CN116730903A

CN116730903A - Carbazole compound and organic electroluminescent device thereof

Info

Publication number: CN116730903A
Application number: CN202310693332.1A
Authority: CN
Inventors: 孙月; 杜明珠; 孙敬
Original assignee: Changchun Hyperions Technology Co Ltd
Current assignee: Changchun Hyperions Technology Co Ltd
Priority date: 2023-06-12
Filing date: 2023-06-12
Publication date: 2023-09-12

Abstract

The invention provides a carbazole compound and an organic electroluminescent device thereof, belonging to the technical field of organic electroluminescent. The carbazole compound provided by the invention has strong molecular structure, so that the material has high thermal stability and good film forming property, and the triplet state energy level of the carbazole compound is high, can be well matched with the energy level of an adjacent layer, and can greatly improve the luminous efficiency of the device and prolong the service life of the device when being used as a main material in an organic electroluminescent device. The carbazole compound and the organic electroluminescent device thereof have good application effect and industrialization prospect.

Description

Carbazole compound and organic electroluminescent device thereof

Technical Field

The invention relates to the technical field of organic electroluminescence, in particular to a carbazole compound and an organic electroluminescent device thereof.

Background

Organic electroluminescent devices (Organic Light Emission Diodes, OLED) are a class of devices with a sandwich-like structure comprising an anode, a cathode and organic layers between or outside. At present, the technology is widely applied to display panels of products such as novel illumination lamps, smart phones and tablet computers, and gradually transits to the field of large-size display products such as televisions, and is a novel display technology with rapid development and high technical requirements. Compared with a liquid crystal display device, the OLED has the advantages of self-luminescence, low-voltage direct current drive, full solidification, wide viewing angle, rich colors and the like, does not need a backlight source, and has wider viewing angle, low power consumption and wider application prospect.

Since OLEDs were first reported, many scholars have been devoted to research on how to improve the efficiency and lifetime of the device. The research team of Forrest and Thompson finds that the transition metal complex can be applied to Ph OLEDs (phosphorescent OLEDs), the phosphorescent material has strong spin orbit coupling effect, and singlet excitons and triplet excitons can be utilized simultaneously, so that the quantum efficiency in the phosphorescent electroluminescent device reaches 100% in theory. However, phosphorescent materials have a long excited state lifetime, and triplet-triplet annihilation and triplet-polaron annihilation are easily formed when the triplet exciton concentration is high, so that the phosphorescent materials are often doped as guests into host materials in practical applications, thereby reducing the self-concentration quenching process. Therefore, it is also very important to select a suitable host material in phosphorescent organic electroluminescent devices. The host material needs to possess the following properties: (1) possess a higher triplet energy level; (2) The carrier mobility is better and can be matched with the energy level of the adjacent layer; (3) has high thermal stability and film-forming stability. At present, with the wide commercial application of OLED display and illumination, the efficiency and service life requirements of a client terminal on the OLED are continuously improved, in order to cope with the requirements, besides the requirement on the panel manufacturing process is continuously perfected, the development of an OLED material capable of meeting higher device indexes is particularly important, and particularly, the development of a stable and efficient main material is realized to achieve the purposes of improving the luminous efficiency of the device and prolonging the service life of the device, so that the OLED material has important practical application value.

Disclosure of Invention

In order to achieve the purposes of improving the luminous efficiency of the device and prolonging the service life of the device, the invention provides a carbazole compound and an organic electroluminescent device thereof, wherein the carbazole compound has higher triplet energy level and good carrier mobility, can be matched with the energy level of an adjacent organic layer, has higher thermal stability and better film forming property, and can effectively improve the luminous efficiency of the device and prolong the service life of the device when being applied to the organic electroluminescent device.

The invention provides a carbazole compound, which has a structure shown in a formula 1,

the x, z and v are the same or different and are selected from CH or N;

the Ra is selected from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, C1-C12 alkyl, C3-C12 alicyclic and C6-C30 aryl;

the Ra may be substituted with one or more substituents selected from any one of deuterium, halogen, cyano, trifluoromethyl, C1-C12 alkyl, C3-C12 alicyclic, C6-C30 aryl;

the Ar is as follows ₁ 、Ar ₂ The same or different aryl groups are selected from any one of substituted or unsubstituted C1-C12 alkyl groups, substituted or unsubstituted C3-C12 alicyclic groups and substituted or unsubstituted C6-C30 aryl groups;

The R is ₁ The same or different one is selected from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic and substituted or unsubstituted C6-C30 aryl;

the a is selected from 1, 2, 3, 4, 5, 6, 7 or 8; when two or more R's are present ₁ When two areOne or more R ₁ Are identical or different from each other, or adjacent R ₁ Are connected with each other to form a substituted or unsubstituted ring;

the R is ₂ 、R ₃ The same or different one is selected from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic and substituted or unsubstituted C6-C30 aryl;

said b is selected from 1, 2, 3, 4, 5 or 6; when two or more R's are present ₂ When two or more R' s ₂ Are identical or different from each other, or adjacent R ₂ Are connected with each other to form a substituted or unsubstituted ring;

said c is selected from 1, 2, 3, 4, 5, 6 or 7; when two or more R's are present ₃ When two or more R' s ₃ Are identical or different from each other, or adjacent R ₃ Are connected with each other to form a substituted or unsubstituted ring;

the L is ₀ 、L ₁ 、L ₂ Any one selected from single bond, substituted or unsubstituted C3-C12 alicyclic group and substituted or unsubstituted C6-C30 arylene group;

The formula 1 contains at least one deuterium atom.

The invention also provides an organic electroluminescent device, which comprises an anode, an organic layer and a cathode, wherein the organic layer comprises one or a combination of at least two of the carbazole compounds.

The invention has the beneficial effects that:

the carbazole compound provided by the invention has the advantages that the vibration coupling is lower, the molecular structure stability is higher, so that the carbazole compound has good thermal stability and good film forming property, when the carbazole compound is used as a main material to be applied to an organic electroluminescent device, the service life of the device can be effectively prolonged, and the carbazole compound has higher triplet state energy level and better matching property with an adjacent organic layer, so that the carbazole compound can greatly improve the luminous efficiency of the device when being applied to the device.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below in connection with the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. And embodiments of the invention and features of the embodiments may be combined with each other without conflict. All other embodiments, which can be made by a person skilled in the art without creative efforts, based on the described embodiments of the present invention fall within the protection scope of the present invention.

Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.

In the compounds of the present invention, any atom not designated as a particular isotope is included as any stable isotope of that atom, and includes atoms in both its natural isotopic abundance and non-natural abundance.

In the present specification, "×" means a moiety attached to another substituent.

In this specification, when a substituent or linkage site is located across two or more rings, it is meant that it may be attached to either of the two or two rings, in particular to either of the respective selectable sites of the rings. For example, the number of the cells to be processed,can indicate-> Can indicate->And so on.

In this specification, when a substituent is not fixed in position on a ring, it is meant that it can be attached to any of the corresponding selectable positions of the ring.

For example, the number of the cells to be processed,can indicate->Can indicate->Can indicate->And so on.

In this specification, when a substituent or linkage site is located across two or more rings, it is meant that it may be attached to either of the two or two rings, in particular to either of the respective selectable sites of the rings. For example Can indicate-> And so on.

Halogen refers to fluorine, chlorine, bromine and iodine;

the alkyl group according to the present invention means a monovalent group obtained by removing one hydrogen atom from an alkane molecule, and may be a straight chain alkyl group, a branched chain alkyl group, preferably having 1 to 25 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, and examples may include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, etc., but are not limited thereto.

The alicyclic group according to the present invention means a monovalent group obtained by removing at least one hydrogen atom from an alicyclic hydrocarbon molecule, and may be a cycloalkyl group, a cycloalkenyl group, etc., preferably having 3 to 20 carbon atoms, preferably 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, most preferably 3 to 7 carbon atoms, and examples may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, etc., but are not limited thereto.

The aryl group according to the present invention means a monovalent group obtained by removing one hydrogen atom from the aromatic nucleus carbon of an aromatic hydrocarbon molecule, and may be a monocyclic aryl group, a polycyclic aryl group or a condensed ring aryl group, preferably having 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms, and examples may include phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, indenyl, indanyl, dihydronaphthyl, tetrahydronaphthyl, anthracenyl, phenanthryl, pyrenyl, triphenylenyl, perylenyl, and the like, but are not limited thereto.

The arylene group refers to a bivalent group formed by removing two hydrogen atoms from the aromatic nucleus carbon of an aromatic hydrocarbon molecule. These are not only divalent groups but also aryl groups as described above.

The alicyclic group refers to a divalent group formed by removing two hydrogen atoms from an alicyclic hydrocarbon molecule. These are not only divalent groups but also alicyclic groups as described above.

"substituted" as used herein means that a hydrogen atom in a compound group is replaced with another atom or group, and the position of substitution is not limited.

