermediate 4-3-52 (0.01 mol) was used instead of intermediate 4-1-82, benzophenone was used instead of acetone, intermediate 5-3-52 (4.54 g, 86% yield).

(6) Synthesis of Compounds 3-52: the synthesis of 1-82 was repeated except that intermediate 5-3-52 (0.01 mol) was used instead of intermediate 5-1-82 to give compound 3-52 (4.39 g, 86% yield).

Elemental analysis: theoretical value of C38H26N 2: c,89.38, h,5.13, n,5.49, found: c,89.42, H,5.11, N,5.47, HRMS (ESI) M/z (M+): theoretical value: 510.2096, found: 510.2102.

synthesis example 15

In this example, compounds 3-59 were synthesized by the following routes:

the preparation method comprises the following steps:

(1) Synthesis of intermediate 1-3-59: the synthesis of 2-31 was repeated except that intermediate 3-3-12 (0.01 mol) was used instead of intermediate 5-2-31, and starting material 16 (0.01 mol) was used instead of starting material 3 to give intermediate 1-3-59 (5.26 g, yield 88%).

(2) Synthesis of intermediate 2-3-59: the synthesis of intermediate 1-3-33 was repeated except that intermediate 1-3-59 (0.01 mol) was used instead of intermediate 3-3-12 to give intermediate 2-3-59 (4.53 g, 67% yield).

(3) Synthesis of intermediate 3-3-59: the synthesis of intermediate 1-1-60 was repeated except that intermediate 2-3-59 (0.01 mol) was used instead of intermediate 2-1-96 to give intermediate 3-3-59 (4.68 g, 65% yield).

(4) 3-59: the synthesis was identical to that of 1-60, except that intermediate 3-3-59 (0.01 mol) was used instead of intermediate 1-1-60 to give compound 3-59 (5.21 g, yield 74%).

Elemental analysis: theoretical value of C49H28N 4S: c,83.50, h,4.00, n,7.95, s,4.55, found: c,83.54, H,3.99, N,7.93, S,4.54, HRMS (ESI) M/z (M+): theoretical value: 704.2035 found: 704.2038.

synthesis example 16

In this example, compounds 3-51 were synthesized by the following routes:

the preparation method comprises the following steps:

(1) Synthesis of intermediate 1-3-51: in a 100 ml-line, adding intermediate 2-3-59 (0.01 mol), o-hydroxyphenylboric acid (0.01 mol), tetrakis (triphenylphosphine) palladium (0.5 mol), potassium carbonate (0.15 mol), toluene (30 ml), ethanol (10 ml), water (10 ml), and 80 ℃ for 6 hours, extracting with dichloromethane, sequentially adding magnesium sulfate into the obtained extract, drying, filtering, and spin-drying; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to give intermediate 1-3-51 (4.03 g, 83% yield).

(2) 3-51 synthesis: in a 100 mL three-necked flask, under nitrogen protection, intermediate 1-3-51 (0.01 mol), palladium acetate (0.5 mmol), 3-nitropyridine (0.5 mol), nitrogen exchange 3 times, then hexafluorobenzene (0.01 mL), o-nitroaniline (0.01 mL), tert-butyl peroxybenzoate (10 mmol) were added, the system was reacted at 90℃for 4 hours, after the reaction was completed, cooled to room temperature, and the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to give 3-51 (3.29 g, yield 68%).

Elemental analysis: theoretical value of C35H20N 2O: c,86.76, h,4.16, n,5.78, found: c,86.80, H,4.14, N,5.76, HRMS (ESI) M/z (M+): theoretical value: 484.1576, found 484.1582.

Synthesis example 17

In this example, compounds 3-97 were synthesized by the following routes:

the preparation method comprises the following steps:

(1) Synthesis of intermediate 1-3-97: the synthesis of 2-31 was different in that intermediate 3-3-12 (0.01 mol) was used instead of intermediate 5-2-31, and starting material 17 (0.01 mol) was used instead of starting material 3 to give intermediate 1-3-97 (4.83 g, yield 88%).

(2) Synthesis of intermediate 2-3-97: the synthesis of intermediate 1-3-33 was repeated except that intermediate 1-3-97 (0.01 mol) was used instead of intermediate 3-3-12 to obtain intermediate 2-3-97 (3.51 g, 56% yield).

(3) Synthesis of intermediate 3-3-97: the synthesis method of intermediate 2-3-33 was identical, except that intermediate 1-3-33 was replaced with 2-3-97 (0.01 mol), to give intermediate 3-3-97 (5.09 g, yield 76%).

(4) Synthesis of intermediate 4-3-97: the synthesis of intermediate 2-2-31 was distinguished by the fact that intermediate 3-3-97 (0.01 mol) was used instead of intermediate 1-2-31, intermediate 4-3-97 (4.53 g, 71% yield).

