CN114685484A

CN114685484A - Organic electroluminescent compound and organic electroluminescent device comprising same

Info

Publication number: CN114685484A
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: 2022-07-01
Anticipated expiration: 2040-12-28
Also published as: CN114685484B

Abstract

The invention provides an organic electroluminescent compound and an organic electroluminescent device comprising 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 (hereinafter referred to as OLED) has a series of advantages of self-luminescence, low-voltage direct current drive, full curing, wide viewing angle, light weight, simple composition and process and the like, and compared with the liquid crystal display, the organic electroluminescent display does not need a backlight source, has large viewing angle, low power, 1000 times of response speed of the liquid crystal display, and lower manufacturing cost than the liquid crystal display with the same resolution, so the organic electroluminescent device has wide application prospect.

With the continuous advance of the OLED technology in both lighting and display fields, people pay more attention to the research on efficient organic materials affecting the performance of OLED devices, and an organic electroluminescent device with good efficiency and long service life is generally the result of the optimized matching of the device structure and various organic materials. In the most common OLED device structures, the following classes of organic materials are typically included: hole injection materials, hole transport materials, electron transport materials, and light emitting materials (dyes or doped guest materials) and corresponding host materials of each color. The phosphorescent host materials used at present have single carrier transport capability, such as hole-based transport hosts and electron-based transport hosts. The single carrier transport ability causes mismatching of electrons and holes in the light emitting layer, resulting in severe roll-off of efficiency and shortened lifetime.

However, materials used in organic electroluminescent devices have room for improvement, and organic electroluminescent materials having superior luminescent properties, longer lifetime, and higher efficiency are urgently desired in the industry. At present, in the process of using a phosphorescent host, the problem of unbalanced charge carriers of a single host material is solved through the research of the host material, but the performance is not satisfactory, and a new luminescent host material still needs to be developed.

Disclosure of Invention

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

In order 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 represented by formula I below:

wherein, X¹、X²Each independently is N or CR²⁵，

R¹、R²、R²⁵Each independently selected from hydrogen, deuterium, tritium, cyano, nitro, halogen, substituted or unsubstituted C1-C10 straight-chain alkyl, substituted or unsubstituted C3-C10 branched-chain alkyl, substituted or unsubstituted C1-C10 cycloalkyl, 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, and,

The dotted line represents the attachment site of the group,

substituent R¹、R²Are not connected with each other, or are connected with each other or separated by 2 substituents with 1-3 carbon atoms through chemical bonds to form a ring A,

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

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

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

R²³、R²⁴substituted or unsubstituted C1-C10 linear alkyl, substituted or unsubstituted C3-C10 branched alkyl, substituted or unsubstituted C6-C15 aryl, substituted or unsubstituted C3-C15 heteroaryl,

L、L¹each independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group,

ar is selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl and-NAr¹Ar²，

Ar¹、Ar²Each independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl.

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

wherein R is¹、R²L and Ar, and m and n are as defined for formula I.

Preferably, the organic electroluminescent compound has a structure shown as formula IV or formula V below:

wherein R is¹、R²L and Ar and m and n are as defined for formula I, T^a、T^bEach independently selected from the group consisting of a single bond, O, S, -NR²⁷or-CR²⁸R²⁹，

R²⁷Selected from substituted or unsubstituted C1-C4 straight chain or branched chain alkyl, substituted or unsubstituted C6EC60 aryl, substituted or unsubstituted C3-C60 heteroaryl,

R²⁸-R²⁹each independently selected from substituted or unsubstituted C1-C4 straight chain or branched chain alkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl,

R²⁸-R²⁹independently exist or are connected to form a ring M, the ring M is selected from substituted or unsubstituted fluorene rings,

R²²selected from deuterium, tritium, cyano, nitro, halogen, substituted or unsubstituted C1-C10 straight-chain alkyl, substituted or unsubstituted C3-C10 branched-chain alkyl, 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; k is an integer from 0 to 4 (e.g., 0, 1, 2, 3, or 4);

R²²independently exist or are adjacent to each other to form a ring F;

preferably, ring F is a benzene ring;

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

preferably, Ar, R²⁷Independently selected from any one of the following groups

Y¹、Y²、Y³、Y⁴、Y⁵、Y⁶、Y⁷、Y⁸Each independently selected from N or C-R^Y；

T¹Selected from O, S, N-R^T1Or CR^T2R^T3；

R^Y、R^T1、R^T2、R^T3、R³、R⁴、R⁵、R⁶、R⁷、R⁸Each independently selected from hydrogen, deuterium, tritium, cyano, nitro, halogen, substituted or unsubstituted C1-C4 linear or branched alkyl, substituted or unsubstituted C1-C4 linear or branched alkoxy, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl;

substituent R^YAt least 2 substituents not linked or adjacent to each other are linked by a chemical bond to form ring B;

R⁵、R⁶、R⁷、R⁸at least 2 substituents not linked or adjacent to each other are linked by a chemical bond to form a ring C;

Z¹selected from O, S;

Ar¹、Ar²each independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;

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

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

preferably, Ar, R²⁷Independently selected from the group

R⁹-R²¹、R²⁶Each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C4 straight or branched chain alkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl;

R¹⁷-R²⁰independently exist or are adjacent to each other to form a ring D;

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

R¹⁵-R¹⁶independently exist or are adjacent to each other to form a ring E;

ring E is preferably a fluorene ring.