"substituted or unsubstituted" as used herein means unsubstituted or substituted with one or more substituents selected from the group consisting of: protium, deuterium, tritium, cyano, halogen atom, amino, nitro, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C30 alicyclic group, substituted or unsubstituted C1-C25 heterocycloalkyl group, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C3-C30 alicyclic group and C6-C30 aromatic ring fused ring group, substituted or unsubstituted C1-C25 heterocycloalkyl group and C6-C30 aromatic ring fused ring group, substituted or unsubstituted C2-C30 heteroaryl group, substituted or unsubstituted C3-C25 alicyclic group and C2-C30 heteroaromatic ring fused ring group, substituted or unsubstituted C6-C30 arylamine group, substituted or unsubstituted C2-C30 heteroaromatic ring fused ring group The aryloxy group of C6 to C30, preferably protium, deuterium, tritium, halogen atom, cyano group, alkyl group of C1 to C12, alicyclic group of C3 to C18, aryl group of C6 to C25, heteroaryl group of C2 to C25, specific examples may include protium, deuterium, tritium, fluorine, chlorine, bromine, iodine, cyano group, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, cyclopentenyl, cyclohexenyl, benzocyclobutyl, benzocyclopentyl, benzocyclohexyl, benzocyclopentenyl, benzocyclohexenyl, phenyl, tolyl, mesityl, pentaphenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, benzophenyl, pyrenyl, triphenylenyl,A group, perylene group, fluoranthenyl group, 9-dimethylfluorenyl group, 9-diphenylfluorenyl group, 9-methyl-9-phenylfluorenyl group, carbazolyl group, 9-phenylcarbazolyl group, spirobifluorenyl group, carbazoloindolyl group, pyrrolyl group, furanyl group, thienyl group, indolyl group, benzofuranyl group, benzothienyl group, dibenzofuranyl group, dibenzothienyl group, pyridyl group, pyrimidinyl group, pyridazinyl group, pyrazinyl group, triazinyl group, oxazolyl group, thiazolyl group, imidazolyl group, benzoxazolyl group, benzothiazolyl group, benzotriazolyl group, benzimidazolyl group, pyridooxazolyl group, pyridothiazolyl group, pyridoimidazolyl group, pyrimidothiazolyl group, pyrimidoimidazolyl group, quinolino oxazolyl group, quinophthiazolyl group, quinolizinyl group, phenoxazinyl group, acridinyl group, and the like, but are not limited thereto. Or when the substituents are two or more, adjacent substituents may be bonded to form a ring; when the substituents are two or more, the two or more substituents are the same or different from each other.

The linkage described herein to form a substituted or unsubstituted ring means that the two groups are linked to each other by a chemical bond and optionally aromatized. As exemplified below:

in the present invention, the ring formed by the connection may be a five-membered ring or a six-membered ring or a condensed ring, and examples may include benzene, pyridine, pyrimidine, naphthalene, fluorene, cyclopentene, cyclohexene, cyclopentane, cyclohexane acene, quinoline, isoquinoline, dibenzothiophene, phenanthrene, or pyrene, but are not limited thereto.

Embodiments of the organic electroluminescent device according to the present invention will be described below with reference to the drawings, but the embodiments of the present invention may be modified into other forms, and the scope of the present invention is not limited to the embodiments described below.

In the present invention, "at least one deuterium is contained" means one, two, three, four, five, six, seven, eight, nine, ten or more deuterium is contained.

In the present invention, "at least one is deuterium" means one, two, three, four, five, six, seven, eight, nine, ten or more are deuterium.

In describing the structural elements of the present invention, the use of the terms "comprising" or "comprises" and the like in the present invention means that the device or article preceding the term encompasses the device or article listed after the term and equivalents thereof without excluding other devices or articles. The terms "connected" or "connected," and the like, are not limited to physical or mechanical connections, but may include electrical connections, whether direct or indirect. "inner", "outer", "upper", "lower" and the like are used merely to indicate relative positional relationships, which may also be changed when the absolute positions of the structural elements being described are changed. In the case where a structural element such as a layer, a film, a region, or a plate is located "on" another structural element, it is understood that the structural element is located "directly above" the other structural element, and that the structural element is located in the middle. In contrast, when one structural element is located "directly above" another structural element, it is understood that there are no other structural elements in between.

the x, z and v are the same or different and are selected from CH or N;

the a is selected from 1, 2, 3, 4, 5, 6, 7 or 8; when two or more R's are present ₁ When two or more R' s ₁ Are identical or different from each other, or adjacent R ₁ Are connected with each other to form a substituted or unsubstituted ring;

said c is selected from 1, 2, 3, 4, 5, 6 or 7; when storedAt two or more R ₃ When two or more R' s ₃ Are identical or different from each other, or adjacent R ₃ Are connected with each other to form a substituted or unsubstituted ring;

the formula 1 contains at least one deuterium atom.

Preferably, the carbazole compound has a structure shown as a formula 1-1 or a formula 1-2,

preferably, in the structures of formula I, formula 1-1 and formula 1-2, at most four of the eight x groups are selected from N, more preferably at most two of the eight x groups are selected from N; of the four x groups per ring, at most two are selected from N, more preferably at most one from N.

Preferably, in the structures of formula I, formula 1-1 and formula 1-2, at most four of the eight z's are selected from N, more preferably at most two are selected from N; of the four z groups per ring, at most two are selected from N, more preferably at most one are selected from N.

Preferably, in the structures of formula I, formula 1-1 and formula 1-2, at most four of the eight v are selected from N, more preferably at most two of the eight v are selected from N; of the four v per ring, at most two are selected from N, more preferably at most one are selected from N.

Preferably, said R ₂ 、R ₃ The same or different radicals are selected from hydrogen, deuterium, halogen, cyano, methyl, deuteromethyl, ethyl, deuteroethyl, isopropyl, deuteroisopropyl, tert-butyl, deuterated tert-butyl, cyclobutyl, deuterated cyclobutyl, cyclopentyl, deuterated cyclopentyl, cyclohexyl, deuterated cyclohexyl, adamantyl, deuterated adamantyl, norbornyl, deuterated norbornyl, cyclopentenyl, deuterated cyclopentenyl, cyclohexenyl, deuterated cyclohexenyl, phenyl, deuterated phenyl, cyanophenyl, pentafluorophenyl, pentamethylAny one of phenyl, biphenyl, deuterated biphenyl, terphenyl, naphthyl and deuterated naphthyl;

said c is selected from 1, 2, 3, 4, 5, 6 or 7; when two or more R's are present ₃ When two or more R' s ₃ Are identical or different from each other, or adjacent R ₃ Are linked to each other to form a substituted or unsubstituted ring.

Preferably, the saidSelected from any one of the structures shown below,

the Ra is selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornyl, substituted or unsubstituted cyclopentenyl, substituted or unsubstituted cyclohexenyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylenyl, and substituted or unsubstituted fluorenyl;

The Ra may be substituted with one or more substituents selected from any one or a combination of at least two of deuterium, halogen, cyano, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, cyclopentenyl, cyclohexenyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylenyl, fluorenyl, deuteromethyl, deuteroisopropyl, deuterated tert-butyl, deuterophenyl, deuterated biphenyl, deuterated naphthyl, trifluoromethyl, trifluoromethylphenyl, when two or more substituents are present, the two or more substituents may be the same or different from each other.

Preferably, the method comprises the steps of,selected from those containing deuterium in the structures shown above.

Preferably, the Ar ₁ 、Ar ₂ The same or different one is selected from any one of the following structures,

*-CH ₃ *-CD ₃ />

the Rb and Rc are the same or different and are selected from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic and substituted or unsubstituted C6-C30 aryl;

the R is ₄ The same or different one selected from hydrogen, deuterium, halogen, cyano, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C25 silyl;

The m is ₁ Selected from 1, 2, 3, 4, 5, 6 or 7; the m is ₂ Selected from 1, 2, 3, 4, 5, 6, 7, 8 or 9; the m is ₃ Selected from 1, 2, 3, 4,5. 6, 7, 8, 9, 10 or 11; the m is ₄ Selected from 1, 2, 3, 4 or 5; the m is ₅ Selected from 1, 2, 3 or 4; the m is ₆ Selected from 1, 2, 3, 4, 5, 6, 7 or 8; when two or more R's are present ₄ When two or more R' s ₄ Identical or different from each other, or two adjacent R' s ₄ Are linked to each other to form a substituted or unsubstituted ring.

*-CH ₃ *-CD ₃ />

/>

the Rb and Rc are the same or different and are selected from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tertiary butyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornyl, substituted or unsubstituted cyclopentenyl, substituted or unsubstituted cyclohexenyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl and substituted or unsubstituted naphthyl;

The Rb, rc may be substituted with one or more substituents selected from any one or a combination of at least two of deuterium, halogen, cyano, methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornyl, phenyl, biphenyl, naphthyl, deuterated methyl, deuterated isopropyl, deuterated tert-butyl, deuterated phenyl, deuterated biphenyl, deuterated naphthyl, trifluoromethyl, trifluoromethylphenyl, and when two or more substituents are present, the two or more substituents may be the same as or different from each other.

*-CD ₃

/>

the Rb and Rc are the same or different and are selected from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tertiary butyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl and substituted or unsubstituted naphthyl;

Preferably, the Ar ₁ 、Ar ₂ The same or different are selected from those containing deuterium in the structures shown above.

Preferably, the L ₀ 、L ₁ 、L ₂ The same or different is selected from single bond or any one of the structures shown below,

the Re, rf and Rg are the same or different and are selected from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic and substituted or unsubstituted C6-C30 aryl;

the R is ₅ The same or different hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic, substituted or unsubstituted C6-C18 aryl;

said n ₁ The same or different is selected from 1, 2, 3 or 4; said n ₂ The same or different is selected from 1, 2, 3, 4, 5 or 6; said n ₃ The same or different is selected from 1, 2, 3, 4, 5, 6, 7 or 8; said n ₄ The same or different is selected from 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; said n ₅ The same or different is selected from 1, 2, 3, 4, 5, 6 or 7; when two or more R's are present ₅ When two or more R' s ₅ Are identical or different from each other, or adjacent R ₅ Are linked to each other to form a substituted or unsubstituted ring.

Preferably, the L ₀ 、L ₁ 、L ₂ The same or different are selected from single bonds or as followsAny one of the structures shown in the figures,

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the Re, rf and Rg are the same or different and are selected from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tertiary butyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornyl, substituted or unsubstituted cyclopentenyl, substituted or unsubstituted cyclohexenyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl and substituted or unsubstituted naphthyl;

the Re, rf, rg may be substituted with one or more substituents selected from any one or a combination of at least two of deuterium, halogen, cyano, methyl, ethyl, isopropyl, t-butyl, adamantyl, norbornyl, phenyl, biphenyl, naphthyl, deuterated methyl, deuterated isopropyl, deuterated t-butyl, deuterated phenyl, deuterated biphenyl, deuterated naphthyl, trifluoromethyl, and trifluoromethylphenyl, and when two or more substituents are present, the two or more substituents may be the same or different from each other.

Preferably, the L ₀ 、L ₁ 、L ₂ The same or different are selected from single bonds or those containing deuterium in the structures shown above.

Preferably, the L ₁ Contains at least one deuterium.

Preferably, the L ₂ Contains at least one deuterium.

Preferably, the Ar ₁ Contains at least one deuterium.

Preferably, the Ar ₂ Contains at least one deuterium.

Preferably, the "/L ₁ -Ar ₁ "contains at least one deuterium.

Preferably, the "/L ₂ -Ar ₂ "contains at least one deuterium.

Preferably, the "/L ₁ -Ar ₁ "sum". Times. -L ₂ -Ar ₂ "contains at least one deuterium.

Preferably, said R ₁ Contains at least one deuterium. More preferably, said R ₁ At least one of which is deuterium.

Preferably, said R ₂ Contains at least one deuterium. More preferably, said R ₂ At least one of which is deuterium.

Preferably, said R ₃ Contains at least one deuterium. More preferably, said R ₃ At least one of which is deuterium.

Preferably, said R ₂ And R is ₃ Contains at least one deuterium. More preferably, said R ₂ And R is ₃ At least one of which is deuterium. Preferably, the carbazole compound is selected from any one of the structures shown in the specification,

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the invention also provides a preparation method of the carbazole compound,

the Xa is the same or different and is selected from any one of I, br and Cl;

The present invention may bond the above substituents by a method known in the art, and the kind and position of substituents or the number of substituents may be changed according to a technique known in the art.

The invention provides an organic electroluminescent device, which comprises an anode, an organic layer and a cathode, wherein the organic layer comprises one or a combination of at least two carbazole compounds.

Preferably, the organic layer according to the present invention comprises a light emitting layer comprising one or a combination of at least two of the carbazole-based compounds according to the present invention.

The organic layer of the present invention may further include a hole injection layer, a hole transport layer, a light emitting auxiliary layer, an electron injection layer, an electron transport layer, a hole blocking layer, a capping layer, an encapsulation layer, etc. However, the structure of the organic electroluminescent device of the present invention is not limited to the above-described structure, and if necessary, a plurality of organic layers may be omitted or simultaneously provided, and an organic layer having the same function may be formed in a laminated structure of two or more layers.

The organic electroluminescent device of the invention has the structure that:

a substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode;

A substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode/capping layer;

a substrate/anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;

a substrate/anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/capping layer;

a substrate/anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;

a substrate/anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/capping layer;

a substrate/anode/hole injection layer/hole transport layer/light emitting auxiliary layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;

a substrate/anode/hole injection layer/hole transport layer/light emitting auxiliary layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/cover layer;

however, the structure of the organic electroluminescent device is not limited thereto. The organic electroluminescent device can be selected and combined according to the device parameter requirement and the material characteristics, partial organic layers can be added or omitted, and the organic layers with the same function can be made into a laminated structure with more than two layers.

The organic electroluminescent device of the present invention is generally formed on a substrate. The substrate may be a substrate made of glass, plastic, polymer film, silicon, or the like, as long as it is not changed when an electrode is formed or an organic layer is formed.

In the organic electroluminescent device according to the present invention, the anode material preferably uses a high work function material capable of promoting injection of holes into the organic layer. Specific examples of the anode material that can be used in the present invention may include: metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), indium Zinc Oxide (IZO); combinations of metals and oxides, such as ITO-Ag-ITO; conductive polymers such as poly (3-methylthiophene), polypyrrole, polyaniline, poly [3,4- (ethylene-1, 2-dioxy) thiophene ] (PEDT), and the like, but are not limited thereto.

In the organic electroluminescent device of the present invention, the hole injection material is preferably a material having a good hole accepting ability. Specific examples of the hole injecting material that can be used in the present invention may include: silver oxide, vanadium oxide, tungsten oxide, copper oxide, titanium oxide, other metal oxides, phthalocyanine compounds, biphenylamine compounds, phenazine compounds, other materials, such as copper phthalocyanine (CuPc), titanyl phthalocyanine, N ' -diphenyl-N, N ' -di- [4- (N, N-diphenylamine) phenyl ] benzidine (NPNPB), N ' -tetra (4-methoxyphenyl) benzidine (MeO-TPD), and bisquinoxalino [2,3-a:2',3' -c ] phenazine (HATNA), 4',4 "-tris [ 2-naphthylphenylamino ] triphenylamine (2T-NATA), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene (HAT-CN), 4',4" -tris (N, N-diphenylamino) triphenylamine (TDATA), and the like, but are not limited thereto.

In the organic electroluminescent device according to the present invention, the hole transporting material is preferably a material having excellent hole transporting property and HOMO level matching with the corresponding anode material. Specific examples of the hole transporting material that can be used in the present invention may include materials such as diphenylamines, triphenylamines, fluorenes, and carbazoles, such as N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), N ' -di (naphthalen-1-yl) -N, N ' -di (phenyl) -2,2' -dimethylbenzidine (α -NPD), N ' -diphenyl-N, N ' -di (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (TPD), 4- [1- [4- [ di (4-methylphenyl) amino ] phenyl ] cyclohexyl ] -N- (3-methylphenyl) -N- (4-methylphenyl) aniline (TAPC), and the like, but are not limited thereto.

In the organic electroluminescent device, the luminescent auxiliary layer is preferably a material with good hole transmission performance and electron blocking performance. Specific examples of the light-emitting auxiliary material that can be used in the present invention may include triarylamine derivatives, spirofluorene derivatives, furan derivatives, and the like, such as TPD, NPB, N, N4-bis ([ 1,1 '-biphenyl ] -4-yl) -N4' -phenyl N4'- [1,1':4',1 "-terphenyl ] -4-yl- [1,1' -biphenyl ] -4,4 '-diamine, N- ([ 1,1' -diphenyl ] -4-yl) -N- (9, 9-dimethyl-9H-furan-2-yl) -9,9 '-spirobifluorene-2-amine, N-bis ([ 1,1' -biphenyl ] -4-yl) -3'- (dibenzo [ b, d ] furan-4-yl) - [1,1' -biphenyl ] -4-amine, and the like, but is not limited thereto.

In the organic electroluminescent device of the present invention, the luminescent layer material comprises a luminescent layer host material and a luminescent layer doping material, and the luminescent layer host material may be selected from 4,4 '-bis (9-Carbazolyl) Biphenyl (CBP), 9, 10-bis (2-naphthyl) Anthracene (ADN), 4-bis (9-carbazolyl) biphenyl (CPB), 9' - (1, 3-phenyl) bis-9H-carbazole (mCP), 4',4 "-tris (carbazol-9-yl) triphenylamine (TCTA), 9, 10-bis (1-naphthyl) anthracene (α -ADN), N' -bis- (1-naphthyl) -N, N '-diphenyl- [1,1':4', 1':4', 1' -tetrabiphenyl]-4, 4' -diamine (4 PNPB), 1,3, 5-tris (9-carbazolyl) benzene (TCP), etc., but is not limited thereto. Preferably, the host material of the light emitting layer of the present invention is selected from 9, 10-bis (2-naphthyl) Anthracene (ADN), 9'- (1, 3-phenyl) bis-9H-carbazole (mCP), 4',4 "-tris (carbazol-9-yl) triphenylamine (TCTA), 9, 10-bis (1-naphthyl) anthracene (α -AND), carbazole-based compounds of the present invention, AND the like. The light emitting layer doping material can be selected from (6- (4- (diphenylamino (phenyl) -N, N-diphenylpyrene-1-amine) (DPAP-DPPA), 2,58, 11-tetra-tert-butylperylene (TBPe), 4' -bis [4- (diphenylamino) styryl group]Biphenyl (BDAVBi), 4' -di [4- (di-p-tolylamino) styryl]Diphenyl (DPAVBi), bis (2-hydroxyphenylpyridine) beryllium (Bepp 2), bis (4, 6-difluorophenylpyridine-C2, N) iridium picolinate (FIrpic), tris (2-phenylpyridine) iridium (Ir (ppy) ₃ ) Bis (2-phenylpyridine) iridium acetylacetonate (Ir (ppy) ₂ (acac)), 9, 10-bis [ N- (p-tolyl) anilino group]Anthracene (TPA), 4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminostyryl) -4H-pyran (DCM), tris [ 1-phenylisoquinoline-C2, N]Iridium (III) (Ir (piq) ₃ ) Ir (piq) iridium bis (1-phenylisoquinoline) (acetylacetonate) ₂ (acac)) and the like, but is not limited thereto. Preferably, the light-emitting layer guest according to the present invention is selected from the group consisting of 4,4' -bis [4- (di-p-tolylamino) styryl]Biphenyl (DPAVBi), 2,5,8, 11-tetra-tert-butylperylene (TBPe), 9, 10-di [ N- (p-tolyl) anilino group]Anthracene (TPA), 4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminostyryl) -4H-pyran (DCM), and the like.

The doping ratio of the host material for the light-emitting layer and the doping material for the light-emitting layer may be varied depending on the materials used, and is usually 0.01% to 20%, preferably 0.1% to 15%, and more preferably 1% to 10%.

In the organic electroluminescent device according to the present invention, the hole blocking material has a strong hole blocking ability and suitable HOMO and LUMO energy levels, and specific examples of the hole blocking material that can be used in the present invention may include imidazoles, triazoles, phenanthroline derivatives, etc., such as 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), 3- (biphenyl-4-yl) -5- (4-t-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ), bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (BAlq), etc., but are not limited thereto.

In the organic electroluminescent device according to the present invention, the electron transport material is preferably a material having a strong electron withdrawing ability and low HOMO and LUMO energy levels, and specific examples of the electron transport material usable in the present invention may include imidazoles, triazoles, phenanthroline derivatives, quinolines, and the like, such as 2,9- (dimethyl) -4, 7-biphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tris [ (3-pyridyl) -phenyl ] benzene (TmPyPB), 4' -bis (4, 6-diphenyl-1, 3, 5-triazinyl) biphenyl (BTB), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ), 2- (naphthalene-2-yl) -4,7- (diphenyl) -1, 10-phenanthrene (hnb), 8-hydroxy-Lithium (LiQ), and the like, but not limited thereto.

In the organic electroluminescent device according to the present invention, the electron injection material preferably has a small potential barrier difference from an adjacent organic transport material, host material, or the like, and at the same time has an effect of injecting electrons from the cathode. Examples of electron injection materials that can be used in the present invention include: alkali metal salts (e.g., liF, csF), alkaline earth metal salts (e.g., mgF) ₂ ) Metal oxides (such as Al ₂ O ₃ 、MoO ₃ ) But is not limited thereto.

In the organic electroluminescent device according to the present invention, the cathode material preferably uses a low work function material capable of promoting electron injection into the organic layer. Specific examples of the cathode material that can be used in the present invention may include: metals such as aluminum, magnesium, silver, indium, tin, titanium, and the like, and alloys thereof; multilayer metallic materials, e.g. LiF/Al, mg/Ag, li/Al, liO ₂ /Al、BaF ₂ Al, etc., but is not limited thereto.

In the organic electroluminescent device according to the present invention, the material for the cover layer is preferably a material for improving optical coupling. Specific examples of the capping layer material that can be used in the present invention may include, but are not limited to, arylamine derivatives, carbazole derivatives, benzimidazole derivatives, triazole derivatives, lithium fluoride, and the like. The coating layer may be formed at the same time on the outer side of the anode and the outer side of the cathode, or may be disposed on the outer side of the anode or the outer side of the cathode, and preferably, the coating layer according to the present invention is disposed on the outer side of the cathode.

The thickness of each organic layer of the organic electroluminescent device is not particularly limited, and may be any thickness commonly used in the art.

The organic electroluminescent device of the present invention may be any one of a vacuum evaporation method, a spin coating method, a vapor deposition method, a blade coating method, a laser thermal transfer method, an electrospray coating method, a slit coating method, and a dip coating method, and in the present invention, a vacuum evaporation method is preferably used.

The organic electroluminescent device can be widely applied to the fields of panel display, illumination light sources, flexible OLED, electronic paper, organic solar cells, organic photoreceptors or organic thin film transistors, indication boards, signal lamps and the like.

The present invention is explained more fully by the following examples, but is not intended to be limited thereby. Based on this description, one of ordinary skill in the art will be able to practice the invention and prepare other compounds and devices according to the invention within the full scope of the disclosure without undue burden.

Preparation and characterization of the Compounds

Description of the starting materials, reagents and characterization equipment:

the raw materials and reagent sources used in the following examples are not particularly limited, and may be commercially available products or prepared by methods well known to those skilled in the art.

The mass spectrum uses a Wotes G2-Si quadrupole tandem time-of-flight high resolution mass spectrometer in UK, chloroform as a solvent;

the elemental analysis uses a Vario EL cube type organic elemental analyzer of Elementar, germany, and the mass of the sample is 5-10 mg;

synthetic examples

Synthesis example 1 Synthesis of intermediate 6-d

6-A (10.55 g,50.00 mmol) was dissolved in NMP (500 ml), 6-B (8.43 g,52.00 mmol), sodium sulfate (7.10 g,50 mmol), potassium carbonate (6.91 g,50 mmol) and copper (0.96 g,15 mmol) were added, heated to 200℃and reacted for 18 hours; after the reaction was completed, the solvent was removed by distillation under reduced pressure, followed by extraction with dichloromethane and water, and the organic phase was dried over anhydrous magnesium sulfate, followed by distillation under reduced pressure, purification by column chromatography and recrystallization, to give intermediate 6-d (12.12 g, yield 83%), HPLC purity: 99.85%, mass spectrum m/z:292.1458 (theory: 292.1431).

Synthesis example 2 Synthesis of intermediate 9-d

According to the preparation method of synthetic example 1, 6-A and 6-B were replaced with equimolar amounts of 9-A and 9-B, respectively, to give intermediate 9-d (12.19 g) having an HPLC purity of 99.76% or more. Mass spectrum m/z:290.1318 (theory: 290.1306).

Synthesis example 3 Synthesis of intermediate 14-d

The procedure of synthesis example 1 was followed, substituting 6-A for equimolar 14-A, to give intermediate 14-d (12.92 g) with an HPLC purity of 99.58%. Mass spectrum m/z:315.2197 (theory: 315.2184).

Synthesis example 4 Synthesis of intermediate 33-d

The procedure of synthesis example 1 was followed, substituting 6-A for equimolar 33-A to give intermediate 33-d (13.08 g) with an HPLC purity of 99.81%. Mass spectrum m/z:315.2168 (theory: 315.2184).

Synthesis example 5 Synthesis of intermediate 45-d

According to the preparation method of synthetic example 1, 6-A and 6-B were replaced with 33-A and 9-B, respectively, in equimolar amounts, to give intermediate 45-d (12.36 g) with an HPLC purity of 99.75% or more. Mass spectrum m/z:294.1569 (theory: 294.1557).

Synthesis example 6 Synthesis of intermediate 51-d

According to the preparation method of synthetic example 1, 6-A and 6-B were replaced with equimolar amounts of 51-A and 51-B, respectively, to give intermediate 51-d (15.08 g) having an HPLC purity of 99.60% or more. Mass spectrum m/z:377.0629 (theory: 377.0647).

Synthesis example 7 Synthesis of intermediate 105-d

According to the preparation method of synthetic example 1, 6-A and 6-B were replaced with 105-A and 9-B, respectively, to give intermediate 105-d (12.06 g) with an HPLC purity of 99.48%. Mass spectrum m/z:294.1573 (theory: 294.1557).

Synthesis example 8 Synthesis of intermediate 178-d

According to the preparation method of synthetic example 1, 6-A and 6-B are replaced by 178-A and 178-B respectively in equimolar form, to obtain an intermediate 178-d (13.60 g), and the HPLC purity is more than or equal to 99.78%. Mass spectrum m/z:344.1702 (theory: 344.1713).

Synthesis example 9 Synthesis of intermediate 201-d

The procedure of synthesis example 1 was followed, substituting 6-A for equimolar 201-A, to give intermediate 201-d (13.86 g) with an HPLC purity of 99.87%. Mass spectrum m/z:342.1599 (theory: 342.1588).

Synthesis example 10 Synthesis of intermediate 206-d

Synthesis of intermediate 33-d

33-A (23.41 g,100.00 mmol) was dissolved in NMP (1000 ml), 6-B (17.01 g,105.00 mmol), sodium sulfate (14.20 g,100 mmol), potassium carbonate (13.82 g,100 mmol) and copper (1.92 g,130 mmol) were added, heated to 200℃and reacted for 18 hours; after the completion of the reaction, the solvent was removed by distillation under reduced pressure, followed by extraction with methylene chloride and water, and the organic phase was dried over anhydrous magnesium sulfate, then distilled under reduced pressure, and purified by column chromatography and recrystallization to give intermediate 33-d (26.17 g, yield 83%), purity by HPLC was not less than 99.81%. Mass spectrum m/z:315.2168 (theory: 315.2184).

Synthesis of intermediate 206-E

33-D (25.85 g,82.00 mmol), 206-D (18.52 g,80 mmol), tetrakis (triphenylphosphine) palladium (1.85 g,1.60 mmol), potassium carbonate (22.11 g,160.00 mmol) and toluene (300 mL), ethanol (100 mL) were added to the reaction flask under nitrogen, the mixture was stirred, and the reaction was heated at reflux for 6.5 hours. After the reaction was completed down to room temperature, a filter cake was obtained by suction filtration, and the filter cake was rinsed with ethanol, and finally the filter cake was washed with toluene/ethanol=5: 1 to give intermediate 206-E (23.06 g, 71%); HPLC purity is more than or equal to 99.63%. Mass spectrum m/z:405.2049 (theory: 405.2037).

Synthesis of intermediate 206-d

206-E (20.30 g,50.00 mmol), pinacol ester of biboronic acid (13.20 g,52.00 mmol), potassium acetate (9.81 g,100.00 mmol), 1' -bis-diphenylphosphino ferrocene palladium dichloride (0.73 g,1.00 mmol) and 1, 4-dioxane (200 mL) were added to the reaction flask under nitrogen, the mixture was stirred and heated under reflux for 5 hours. After the reaction is completed and cooled to room temperature, filtering to obtain a filter cake, flushing the filter cake with ethanol, and finally recrystallizing the filter cake with toluene to obtain an intermediate 206-d (17.91 g, 72%); HPLC purity is more than or equal to 99.88%. Mass spectrum m/z:497.3262 (theory: 497.3279).

Synthesis example 11 Synthesis of intermediate 217-d

According to the preparation method of Synthesis example 10, 33-A and 206-D were replaced with 6-A and 217-D, respectively, to obtain intermediate 217-D (16.44 g), and the HPLC purity was not less than 99.64%. Mass spectrum m/z:450.2539 (theory: 450.2527).

Synthesis example 12 Synthesis of intermediate 244-d

According to the preparation method of Synthesis example 10, 33-A, 6-B and 206-D were replaced with 6-A, 244-B and 244-D, respectively, to obtain intermediate 244-D (22.35 g) having an HPLC purity of 99.49% or more. Mass spectrum m/z:629.3449 (theory: 629.3465).

Synthesis example 13 Synthesis of intermediate 311-d

According to the preparation method of Synthesis example 10, 33-D and 206-D were replaced with equimolar amounts of 311-C and 217-D, respectively, to obtain intermediate 311-D (17.84 g), and the HPLC purity was not less than 99.85%. Mass spectrum m/z:495.2388 (theory: 495.2370).

Synthesis example 14 Synthesis of intermediate 364-d

Synthesis of intermediate 364-I

364-G (28.99G, 100.00 mmol), tetrahydrofuran (450 mL) and n-butyllithium (55 mL of 1.6M hexane solution) were added to the flask under nitrogen, and the reaction was stirred at-78℃for 1 hour. A solution of 364-H (25.83 g,100 mmol) in tetrahydrofuran (150 mL) was then added dropwise to the flask and the reaction was continued with stirring at-78℃for 1 hour, followed by stirring at room temperature for 4 hours. After the reaction, a saturated ammonium chloride solution was added to separate an organic layer, and the organic layer was concentrated. Concentrated organic solid, acetic anhydride (800 mL) and hydrochloric acid (40 mL) are added into a reaction bottle, stirred at 100 ℃ for reaction for 4 hours, cold water (350 mL) is added after the reaction is finished to separate out solid products, the solid products are filtered, and then silica gel column purification (petroleum ether/dichloromethane=9:1) is carried out to obtain an intermediate 364-I (34.75 g, yield 77%), the HPLC purity is more than or equal to 99.61%, mass spectrum m/z:451.1730 (theory: 451.1744).

Synthesis of intermediate 364-d

Intermediate 364-I (24.82 g,55 mmol), toluene (300 mL), 6-B (8.1 g,50 mmol), dibenzylideneacetone dipalladium (0.46 g,0.50 mmol), 1 '-binaphthyl-2, 2' -bisdiphenylphosphine (1.00 g,1.6 mmol) and sodium tert-butoxide (15.36 g,160 mmol) were added to a reaction flask under nitrogen protection, stirred and dissolved, reflux reaction was carried out for 8 hours, after completion of the reaction, the mixture was cooled to room temperature, filtered, the organic solvent was removed from the filtrate by distillation under reduced pressure, and the obtained solid material was recrystallized from methanol to give intermediate 364-d (21.03 g, yield 79%) with HPLC purity of not less than 99.74%. Mass spectrum m/z:532.2385 (theory: 532.2370).

Synthesis example 15 Synthesis of intermediate 376-d

According to the preparation method of Synthesis example 14, 364-H and 6-B were replaced with 376-H and 376-J, respectively, to obtain intermediate 376-d (23.20 g), and the HPLC purity was not less than 99.64%. Mass spectrum m/z:602.3141 (theory: 602.3153).

Synthesis example 16 Synthesis of intermediate 382-d

According to the preparation method of synthetic example 1, 6-B was replaced with 382-B in equimolar amount to obtain intermediate 382-d (18.07 g), and HPLC purity was not less than 99.75%. Mass spectrum m/z:463.1732 (theory: 463.1744).

Synthesis example 17 Synthesis of intermediate 391-d

The preparation of synthetic example 1 was followed by substituting 6-B with equimolar 391-B to give intermediate 391-d (14.38 g) with an HPLC purity of 99.45%. Mass spectrum m/z:351.0980 (theory: 351.0991).

Synthesis example 18 Synthesis of intermediate 411-d

The preparation method of synthetic example 1 was followed by substituting 6-A with equimolar 411-A to give intermediate 411-d (12.92 g) with an HPLC purity of 99.63%. Mass spectrum m/z:315.2199 (theory: 315.2184).

Synthesis example 19 Synthesis of intermediate 451-d

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According to the preparation method of Synthesis example 1, 6-A and 6-B were replaced with equimolar amounts of 451-A and 451-B, respectively, to give intermediate 451-d (14.49 g), with HPLC purity of 99.71% or more. Mass spectrum m/z:362.1215 (theory: 362.1227).

Synthesis example 20 Synthesis of intermediate 468-d

According to the preparation method of synthetic example 1, 6-A and 6-B were replaced with 33-A and 468-B, respectively, in equimolar amounts, to give intermediate 468-d (17.55 g), with an HPLC purity of 99.88% or more. Mass spectrum m/z:444.2039 (theory: 444.2026).

Synthesis example 21 Synthesis of intermediate 473-d

According to the preparation method of Synthesis example 14, 364-H and 6-B were replaced with 473-H and 473-J, respectively, to obtain intermediate 473-d (27.52 g) with an HPLC purity of 99.68% or more. Mass spectrum m/z:705.2817 (theory: 705.2839).

Synthesis example 22 Synthesis of intermediate 493-d

According to the preparation method of Synthesis example 1, 6-A and 6-B were replaced with 33-A and 451-B, respectively, in equimolar amounts, to give intermediate 493-d (13.94 g), and the HPLC purity was not less than 99.52%. Mass spectrum m/z:344.1702 (theory: 344.1713).

Synthesis example 23 Synthesis of Compound 2

Synthesis of intermediate 2-c

2-a (21.04 g,75.00 mmol), tetrahydrofuran (350 mL) and n-butyllithium (40 mL of 1.6M hexane solution) were added to the flask under nitrogen, and the reaction was stirred at-78℃for 1 hour. Then, a tetrahydrofuran solution (150 mL) containing 2-b (15.02 g,75 mmol) was added dropwise to the flask, and the reaction was continued with stirring at-78℃for 1 hour, followed by stirring at room temperature for 4 hours. After the reaction, a saturated ammonium chloride solution was added to separate an organic layer, and the organic layer was concentrated. Concentrated organic solid, acetic anhydride (700 mL) and hydrochloric acid (30 mL) are added into a reaction bottle, stirred at 100 ℃ for reaction for 4 hours, cold water (300 mL) is added after the reaction is finished to separate out a solid product, and the solid product is filtered, and then purified by a silica gel column (petroleum ether/dichloromethane=10:1) to obtain an intermediate 2-c (22.46 g, yield 78%), the HPLC purity is more than or equal to 99.46%, and the mass spectrum m/z:383.0826 (theory: 383.0877).

Synthesis of intermediate 2-e

2-d (12.63 g,44 mmol), intermediate 2-c (15.35 g,40 mmol), tetrakis triphenylphosphine palladium (0.58 g,0.50 mmol), potassium acetate (7.65 g,78.00 mmol), toluene (200 mL), ethanol (75 mL), and water (75 mL) were sequentially added to a reaction flask under argon atmosphere, and the mixture was stirred and reacted under reflux for 4 hours; after the reaction was completed, cooled to room temperature, suction filtered to obtain a filter cake, and the filter cake was rinsed with ethanol, and finally the filter cake was purified with toluene/ethanol=10: 3, to obtain intermediate 2-e (19.85 g, yield 84%) with HPLC purity greater than or equal to 99.83%. Mass spectrum m/z:590.2173 (theory: 590.2158).

Synthesis of Compound 2

Under nitrogen protection, intermediate 2-e (16.54 g,28 mmol), toluene (150 mL), 2-f (4.05 g,25 mmol), dibenzylideneacetone dipalladium (0.23 g,0.25 mmol), 1 '-binaphthyl-2, 2' -bisdiphenylphosphine (0.50 g,0.8 mmol) and sodium tert-butoxide (7.68 g,80 mmol) were added to a reaction flask, stirred and dissolved, the reaction was refluxed for 8 hours, after completion of the reaction, the mixture was cooled to room temperature, filtered, the organic solvent was removed from the filtrate by distillation under reduced pressure, and the obtained solid was recrystallized from methanol to give compound 2 (13.60 g, yield 81%) with HPLC purity of 99.94%. Mass spectrum m/z:671.2796 (theory: 671.2785). Theoretical element content (%) C ₄₉ H ₂₆ D ₅ FN ₂ : c,87.60; h,5.40; n,4.17. Measured element content (%): c,87.62; h,5.41; n,4.14.

Synthesis example 24 Synthesis of Compound 6

According to the preparation method of Synthesis example 23, 2-a, 2-b, 2-d, 2-e and 2-f were replaced with 6-a, 6-b, 6-d, 6-e and 6-f in equimolar amounts, respectively, to give Compound 6 (14.30 g) having an HPLC purity of 99.98% or more. Mass spectrum m/z:794.4328 (theory: 794.4383). Theoretical element content (%) C ₅₉ H ₃₀ D ₁₄ N ₂ : c,89.13; h,7.35; n,3.52. Measured element content (%): c,89.11; h,7.36; n,3.54.

Synthesis example 25 Synthesis of Compound 9

According to the preparation method of Synthesis example 23, 2-a, 2-B, 2-d, 2-e and 2-f were replaced with equimolar amounts of 9-a, 9-B, 9-d, 9-e and 9-B, respectively, to give Compound 9 (15.58 g) with an HPLC purity of 99.96% or more. Mass spectrum m/z:788.4052 (theory: 788.4038). Theoretical element content (%) C ₅₉ H ₄₀ D ₆ N ₂ : c,89.81; h,6.64; n,3.55. Measured element content (%): c,89.84; h,6.62; n,3.57.

Synthesis example 26 Synthesis of Compound 14

According to the preparation method of Synthesis example 23, 2-a, 2-B, 2-d, 2-e and 2-f were replaced with equimolar amounts of 14-a, 14-B, 14-d, 14-e and 9-B, respectively, to give Compound 14 (15.70 g) with an HPLC purity of 99.91% or more. Mass spectrum m/z:804.3518 (theoretical value: 804.3506 theoretical element content (%) C ₅₆ H ₂₃ D ₁₂ F ₃ N ₂ : c,83.56; h,5.88; n,3.48. Measured element content (%): c,83.59; h,5.85; n,3.46.

Synthesis example 27 Synthesis of Compound 27

According to the preparation method of Synthesis example 23, 2-B, 2-d, 2-e and 2-f were replaced with 27-B, 6-d, 27-e and 6-B, respectively, in equimolar amounts, to give Compound 27 (14.63 g) having an HPLC purity of 99.97% or more. Mass spectrum m/z:759.3445 (theory: 759.3459). Theoretical element content (%) C ₅₆ H ₂₅ D ₁₀ N ₃ : c,88.50; h,5.97; n,5.53. Measured element content (%): c,88.55; h,5.94; n,5.56.

Synthesis example 28 Synthesis of Compound 33

Synthesis of intermediate 33-c

33-a (14.27 g,40.00 mmol), tetrahydrofuran (200 mL) and n-butyllithium (25 mL of 1.6M hexane solution) were added to the flask under nitrogen and reacted at-78℃for 1 hour with stirring. Then, a tetrahydrofuran solution (100 mL) containing 33-b (12.58 g,40 mmol) was added dropwise to the flask, and the reaction was continued with stirring at-78℃for 1 hour, followed by stirring at room temperature for 4 hours. After the reaction, a saturated ammonium chloride solution was added to separate an organic layer, and the organic layer was concentrated. The concentrated organic solid, acetic anhydride (500 mL) and hydrochloric acid (20 mL) were added into a reaction flask, stirred at 100 ℃ for 4 hours, after the reaction was completed, cold water (200 mL) was added to precipitate a solid product, which was filtered, and then purified by a silica gel column (petroleum ether/dichloromethane=10:1) to obtain intermediate 33-c (17.91 g, yield 78%), HPLC purity not less than 99.66%, mass spectrum m/z:573.2241 (theory: 573.2223).

Synthesis of Compound 33

33-d (8.83 g,28 mmol), intermediate 33-c (14.35 g,25 mmol), tetrakis triphenylphosphine palladium (0.35 g,0.30 mmol), potassium acetate (4.91 g,78.00 mmol), toluene (150 mL), ethanol (50 mL), and water (50 mL) were sequentially added to the reaction flask under argon atmosphere, and the mixture was stirred and reacted under reflux for 5 hours; after the reaction was completed, cooled to room temperature, suction filtered to obtain a filter cake, and the filter cake was rinsed with ethanol, and finally the filter cake was purified with toluene/ethanol=5: 1 to obtain intermediate 33 (16.26 g, yield 82%) with HPLC purity greater than or equal to 99.95%. Mass spectrum m/z:792.4245 (theory: 792.4258). Theoretical element content (%) C ₅₉ H ₃₂ D ₁₂ N ₂ : c,89.35; h,7.11; n,3.53. Measured element content (%): c,89.38h,7.14; n,3.50..

Synthesis example 29 Synthesis of Compound 40

According to the preparation method of Synthesis example 23, 2-a, 2-b, 2-d, 2-e, 2-f were replaced with 40-a, 40-f in equimolar amounts, respectivelyb. 33-d, 40-e, 6-B to give compound 40 (14.72 g), with HPLC purity not less than 99.92%. Mass spectrum m/z:735.4336 (theory: 735.4322). Theoretical element content (%) C ₅₄ H ₁₃ D ₂₃ N ₂ : c,88.12; h,8.07; n,3.81. Measured element content (%): c,88.16; h,8.04; n,3.85.

Synthesis example 30 Synthesis of Compound 45

According to the preparation method of Synthesis example 28, 33-b and 33-d were replaced with 364-H and 45-d, respectively, to give Compound 45 (15.19 g), with an HPLC purity of 99.98%. Mass spectrum m/z:731.3302 (theory: 731.3318). Theoretical element content (%) C ₅₅ H ₂₉ D ₇ N ₂ : c,90.25; h,5.92; n,3.83. Measured element content (%): c,90.29; h,5.90; n,3.85.

Synthesis example 31 Synthesis of Compound 51

According to the preparation method of Synthesis example 23, 2-a, 2-B, 2-d, 2-e and 2-f were replaced with equimolar amounts of 51-a, 473-H, 51-d, 51-e and 6-B, respectively, to give Compound 51 (15.28 g) with an HPLC purity of 99.93%. Mass spectrum m/z:763.2956 (theory: 763.2941). Theoretical element content (%) C ₅₀ H ₁₈ D ₁₁ F ₅ N ₂ : c,78.62; h,5.28; n,3.67. Measured element content (%): c,78.66; h,5.25; n,3.64.

Synthesis example 32 Synthesis of Compound 58

According to the preparation method of Synthesis example 23, 2-b, 2-d, 2-e and 2-f were replaced with respective ones of 473-H, 58-d, 58-e and 58-f in equimolar amounts to give Compound 58 (14.19)g) HPLC purity is more than or equal to 99.96%. Mass spectrum m/z:819.3674 (theory: 819.3662). Theoretical element content (%) C ₆₂ H ₃₇ D ₅ N ₂ : c,90.81; h,5.78; n,3.42. Measured element content (%): c,90.80; h,5.77; n,3.44.

Synthesis example 33 Synthesis of Compound 105

According to the preparation method of Synthesis example 23, 2-b, 2-d, 2-e and 2-f were replaced with 473-H, 105-d, 105-e and 105-f, respectively, to give compound 105 (15.13 g) with an HPLC purity of 99.98%. Mass spectrum m/z:775.3958 (theory: 775.3944). Theoretical element content (%) C ₅₈ H ₃₇ D ₇ N ₂ : c,89.77; h,6.62; n,3.61. Measured element content (%): c,89.73; h,6.65; n,3.63.

Synthesis example 34 Synthesis of Compound 124

According to the preparation method of Synthesis example 23, 2-a, 2-B, 2-e and 2-f were replaced with 40-a, 364-H, 124-e and 9-B, respectively, to give compound 124 (14.98 g) having an HPLC purity of 99.93%. Mass spectrum m/z:730.3242 (theory: 730.3255). Theoretical element content (%) C ₅₅ H ₃₀ D ₆ N ₂ : c,90.38; h,5.79; n,3.83. Measured element content (%): c,90.35; h,5.77; n,3.86.

Synthesis example 35 Synthesis of Compound 129

According to the preparation method of Synthesis example 28, 33-b and 33-d were replaced with 129-b and 2-d, respectively, to give compound 129 (15.31 g), with an HPLC purity of 99.94% or more. Mass spectrum m/z:737.3682 (theory: 737.3694). Theoretical element content (%) C ₅₅ H ₂₃ D ₁₃ N ₂ : c,89.51; h,6.69; n,3.80. Measured element content (%): c,89.53; h,6.65; n,3.82.

Synthesis example 36 Synthesis of Compound 138

According to the preparation method of Synthesis example 23, 2-B, 2-d, 2-e and 2-f were replaced with 364-H, 6-d, 138-e and 6-B, respectively, to give compound 138 (14.88 g) having an HPLC purity of 99.98%. Mass spectrum m/z:734.3519 (theory: 734.3506). Theoretical element content (%) C ₅₅ H ₂₆ D ₁₀ N ₂ : c,89.88; h,6.31; n,3.81. Measured element content (%): c,89.86; h,6.33; n,3.86.

Synthesis example 37 Synthesis of Compound 143

According to the preparation method of Synthesis example 23, 2-B, 2-e and 2-f were replaced with equimolar amounts of 143-B, 143-e and 51-B, respectively, to give compound 143 (15.97 g) with an HPLC purity of not less than 99.92%. Mass spectrum m/z:818.2646 (theory: 818.2658). Theoretical element content (%) C ₅₅ H ₂₇ D ₄ F ₅ N ₂ : c,80.67; h,4.31; n,3.42. Measured element content (%): c,80.65; h,4.35; n,3.40.

Synthesis example 38 Synthesis of Compound 145

According to the preparation method of Synthesis example 23, 2-b, 2-d, 2-e and 2-f were replaced with 364-H, 45-d, 145-e and 145-f, respectively, to obtain compound 145 (15.56 g) having an HPLC purity of 99.97%. Mass spectrum m/z:787.3959 (theory: 787.3944). Theoretical element content (%) C ₅₉ H ₃₇ D ₇ N ₂ : c,89.92; h,6.52; n,3.55. Measured element content (%): c,89.90; h,6.55; n,3.53.

Synthesis example 39 Synthesis of Compound 156

According to the preparation method of Synthesis example 23, 2-b, 2-d, 2-e and 2-f were replaced with 376-H, 6-d, 156-e and 156-f, respectively, to give compound 156 (14.82 g) having an HPLC purity of 99.91% or more. Mass spectrum m/z:759.3442 (theory: 759.3459). Theoretical element content (%) C ₅₆ H ₂₅ D ₁₀ N ₃ : c,88.50; h,5.97; n,5.53. Measured element content (%): c,88.55; h,5.94; n,5.50.

Synthesis example 40 Synthesis of Compound 178

According to the preparation method of Synthesis example 23, 2-a, 2-B, 2-d, 2-e and 2-f were replaced with 14-a, 376-H, 178-d, 178-e and 178-B, respectively, to give compound 178 (16.04 g) having an HPLC purity of 99.96%. Mass spectrum m/z:843.4396 (theory: 843.4384). Theoretical element content (%) C ₆₃ H ₂₁ D ₁₉ N ₂ : c,89.64; h,7.04; n,3.32. Measured element content (%): c,89.66; h,7.08; n,3.30.

Synthesis example 41 Synthesis of Compound 201

According to the preparation method of synthetic example 23, 2-a, 2-B, 2-d, 2-e and 2-f were replaced with equimolar 201-a, 364-H, 201-d, 201-e and 6-B, respectively, to give compound 201 (15.50 g) with HPLC purity of 99.93%. Mass spectrum m/z:784.3650 (theory: 784.3663). Theoretical element content (%) C ₅₉ H ₂₈ D ₁₀ N ₂ : c,90.27; h,6.16; n,3.57. Measured element content (%): c,90.23; h,6.18; n,3.55.

Synthesis example 42 Synthesis of Compound 206

Synthesis of intermediate 206-c

The preparation of synthetic example 28 was followed by substituting 33-b with equimolar 473-H to give intermediate 206-c (14.59 g) with an HPLC purity of 99.78%. Mass spectrum m/z:455.1459 (theory: 455.1441).

Synthesis of Compound 206

To a reaction flask were successively added, under nitrogen, intermediate 206-d (12.44 g,25.00 mmol), 206-c (11.40 g,25.00 mmol), dibenzylideneacetone dipalladium (0.27 g,0.30 mmol), tri-tert-butylphosphine (1.20 mL of a 0.5M toluene solution, 0.60 mmol), potassium carbonate (5.53 g,40.00 mmol) and tetrahydrofuran (250 mL), and the mixture was stirred, and the above-mentioned reactant system was heated to reflux for 5 hours; after the reaction, cooling to room temperature, suction filtering to obtain a filter cake, flushing the filter cake with a small amount of toluene, and finally recrystallizing the filter cake with toluene to obtain a compound 206 (16.22 g, yield 82%); HPLC purity is more than or equal to 99.98%. Mass spectrum m/z:790.4142 (theory: 790.4101). Theoretical element content (%) C ₅₉ H ₃₀ D ₁₂ N ₂ : c,89.58; h,6.88; n,3.54. Measured element content (%): c,89.55; h,6.86; n,3.59.

Synthesis example 43 Synthesis of Compound 217

Synthesis of intermediate 217-c

According to the preparation method of Synthesis example 23, 2-a and 2-b were replaced with 40-a and 473-H, respectively, to obtain intermediate 217-c (23.16 g), with an HPLC purity of 99.68% or more. Mass spectrum m/z:385.1518 (theory: 385.1504).

Synthesis of intermediate 217-e

To a reaction flask were successively added, under nitrogen, intermediate 217-d (18.02 g,40.00 mmol), 206-c (15.44 g,40.00 mmol), dibenzylideneacetone dipalladium (0.44 g,0.48 mmol), tri-tert-butylphosphine (1.92 mL of a 0.5M toluene solution, 0.96 mmol), potassium carbonate (8.85 g,64.00 mmol) and tetrahydrofuran (300 mL), and the mixture was stirred, and the above-mentioned reactant system was heated to reflux for 5 hours; after the reaction, cooling to room temperature, suction filtering to obtain a filter cake, flushing the filter cake with a small amount of toluene, and finally recrystallizing the filter cake with toluene to obtain an intermediate 217-e (21.56 g, yield 80%); HPLC purity is more than or equal to 99.42%. Mass spectrum m/z:673.3401 (theory: 673.3412).

Synthesis of Compound 217

According to the preparation method of Synthesis example 23, 2-e and 2-f were replaced with equimolar 217-e and 6-B, respectively, to give compound 217 (15.29 g), with an HPLC purity of 99.98% or more. Mass spectrum m/z:754.4052 (theory: 754.4039). Theoretical element content (%) C ₅₆ H ₂₂ D ₁₆ N ₂ : c,89.08; h,7.21; n,3.71. Measured element content (%): c,89.03; h,7.26; n,3.74.

Synthesis example 44 Synthesis of Compound 244

According to the preparation method of Synthesis example 43, 40-a, 217-d, 217-e and 6-B were replaced with 244-a, 244-d, 244-e and 9-B in equimolar amounts, respectively, to give compound 244 (18.59 g) with an HPLC purity of 99.93%. Mass spectrum m/z:928.4652 (theory: 928.4664). Theoretical element content (%) C ₇₀ H ₄₈ D ₆ N ₂ : c,90.48; h,6.51; n,3.01. Measured element content (%): c,90.45; h,6.53; n,3.06.

Synthesis example 45 Synthesis of Compound 311

According to the preparation method of Synthesis example 43, 473-H, 217-d and 217-e were replaced with equimolar amounts of 311-b, 311-d and 311-e, respectively, to give compound 311 (17.79 g) with an HPLC purity of 99.96% or more. Mass spectrum m/z:911.3956 (theory: 911.3943). Theoretical element content (%) C ₆₇ H ₂₉ D ₁₁ N ₄ : c,88.22; h,5.63; n,6.14. Measured element content (%): c,88.26; h,5.60; n,6.11.

Synthesis example 46 Synthesis of Compound 364

According to the preparation method of Synthesis example 23, 2-B, 2-d, 2-e and 2-f were replaced with equimolar amounts of 364-H, 364-d, 364-e and 6-B, respectively, to give compound 364 (19.26 g) having an HPLC purity of 99.91%. Mass spectrum m/z:974.4431 (theory: 974.4445). Theoretical element content (%) C ₇₄ H ₃₈ D ₁₀ N ₂ : c,91.13; h,5.99; n,2.87. Measured element content (%): c,91.18; h,5.97; n,2.84.

Synthesis example 47 Synthesis of Compound 376

According to the preparation method of Synthesis example 23, 2-b, 2-d, 2-e and 2-f were replaced with 376-H, 376-d, 376-e and 376-J, respectively, to give Compound 376 (21.47 g) with an HPLC purity of 99.97%. Mass spectrum m/z:1114.6024 (theory: 1114.6010). Theoretical element content (%) C ₈₄ H ₅₈ D ₁₀ N ₂ : c,90.44; h,7.05; n,2.51. Measured element content (%): c,90.48; h,7.03; n,2.56.

Synthesis example 48 Synthesis of Compound 382

Preparation according to Synthesis example 23In the method, 2-B, 2-d, 2-e and 2-f are respectively replaced by 473-H, 382-d, 382-e and 178-B with equimolar amounts to obtain a compound 382 (17.70 g), wherein the HPLC purity is more than or equal to 99.93%. Mass spectrum m/z:895.3930 (theoretical value: 895.3944 theoretical element content (%) C ₆₈ H ₃₇ D ₇ N ₂ : c,91.14; h,5.74; n,3.13. Measured element content (%): c,91.18; h,5.70; n,3.11.

Synthesis example 49 Synthesis of Compound 388

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According to the preparation method of Synthesis example 23, 2-a, 2-B, 2-e and 2-f were replaced with 40-a, 473-H, 388-e and 6-B, respectively, to give compound 388 (13.82 g) with an HPLC purity of 99.94% or more. Mass spectrum m/z:673.3425 (theoretical value: 673.3412 theoretical element content (%) C ₅₀ H ₂₃ D ₁₁ N ₂ : c,89.12; h,6.73; n,4.16. Measured element content (%): c,89.15; h,6.70; n,4.14.

Synthesis example 50 Synthesis of Compound 391

According to the preparation method of Synthesis example 23, 2-b, 2-d, 2-e and 2-f were replaced with 473-H, 391-d, 391-e and 6-f, respectively, to give compound 391 (16.32 g) with an HPLC purity of 99.97%. Mass spectrum m/z:815.3460 (theoretical value: 815.3474 theoretical element content (%) C ₅₇ H ₂₈ D ₉ F ₃ N ₂ : c,83.90; h,5.68; n,3.43. Measured element content (%): c,83.93; h,5.65; n,3.46.

Synthesis example 51 Synthesis of Compound 405

According to the preparation method of synthetic example 23, 2-a, 2-b, 2-dThe 2-e and 2-f are replaced by equimolar 51-a, 405-B, 33-d, 405-e and 6-B respectively, so that the compound 405 (15.76 g) is obtained, and the HPLC purity is more than or equal to 99.92%. Mass spectrum m/z:797.4490 (theoretical value: 797.4479 theoretical element content (%) C ₅₉ H ₁₅ D ₂₃ N ₂ : c,88.79; h,7.70; n,3.51. Measured element content (%): c,88.76; h,7.72; n,3.53.

Synthesis example 52 Synthesis of Compound 411

According to the preparation method of Synthesis example 23, 2-a, 2-b, 2-d, 2-e and 2-f were replaced with equimolar amounts of 411-a, 364-H, 411-d, 411-e and 411-f, respectively, to give Compound 411 (16.32 g), with an HPLC purity of 99.96% or more. Mass spectrum m/z:836.3931 (theoretical value: 836.3945 theoretical element content (%) C ₆₃ H ₂₈ D ₁₂ N ₂ : c,90.39; h,6.26; n,3.35. Measured element content (%): c,90.36; h,6.22; n,3.39.

Synthesis example 53 Synthesis of Compound 421

According to the preparation method of synthetic example 23, 2-a, 2-B, 2-d, 2-e and 2-f were replaced with equimolar amounts of 421-a, 364-H, 6-d, 421-e and 6-B, respectively, to give compound 421 (15.70 g) with an HPLC purity of 99.98%. Mass spectrum m/z:784.3678 (theoretical value: 784.3663 theoretical element content (%) C ₅₉ H ₂₈ D ₁₀ N ₂ : c,90.27; h,6.16; n,3.57. Measured element content (%): c,90.22; h,6.18; n,3.55.

Synthesis example 54 Synthesis of Compound 428

According to the preparation method of synthetic example 23, 2-a, 2-b, 2-d, 2-e, 2-f were replaced with equimolar amounts of 40-a, 364-H, 33-d, 428-e, 6-B, respectively, to give compound 428 (15.15 g), with an HPLC purity of 99.91% or more. Mass spectrum m/z:747.431 (theoretical value: 747.4322 theoretical element content (%) C ₅₅ H ₁₃ D ₂₃ N ₂ : c,88.31; h,7.94; n,3.74. Measured element content (%): c,88.35; h,7.90; n,3.77.

Synthesis example 55 Synthesis of Compound 438

The preparation of synthetic example 28 was followed by substituting 33-b with equimolar 438-b to give compound 438 (17.16 g) with an HPLC purity of 99.94%. Mass spectrum m/z:836.3932 (theory: 836.3945). Theoretical element content (%) C ₆₃ H ₂₈ D ₁₂ N ₂ : c,90.39; h,6.26; n,3.35. Measured element content (%): c,90.35; h,6.22; n,3.39.

Synthesis example 56 Synthesis of Compound 441

According to the preparation method of Synthesis example 23, 2-a, 2-b, 2-d, 2-e and 2-f were replaced with 40-a, 364-H, 6-d, 441-e and 441-f, respectively, to give compound 441 (19.04 g) having an HPLC purity of 99.95%. Mass spectrum m/z:975.4519 (theoretical value: 975.4508 theoretical element content (%) C ₇₄ H ₃₇ D ₁₁ N ₂ : c,91.04; h,6.09; n,2.87. Measured element content (%): c,91.08; h,6.03; n,2.85.

Synthesis example 57 Synthesis of Compound 451

According to the preparation method of Synthesis example 23, 2-a, 2-b, 2-d, 2-e, 2-f were replaced with equimolar amounts of 451-a, 473-H, 4, respectively51-d, 451-e, 451-f to give compound 451 (18.91 g), HPLC purity not less than 99.93%. Mass spectrum m/z:981.3978 (theoretical value: 981.3990 theoretical element content (%) C ₇₄ H ₃₉ D ₆ N ₃ : c,90.49; h,5.23; n,4.28. Measured element content (%): c,90.46; h,5.25; n,4.25.

Synthesis example 58 Synthesis of Compound 468

According to the preparation method of Synthesis example 23, 2-a, 2-b, 2-d, 2-e and 2-f were replaced with 40-a, 473-H, 468-d, 468-e and 468-f in equimolar amounts, respectively, to give compound 468 (18.81 g), and the HPLC purity was not less than 99.96%. Mass spectrum m/z:951.4489 (theoretical value: 951.4477 theoretical element content (%) C ₇₂ H ₃₃ D ₁₃ N ₂ : c,90.82; h,6.24; n,2.94. Measured element content (%): c,90.80; h,6.26; n,2.92.

Synthesis example 59 Synthesis of Compound 473

According to the preparation method of Synthesis example 23, 2-a, 2-B, 2-d, 2-e and 2-f were replaced with 40-a, 473-H, 473-d, 473-e and 6-B in equimolar amounts, respectively, to give compound 473 (21.85 g) with an HPLC purity of not less than 99.92%. Mass spectrum m/z:1091.5120 (theoretical value: 1091.5134 theoretical element content (%) C ₈₃ H ₄₅ D ₁₁ N ₂ : c,91.26; h,6.18; n,2.56. Measured element content (%): c,91.29; h,6.16; n,2.58.

Synthesis example 60 Synthesis of Compound 493

According to the preparation method of Synthesis example 23, 2-a, 2-b, 2-d, 2-e, 2-f were replaced with 40-a, 14-o in equimolar amounts, respectivelyb. 493-d, 493-e, 9-B to give compound 493 (19.38 g), HPLC purity not less than 99.97%. Mass spectrum m/z:956.3973 (theoretical value: 956.3990 theoretical element content (%) C ₆₇ H ₂₇ D ₁₃ F ₃ N ₃ : c,84.08; h,5.58; n,4.39. Measured element content (%): c,84.10; h,5.55; n,4.37.

Synthesis example 61 Synthesis of Compound 527

According to the preparation method of Synthesis example 23, 2-b, 2-d, 2-e and 2-f were replaced with respective ones of 473-H, 527-d, 58-e and 527-f in equimolar amounts, to give compound 527 (17.14 g) having an HPLC purity of 99.98%. Mass spectrum m/z:820.3685 (theory: 820.3614). Theoretical element content (%) C ₆₁ H ₃₆ D ₅ N ₃ : c,89.24; h,5.65; n,5.12. Measured element content (%): c,89.21; h,5.66; n,5.14.

Device examples 1 to 38

Device example 1: the ITO glass substrate is ultrasonically cleaned by 5% glass cleaning liquid for 2 times each for 20 minutes, and then ultrasonically cleaned by deionized water for 2 times each for 10 minutes. Sequentially ultrasonic cleaning with acetone and isopropanol for 20 min, and drying at 120deg.C. Vacuum evaporation HI is carried out on the ITO substrate as a hole injection layer, and the evaporation thickness is 25nm; vacuum evaporation HT is carried out on the hole injection layer to serve as a hole transport layer, and the evaporation thickness is 80nm; vacuum evaporation of inventive compound 2 on hole transport layer: gd=94:6 (mass ratio) as light-emitting layer, evaporation thickness 20nm; vacuum evaporating ET on the luminous layer as an electron transport layer, wherein the evaporating thickness is 30nm; vacuum evaporating LiF on the electron transport layer as an electron injection layer, wherein the evaporating thickness is 1nm; al is vacuum evaporated on the electron injection layer as a cathode, and the evaporation thickness is 70nm.

Device examples 2 to 38: an organic electroluminescent device was produced by the same procedure as in device example 1, except that the compound 2 of the present invention in device example 1 was used as the host material, in place of the compound 2 of the present invention in device example 1, respectively, 6, 9, 14, 27, 33, 40, 45, 51, 58, 105, 124, 129, 138, 143, 145, 156, 178, 201, 206, 217, 244, 311, 364, 376, 382, 388, 391, 405, 411, 421, 428, 438, 441, 451, 468, 473, 493, 527.

Comparative examples 1-2: an organic electroluminescent device was produced by the same procedure as in device example 1, except that the compound 2 of the present invention in device example 1 was replaced with the comparative compound 1 and the comparative compound 2, respectively, as host materials.

Test software, a computer, a K2400 digital source list manufactured by Keithley company, U.S. and a PR788 spectrum scanning luminance meter manufactured by Photo Research company, U.S. are combined into a combined IVL test system to test the luminous efficiency of the electroluminescent device. Life testing an M6000 OLED life test system from McScience was used. The environment tested was atmospheric and the temperature was room temperature.

The results of the luminescence characteristic test of the obtained organic electroluminescent device are shown in table 1. Table 1 shows the results of the test of the luminescence characteristics of the organic electroluminescent devices prepared from the compounds according to the examples of the present invention and the comparative materials.

Table 1 test of light emitting characteristics of organic electroluminescent device

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As can be seen from the results in table 1, the organic electroluminescent devices in device examples 1 to 38 have higher luminous efficiency and longer device lifetime than those in comparative examples 1 to 2.

Device examples 39 to 76

Device example 39: the ITO glass substrate is ultrasonically cleaned by 5% glass cleaning liquid for 2 times each for 20 minutes, and then ultrasonically cleaned by deionized water for 2 times each for 10 minutes. Sequentially ultrasonic cleaning with acetone and isopropanol for 20 min, and drying at 120deg.C. Vacuum evaporation HI is carried out on the ITO substrate as a hole injection layer, and the evaporation thickness is 25nm; vacuum evaporation HT is carried out on the hole injection layer to serve as a hole transport layer, and the evaporation thickness is 80nm; vacuum evaporation of inventive compound 2 on hole transport layer: RD=92:8 (mass ratio) as a light-emitting layer, and the vapor deposition thickness is 20nm; vacuum evaporating ET on the luminous layer as an electron transport layer, wherein the evaporating thickness is 30nm; vacuum evaporating LiF on the electron transport layer as an electron injection layer, wherein the evaporating thickness is 1nm; al is vacuum evaporated on the electron injection layer as a cathode, and the evaporation thickness is 70nm.

Device examples 40 to 76: an organic electroluminescent device was produced by the same procedure as in device example 9, except that the compound 2 of the present invention in device example 39 was used as the host material, in place of the compound 2 of the present invention, in device example 39, respectively, 6, 9, 14, 27, 33, 40, 45, 51, 58, 105, 124, 129, 138, 143, 145, 156, 178, 201, 206, 217, 244, 311, 364, 376, 382, 388, 391, 405, 411, 421, 428, 438, 441, 451, 468, 473, 493, 527.

Comparative examples 3 to 4: an organic electroluminescent device was produced by the same procedure as in device example 39, except that the compound 2 of the present invention in device example 39 was replaced with the comparative compound 1 and the comparative compound 2, respectively, as the host material.

Test software, a computer, a K2400 digital source list manufactured by Keithley company, U.S. and a PR788 spectral scanning luminance meter manufactured by Photo Research, U.S. are combined into a combined IVL test system to test the luminous efficiency of the organic electroluminescent device. Life testing an M6000 OLED life test system from McScience was used. The environment tested was atmospheric and the temperature was room temperature.

The results of the luminescence characteristic test of the obtained organic electroluminescent device are shown in table 2. Table 2 shows the results of the test of the luminescence characteristics of the organic electroluminescent devices prepared from the compounds prepared in the inventive examples and the comparative substances.

Table 2 test of light emission characteristics of organic electroluminescent devices

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As can be seen from the results in table 2, the devices of examples 39 to 76 exhibited higher luminous efficiency and longer device lifetime than those of comparative examples 3 to 4.

It should be noted that while the invention has been particularly described with reference to individual embodiments, those skilled in the art may make various modifications in form or detail without departing from the principles of the invention, which modifications are also within the scope of the invention.

Claims

1. A carbazole compound is characterized in that the carbazole compound has a structure shown in a formula 1,

the x, z and v are the same or different and are selected from CH or N;

The formula 1 contains at least one deuterium atom.

2. A carbazole compound according to claim 1, wherein theSelected from any one of the structures shown below,

the Ra is selected from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornyl, substituted or unsubstituted cyclopentenyl, substituted or unsubstituted cyclohexenyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylenyl, and substituted or unsubstituted fluorenyl;

3. A carbazole compound according to claim 1, wherein Ar ₁ 、Ar ₂ The same or different one is selected from any one of the following structures,

the m is ₁ Selected from 1, 2, 3, 4, 5, 6 or 7; the m is ₂ Selected from 1, 2, 3, 4, 5, 6, 7, 8 or 9; the m is ₃ Selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11; the m is ₄ Selected from 1, 2, 3, 4 or 5; the m is ₅ Selected from 1, 2, 3 or 4; the m is ₆ Selected from 1, 2, 3, 4, 5, 6, 7 or 8; when two or more R's are present ₄ When two or more R' s ₄ Identical or different from each other, or two adjacent R' s ₄ Are linked to each other to form a substituted or unsubstituted ring.

4. A carbazole compound according to claim 1, wherein Ar ₁ 、Ar ₂ The same or different one is selected from any one of the following structures,

5. A carbazole compound according to claim 1, wherein L ₀ 、L ₁ 、L ₂ The same or different is selected from single bond or any one of the structures shown below,

6. A carbazole-based compound according to claim 1, characterized in that the "x-L ₁ -Ar ₁ "or" -L ₂ -Ar ₂ "contains at least one deuterium.

7. A carbazole compound according to claim 1, wherein R ₂ Or R is ₃ Contains at least one deuterium.

8. A carbazole compound according to claim 1, wherein the carbazole compound is selected from any one of the structures shown below,

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9. an organic electroluminescent device comprising an anode, an organic layer, and a cathode, wherein the organic layer comprises one or a combination of at least two of the carbazole-based compounds as claimed in any one of claims 1 to 8.

10. An organic electroluminescent device according to claim 9, wherein the organic layer comprises a light-emitting layer comprising one or a combination of at least two of the carbazole-based compounds according to any one of claims 1 to 8.