(5) 3-97 synthesis: the synthesis of 2-31 was repeated except that intermediate 4-3-97 (0.01 mol) was used instead of intermediate 5-2-31 and bromobenzene (0.01 mol) was used instead of starting material 3 to give compound 3-97 (6.00 g, 84% yield).

Elemental analysis: theoretical C50H30N 6: c,84.01, h,4.23, n,11.76, found: c,84.04, H,4.24, N,11.72, HRMS (ESI) M/z (M+): theoretical value: 714.2532, found: 714.2526.

example 18

The preparation method comprises the following steps:

(1) Synthesis of intermediate 1-1-150: the synthesis of intermediate 3-1-10 is different in that raw material 18 is used to replace 1-bromo-2-nitronaphthalene to obtain intermediate 1-1-150 (yield 64%).

(2) Synthesis of intermediate 2-1-150: the difference from intermediate 2-2-31 is that intermediate 1-1-150 was used instead of intermediate 1-2-31, intermediate 2-1-150 (yield 71%).

(3) Synthesis of intermediate 3-1-150: the same as intermediate 1-1-60 except that intermediate 2-1-150 was used instead of intermediate 2-1-96 to give intermediate 3-1-150 (yield 74%).

(4) Synthesis of intermediate 4-1-150: the synthesis of compound 1-60 is different in that 3-1-150 is used instead of intermediate 1-1-60 to obtain intermediate 4-1-150 (yield 70%).

(5) Synthesis of Compounds 1-150: the synthesis of compound 2-31 is different in that intermediate 4-1-150 is used instead of intermediate 5-2-31 and raw material 19 is used instead of raw material 3 to obtain compound 1-150 (yield 78%).

Elemental analysis: theoretical value of C49H26N4 OS: c,81.87, h,3.65, n,7.79, s,4.46, found: c,81.91, H,3.64, N,7.77, S,4.45, HRMS (ESI) M/z (M+): theoretical value: 718.1827, found: 718.1833.

device embodiment

The present embodiment provides an organic electroluminescent device, as shown in fig. 1, comprising an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode 8, which are sequentially stacked on a substrate 1.

Wherein, the anode 2 is made of ITO material;

the hole injection layer 3 material is formed by doping a compound PD with a structure shown in the following formula with a compound HI-1: wherein the mass ratio of PD to HI-1 doping is 3:97;

The hole transport layer 4 is made of a compound NPB with the following structure:

the light-emitting layer 5 is formed by co-doping a host material and a guest material, wherein the host material is selected from the compound of the present invention or a contrast material (shown in Table 3), and the guest material is selected from the compound Ir (DBQ) ₂ (acac) the mass ratio of the host material to the guest material doping is 95:5; wherein the compound Ir (DBQ) ₂ The chemical structure of (acac) is as follows:

the electron transport layer 6 material is formed by doping a compound BPhen with a compound LiQ with the following structure: wherein the mass ratio of BPhen to LiQ doping is 1:1;

the electron injection layer 7 is made of a compound LiQ with the following structure:/>

the cathode 8 is made of a mixed material of metal Mg and Ag, wherein the mass ratio of the metal Mg to the metal Ag is 9:1.

The preparation of the organic electroluminescent device comprises the following steps:

1) Cleaning a substrate:

the glass substrate 1 coated with the ITO transparent electrode is subjected to ultrasonic treatment in an aqueous cleaning agent (the components and the concentration of the aqueous cleaning agent are that an ethylene glycol solvent is less than or equal to 10wt% and triethanolamine is less than or equal to 1wt%) and is washed in deionized water, and then the glass substrate is subjected to acetone: ultrasonic degreasing in ethanol mixed solvent (volume ratio 1:1), baking in clean environment until completely removing water, and cleaning with ultraviolet light and ozone;

2) Vapor deposition:

placing the above glass substrate 1 with anode 2 into a vacuum chamber, and vacuumizing to 1×10 ^-6 Up to 2X 10 ^-4 Pa, vacuum evaporating a hole injection layer 3 material on the anode layer film in a co-evaporation mode, wherein the evaporation thickness is 10nm;

3) Evaporating a hole transport layer 4 on the hole injection layer 3, wherein the film thickness of the evaporation film is 80nm;

4) A light-emitting layer 5 is deposited on the hole-transporting layer 4, a light-emitting host material and a guest material are deposited in a co-evaporation manner in a vacuum manner, and the total film thickness of the deposited materials is 40nm;

5) Vacuum evaporating an electron transport layer 6 on the luminescent layer 5, wherein the total film thickness of the evaporation is 30nm;

6) Vacuum evaporating an electron injection layer 7 on the electron transport layer 6, wherein the total film thickness of the evaporation is 1nm;

7) The cathode 8 was vapor-deposited on the electron injection layer 7, and the total vapor deposition film thickness was 80nm.