Preferably, R⁹-R²¹、R²⁶、Ar¹、Ar²Independently selected from hydrogen, deuterium, halogen, cyano, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl or any one or combination of at least two of the following groups substituted or unsubstituted by deuterium, halogen, cyano, methyl, ethyl, propyl, isopropyl, butyl or tert-butyl:

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

r' is selected from deuterium, halogen or cyano.

Preferably L, L¹Each independently selected from the group consisting of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted nitrogen-containing dibenzofuranyl group, and a substituted or unsubstituted nitrogen-containing dibenzothiophenyl group; the substituted substituent is selected from deuterium, halogen, cyano, C1-C4 straight chain or branched chain alkyl.

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

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

Cycloalkyl groups described herein include, but are not limited to, cyclopropane, cyclobutane, cyclohexane.

The alkenyl group in the present invention means a monovalent substituent derived from a straight or branched chain 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.

The aryl groups of the present invention include monocyclic, polycyclic, fused ring aromatic groups, which rings may be interrupted by short nonaromatic units such as methylene. The aryl group is selected from phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthryl, anthracenyl, indenyl, triphenylene, pyrenyl, tetracenyl, perylenyl, chrysenyl, fused tetraphenyl, fluoranthenyl or spirobifluorenyl.

The heteroaryl groups of the present invention include monocyclic, polycyclic, fused ring groups, and the rings may be interrupted by short nonaromatic units such as methylene, O, S, N. The heteroaryl group 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, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl or dihydroacridinyl.

In the present invention, the definition of the group defines a range of carbon numbers, the number of carbon atoms of which is any integer within the defined range, such as C6-C30 aryl, and the number of carbon atoms representing the aryl group can be any integer within the range of 6-30 inclusive, such as 6, 8, 10, 15, 18, 20, 23, 25, 28, or 30, and the like.

In another aspect, the present invention provides an organic electroluminescent composition comprising the 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 difference in thermal decomposition temperature of the further compound W and the organic electroluminescent compound as described above is less than 20 degrees celsius. More preferably, the difference in thermal decomposition temperature of the further compound W and the organic electroluminescent compound as described above is less than 10 degrees celsius; further preferably, the difference in thermal decomposition temperature between 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 and A3;

wherein L is²-L⁴Each independently selected from a single bond, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl,

Ar³selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, NR³²R³³，

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, n2 is an integer from 1 to 2; n3 is an integer from 1 to 2,

L³is a single bond, n1 is 1; l is⁴Is a single bond, n2 is 1,

R³⁰-R³¹each 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, OR³⁷、SR³⁷、NR³²R³³，

n1 Xm 1R³⁰Identical or different, n2 Xm 2R³¹The same or different, and the same or different,

when m1 is 2 or more, R³⁰Either alone or in a loop adjacent to both,

when m2 is 2 or more, R³¹Either alone or in a loop adjacent to both,

Z²-Z³each independently selected from O, S, NL⁵Ar⁵、CR³⁵R³⁶，

Ar⁵Selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, NR³²R³³，

L⁵Is selected fromA bond, a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted C3-C30 heteroaryl,

R³⁵-R³⁷each independently 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,

R³⁵、R³⁶either alone or linked to form a spiro ring,

R³²、R³³each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted benzonaphthofuranyl, 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, Ar³、Ar⁵Each 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 anthracenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted fluorenyl, NR³²R³³Or a combination thereof.

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

preferably, the electron transport compound is a compound having an electron-withdrawing group attached thereto, such as 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 as follows B1:

wherein, X⁸-X¹⁰Each of which is independently selected from the group consisting of N,

wherein L is⁶-L⁸Each independently selected from single bond, substituted or unsubstituted aryl of C6-C30, Ar⁶-Ar⁸Each 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 selected from a substituted or unsubstituted C6-C20 aromatic ring, a substituted or unsubstituted C3-C20 aromatic heterocyclic ring;

the ring is more preferably selected from the group consisting of substituted or unsubstituted: a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, an indene ring, an indole ring, a benzofuran ring or a benzothiophene ring;

when the number of rings is two or more, the rings may be the same or different.

Preferably, the structural formula of the pyrimidine compound is as follows:

wherein, X⁸-X¹⁰Each independently selected from N, CR³⁸Wherein two of the groups are selected from N,

R³⁸selected 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,

L⁶-L⁸each independently selected from single bond, substituted or unsubstituted aryl of C6-C30,

Ar⁶-Ar⁸each 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;

Preferably, the quinoxaline compound has the following structure:

wherein, X⁴And X⁷Is selected from N, X⁵And X⁶Selected from the group consisting of CR³⁸，L⁹Each independently selected from single bond, substituted or unsubstituted aryl of C6-C30, R³⁸Selected 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,

Ar⁹each independently selected from hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl,

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

Preferably, the quinazoline compound has the following structure B4:

wherein, X⁵And X⁷Is selected from N, X⁴And X⁶Selected from the group consisting of CR³⁸(ii) a Or X⁴And X⁶Is selected from N, X⁵And X⁷Selected from the group consisting of CR³⁸；

L⁹Each independently selected from single bond, substituted or unsubstituted aryl of C6-C30, R³⁸Selected 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 more than or equal to two, the rings are the same or different;

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

the substituents are as defined above.

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

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 of the organic electroluminescent compounds described above or a combination of at least two thereof.

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

Preferably, the guest material comprises a phosphorescent dopant.

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

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

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

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

the organic electroluminescent compound of the invention 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, in which 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 solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

Synthetic examples

Synthesis example 1

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

the preparation method comprises the following steps:

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

(2) Synthesis of intermediates 2-2-31: taking a 100 ml double-neck round-bottom bottle, putting a stirrer and an upper reflux pipe, drying, introducing nitrogen, respectively adding an intermediate 1-2-31(3.28 g, 0.01mol), triphenylphosphine (0.02mol) and 1, 2-dichlorobenzene (40ml), heating at 180 ℃ for reaction for 8 hours, cooling to room temperature after the reaction is finished, concentrating a reaction system, and purifying a crude product by chromatography (ethyl acetate/n-hexane, 1/10 (volume ratio)) to obtain an 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, putting a stirrer and an upper connecting reflux pipe, filling nitrogen after drying, respectively adding 2-2-31(0.01mol) of an intermediate,

(0.01mol), sodium hydrogencarbonate (0.013mol), tetratriphenylphosphine palladium (0.5mmol), tetrahydrofuran (60 ml) and water (30 ml), and nitrogen was replaced three times. Heating to 65 ℃ under the protection of nitrogen, reacting for 2 hours, extracting by ethyl acetate after the reaction is finished, and sequentially adding magnesium sulfate into the obtained extract liquor for drying, filtering and spin-drying; subjecting the crude product to chromatographyPurification (ethyl acetate/n-hexane, 1/10, vol.) afforded intermediate 3-2-31(1.39 g, 43% yield).

(4) Synthesis of intermediate 4-2-31: a100 ml double-neck round-bottom bottle is taken, a stirrer and an upper connecting reflux pipe are placed in the bottle, nitrogen is filled after the bottle is dried, 3-2-31(0.01mol), (methoxymethyl) triphenyl phosphonium chloride (0.015mol) and tetrahydrofuran (40ml) are respectively added, and nitrogen is replaced for three times. Under the protection of nitrogen, the temperature is reduced to-5 to-10 ℃, after the temperature is reached, a t-BuOK (0.015mol) tetrahydrofuran (15 ml) solution is slowly dripped by a constant pressure dropping funnel, and the temperature is always kept below-5 ℃. After the addition was complete, the reaction was carried out at this temperature for 20 min. Slowly heating to room temperature, continuing to react for 1h after the reaction solution reaches the room temperature, adding water into the system after the reaction is finished, extracting by dichloromethane, and sequentially adding magnesium sulfate into the obtained extract for drying, filtering and spin-drying; the crude product was purified by chromatography (dichloromethane/n-hexane, 1/10, vol.) to give intermediate 4-2-31(2.70 g, 77% yield).

(5) Intermediate 5-2-31: a100 mL two-necked round-bottomed flask was taken, and a stirrer and an upper reflux tube were placed in the flask, and after drying, nitrogen gas was introduced, and intermediate 4-2-31(0.01mol) and hexafluoroisopropanol (14mL) were added, respectively. Under the protection of nitrogen, the temperature is reduced to-5 to-10 ℃, after the temperature is reached, trifluoromethanesulfonic acid (0.02mol) is slowly dripped by a constant pressure dropping funnel, and the temperature is always maintained below-5 ℃. After the addition was complete, the reaction was carried out at this temperature for 20 min. Slowly heating to room temperature, continuing to react for 1h after the reaction solution reaches the room temperature, adding water into the system after the reaction is finished, extracting by dichloromethane, and sequentially adding magnesium sulfate into the obtained extract for drying, filtering and spin-drying; the crude product was purified by chromatography (dichloromethane/n-hexane, 1/10, vol.) to afford intermediate 5-2-31(2.84 g, 89% yield).

(6) Synthesis of Compounds 2-31: a100 ml two-necked round-bottomed flask was taken, and a stirrer and an upper reflux tube were placed, and after drying, nitrogen gas was introduced, and 5-2-31(3.19 g, 0.01mol), 5 (3.16 g, 0.01mol), 3(3.16 g, 0.01mol), cesium carbonate (0.015mol), tris (dibenzylideneacetone) dipalladium (0.5mmol) and 2-dicyclohexylphosphorus-2 ', 4 ', 6 ' -triisopropylbiphenyl (0.55mmol) were added, followed by refluxing of the mixture for 12 hours, cooling to room temperature after reaction, filtration and concentration of the reaction system, and chromatography purification (ethyl acetate/n-hexane, 1/10 (volume ratio)) of the crude product to obtain 2-31(4.85 g, 81% yield).

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 values are as follows: 599.2110, found: 599.2118.

synthesis example 2

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

the preparation method comprises the following steps:

(1)2-13 Synthesis: the synthesis was identical to that of 2-31 except that starting material 15(0.01mol) was used instead of starting material 3 to give compounds 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 synthetic route:

the preparation method comprises the following steps:

(1) synthesis of intermediates 1-1-10: in a 100 ml three-neck bottle, raw material 4(0.01mol), palladium acetate (0.5mmol), NBS (0.011mol) and toluene (40ml) are added under the protection of nitrogen, the mixture reacts for 6h at 110 ℃, after the reaction is finished, the solvent is removed, and the crude product passes through a chromatographic column (ethyl acetate/n-hexane, 1/10 (volume ratio)) to obtain an intermediate 1-1-10(2.06 g, yield 80%).

(2) Synthesis of intermediates 2-1-10: in a 100 ml three-necked flask, intermediate 1-1-10(0.01mol) and tetrahydrofuran (40ml) were added, the reaction solution was cooled to-78 ℃, n-butyllithium (0.01mol) was slowly added, followed by addition of 2-isopropoxy-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborane (0.01mol), the reaction system was warmed to room temperature, stirring was continued for 10 hours, after the reaction was completed, water was added for quenching, the product was washed with water, ethyl acetate was extracted 3 times, the organic layer was dried over 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 give intermediate 2-1-10 (yield 52%).

(3) Synthesis of intermediates 3-1-10: a100 ml three-necked flask is added with the intermediate 2-1-10(0.01mol), 1-bromo-2-nitronaphthalene (0.01mol), tetrakis (triphenylphosphine) palladium (0.5mmol), tetrabutylammonium bromide (0.5mmol), sodium carbonate (0.02mol), toluene 30 ml, ethanol (5 ml), water (5 ml), the system is heated to 80 ℃ to react for 12 hours, after the reaction is finished, the system is cooled to room temperature, water is added, ethyl acetate is extracted, an organic layer is dried by anhydrous magnesium sulfate, the solvent is removed, and a crude product is separated by column chromatography (ethyl acetate/n-hexane, 1/10 (volume ratio)) to obtain the intermediate 3-1-10 (yield 81%).

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

(5)1-10 Synthesis: the same synthesis as 2-31 except that intermediate 4-1-10(0.01mol) was used instead of intermediate 5-2-31 and starting material 5(0.01mol) was used instead of starting material 3 gave 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 synthetic route:

the preparation method comprises the following steps:

(1)1-28 Synthesis: the same synthesis as for 2-31, except that intermediate 4-1-10(0.01mol) was used instead of intermediate 5-2-31 and starting material 6(0.01mol) was used instead of starting material 3, gave compounds 1-28(5.93 g, 83% yield).

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 synthetic route:

the preparation method comprises the following steps:

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

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

(3) Synthesis of Compounds 1-105: a100 ml two-neck round-bottom flask was taken, a stirrer and an upper reflux pipe were placed, nitrogen was introduced after drying, intermediates 2-1-105(4.72 g, 0.01mol), diphenylamine (1.69 g, 0.01mol), cesium carbonate (0.012mol), tris (dibenzylideneacetone) dipalladium (Pd2(dba)3, 0.5mmol) and 2-dicyclohexylphosphonium-2 ', 4 ', 6 ' -triisopropylbiphenyl (xphos, 0.55mmol) were added, toluene was then added, the mixture was refluxed for 24 hours, cooled to room temperature after reaction, the reaction system was filtered and concentrated, and the crude product was purified by chromatography (dichloromethane/n-hexane, 1/10 (volume ratio)) to give compounds 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 synthetic route:

the preparation method comprises the following steps:

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

(2) Synthesis of intermediates 2-3-12: in a 100 ml three-necked flask, the intermediates 2-2-31(0.01mol), (methoxymethyl) triphenylphosphine chloride (0.012mol) and tetrahydrofuran (40ml) were added, and nitrogen gas was replaced three times. Under the protection of nitrogen, the temperature is reduced to-5 to-10 ℃, after the temperature is reached, a t-BuOK (0.015mol) tetrahydrofuran (15 ml) solution is slowly dripped by a constant pressure dropping funnel, and the temperature is always kept below-5 ℃. After the addition was complete, the reaction was carried out at this temperature for 20 min. Slowly heating to room temperature, continuing to react for 1h after the reaction solution reaches the room temperature, and stopping the reaction. After the reaction was completed, 20 ml of water was slowly added, 100 ml of ethyl acetate was added, and then the mixture was separated by a separatory funnel, the organic layer was separated and left, the aqueous layer was extracted once with dichloromethane, the organic layers were combined, and the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to obtain 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(0.01mol) and hexafluoroisopropanol (25 ml) were added. Under the protection of nitrogen, the temperature is reduced to-5 to-10 ℃, and after reaching the temperature, trifluoromethanesulfonic acid (0.018mol) is slowly added by a constant pressure dropping funnel, and the temperature is always maintained below-5 ℃. After the addition was complete, the reaction was carried out at this temperature for 20 min. Slowly heating to room temperature, continuing to react for 1h after the reaction solution reaches the room temperature, and stopping the reaction. After the reaction was completed, 20 ml of water was slowly added, ethyl acetate was extracted three times, the organic phases were combined, and the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to give intermediate 3-3-12(2.51 g, yield 79%).

(4)3-12 was synthesized as in 2-31 except that intermediate 3-3-12(0.01mol) was used instead of intermediate 5-2-31 and starting material 7(0.01mol) was used instead of starting material 3 to give compound 3-12(6.23 g, 78% yield).

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 synthetic route:

the preparation method comprises the following steps:

(1) synthesis of intermediates 1-3-33: taking a 100 ml double-neck round-bottom bottle, putting a stirrer and an upper reflux pipe, drying, filling nitrogen, respectively adding 3-3-12(0.01mol) of an intermediate, 0.015mol of N-bromosuccinimide and 50 ml of tetrahydrofuran, and stirring at room temperature for 12 hours; after the reaction is finished, adding water for quenching, extracting a reaction system for three times by ethyl acetate, and sequentially adding magnesium sulfate into the obtained extract liquor for drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to afford intermediates 1-3-33 (47% yield).

(2) Synthesis of intermediates 2-3-33: a100 ml three-neck bottle is taken, a stirrer and an upper reflux pipe are placed in the bottle, nitrogen is filled in the bottle, 1-3-33(0.01mol) of an intermediate, 0.01mol of phenylboronic acid, 0.015mol of potassium carbonate, 0.5mmol of palladium tetrakis (triphenylphosphine), 30 ml of toluene, 5 ml of water are added in the bottle, the mixture reacts at 60 ℃ for 10 hours under the protection of nitrogen, the mixture is cooled to room temperature after the reaction is finished, 3 ml of ice water is added in the bottle for quenching, ethyl acetate (3 x 20 ml) is extracted, magnesium sulfate is sequentially added in the obtained extract liquid for drying, filtering and spin-drying, and the crude product is purified by chromatography (ethyl acetate/n-hexane, 1/10 (volume ratio)) to obtain 2-3-33 (yield 91%).

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

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 synthetic route:

the preparation method comprises the following steps:

(1) synthesis of intermediates 1-3-106: the same procedure as for the synthesis of intermediate 2-3-33, except that pyridine-3-boronic acid (0.01mol) was used instead of phenylboronic acid, gave intermediate 1-3-106(3.04 g, 77% yield).

(2)3-106 Synthesis: the same synthesis as 2-31 except that intermediate 1-3-106(0.01mol) was used instead of intermediate 5-2-31 and starting material 9(0.01mol) was used instead of starting material 3 gave compounds 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 synthetic route:

the preparation method comprises the following steps:

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

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

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

(4) Synthesis of intermediates 4-1-96: the same synthesis as intermediate 2-2-31 was performed except that intermediate 3-1-96(0.01mol) 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 same synthesis as 2-31 except that intermediate 4-1-96(0.01mol) was used instead of intermediate 5-2-31 and bromobenzene (0.01mol) was used instead of starting material 3 gave compounds 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 synthetic route:

the preparation method comprises the following steps:

(1) synthesis of intermediates 1-1-60: intermediate 2-1 to 96(0.01mol), raw material 11(0.01mol), tetrakis (triphenylphosphine) palladium (0.58 g, 0.5mmol), toluene (40ml), an aqueous solution of potassium carbonate (0.012mol) (5 ml) were added to a 100 ml three-necked flask, heated to 100 ℃ to react for 8 hours, quenched with water after the reaction was completed, extracted with dichloromethane three times, the organic layer was dried over anhydrous magnesium sulfate, and then 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 to 60 (yield 78%).

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

Elemental analysis: theoretical value of 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 synthetic route:

the preparation method comprises the following steps:

(1) synthesis of intermediates 1-1-82: the synthesis was identical to that of 2-31, except that intermediate 4-1-10(0.01mol) was used instead of intermediate 5-2-31 and starting material 12(0.01mol) was used instead of starting material 3, giving intermediate 1-1-82(5.07 g, 84% yield).

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

(3) Synthesis of intermediate 3-1-82: taking a 50 ml three-necked bottle, placing a stirrer and an upper reflux pipe, drying, introducing nitrogen, heating an intermediate 2-1-82(0.1mol), bis (pinacolato) diboron (0.12mol), dioxane (8 ml), potassium tert-butoxide (0.12mol), and [1, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride (5mmol) at 70 ℃ for 12 hours, adding water to quench after the reaction is finished, extracting with ethyl acetate (3X 20 ml), sequentially adding magnesium sulfate to the obtained extract, drying, filtering and spin-drying, and purifying the crude product by chromatography (ethyl acetate/n-hexane, 1/10 (volume ratio)) to obtain an intermediate 3-1-82 (yield of 50%).

(4) Synthesis of intermediates 4-1-82: intermediate 2-1-96(0.01mol), raw material 11(0.01mol), tetrakis (triphenylphosphine) palladium (0.5mmol), toluene (40ml), aqueous solution (5 ml) of sodium hydrogen carbonate (0.012mol) were added to a 100 ml three-necked flask, heated to 100 ℃ to react for 8 hours, after the reaction was completed, quenched by adding water, extracted with dichloromethane 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 give intermediate 4-1-82(4.84 g, 64% yield).

(5) Synthesis of intermediates 5-1-82: intermediate 4-1-82(0.01mol), anhydrous THF (30 ml) was added under nitrogen in a 100 ml three-necked flask and the reaction was cooled to-78 ℃. N-butyllithium (4.4ml,0.025mol) was added with stirring and reacted at this temperature for 1 hour. Acetone (0.01mol) was dissolved in 10ml of anhydrous tetrahydrofuran and added dropwise to the reaction flask. Reacting for 1h at room temperature, adding water into the reaction system, extracting by 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 afford intermediate 5-1-82 (81% yield).

(6)1-82 Synthesis: in a 100 ml three-necked flask, intermediate 5-1-82(0.01mol) was added, 30 ml acetic acid was added, refluxing was carried out for 4 hours, washing was carried out with saturated sodium hydrogen carbonate, the organic layer was dried over anhydrous magnesium sulfate, the organic solvent was removed, and the crude product was purified with tetrahydrofuran: recrystallization from 1:4 ethanol gave 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 synthetic route:

the preparation method comprises the following steps:

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

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

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

(4) Synthesis of intermediates 4-1-89: the difference from the synthesis of intermediate 5-1-82 was that intermediate 3-1-89(0.01mol) 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 same synthesis as 1-82, except that intermediate 4-1-89(0.01mol) was used instead of intermediate 5-1-82, gave compounds 1-89(6.80 g, 88% yield).

Elemental analysis: theoretical value of 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 values are as follows: 773.2467, found: 773.2474.

synthesis example 13

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

the preparation method comprises the following steps:

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

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

(3) Synthesis of intermediates 3-1-92: the difference from the synthesis of intermediate 3-1-82 was that intermediate 2-1-92(0.01mol) was used instead of intermediate 2-1-82, to give intermediate 3-1-92(4.27, 62% yield).

(4) Synthesis of intermediates 4-1-92: the same synthesis as intermediate 4-1-82 was performed except that intermediate 3-1-92(0.01mol) was used instead of intermediate 3-1-82 to give intermediate 4-1-92(4.37 g, 61% yield).

(5) Synthesis of intermediates 5-1-92: the difference from the synthesis of intermediate 5-1-82 was that intermediate 4-1-92(0.01mol) was used instead of intermediate 4-1-82 and benzophenone was used instead of acetone to give intermediate 5-1-92(6.64 g, 81% yield).

(6) Synthesis of Compounds 1-92: the same synthesis as 1-82, except that intermediate 5-1-92(0.01mol) was used instead of intermediate 5-1-82, gave 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 synthetic route:

the preparation method comprises the following steps:

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

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

(3) Synthesis of intermediate 3-3-52: the difference from the synthesis of intermediate 3-1-82 was that intermediate 2-3-52(0.01mol) was used instead of intermediate 2-1-82, resulting in intermediate 3-3-52(3.38, 65% yield).

(4) Synthesis of intermediate 4-3-52: the same synthesis as intermediate 4-1-82 was performed except that intermediate 3-3-52(0.01mol) 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 difference from the synthesis of intermediate 5-1-82 was that intermediate 4-3-52(0.01mol) was used instead of intermediate 4-1-82 and benzophenone was used instead of acetone to give intermediate 5-3-52(4.54 g, 86% yield).

(6) Synthesis of Compounds 3-52: the same synthesis as 1-82, except that intermediate 5-3-52(0.01mol) was used instead of intermediate 5-1-82, gave 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 values are as follows: 510.2096, found: 510.2102.

synthesis example 15

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

the preparation method comprises the following steps:

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

(2) Synthesis of intermediates 2-3-59: the same synthesis as intermediate 1-3-33 was performed except that intermediate 1-3-59(0.01mol) 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 same synthesis as intermediate 1-1-60 was performed except that intermediate 2-3-59(0.01mol) was used instead of intermediate 2-1-96 to give intermediate 3-3-59(4.68 g, 65% yield).

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

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 synthetic route:

the preparation method comprises the following steps:

(1) synthesis of intermediates 1-3-51: adding the intermediate 2-3-59(0.01mol), o-hydroxyphenylboronic acid (0.01mol), tetrakis (triphenylphosphine) palladium (0.5mol), potassium carbonate (0.15mol), toluene (30 ml), ethanol (10 ml), water (10 ml) into a 100 ml Hilenk tube, reacting for 6 hours at 80 ℃, extracting by dichloromethane, 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) to afford 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(0.01mol), palladium acetate (0.5mmol), 3-nitropyridine (0.5mol), nitrogen exchange 3 times, followed by hexafluorobenzene (0.01 ml), o-nitroaniline (0.01 ml), tert-butyl peroxybenzoate (10mmol) were added, the system was reacted at 90 ℃ for 4 hours, after completion of the reaction, 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, 68% yield).

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 values are as follows: 484.1576, found, 484.1582.

Synthesis example 17

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

the preparation method comprises the following steps:

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

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

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

(4) Synthesis of intermediates 4-3-97: the same synthesis as intermediate 2-2-31 was performed except that intermediate 3-3-97(0.01mol) was used instead of intermediate 1-2-31 to give intermediate 4-3-97(4.53 g, 71% yield).

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

Elemental analysis: theoretical value of 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 intermediates 1-1-150: the same synthesis as intermediate 3-1-10, except that 1-bromo-2-nitronaphthalene was replaced with 18 as the starting material, gave intermediate 1-1-150 (64% yield).

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

(3) Synthesis of intermediates 3-1-150: the difference from intermediate 1-1-60 lies in that intermediate 2-1-150 is used to replace intermediate 2-1-96, and intermediate 3-1-150 is obtained (yield 74%).

(4) Synthesis of intermediates 4-1-150: synthesis of Compounds 1-60, except that intermediates 1-1-60 were replaced with 3-1-150, yielded intermediates 4-1-150 (70% yield).

(5) Synthesis of Compounds 1-150: synthesis of Compounds 2-31, except that intermediates 4-1-150 were used in place of intermediates 5-2-31 and starting material 19 was used in place of starting material 3, gave compounds 1-150 (78% yield).

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 embodiments

The present embodiment provides an organic electroluminescent device 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 and disposed on a substrate 1, as shown in fig. 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 compound HI-1 of the following structure: 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 structure as follows:

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

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

the material of the electron injection layer 7 is 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 Ag is 9: 1.

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

1) substrate cleaning:

carrying out ultrasonic treatment on the glass substrate 1 coated with the ITO transparent electrode in an aqueous cleaning agent (the components and the concentration of the aqueous cleaning agent are that glycol solvent is less than or equal to 10wt percent, and triethanolamine is less than or equal to 1wt percent), washing in deionized water, and carrying out ultrasonic treatment in a water-based solvent system under the conditions of acetone: ultrasonically removing oil in an ethanol mixed solvent (volume ratio is 1: 1), baking in a clean environment until water is completely removed, and then cleaning by using ultraviolet light and ozone;

2) evaporation:

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

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

4) evaporating a luminescent layer 5 on the hole transport layer 4, and evaporating a luminescent host material and an object material in vacuum in a co-evaporation mode, wherein the total film thickness is 40 nm;

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

6) an electron injection layer 7 is evaporated on the electron transport layer 6 in vacuum, and the total film thickness of the evaporation is 1 nm;

7) a cathode 8 was deposited on the electron injection layer 7 to a total thickness of 80 nm.

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

1. determination of the thermal decomposition temperature of the Compound

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

TABLE 1 thermal decomposition temperature of nitrogen-containing heterocyclic compound

Compound (I)	T_d(℃)	Compound (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

As can be seen from the results in table 1, the compound of the present invention has a suitable thermal decomposition temperature, which is beneficial to the extension of device lifetime and the evaporation of materials.

2. LUMO and HOMO energy level testing

The LUMO and HOMO levels of the nitrogen-containing heterocyclic compounds prepared in examples 1 to 18 were measured by cyclic voltammetry (CV shanghai hua CHI-600E) using an electrochemical workstation, with a platinum wire (Pt) as a counter electrode and silver/silver chloride (Ag/AgCl) as a reference electrode, in a dichloromethane electrolyte containing 0.1M tetrabutylammonium hexafluorophosphate under a nitrogen atmosphere at a scan rate of 100mV/s, with ferrocene as a potential marker, and the absolute level of the potential of ferrocene under vacuum was set to-4.8 eV:

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

LUMO energy order-E (E)_re-E_{1/2,ferrocene})+(-4.8)eV；

Wherein E_oxTo oxidation potential, E_reTo reduce the potential, E_{1/2,ferrocene}Is the ferrocene potential.

Triplet state energy level test conditions: the compounds to be tested were formulated as solutions (concentration 2 x 10) in toluene as solvent^- ⁵mol/L) was measured at-78 ℃ using a fluorescence spectrophotometer (Hitachi F-4600). Wherein E_T1(eV) represents the triplet level of the compound, which is calculated by the following formula,

E_T11240/shortest absorption wavelength.

The test results are shown in table 2.

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

Compound (I)	E_T1(eV)	Compound (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 state energy level of the material of the invention is high, energy backflow is avoided, and the efficiency of the device is prevented from being reduced.

Test example 2

The instrument comprises the following steps: the characteristics of the device such as current, voltage, brightness and luminescence spectrum are synchronously tested by a PR 650 spectrum scanning brightness meter and a Keithley K2400 digital source meter system;

and (3) testing conditions are as follows: the current density is 20mA/cm²Room temperature.

And (3) life test: the time (in hours) was recorded when the device brightness dropped to 98% of the original brightness.

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 of table 3, it can be seen that the compound of the present invention has an extended lifespan and higher current efficiency compared to the comparative example due to the higher triplet level of the material, the balance of electron and hole transport rates, and the better thermal stability of the material.

The applicant states that the present invention is illustrated by the above examples of the organic electroluminescent compound of the present invention and the organic electroluminescent device comprising the same, but the present invention is not limited to the above examples, i.e., it does not mean that the present invention must be implemented by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims

1. An organic electroluminescent compound, wherein the organic electroluminescent compound has a structure represented by formula I:

wherein, X¹、X²Each independently is N or CR²⁵，

R¹、R²、R²⁵Each independently selected from hydrogen, deuterium, tritium, cyano, nitro, halogen, substituted or unsubstituted C1-C10 straight-chain alkyl, substituted or unsubstituted C3-C10 branched-chain 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, and,

The dotted line represents the attachment site of the group,

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

n and m are integers from 0 to 5; d is selected from the group consisting of integers from 0 to 3,

R²³、R²⁴substituted or unsubstituted C1-C10 linear alkyl, substituted or unsubstituted C3-C10 branched alkyl, substituted or unsubstituted C6-C15 aryl, and substituted or unsubstituted C3-C15 heteroarylThe base group is a group of a compound,

L、L¹each independently selected from a single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroaryl,

2. The organic electroluminescent compound according to claim 1, wherein the organic electroluminescent compound is a compound having a structure represented by formula II or formula III below:

wherein R is¹、R²L and Ar, and m and n are as defined for formula I;

R²⁷Selected from substituted or unsubstituted C1-C4 straight chain or branched chain alkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl,

The dotted line represents the attachment site of the group,

R²²independently exist or are adjacent to each other to form a ring F,

k is an integer of 0 to 4.

3. The organic electroluminescent compound according to claim 1 or 2, wherein ring F is a benzene ring;

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

preferably, Ta is a single bond, Tb is not a single bond;

preferably, Tb is a single bond and Ta is not a single bond;

preferably, Ar, R²⁷Independently selected from any one of the following groups;

Y¹、Y²、Y³、Y⁴、Y⁵、Y⁶、Y⁷、Y⁸each independently selected from N or C-R^Y，

T¹Selected from O, S, N-R^T1Or CR^T2R^T3，

R^Y、R^T1、R^T2、R^T3、R³、R⁴、R⁵、R⁶、R⁷、R⁸Each independently selected from hydrogen, deuterium, tritium, cyano, nitro, halogen, substituted or unsubstituted C1-C4 linear or branched alkyl, substituted or unsubstituted C1-C4 linear or branched alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl,

substituent R^YAt least 2 substituents which are not linked or adjacent to each other are linked by a chemical bond to form ring B,

R⁵、R⁶、R⁷、R⁸at least 2 substituents which are not linked or adjacent to each other are linked by a chemical bond to form a ring C,

Z¹is selected from the group consisting of O, S,

preferably, ring B is selected from phenyl, pyridyl; more preferably a phenyl group;

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

preferably, Ar, R²⁷Independently selected from the group consisting of:

R⁹-R²¹、R²⁶each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstitutedSubstituted C1-C4 straight chain or branched chain alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl,

R¹⁷-R²⁰independently exist or are adjacent to each other to form a ring D,

the ring D is preferably selected from a benzene ring, a naphthalene ring,

R¹⁵-R¹⁶independently exist or are adjacent to each other to form a ring E,

ring E is preferably a fluorene ring;

4. an organic electroluminescent compound according to any one of claims 1 to 3, wherein when the group contains a substituent, each of the substituents is independently selected from deuterium, halogen, cyano, unsubstituted or R ' substituted C1-C4 linear or branched 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, L¹Each independently selected from the group consisting of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or substituted phenanthrenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or substituted phenanthrenyl group, a substituted or substituted phenanthrenyl group, a substituted or a substituted dibenzothiophenyl group, a substituted or a substituted dibenzothiophenyl group, a substituted or a substituted dibenzothiophenyl group, a substituted or a substituted dibenzothiophenyl group, or a substituted dibenzothiophenyl group, a substituted or aOr an unsubstituted nitrogen-containing dibenzofuranyl group, a substituted or unsubstituted nitrogen-containing dibenzothiophenyl group; the substituted substituent is selected from deuterium, halogen, cyano, C1-C4 straight chain or branched chain alkyl.

5. The organic electroluminescent compound according to any one of claims 1 to 4, wherein 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:

6. an organic electroluminescent composition, characterized in that it comprises an organic electroluminescent compound according to any one of claims 1 to 5;

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

preferably, the further compound W has a thermal decomposition temperature difference with the organic electroluminescent compound according to any one of claims 1 to 5 of less than 20 degrees celsius;

more preferably, the difference in thermal decomposition temperature of the further compound W and the organic electroluminescent compound according to any one of claims 1 to 5 is less than 10 degrees celsius;

further preferably, the further compound W has a thermal decomposition temperature difference with the organic electroluminescent compound according to any one of claims 1 to 5 of less than 5 degrees celsius.

7. The organic electroluminescent composition according to claim 6, wherein the hole transport compound is any one of A1, A2 and A3,

L³is a single bond, n1 is 1; l is a radical of an alcohol⁴Is a single bond, n2 is 1,

when m1 is 2 or more, R³⁰Either alone or in a loop adjacent to both,

when m2 is 2 or more, R³¹Are singly arranged or are arranged adjacent to each other to form a ring,

Z²-Z³each independently selected from O, S, NL⁵Ar⁵、CR³⁵R³⁶，

L⁵Selected from single bond, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl,

R³⁵、R³⁶either alone or linked to form a spiro ring,

R³²、R³³each 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 anthracenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyridyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted benzonaphthofuranyl, substituted or unsubstituted benzonaphthothienyl, substituted or unsubstituted benzonaphthocarbazolyl, substituted or unsubstituted benzonaphthofluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted carbazolyl, and substituted or unsubstituted fluorenyl;

preferably, Ar³、Ar⁵Each 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 anthracenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted fluorenyl, NR³²R³³Or a combination thereof;

the substituents are as defined in claim 4.

8. The organic electroluminescent composition according to claim 6 or 7, wherein the electron transport compound is a compound having attached an electron-withdrawing group comprising a triazinyl group, a pyrimidinyl group, a quinoxalinyl group or a quinazolinyl group,

the structural formula of the compound containing the triazinyl is B1 as follows:

wherein L is⁶-L⁸Each independently selected from single bond, substituted or unsubstituted C6-C30 aryl, Ar⁶-Ar⁸Each 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 more preferably selected from the group consisting of substituted or unsubstituted: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, indene ring, indole ring, benzofuran ring or benzothiophene ring, and when the number of rings is more than or equal to two, each ring is the same or different;

preferably, the pyrimidinyl-containing compound has the following structural formula B2:

wherein X⁸-X¹⁰Each independently selected from N, CR³⁸Wherein two of the groups are selected from the group consisting of N,

Ar⁶-Ar⁸each independently selected from hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstitutedSubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl,

adjacent substituents are not connected or connected to form a ring, and the ring is preferably selected from a substituted or unsubstituted C6-C20 aromatic ring, a substituted or unsubstituted C3-C20 aromatic heterocyclic ring; the ring is more preferably selected from the group consisting of substituted or unsubstituted: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, indene ring, indole ring, benzofuran ring or benzothiophene ring, and when the number of rings is more than or equal to two, each ring is the same or different;

preferably, the quinoxalinyl-containing compound has the following structure B3:

e is an integer from 1 to 2, ring E is a substituted or unsubstituted aryl group from C6 to C30, a substituted or unsubstituted heteroaryl group from C6 to C30,

preferably, the quinazoline group-containing compound has the following structure B4:

e is selected from an integer of 1 to 2, ring E is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 heteroaryl,

the substituents are as defined in claim 4.

9. 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 claimed in any one of claims 1 to 5;

preferably, the organic layer comprises a light-emitting layer comprising any one of the organic electroluminescent compounds as claimed in any one of claims 1 to 5 or a combination of at least two thereof;

preferably, the light-emitting layer comprises a host material and a guest material, the light-emitting layer host material comprises any one of the organic electroluminescent compounds according to any one of claims 1 to 5 or a combination of at least two of the organic electroluminescent compounds or the organic electroluminescent composition as described above;

preferably, the guest material comprises a phosphorescent dopant.

10. The organic electroluminescent device according to claim 9, 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;

preferably, the material of the hole transport layer comprises the organic electroluminescent compound according to any one of claims 1 to 5;

preferably, the material of the electron blocking layer comprises the organic electroluminescent compound according to any one of claims 1 to 5.