The comparative example material was Ref-1, having the following structure:

1. determination of the thermal decomposition temperature of the Compound

Determination of the thermal decomposition temperature of the compound: the nitrogen-containing heterocyclic compound of the present invention was subjected to a thermal decomposition temperature (Td) test using a thermogravimetric analyzer (TA TGA55 in the united states) ranging from room temperature to 600 c at a heating rate of 10 c/min, and a temperature at which 5% of the weight was lost under a nitrogen atmosphere was defined as a decomposition temperature, and the test results are shown in table 1.

TABLE 1 thermal decomposition temperatures of nitrogen-containing heterocyclic compounds

Compounds of formula (I)	T _d (℃)	Compounds of formula (I)	T _d (℃)
				2-31	356	1-60	431
2-13	423	1-82	418
				1-10	333	1-89	453
1-28	412	1-92	461
				1-105	339	3-52	322
3-12	457	3-59	407
				3-33	380	3-51	318
3-106	316	3-97	411
				1-96	460	1-150	435

From the results of Table 1, it can be seen that the compounds of the present invention have a suitable thermal decomposition temperature, which is advantageous for the extension of the lifetime of the device, and for the evaporation of the material.

2. LUMO and HOMO energy level testing

The nitrogen-containing heterocyclic compounds prepared in examples 1 to 18 were tested for LUMO and HOMO levels using an electrochemical workstation using cyclic voltammetry (CV Shanghai chei-600E), using a platinum wire (Pt) as a counter electrode, silver/silver chloride (Ag/AgCl) as a reference electrode, and under a nitrogen atmosphere, in a methylene chloride electrolyte containing 0.1M tetrabutylammonium hexafluorophosphate at a scan rate of 100mV/s, and were subjected to potential calibration with ferrocene, setting the absolute level of ferrocene in a vacuum state to be-4.8 eV:

HOMO energy level= -E (Eox-E) _{1/2,ferrocene} )+(-4.8)eV

LUMO energy level= -E (E _re -E _{1/2,ferrocene} )+(-4.8)eV；

Wherein E is _ox For oxidation potential, E _re For reducing potential E _{1/2,ferrocene} Is ferrocene potential.

Triplet energy level test conditions: the compound to be tested is formulated as a solution (concentration 2 x 10 ^- ⁵ mol/L), the above solution was tested at-78deg.C using a fluorescence spectrophotometer (Ri Li F-4600). Wherein E is _T1 (eV) represents the triplet energy level of the compound, which is calculated by the following formula,

E _T1 1240/shortest absorption wavelength.

The test results are shown in Table 2.

TABLE 2 energy level test results of nitrogen-containing heterocyclic compounds

Compounds of formula (I)	E _T1 (eV)	Compounds of formula (I)	E _T1 (eV)
				2-31	2.31	1-60	2.30
2-13	2.37	1-82	2.33
				1-10	2.32	1-89	2.34
1-28	2.35	1-92	2.33
				1-105	2.36	3-59	2.32
3-12	2.42	3-51	2.34
				3-33	2.43	3-97	2.43
3-106	2.29	1-150	2.38
				1-96	2.30

As can be seen from table 2, the triplet energy level of the material of the present invention is high, so that the energy backflow is avoided, and the efficiency of the device is prevented from being reduced.

Test example 2

Instrument: the characteristics of current, voltage, brightness, luminescence spectrum and the like of the device are synchronously tested by adopting a PR 650 spectrum scanning luminance meter and a Keithley K2400 digital source meter system;

test conditions: the current density was 20mA/cm ² Room temperature.

Life test: the time (in hours) for the device brightness to drop to 98% of the original brightness was recorded.

The organic electroluminescent devices provided in device examples 1 to 18 and comparative example 1 were tested, and the results are shown in table 3:

TABLE 3 device Performance test results

From the data in Table 3, it can be seen that the compounds of the present invention have an extended lifetime and higher current efficiency compared to the comparative examples, because the triplet energy level of the material is higher, the electron and hole transport rates are balanced, and the thermal stability of the material is better.

The applicant states that the organic electroluminescent compounds according to the present invention and the organic electroluminescent device comprising the same are illustrated by the above examples, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must be carried out in dependence on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims

1. An organic electroluminescent compound, characterized in that the organic electroluminescent compound is any one of the following compounds:

2. an organic electroluminescent device comprising a first electrode, a second electrode, and an organic layer between the first electrode and the second electrode, the organic layer comprising any one or a combination of at least two of the organic electroluminescent compounds according to claim 1.

3. The organic electroluminescent device according to claim 2, wherein the organic layer comprises a light-emitting layer comprising any one or a combination of at least two of the organic electroluminescent compounds according to claim 1.

4. The organic electroluminescent device according to claim 3, wherein the light-emitting layer comprises a host material and a guest material, the light-emitting layer host material comprising any one or a combination of at least two of the organic electroluminescent compounds according to claim 1; the guest material is a phosphorescent dopant.

5. The organic electroluminescent device of claim 2, wherein the organic layer further comprises any one or a combination of at least two of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer.