CN117082886A

CN117082886A - Organic electroluminescent device

Info

Publication number: CN117082886A
Application number: CN202311108392.9A
Authority: CN
Inventors: 郭建华; 陆影; 韩春雪; 孙月
Original assignee: Changchun Hyperions Technology Co Ltd
Current assignee: Changchun Hyperions Technology Co Ltd
Priority date: 2023-08-30
Filing date: 2023-08-30
Publication date: 2023-11-17

Abstract

The invention provides an organic electroluminescent device, and particularly relates to the technical field of organic electroluminescent. In order to solve the problems of low luminous efficiency and short service life of the organic electroluminescent device in the prior art, the invention provides the organic electroluminescent device, and the structure shown in the hole transmission area formula I and the structure shown in the electron transmission area formula II in the device can efficiently transmit holes/electrons, and the organic electroluminescent device has the advantages of proper HOMO energy level, good thermal stability, difficult crystallization, good film forming property and the like, reduces the energy barrier of holes/electrons in the transmission process, increases the balance of the holes and electrons in the transmission process, and enables the holes and electrons to be effectively compounded in the luminous layer, thereby obtaining the organic electroluminescent device with high luminous efficiency and long service life.

Description

Organic electroluminescent device

Technical Field

The invention relates to the technical field of organic electroluminescence, in particular to an organic electroluminescent device.

Background

The Organic Light-Emitting Diode (OLED) operates on the principle that holes and electrons are injected into an Organic layer from an anode and a cathode under the action of an external electric field, and then enter a Light-Emitting region through a hole-transporting region and an electron-transporting region, which are combined to generate excitons, releasing energy, the excitons migrate under the action of the electric field, the energy is transferred to a Light-Emitting substance in the Light-Emitting region, electrons in molecules of the Light-Emitting substance are excited to transit from a ground state to an excited state, and when the electrons return from the excited state to the ground state, the energy is released in the form of Light, thereby generating a Light-Emitting phenomenon. The organic electroluminescent device has the characteristics of energy saving, high response speed, stable color, strong environmental adaptability, no radiation, light weight, thin thickness and the like, and along with the rapid development of the fields of photoelectric communication and multimedia in recent years, the organic optoelectronic material has become the core of the modern social information and electronic industry.

The OLED has the following structure: a cathode, an anode, and one or more layers of organic material disposed between and beyond the cathode and anode. In order to improve efficiency and stability of the organic light emitting device, the organic material layer includes a plurality of layers having different materials, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), a light emitting layer, a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), and a capping layer (CPL). The OLED devices can be classified into top emission devices (cathode side emission), bottom emission devices (anode side emission) and bi-directional emission devices (both cathode and anode simultaneously emission) according to the direction of light emission.

With the continuous development of OLED products, the requirements on the performance such as efficiency, service life and the like of the OLED products are higher and higher. The material for the hole transport layer should have good film forming property and thermal stability, proper energy level, being beneficial to injection and transport of holes, reducing energy barrier to be overcome in the hole transport process, high glass transition temperature, etc., however, in order to obtain the OLED with high luminous efficiency and long service life, the hole and the electron need to be controlled in the luminous layer to be effectively compounded, and the collocation between the functional layers is also important. In general, the direction of the future OLED is to develop an organic electroluminescent device with high efficiency, long service life and low cost, but the industrialization process of the technology still faces a lot of key problems, how to develop materials with better performance, and obtaining an efficient organic electroluminescent device is always a problem to be solved by those skilled in the art.

Disclosure of Invention

Aiming at the problems of low luminous efficiency and short service life of the device caused by low effective recombination probability of holes and electrons in the luminous layer in the prior art, the invention provides an organic electroluminescent device. Specifically, the technical scheme of the invention is as follows:

the invention provides an organic electroluminescent device, which comprises an anode, an organic layer and a cathode, wherein the organic layer comprises a hole transmission region, a luminescent layer, an electron transmission region and a covering layer, and is characterized in that the hole transmission region comprises a structure shown in a formula I, and the electron transmission region comprises a structure shown in a formula II;

in formula I, the Ar ₁ 、Ar ₂ Are the same or different from each other and are selected from any one of the groups shown in the formula I-1 and the formula I-2;

the R are the same or different from each other and are selected from any one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or two adjacent R can be mutually connected to form a substituted or unsubstituted ring, or R can be directly connected with L ₁ Or L ₂ Bonding;

the R is ₂ 、R ₃ Are identical or different from each other and are selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 aromatic ring and C3-C30 aliphatic ringAny one of the fused ring groups of (a);

said n ₃ Selected from 0, 1, 2, 3, 4 or 5, when two or more R's are present ₂ When two or more R' s ₂ Identical or different from each other, or two adjacent R' s ₂ May be linked to each other to form a substituted or unsubstituted ring;

said n ₄ Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, when two or more R's are present ₃ When two or more R' s ₃ Identical or different from each other, or two adjacent R' s ₃ May be linked to each other to form a substituted or unsubstituted ring;

the saidAt least one deuterium;

said n ₂ Selected from 1, 2 or 3;

the R is ₀ Any one selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl and substituted or unsubstituted C6-C30 aryl;

said n ₀ Selected from 1, 2, 3 or 4, when two or more R's are present ₀ When two or more R' s ₀ Identical or different from each other, or two adjacent R' s ₀ May be linked to each other to form a substituted or unsubstituted ring;

the Ar is as follows ₃ Any one selected from a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C3-C12 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 heteroaryl group, a substituted or unsubstituted C6-C30 aromatic ring and a C3-C30 aliphatic ring condensed ring group;

the R is ₁ Are the same or different from each other, and are selected from any one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;

said n ₁ Selected from 0, 1, 2, 3, 4, 5, 6 or 7; when two or more R's are present ₁ When two or more R' s ₁ Identical or different from each other, or two adjacent R' s ₁ May be linked to each other to form a substituted or unsubstituted ring;

the L is ₁ 、L ₂ Are the same or different from each other, and are selected from any one of single bond, substituted or unsubstituted arylene of C6-C30, bivalent substituted or unsubstituted aromatic ring of C6-C30 and condensed ring group of aliphatic ring of C3-C30;

in formula II, the Ar ₄ 、Ar ₅ Are identical or different from each other and are selected fromA group shown;

the X is ₁ Selected from O, S, N (R) _e ) Any one of them;

the R is _e Any one selected from the group consisting of a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C2-C30 heteroaryl group;

z is selected from CH or N, and when Z is bonded with other groups, Z is selected from C atoms;

the R is _f Any one selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;

wherein f is selected from 0, 1, 2, 3 or 4, when two or more R's are present _f When two or more R' s _f Identical or different from each other, or adjacent two R _f May be linked to each other to form a substituted or unsubstituted ring;

the R is _a 、R _b Are identical or different from each other and are selected from hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substitutedOr any one of unsubstituted C6-C30 aromatic ring and C3-C30 aliphatic ring condensed ring radical, or R _a 、R _b Can be linked to each other to form a substituted or unsubstituted spiro ring, or R _a 、R _b Any one of them can be directly connected with L _a Bonding;

the R is _c Is the same or different from each other, and is selected from any one of hydrogen, deuterium, cyano, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C6-C30 aromatic ring and C3-C30 aliphatic ring condensed ring group;

the m is ₁ Selected from 0, 1, 2 or 3, said m ₂ Selected from 0, 1, 2, 3 or 4; when two or more R's are present _c When two or more R' s _c Identical or different from each other, or two adjacent R' s _c May be linked to each other to form a substituted or unsubstituted ring;

the R' is selected from any one of hydrogen, deuterium, cyano, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C6-C30 aromatic ring and C3-C30 aliphatic ring condensed ring group;

the a' is selected from 0, 1, 2 or 3;

The L is _a 、L _b 、L _c Are the same or different from each other, and are selected from any one of single bond, substituted or unsubstituted arylene of C6-C30, bivalent substituted or unsubstituted condensed ring group of aromatic ring of C6-C30 and aliphatic ring of C3-C30, and the combination thereof.

The beneficial effects are that:

the organic electroluminescent device provided by the invention has high luminous efficiency and long service life, and has the advantages of good thermal stability, difficult crystallization, good film forming property and the like, and the use performance of the device is greatly improved because the structure shown in the cavity transmission region formula I and the structure shown in the electron transmission region formula II in the organic electroluminescent device can efficiently transmit holes/electrons, have proper HOMO energy level, reduce energy barrier of the holes/electrons in the transmission process, increase balance of the holes and electrons in the transmission process, and enable the holes and the electrons to be effectively compounded in the luminous layer.

Detailed Description

The following description of the embodiments of the present invention will be made more complete and obvious by the following description of the embodiments of the present invention, wherein the embodiments are described in some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to fall within the scope of the present invention.

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, "D" means isotopic deuterium of hydrogen.

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

In this specification, when a substituent is not fixed in position on a ring, it means 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 representCan represent 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, the number of the cells to be processed,can indicate-> Can indicate->And so on.

Examples of the halogen atom according to the present invention may include fluorine, chlorine, bromine or iodine.

Alkyl according to the invention is understood to mean a monovalent radical obtained by removing one hydrogen atom from an alkane molecule, which may be a straight-chain alkyl radical or a branched alkyl radical, preferably having from 1 to 12 carbon atoms, more preferably having from 1 to 8 carbon atoms, particularly preferably having from 1 to 6 carbon atoms. Alkyl groups may be substituted or unsubstituted. Specific examples may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl and the like, but are not limited thereto.

Cycloalkyl according to the present invention means a monovalent group obtained by removing one hydrogen atom from a cyclic alkane molecule, preferably having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. Cycloalkyl groups may be substituted or unsubstituted. The cycloalkyl group includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, and the like.

Aryl according to the invention is understood to mean a monovalent radical obtained by removing one hydrogen atom from the aromatic nucleus of an aromatic compound molecule, which may be a monocyclic aryl, polycyclic aryl or fused ring aryl, preferably having from 6 to 30 carbon atoms, more preferably from 6 to 18 carbon atoms, particularly preferably from 6 to 12 carbon atoms. Aryl groups may be substituted or unsubstituted. The monocyclic aryl refers to aryl having only one aromatic ring in the molecule, for example, phenyl, etc., but is not limited thereto; the polycyclic aryl group refers to an aryl group having two or more independent aromatic rings in the molecule, for example, biphenyl, terphenyl, tetrabiphenyl, etc., but is not limited thereto; the condensed ring aryl group means an aryl group having two or more aromatic rings in the molecule and condensed with each other by sharing two adjacent carbon atoms, for example, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, Radicals, triphenylene radicals, fluoranthenyl radicals, fluorenyl radicals, spirobifluorenyl radicals, and the like, but are not limited thereto.

Heteroaryl according to the present invention refers to the generic term for groups in which one or more of the aromatic nucleus carbon atoms in the aryl group is replaced by a heteroatom, including but not limited to O, S, N, si or P atoms, preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, even more preferably 3 to 12 carbon atoms. The attachment site of the heteroaryl group may be on a ring-forming carbon atom or on a ring-forming heteroatom, and the heteroaryl group may be a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a fused ring heteroaryl group. Heteroaryl groups may be substituted or unsubstituted. The monocyclic heteroaryl group includes, but is not limited to, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, and the like; the polycyclic heteroaryl group includes bipyridyl, bipyrimidinyl, phenylpyridyl, phenylpyrimidinyl, etc., but is not limited thereto; the fused ring heteroaryl group includes quinolinyl, isoquinolinyl, benzoquinolinyl, benzoisoquinolinyl, quinazolinyl, quinoxalinyl, benzoquinazolinyl, benzoquinoxalinyl, phenanthroline, naphthyridinyl, indolyl, benzothienyl, benzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, N-heterobenzoxazolyl, N-heterobenzothiazolyl, dibenzofuranyl, benzodibenzofuranyl, dibenzothiophenyl, benzodibenzothiophenyl, dibenzooxazolyl, dibenzoimidazolyl, dibenzozolyl, carbazolyl, benzocarbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenoxazinyl, spirofluorene oxaanthracenyl, spirofluorene thioanthracenyl, and the like, but is not limited thereto.

The aliphatic ring according to the present invention is a cyclic hydrocarbon having aliphatic properties, and the molecule contains a closed carbon ring, preferably 3 to 30 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms, and still more preferably 3 to 7 carbon atoms. Which may form mono-or polycyclic hydrocarbons and may be fully unsaturated or partially unsaturated. The aliphatic ring may be substituted or unsubstituted. Specific examples may include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclobutene, cyclopentene, cyclohexene, cycloheptene, and the like. The plurality of monocyclic hydrocarbons may also be linked in a variety of ways: two rings in the molecule can share one carbon atom to form a spiro ring; the two carbon atoms on the ring can be connected by a carbon bridge to form a bridge ring; several rings may also be interconnected to form a cage-like structure.

The fused ring of an aromatic ring and an aliphatic ring in the present invention means a ring having one or more aromatic rings and having one or more aliphatic rings fused to each other by sharing two adjacent carbon atoms, the aromatic ring preferably has 6 to 30 carbon atoms, more preferably has 6 to 18 carbon atoms, most preferably has 6 to 12 carbon atoms, and the aliphatic ring preferably has 3 to 30 carbon atoms, more preferably has 3 to 18 carbon atoms, more preferably has 3 to 12 carbon atoms, and most preferably has 3 to 7 carbon atoms. The fused ring of the aromatic ring and the aliphatic ring may be substituted or unsubstituted. Examples include, but are not limited to, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexane, benzocycloheptane, benzocyclobutene, benzocyclopentene, benzocyclohexene, benzocycloheptene, naphthocyclopropane, naphthocyclobutane, naphthocyclopentane, naphthocyclohexene, naphthocyclopentene, naphthocyclohexene, and the like.

The arylene group according to the present invention is a generic term for divalent groups remaining after two hydrogen atoms are removed from the aromatic nucleus carbon of an aromatic hydrocarbon molecule, and may be a monocyclic arylene group, a polycyclic arylene group or a condensed ring arylene group, preferably having 6 to 30 carbon atoms, more preferably having 6 to 22 carbon atoms, still more preferably having 6 to 18 carbon atoms, and most preferably having 6 to 12 carbon atoms. Arylene groups may be substituted or unsubstituted. The polycyclic arylene group may be, but is not limited to, biphenylene, terphenylene, tetra-biphenylene, and the like. As the condensed ring arylene group, naphthylene, anthrylene, phenanthrylene, pyreylene, fluorenylene, spirofluorenylene, triphenylene, perylene, fluoranthrylene, and phenylene groups may be mentionedA base, etc., but is not limited thereto.

The fused ring group of the divalent aromatic ring and the aliphatic ring in the present invention means that there are two linked positions, i.e., a divalent group, on the fused ring group of the aromatic ring and the aliphatic ring. In addition to the divalent groups, the above description of the condensed ring groups of the aromatic ring and the aliphatic ring may be applied.

"unsubstituted" in "substituted or unsubstituted" as used herein means that the hydrogen atom on the group is not substituted with any substituent; "substituted" means that at least one hydrogen atom on the group is replaced with a substituent, and the position of substitution is not limited. When a plurality of hydrogens are substituted with a plurality of substituents, the plurality of substituents may be the same or different, or adjacent substituents may be linked to each other to form a substituted or unsubstituted ring.

The substituents in the "substituted or unsubstituted" described in the present invention may be independently selected from deuterium, cyano, nitro, amino, halogen atom, substituted or unsubstitutedAny one of an alkyl group of C1 to C12, an alkenyl group of substituted or unsubstituted C2 to C12, a cycloalkyl group of substituted or unsubstituted C3 to C12, an alkylamino group of substituted or unsubstituted C1 to C12, an arylamine group of substituted or unsubstituted C6 to C30, a heterocycloalkyl group of substituted or unsubstituted C2 to C12, an aryl group of substituted or unsubstituted C6 to C30, a silyl group of substituted or unsubstituted C1 to C30, a heteroaryl group of substituted or unsubstituted C2 to C30, a condensed ring group of a condensed ring of a substituted or unsubstituted C6 to C30 aromatic ring and a C3 to C30 aliphatic ring, preferred examples of the deuterium, cyano group, halogen atom, amino group, C1-C12 alkyl group, C3-C12 cycloalkyl group, C1-C12 alkoxy group, C6-C30 aryl group, C2-C30 heteroaryl group include deuterium, fluorine, chlorine, bromine, iodine, cyano group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, adamantyl group, norbornyl group, phenyl group, biphenyl group, terphenyl group, tolyl group, pentadeuterated phenyl group, biphenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, triphenylenyl group, 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, quinoxazinyl group, phenothiazinyl group, acridinyl group, and the like, but is not limited thereto.

The term "link-forming ring" as used herein means that 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 an aromatic ring system, an aliphatic ring system or a ring system formed by the fusion of both, and the ring formed by the connection may be a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring or a fused ring, such as benzene, naphthalene, indene, cyclopentene, cyclopentane, cyclopentaacene, cyclohexene, cyclohexane acene, pyridine, quinoline, isoquinoline, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, naphthalene, phenanthrene or pyrene, but is not limited thereto.

the R is ₂ 、R ₃ Are the same or different from each other and are selected from hydrogen, deuteriumAny one of cyano, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 aromatic ring and C3-C30 aliphatic ring condensed ring group;

the saidAt least one deuterium;

said n ₂ Selected from 1, 2 or 3;

The R is ₁ Are identical or different from each other and are selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstitutedSubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl;

the X is ₁ Selected from O, S, N (R) _e ) Any one of them;

the R is _a 、R _b Are identical or different from each other, and are selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C6-C30 aromatic ring and C3-C30 aliphatic ring condensed ring group, or R _a 、R _b Can be linked to each other to form a substituted or unsubstituted spiro ring, or R _a 、R _b Any one of them can be directly connected with L _a Bonding;

the a' is selected from 0, 1, 2 or 3;

Preferably, the saidAny one selected from the following groups;

the R is ₀ 、R ₈ Identical to or different from each other, selected from hydrogen, deuterium, cyano, halogen or any one of the following groups substituted or unsubstituted by one or more deuterium, C1-C12 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, adamantane, norbornane, phenyl, biphenyl, terphenyl or naphthyl, and said R ₀ At least one deuterium;

the a ₁ Selected from 0, 1, 2, 3 or 4, said a ₂ Selected from 0, 1, 2 or 3, said a ₃ Selected from 0, 1 or 2, said a ₄ Selected from 0, 1, 2, 3, 4, 5 or 6, said a ₅ Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said a ₆ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

Preferably, the saidAny one selected from the following groups;

the R is ₀ 、R ₈ Are the same or different from each other, and are selected from any one of hydrogen, deuterium, methyl, deuteromethyl, ethyl, n-propyl, isopropyl, deuteroiisopropyl, n-butyl, isobutyl, tert-butyl, deuteroi-tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, adamantane, norbornane, phenyl, deuteroi-phenyl, biphenyl and naphthyl;

said b ₁ Selected from 1, 2, 3 or 4, said b ₂ Selected from 1, 2 or 3, said b ₃ Selected from 1 or 2;

the s is ₁ Selected from 0, 1, 2 or 3, said s ₂ Selected from 0, 1, 2, 3 or 4, said s ₃ Selected from 0, 1, 2, 3, 4 or 5, said s ₄ Selected from 0, 1, 2, 3, 4, 5, 6 or 7, said s ₅ Selected from 0, 1 or 2, said s ₆ Selected from 0, 1, 2, 3, 4, 5 or 6, said s ₇ Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said s ₈ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

Preferably, the saidIncluding two, three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty-one, twenty-two, twenty-three, twenty-four, twenty-five or more deuterium.

Preferably, the Ar ₁ 、Ar ₂ Are the same or different from each other, and are selected from any one of the following groups;

the R is ₅ Are the same or different from each other, and are selected from any one of hydrogen, deuterium, or a group shown as the following which is substituted or unsubstituted by one or more deuterium, C1-C12 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, benzocyclopropanyl, benzocyclobutanyl, benzocyclopentanyl, benzocyclohexenyl, benzocycloheptanyl, benzocyclopentenyl, or benzocyclohexenyl;

the c ₁ Selected from 0, 1, 2, 3, 4 or 5, said c ₂ Selected from 0, 1, 2, 3 or 4, said c ₃ Selected from 0, 1, 2, 3, 4, 5, 6 or 7, said c ₄ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, said c ₅ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, said c ₆ Selected from 0, 1, 2 or 3, said c ₉ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, said c ₁₀ Selected from 0, 1, 2, 3, 4, 5 or 6, said c ₁₁ Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said c ₁₂ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, said c ₁₃ Selected from 0, 1 or 2.

Preferably, the saidAny one selected from the following groups;

the R is ₆ Are the same or different from each other, and are selected from any one of hydrogen, deuterium, or a group as described below which is substituted or unsubstituted by one or more deuterium, C1-C12 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, benzocyclopropanyl, benzocyclobutanyl, benzocyclopentanyl, benzocyclohexenyl, benzocycloheptanyl, benzocyclopentenyl, or benzocyclohexenyl;

Said d ₁ Selected from 0, 1, 2, 3, 4, 5, 6 or 7, said d ₂ Selected from 0, 1, 2, 3, 4 or 5, said d ₃ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, said d ₄ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, said d ₅ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, said d ₆ Selected from 0, 1, 2, 3 or 4, said d ₇ Selected from 0, 1, 2 or 3.

Preferably, the L ₁ 、L ₂ Are the same or different from each other, and are selected from any one of single bonds or groups shown as the following and combinations thereof;

the R is ₇ Are the same or different from each other, and are selected from any one of hydrogen, deuterium, or a group shown as the following which is substituted or unsubstituted by one or more deuterium, C1-C12 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, naphthyl, benzocyclopentyl, benzocyclohexenyl or benzocyclohexenyl;

the k is ₁ Selected from 0, 1, 2, 3 or 4, said k ₂ Selected from 0, 1, 2, 3, 4, 5 or 6, said k ₃ Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said k ₄ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

Preferably, the saidAny one selected from the following groups; />

The R is _a 、R _b 、R _x 、R _y 、R _z 、R _d Are the same or different from each other, and are selected from any one of hydrogen, deuterium, or a group as described below which is substituted or unsubstituted by one or more deuterium, C1-C12 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, naphthyl, benzocyclopentyl or benzocyclohexenyl; or said R _a 、R _b Any one of themCan be directly connected with L _a Bonding;

the p is ₁ Selected from 0, 1, 2 or 3, said p ₂ Selected from 0, 1, 2, 3 or 4, said p ₃ Selected from 0, 1, 2, 3, 4 or 5, said p ₄ Selected from 0, 1, 2, 3, 4, 5, 6 or 7, said p ₅ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, said p ₆ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, when two or more R's are present _d When two or more R' s _d Identical or different from each other, or two adjacent R' s _d May be linked to each other to form a substituted or unsubstituted ring.

Preferably, the saidAny one selected from the following groups;

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the R is ₄ Are the same or different from each other, and are selected from any one of hydrogen, deuterium, methyl, deuteromethyl, ethyl, n-propyl, isopropyl, deuteroiisopropyl, n-butyl, tertiary butyl, deuterated tertiary butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, deuterated phenyl, biphenyl, naphthyl and deuterated naphthyl;

The q is ₁ Selected from 0, 1, 2 or 3, said q ₂ Selected from 0, 1, 2, 3 or 4, said q ₃ Selected from 0, 1, 2, 3, 4 or 5, said q ₄ Selected from 0, 1, 2, 3, 4, 5, 6 or 7, said q ₅ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, said q ₆ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, said q ₇ Selected from 0, 1, 2, 3, 4, 5 or 6, said q ₈ Selected from 0, 1, 2, 3, 4, 5, 67 or 8, said q ₉ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

Preferably, the saidAny one selected from the following groups;

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the X is ₁ Selected from O, S, N (R) _e ) Any one of them;

the R is _e Selected from hydrogen, deuterium, or any one of the following groups substituted or unsubstituted with one or more deuterium, C1 to C12 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, adamantane, norbornane, phenyl, biphenyl, terphenyl, naphthyl, benzocyclopentane or benzocyclohexane;

said f ₁ Selected from 0, 1, 2, 3 or 4, said f ₂ Selected from 0, 1, 2, 3, 4 or 5.

Preferably, the L _a 、L _b 、L _c Is the same or different from each other and is selected from any one of single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted anthrylene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenylene, substituted or unsubstituted benzocyclopropylene, substituted or unsubstituted benzocyclobutylene, substituted or unsubstituted benzocyclopentylene, substituted or unsubstituted benzocycloheteroalkyl, and combinations thereof, the "substituent" being selected from deuterium or deuterium-substituted or unsubstituted Any of the groups shown: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, adamantane, norbornane, phenyl, biphenyl, terphenyl, or naphthyl.

Preferably, the structure shown in the formula I is selected from any one of the following structures;

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the specific structural forms of the compounds of formula I according to the present invention are listed above, but the present invention is not limited to the listed chemical structures, and substituents are included in the groups defined above, even when the structures of formula I are used as bases.

Preferably, the structure shown in the formula II is selected from any one of the following structures;

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the specific structural forms of the compound of formula II are listed above, but the invention is not limited to the listed chemical structures, and substituents are included in the groups defined above, even when the structure of formula II is based.

Preferably, the organic electroluminescent device of the present invention comprises an anode, an organic layer, and a cathode, wherein the organic layer is located between the anode and the cathode, and the organic layer comprises at least one layer of a hole transport region, a light emitting layer, and an electron transport region; the organic layer is positioned outside any one of the anode and the cathode, and the organic layer comprises a covering layer.

Preferably, the hole transport region according to the present invention includes at least one of a hole injection layer, a hole transport layer, and an electron blocking layer.

Preferably, the hole transport region according to the present invention comprises at least one of a hole injection layer or a hole transport layer.

Preferably, the hole transport region according to the present invention comprises a hole transport layer, and the hole transport layer comprises any one or more of the structures shown in formula I according to the present invention.

Preferably, the hole transport layer according to the present invention comprises at least one of a first hole transport layer and a second hole transport layer, and at least one of the first hole transport layer and the second hole transport layer comprises any one or more of structures shown in formula I according to the present invention.

Preferably, the hole transport layer of the present invention is located between the light emitting layer and the anode.

Preferably, the hole transport layer of the present invention is located between the light emitting layer and the hole injection layer.

Preferably, the second hole transport layer of the present invention is located between the light emitting layer and the first hole transport layer.

Preferably, the electron transport region according to the present invention includes at least one of an electron injection layer, an electron transport layer, and a hole blocking layer.

Preferably, the electron transport region according to the present invention comprises at least one of an electron transport layer and a hole blocking layer, and the hole blocking layer comprises any one or more of the derivatives of formula II according to the present invention.

Preferably, the electron transport region according to the present invention comprises a hole blocking layer comprising any one or more of the derivatives of formula II according to the present invention.

Preferably, the electron transport layer of the present invention is located between the light emitting layer and the cathode.

Preferably, the electron transport layer of the present invention is located between the light emitting layer and the electron injection layer.

Preferably, the hole blocking layer of the present invention is located between the light emitting layer and the electron transport layer.

In the organic electroluminescent device according to the present invention, each functional layer may be formed of a single layer or two or more thin films, and each thin film may be formed of one material or two or more materials, however, the structure of the organic electroluminescent device is not limited thereto.

The material of each layer of thin film in the organic electroluminescent device is not particularly limited, and materials known in the art can be used. The following describes each organic functional layer of the above-mentioned organic electroluminescent device and the electrodes on both sides of the device, respectively:

The anode material according to the present invention preferably uses a material having a high function to improve hole injection efficiency. Anode materials useful in the present invention are selected from the following: indium Tin Oxide (ITO), indium Zinc Oxide (IZO), and tin oxide (SnO) ₂ ) Zinc oxide (ZnO) or any combination thereof, magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof. The anode may have a single-layer structure or a multilayer structure including two or more layers, for example, the anode may have a single-layer structure of Al or a three-layer structure of ITO/Ag/ITO, butNot limited thereto.

The hole injection layer according to the present invention preferably uses a material having a good hole accepting ability. Specific examples of the hole injection layer material that can be used in the present invention may include metal oxides such as silver oxide, vanadium oxide, tungsten oxide, copper oxide, titanium oxide, etc., phthalocyanine compounds, biphenylamine compounds, phenazine compounds, etc., such as copper phthalocyanine (CuPc), titanylphthalocyanine, N ' -diphenyl-N, N ' -bis- [4- (N, N-diphenylamine) phenyl ] benzidine (npb), N ' -tetrakis (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.

The hole transport layer material according to the present invention is preferably a material having high hole mobility. Can be selected from any one or more of the following structures: carbazole derivatives, triarylamine derivatives, biphenyldiamine derivatives, fluorene derivatives, stilbene derivatives, hexanitrile hexaazabenzophenanthrene compounds, quinacridone compounds, anthraquinone compounds, polyaniline, polythiophene, polyvinylcarbazole, and the like. Examples of the hole transport layer material include, but are not limited to, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine (TPD), N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), 4- [1- [4- [ bis (4-methylphenyl) amino ] phenyl ] cyclohexyl ] -N- (3-methylphenyl) -N- (4-methylphenyl) aniline (TAPC), N '-tetrakis (3-methylphenyl) -3,3' -dimethylbiphenyl diamine (HMTPD), and the like. Preferably, the derivatives of formula I according to the invention are described.

The luminescent layer material comprises a host material AND a doping material, AND the luminescent layer host material can be selected from 4,4 '-bis (9-Carbazole) Biphenyl (CBP), 9, 10-bis (2-naphthyl) Anthracene (ADN), 9' - (1, 3-phenyl) bis-9H-carbazole (mCP), 4 '-tris (carbazole-9-yl) triphenylamine (TCTA), 9, 10-bis (1-naphthyl) anthracene (alpha-AND), N' -bis- (1-naphthyl) -N, N '-diphenyl- [1,1':4',1": 4',1 '-tetrabenzoyl ] -4,4' -diamine group (4 PNPB), 1,3, 5-tris (9-carbazolyl) benzene (TCP), AND the like. In addition to the above materials and combinations thereof, the light emitting layer host material may include other known materials suitable for a light emitting layer, and the like, but is not limited thereto. The light-emitting layer doping material of the present invention is classified into a blue light-emitting material, a green light-emitting material, and a red light-emitting material. The light emitting layer doping material may be selected from (6- (4- (diphenylamino (phenyl) -N, N-diphenylpyren-1-amine) (DPAP-DPPA), 2,5,8, 11-tetra-tert-butylperylene (TBPe), 4 '-bis [4- (diphenylamino) styryl ] biphenyl (BDAVBi), 4' -bis [4- (di-p-tolylamino) styryl ] biphenyl (DPAVBi), bis (2-hydroxyphenylpyridine) beryllium (Bepp 2), bis (4, 6-difluorophenylpyridine-C2, N) picolinic iridium (FIrpic), tris (2-phenylpyridine) iridium (Ir (ppy) 3), bis (2-phenylpyridine) iridium (Ir (ppy) 2 (acac)), 9, 10-bis [ N- (p-tolyl) anilino ] anthracene (TPA), 4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminostyryl) -4H-pyran (DCM), tris [ 1-phenylpyridine-C2, N ] iridium (Ir) (p-phenylpyridine) iridium (p-phenylene) iridium (p-phenylene) 2), tris (p-phenylpyridine) iridium (Ir (p-phenylene) iridium (Ir) 2 (Ir (p-p) iridium) (Ir (q) (Ir) 3), iridium (Ir).

The doping ratio of the host material and the guest material in the light-emitting layer according to the present invention is determined according to the materials used. The amount of the dopant is preferably 0.1 to 70% by mass, more preferably 0.1 to 30% by mass, still more preferably 1 to 20% by mass, and particularly preferably 1 to 10% by mass.

The hole blocking layer according to the present invention preferably uses a material having a strong hole blocking ability and a suitable HOMO/LUMO energy level. The hole blocking layer material can be selected from any one or more of the following structures: phenanthroline derivatives, rare earth derivatives, imidazole derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, triazine derivatives, quinoline derivatives, phenanthroline derivatives, azabenzene derivatives, anthrone derivatives, and the like, but are not limited thereto. Preferably, the derivatives of formula II according to the invention are described.

The electron transport layer material of the present invention is preferably a material having high electron mobility. Can be selected from any one or more of the following structures: 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (TPBi), tris (8-hydroxyquinoline) aluminum (III) (Alq 3), 8-hydroxyquinoline-lithium (Liq), bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (BAlq), 3- (biphenyl-4-yl) -5- (4-t-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ), 4, 7-diphenyl-1, 10-phenanthroline (Bphen), and the like, but are not limited thereto.

The electron injection layer material of the present invention is preferably a material having a small potential barrier difference from a material of an adjacent organic layer, and specific examples may include: alkali metal compounds (for example, lithium oxide, lithium fluoride, cesium carbonate, cesium fluoride, 8-hydroxyquinoline cesium, 8-hydroxyquinoline aluminum), organic metal salts (metal acetate, metal benzoate, or metal stearate), molybdenum trioxide, metal aluminum, and the like, but are not limited thereto.

The cathode material according to the present invention preferably uses a material having a low work function that can promote electron injection into the organic layer to lower the electron injection barrier. Can be selected from any one or more of the following materials: ag. Mg, cu, al, pt, pd, au, ni, nd, ir, cr, li, ca, liF/Ca, liF/Al, mo, ti, compounds including them or mixtures thereof (e.g., mixtures of Ag and Mg), but are not limited thereto.

The coating layer according to the present invention is provided outside either one of the anode and the cathode, and preferably a material capable of improving the optical coupling efficiency inside the device is used. Can be selected from any one or more of the following structures: aryl amine derivatives, biscarbazole derivatives, benzimidazole derivatives, benzoxazole derivatives, benzothiazole derivatives, triazole derivatives, benzofuran derivatives, diamine derivatives, porphyrin derivatives, phthalocyanine derivatives, and the like, but are not limited thereto.

The organic electroluminescent device according to the present invention may further include a substrate, and the substrate according to the present invention preferably uses a material that does not change when forming electrodes and other functional layers, and specific examples of the substrate material that can be used in the present invention may include glass, quartz, plastic, polymer film, silicon, etc., but are not limited thereto. The substrate may remain in a light emitting device or an electronic apparatus using the organic electroluminescent device of the present invention, or may serve as a support only in a manufacturing process of the organic electroluminescent device without remaining in a final product.

However, the structure of the organic electroluminescent device according to the present invention 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 light-emitting type of the organic electroluminescent device can be a top-emitting device or a bottom-emitting device, and the difference between the two is that the light-emitting direction of the device is the direction of emitting light through the substrate or deviating from the substrate. For a bottom emission device, the light emitting direction of the device is through the substrate emission; for top-emitting devices, the light exiting direction of the device is the direction away from the substrate.

The organic electroluminescent device of the present invention may be any one of vacuum evaporation method, spin coating method, vapor deposition method, blade coating method, laser thermal transfer method, electro-spray coating method, slit coating method, and dip coating method.

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

The method for preparing the structure represented by formula I of the present invention is not particularly limited, and conventional methods known to those skilled in the art can be employed.

For example, the structure of formula 1 of the present invention can be prepared by the synthetic route shown below, such as carbon-nitrogen coupling reaction, carbon-carbon coupling reaction, etc.

Wherein X is _a 、X _b Are the same or different from each other and are selected from any one of Cl, br and I; ar (Ar) ₁ ～Ar ₃ 、L ₁ 、L ₂ 、R ₁ 、R ₀ 、n ₀ ～n ₂ The definition of (2) is the same as described above.

The preparation method of the compound shown in the formula II can be prepared through coupling reaction conventional in the field, for example, the preparation method can be prepared through the following synthetic route, but the invention is not limited to the following steps:

the heterocyclic compound is subjected to Suzuki coupling reaction to finally obtain a compound of a formula II, wherein Xa, xb, xc, xd, xe, xf, xg is the same or different from each other and is selected from any one of Cl, br and I; r is R _a ～R _c 、R’Ar ₄ 、Ar ₅ 、L _a ～L _c The definition of m and a' is the same as above.

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 raw materials and the reagents used in the invention are all reagent pure.

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;

synthesis example 1: synthesis of intermediate a-1-12

To the reaction flask were added m-1-12 (80.00 mmol,26.97 g), n-1-12 (80.00 mmol,22.95 g), palladium tetraphenylphosphine (1.60 mmol,1.85 g), potassium carbonate (156.00 mmol,21.56 g) and 450mL toluene, 150mL ethanol, 150mL water under nitrogen atmosphere, and the mixture was stirred, and the above system was heated under reflux for 4 hours. After the reaction was completed, cooling to room temperature, adding distilled water, extracting with dichloromethane, standing for liquid separation, collecting an organic layer, drying with anhydrous magnesium sulfate, concentrating the filtrate by distillation under reduced pressure, cooling for crystallization, suction filtration, and washing with toluene/ethanol=4: 1 recrystallisation to give intermediate a-1-12 (29.31 g, 81% yield); HPLC purity is more than or equal to 99.70%. Mass spectrum m/z:451.0861 (theory: 451.0874).

Synthesis example 2: synthesis of intermediate a-1-36

According to the same manner as that of intermediate a-1-12 of Synthesis example 1, equimolar m-1-12 and n-1-12 were replaced with equimolar m-1-36 and n-1-36, respectively, to give intermediate a-1-36 (29.47 g), and the HPLC purity was not less than 99.65%. Mass spectrum m/z:477.1038 (theory: 477.1030).

Synthesis example 3: synthesis of intermediate a-1-66

According to the same manner as that of intermediate a-1-12 of Synthesis example 1, equimolar m-1-12 was replaced with equimolar m-1-66, respectively, to obtain intermediate a-1-66 (26.01 g), which had an HPLC purity of 99.73% or more. Mass spectrum m/z:405.0980 (theory: 405.0968).

Synthesis example 4: synthesis of intermediate a-1-115

According to the same manner as that of intermediate a-1-12 of Synthesis example 1, equimolar m-1-12 and n-1-12 were replaced with equimolar m-1-115 and n-1-115, respectively, to obtain intermediate a-1-115 (25.11 g), and the HPLC purity was not less than 99.68%. Mass spectrum m/z:401.0708 (theory: 401.0717).

Synthesis example 5: synthesis of intermediate a-1-120

According to the same manner as that of intermediate a-1-12 of Synthesis example 1, equimolar m-1-12 and n-1-12 were replaced with equimolar m-1-36 and n-1-120, respectively, to obtain intermediate a-1-120 (24.14 g), and the HPLC purity was not less than 99.76%. Mass spectrum m/z:401.0728 (theory: 401.0717).

Synthesis example 6: synthesis of intermediate a-1-299

According to the same manner as in Synthesis example 1, intermediate a-1-12, equimolar m-1-12 and n-1-12 were replaced with equimolar m-1-299 and n-1-299, respectively, to give intermediate a-1-299 (28.56 g), and the HPLC purity was not less than 99.71%. Mass spectrum m/z:485.1832 (theory: 485.1817).

Synthesis example 7: synthesis of intermediate a-1-358

According to the same manner as in Synthesis example 1, intermediate a-1-12, equimolar m-1-12 and n-1-12 were replaced with equimolar m-1-358 and n-1-358, respectively, to give intermediate a-1-358 (29.01 g), and the HPLC purity was not less than 99.62%. Mass spectrum m/z:482.1332 (theory: 482.1344).

Synthesis example 8: synthesis of intermediates a-1-371

According to the same manner as that of intermediate a-1-12 of Synthesis example 1, equimolar m-1-12 was replaced with equimolar m-1-371, respectively, to obtain Compound a-1-371 (25.87 g), with an HPLC purity of 99.68% or more. Mass spectrum m/z:408.1141 (theory: 408.1157).

Synthesis example 9: synthesis of Compounds 1-8

Synthesis of intermediate A-1-8:

toluene (150 mL), a-1-8 (40.00 mmol,16.09 g), b-1-8 (40.00 mmol,6.77 g), palladium acetate (0.60 mmol,0.13 g), sodium tert-butoxide (80.00 mmol,7.69 g) and tri-tert-butylphosphine (2.40 mL of a 0.50M toluene solution, 1.20 mmol) were added sequentially to the flask under nitrogen, and dissolved by stirring and the mixture was refluxed for 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature, distilled water was added, extracted with dichloromethane, left to stand for liquid separation, the organic layer was collected and dried over anhydrous magnesium sulfate, the filtrate was concentrated by distillation under reduced pressure, cooled for crystallization, suction filtration, and toluene/methanol=10: 1 is recrystallized and purified to obtain an intermediate A-1-8 (16.09 g, yield 82%), and HPLC purity is more than or equal to 99.70%. Mass spectrum m/z:490.2335 (theory: 490.2347).

Synthesis of Compounds 1-8:

toluene (150 mL), A-1-8 (20.00 mmol,9.81 g), c-1-8 (20.00 mmol,5.32 g), dibenzylideneacetone dipalladium (0.20 mmol,0.19 g), sodium tert-butoxide (40.00 mmol,3.85 g), and tri-tert-butylphosphine (0.80 mL of a 0.50M toluene solution, 0.40 mmol) were added sequentially to the reaction flask under nitrogen, dissolved with stirring, and reacted at reflux for 6.5 hours. After the reaction is completed, cooling the reaction liquid to room temperature, adding distilled water, extracting with chloroform, standing for liquid separation, collecting an organic layer, drying with anhydrous magnesium sulfate, concentrating the filtrate by reduced pressure distillation, cooling for crystallization, filtering,recrystallisation from toluene gives compounds 1-8 (10.81 g, 80% yield) with an HPLC purity of 99.92% or more. Mass spectrum m/z:675.3549 (theory: 675.3538). Theoretical element content (%) C ₅₀ H ₂₁ D ₁₃ N ₂ : c,88.85; h,7.01; n,4.14. Measured element content (%): c,88.82; h,7.05; n,4.09.

Synthesis example 10: synthesis of Compounds 1-10

According to the same manner as that of Compound 1-8 of Synthesis example 9, equimolar amounts of a-1-8, b-1-8 and c-1-8 were replaced with equimolar amounts of a-1-10, b-1-10 and c-1-10, respectively, to give Compound 1-10 (9.53 g), and the purity of the solid as measured by HPLC was not less than 99.93%. Mass spectrum m/z:580.3521 (theory: 580.3539). Theoretical element content (%) C ₄₂ H ₁₂ D ₁₈ N ₂ : c,86.85; h,8.32; n,4.82. Measured element content (%): c,86.87; h,8.29; n,4.79.

Synthesis example 11: synthesis of Compounds 1-12

According to the same manner as that of Compound 1-8 of Synthesis example 9, equimolar amounts of a-1-8, b-1-8 and c-1-8 were replaced with equimolar amounts of a-1-12, b-1-12 and c-1-12, respectively, to obtain Compound 1-12 (10.54 g) having an HPLC purity of 99.90% or more. Mass spectrum m/z:702.3744 (theory: 702.3757). Theoretical element content (%) C ₅₂ H ₂₂ D ₁₄ N ₂ : c,88.85; h,7.17; n,3.99. Measured element content (%): c,88.81; h,7.20; n,3.97.

Synthesis example 12: synthesis of Compounds 1-35

According toSynthesis example 9 the same procedure for preparing Compound 1-8 was repeated except that equimolar amounts of a-1-8, b-1-8 and c-1-8 were replaced with equimolar amounts of a-1-35, b-1-35 and c-1-35, respectively, to obtain Compound 1-35 (11.50 g) having an HPLC purity of 99.94% or more. Mass spectrum m/z:727.3862 (theory: 727.3851). Theoretical element content (%) C ₅₄ H ₂₅ D ₁₃ N ₂ : c,89.09; h,7.06; n,3.85. Measured element content (%): c,89.11; h,7.04; n,3.89.

Synthesis example 13: synthesis of Compounds 1-36

According to the same manner as that for Compound 1-8 of Synthesis example 9, equimolar amounts of a-1-8, b-1-8 and c-1-8 were replaced with equimolar amounts of a-1-36, b-1-36 and c-1-36, respectively, to give Compound 1-36 (12.38 g) having an HPLC purity of 99.91% or more. Mass spectrum m/z:763.3906 (theory: 763.3913). Theoretical element content (%) C ₅₇ H ₃₃ D ₉ N ₂ : c,89.61; h,6.73; n,3.67. Measured element content (%): c,89.57; h,6.71; n,3.70.

Synthesis example 14: synthesis of Compounds 1-62

According to the same manner as that for Compound 1-8 of Synthesis example 9, equimolar amounts of a-1-8, b-1-8 and c-1-8 were replaced with equimolar amounts of a-1-62, b-1-62 and c-1-62, respectively, to give Compound 1-62 (11.84 g) having an HPLC purity of 99.96% or more. Mass spectrum m/z:768.5116 (theory: 768.5104). Theoretical element content (%) C ₅₆ H ₃₂ D ₁₈ N ₂ : c,87.45; h,8.91; n,3.64. Measured element content (%): c,87.48; h,8.88; n,3.60.

Synthesis example 15: synthesis of Compounds 1-66

According to the same manner as that for Compound 1-8 of Synthesis example 9, equimolar amounts of a-1-8, b-1-8 and c-1-8 were replaced with equimolar amounts of a-1-66, b-1-66 and c-1-66, respectively, to give Compound 1-66 (10.51 g) having an HPLC purity of 99.94% or more. Mass spectrum m/z:700.3648 (theory: 700.3632). Theoretical element content (%) C ₅₂ H ₂₄ D ₁₂ N ₂ : c,89.10; h,6.90; n,4.00. Measured element content (%): c,89.08; h,6.87; n,4.02.

Synthesis example 16: synthesis of Compounds 1-111

According to the same manner as that of Compound 1-8 of Synthesis example 9, equimolar amounts of b-1-8 and c-1-8 were replaced with equimolar amounts of b-1-35 and c-1-111, respectively, to give Compound 1-111 (13.46 g), with an HPLC purity of 99.98% or more. Mass spectrum m/z:840.4365 (theory: 840.4382). Theoretical element content (%) C ₆₃ H ₄₈ D ₄ N ₂ : c,89.96; h,6.71; n,3.33. Measured element content (%): c,89.92; h,6.68; n,3.35.

Synthesis example 17: synthesis of Compounds 1-115

According to the same manner as that for preparing Compound 1-8 of Synthesis example 9, equimolar amounts of a-1-8, b-1-8 and c-1-8 were replaced with equimolar amounts of a-1-115, b-1-115 and c-1-115, respectively, to obtain Compound 1-115 (12.53 g) having an HPLC purity of 99.93% or more. Mass spectrum m/z:754.4211 (theory: 754.4225). Theoretical element content (%) C ₅₆ H ₄₆ D ₄ N ₂ : c,89.08; h,7.21; n,3.71. Measured element content (%): c,89.11; h,7.19; n,3.69.

Synthesis example 18: synthesis of Compounds 1-120

According to the same manner as that of Compound 1-8 of Synthesis example 9, equimolar amounts of a-1-8 and c-1-8 were replaced with equimolar amounts of a-1-120 and c-1-120, respectively, to obtain Compound 1-120 (9.90 g), with an HPLC purity of 99.95% or more. Mass spectrum m/z:634.3299 (theory: 634.3286). Theoretical element content (%) C ₄₇ H ₃₄ D ₄ N ₂ : c,88.92; h,6.67; n,4.41. Measured element content (%): c,88.95; h,6.70; n,4.39.

Synthesis example 19: synthesis of Compounds 1-126

According to the same manner as that of Compound 1-8 of Synthesis example 9, equimolar c-1-8 was replaced with equimolar c-1-126, respectively, to obtain Compound 1-126 (9.64 g), with an HPLC purity of 99.99% or more. Mass spectrum m/z:642.2987 (theory: 642.2973). Theoretical element content (%) C ₄₈ H ₃₀ D ₄ N ₂ : c,89.68; h,5.96; n,4.36. Measured element content (%): c,89.70; h,5.93; n,4.38.

Synthesis example 20: synthesis of Compounds 1-132

According to the same manner as that of Compound 1-8 of Synthesis example 9, equimolar c-1-8 was replaced with equimolar c-1-132, respectively, to obtain Compound 1-132 (9.90 g), with HPLC purity of 99.97% or more. Mass spectrum m/z:642.2959 (theory: 642.2973). Theoretical element content (%) C ₄₈ H ₃₀ D ₄ N ₂ : c,89.68; h,5.96; n,4.36. Measured element content (%): c,89.71; h,5.94; n,4.38.

Synthesis example 21: synthesis of Compounds 1-149

According to the same manner as that of Compound 1-8 of Synthesis example 9, equimolar amounts of b-1-8 and c-1-8 were replaced with equimolar amounts of b-1-149 and c-1-149, respectively, to give Compound 1-149 (11.22 g) having an HPLC purity of 99.93% or more. Mass spectrum m/z:700.3771 (theory: 700.3756). Theoretical element content (%) C ₅₂ H ₄₀ D ₄ N ₂ : c,89.10; h,6.90; n,4.00. Measured element content (%): c,89.09; h,6.88; n,4.02.

Synthesis example 22: synthesis of Compounds 1-151

According to the same manner as that of Compound 1-8 of Synthesis example 9, equimolar amounts of b-1-8 and c-1-8 were replaced with equimolar amounts of b-1-151 and c-1-151, respectively, to give Compound 1-151 (14.23 g) having an HPLC purity of 99.96% or more. Mass spectrum m/z:856.3743 (theory: 856.3756). Theoretical element content (%) C ₆₅ H ₄₀ D ₄ N ₂ : c,91.09; h,5.64; n,3.27. Measured element content (%): c,91.11; h,5.61; n,3.30.

Synthesis example 23: synthesis of Compounds 1-170

According to the same manner as that of Compound 1-8 of Synthesis example 9, equimolar c-1-8 was replaced with equimolar c-1-170, respectively, to obtain Compound 1-170 (11.61 g), with an HPLC purity of 99.94% or more. Mass spectrum m/z:682.3274 (theory: 682.3286). Theoretical element content (%) C ₅₁ H ₃₄ D ₄ N ₂ : c,89.70; h,6.20; n,4.10. Measured element content (%): c,89.68; h,6.18; n,4.13.

Synthesis example 24: synthesis of Compounds 1-229

According to the same manner as that for Compound 1-8 of Synthesis example 9, equimolar amounts of a-1-8, b-1-8 and c-1-8 were replaced with equimolar amounts of a-1-229, b-1-229 and c-1-229, respectively, to obtain Compound 1-229 (12.47 g), which had an HPLC purity of 99.97% or more. Mass spectrum m/z:830.4550 (theory: 830.4538). Theoretical element content (%) C ₆₂ H ₅₀ D ₄ N ₂ : c,89.60; h,7.03; n,3.37. Measured element content (%): c,89.57; h,7.01; n,3.40.

Synthesis example 25: synthesis of Compounds 1-292

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According to the same manner as that of Compound 1-8 of Synthesis example 9, equimolar amounts of a-1-8 and c-1-8 were replaced with equimolar amounts of a-1-292 and c-1-170, respectively, to give Compound 1-292 (11.58 g) having an HPLC purity of 99.91% or more. Mass spectrum m/z:732.3452 (theory: 732.3443). Theoretical element content (%) C ₅₅ H ₃₆ D ₄ N ₂ : c,90.13; h,6.05; n,3.82. Measured element content (%): c,90.09; h,6.08; n,3.80.

Synthesis example 26: synthesis of Compounds 1-299

According to the same manner as that of Compound 1-8 of Synthesis example 9, equimolar amounts of a-1-8 and c-1-8 were replaced with equimolar amounts of a-1-299 and c-1-299, respectively, to obtain Compound 1-299 (13.56 g), with an HPLC purity of 99.95% or more. Mass spectrum m/z:836.4027 (theory: 836.4038). Theoretical element content (%) C ₆₃ H ₄₀ D ₆ N ₂ : c,90.39; h,6.26; n,3.35. Measured element content (%): c,90.40; h,6.28; n,3.32.

Synthesis example 27: synthesis of Compounds 1-314

According to the same manner as that for Compound 1-8 of Synthesis example 9, equimolar amounts of a-1-8, b-1-8 and c-1-8 were replaced with equimolar amounts of a-1-314, b-1-314 and c-1-314, respectively, to give Compound 1-314 (12.58 g) having an HPLC purity of 99.94% or more. Mass spectrum m/z:816.4369 (theory: 816.4382). Theoretical element content (%) C ₆₁ H ₄₈ D ₄ N ₂ : c,89.66; h,6.91; n,3.43. Measured element content (%): c,89.64; h,6.89; n,3.41.

Synthesis example 28: synthesis of Compounds 1-358

According to the same manner as that for Compound 1-8 of Synthesis example 9, equimolar amounts of a-1-8, b-1-8 and c-1-8 were replaced with equimolar amounts of a-1-358, b-1-149 and c-1-132, respectively, to give Compound 1-358 (10.71 g) having an HPLC purity of 99.91% or more. Mass spectrum m/z:723.3619 (theory: 723.3600). Theoretical element content (%) C ₅₄ H ₂₉ D ₉ N ₂ : c,89.59; h,6.54; n,3.87. Measured element content (%): c,89.61; h,6.58; n,3.89.

Synthesis example 29: synthesis of Compounds 1-371

According to the same manner as that of Compound 1-8 of Synthesis example 9, equimolar amounts of a-1-8 and c-1-8 were replaced with equimolar amounts of a-1-371 and c-1-371, respectively, to obtain Compound 1-371 (12.67 g), with an HPLC purity of 99.96% or more. Mass spectrum m/z:811.3895 (theory: 811.3882). Theoretical element content (%) C ₆₁ H ₂₉ D ₁₁ N ₂ : c,90.22; h,6.33; n,3.45. Measured element content (%): c,90.19; h,6.31; n,3.48.

Synthesis example 30: synthesis of Compounds 1-388

According to the same manner as that of Compound 1-8 of Synthesis example 9, equimolar amounts of a-1-8 and c-1-8 were replaced with equimolar amounts of a-1-62 and c-1-388, respectively, to obtain Compound 1-388 (12.27 g), with an HPLC purity of 99.92% or more. Mass spectrum m/z:839.4218 (theory: 839.4226). Theoretical element content (%) C ₆₃ H ₃₇ D ₉ N ₂ : c,90.07; h,6.60; n,3.33. Measured element content (%): c,90.11; h,6.57; n,3.31.

Synthesis example 31: synthesis of Compounds 1-389

According to the same manner as that for preparing compound 1-8 of Synthesis example 9, equimolar amounts of a-1-8, b-1-8 and c-1-8 were replaced with equimolar amounts of a-1-62, b-1-389 and c-1-389, respectively, to obtain compound 1-389 (14.25 g), and the HPLC purity was not less than 99.95%. Mass spectrum m/z:901.4367 (theory: 901.4382). Theoretical element content (%) C ₆₈ H ₃₉ D ₉ N ₂ : c,90.53; h,6.37; n,3.11. Measured element content (%): c,90.57; h,6.40; n,3.09.

Synthesis example 32: synthesis of Compounds 1-395

According to the same manner as that of Compound 1-8 of Synthesis example 9, equimolar amounts of a-1-8 and c-1-8 were replaced with equimolar amounts of a-1-395 and c-1-395, respectively, to give Compound 1-395 (13.15 g) having an HPLC purity of 99.97% or more. Mass spectrum m/z:821.4683 (theory: 821.4695). Management deviceTheoretical element content (%) C ₆₁ H ₄₃ D ₉ N ₂ : c,89.12; h,7.48; n,3.41. Measured element content (%): c,89.15; h,7.50; n,3.39.

Synthesis example 33: synthesis of Compounds 1-501

According to the same manner as that for Compound 1-8 of Synthesis example 9, equimolar amounts of a-1-8, b-1-8 and c-1-8 were replaced with equimolar amounts of a-1-501, b-1-501 and c-1-170, respectively, to give Compound 1-501 (11.03 g) having an HPLC purity of 99.93% or more. Mass spectrum m/z:734.4361 (theory: 734.4352). Theoretical element content (%) C ₅₄ H ₂₆ D ₁₆ N ₂ : c,88.24; h,7.95; n,3.81. Measured element content (%): c,88.27; h,7.93; n,3.79.

Synthesis example 34 Synthesis of Compounds 2-90

Preparation of intermediate F-90:

under the protection of nitrogen, the raw material f-90 (120.00 mmol,38.79 g), the raw material g-90 (125.00 mmol,19.55 g) and Pd (PPh) are added into a reaction bottle in sequence ₃ ) ₄ (2.50mmol，2.89g)、K ₂ CO ₃ (240.00 mmol,33.17 g) and 360mL toluene, 120mL ethanol and 120mL water, and the mixture is stirred, and the reactant system is heated and refluxed for reaction for 3 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=4: 1 recrystallisation to give intermediate F-90 (37.05 g, 87% yield); HPLC purity is not less than 98.32%. Mass spectrum m/z:354.1162 (theory: 354.1175).

Preparation of intermediate G-90:

under the protection of nitrogen, the intermediate F-90 (100.00 mmol,35.49 g), the raw material h-90 (105.00 mmol,26.66 g) and Pd (dppf) Cl are added into a reaction bottle in sequence ₂ (1.50 mmol,1.10 g), KOAc (200.00 mmol,19.63 g), 1, 4-dioxane (500 mL), stirring the mixture, heating the above reactant system to reflux for 5.5 hours, cooling to room temperature after the reaction is completed, adding 700mL of distilled water, extracting with ethyl acetate (350 mL. Times.3), and extracting the organic layer with anhydrous MgSO ₄ Drying, rotary evaporation of ethyl acetate followed by recrystallisation from toluene gave intermediate G-90 (35.71G, 80% yield); HPLC purity is not less than 98.61%. Mass spectrum m/z:446.2428 (theory: 446.2417).

Preparation of intermediate H-90:

under the protection of nitrogen, the reaction flask was charged with intermediate G-90 (75.00 mmol, 33.48G), raw material i-90 (80.00 mmol, 18.07G), pd (dppf) Cl in this order ₂ (1.30mmol，0.95g)、Na ₂ CO ₃ (150.00 mmol,15.90 g) and 240mL toluene, 80mL ethanol, 80mL water, and the mixture was stirred, and the above reactant system was heated to reflux for 7.5 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=8: 1 recrystallisation to give intermediate H-90 (27.23 g, 78% yield); HPLC purity is not less than 98.84%. Mass spectrum m/z:464.1085 (theory: 464.1099).

Preparation of intermediate I-90:

under the protection of nitrogen, the intermediate H-90 (55.00 mmol,25.60 g), the raw material H-90 (115.00 mmol,29.20 g) and Pd (dppf) Cl are added into a reaction bottle in sequence ₂ (1.00 mmol,0.73 g), KOAc (110.00 mmol,10.80 g), 1, 4-dioxane (600 mL), stirring the mixture, and heating the reaction system to reflux for reaction for 8 hours; after the completion of the reaction, the mixture was cooled to room temperature, 900mL of distilled water was added, followed by extraction with ethyl acetate (350 mL. Times.3), and the organic layer was dried over anhydrous MgSO ₄ Drying, rotary evaporation of ethyl acetate, then recrystallisation using toluene, drying gives intermediate I-90 (28.53 g, 80% yield); the HPLC purity is more than or equal to 99.56 percent. Mass spectrum m/z:648.3595 (theory: 648.3582).

Preparation of Compounds 2-90:

under the protection of nitrogen, the intermediate I-90 (35.00 mmol,22.70 g), the raw material j-90 (75.00 mmol,11.52 g) and Pd are added into a reaction bottle in sequence ₂ (dba) ₃ (0.60mmol，0.55g)、P(t-Bu) ₃ (1.20 mmol,2.40ml of 0.5M toluene solution), K ₂ CO ₃ (70.00 mmol,9.67 g) and 150ml of tetrahydrofuran, the mixture was stirred, and the above-mentioned reactant system was heated under reflux for 9 hours; after the reaction is finished, cooling to room temperature, carrying out suction filtration to obtain a filter cake, flushing the filter cake with ethanol, and finally recrystallizing the filter cake with toluene to obtain a compound 2-90 (17.44 g, yield 79%); HPLC purity is more than or equal to 99.95%. Mass spectrum m/z:630.2320 (theory: 630.2307). Theoretical element content (%) C ₄₅ H ₃₀ N ₂ O ₂ : c,85.69; h,4.79; n,4.44. Measured element content (%): c,85.71; h,4.78; n,4.47.

Synthesis example 35 Synthesis of Compounds 2-92

Following the procedure for the preparation of synthesis example 34, F-90 was replaced with equimolar F-92 to give compound 2-92 (17.82 g, 81% yield); the HPLC purity is more than or equal to 99.97 percent. Mass spectrum m/z:628.2163 (theory: 628.2151). Theoretical element content (%) C ₄₅ H ₂₈ N ₂ O ₂ : c,85.97; h,4.49; n,4.46. Measured element content (%): c,85.95; h,4.47; n,4.47.

Synthesis example 36 Synthesis of Compounds 2 to 101

Following the procedure for the preparation of Synthesis example 34 substituting f-90 with equimolar f-101 and j-90 with equimolar j-101, compound 2-101 (21.79 g) was obtained; HPLC purity is more than or equal to 99.98%. Mass spectrum m/z:914.3885 (theory: 914.3872). Theoretical element content (%) C ₆₇ H ₅₀ N ₂ O ₂ : c,87.94; h,5.51; n,3.06. Measured element content (%): c,87.91; h,5.53; n,3.08.

Synthesis example 37 Synthesis of Compounds 2-158

Following the procedure for the preparation of Synthesis example 34, substituting f-90 with equimolar f-158, compound 2-158 (19.27 g) is obtained; the HPLC purity is more than or equal to 99.97 percent. Mass spectrum m/z:714.3233 (theory: 714.3246). Theoretical element content (%) C ₅₁ H ₄₂ N ₂ O ₂ : c,85.68; h,5.92; n,3.92. Measured element content (%): c,85.67; h,5.93; n,3.91.

Synthesis example 38 Synthesis of Compounds 2-188

Following the procedure for the preparation of Synthesis example 34 substituting f-90 with equimolar f-188 and j-90 with equimolar j-188, compound 2-188 (18.02 g) was obtained; HPLC purity is more than or equal to 99.96%. Mass spectrum m/z:714.3133 (theory: 714.3122). Theoretical element content (%) C ₅₁ H ₂₆ D ₈ N ₂ O ₂ : c,85.69; h,5.92; n,3.92. Measured element content (%): c,85.66; h,5.91; n,3.95.

Synthesis example 39 Synthesis of Compound 2-277

Following the procedure for the preparation of Synthesis example 34, substituting f-90 with equimolar f-277 and g-90 with equimolar g-277, compound 2-277 (19.76 g) was obtained; HPLC purity is more than or equal to 99.96%. Mass spectrum m/z:752.2473 (theory: 752.2464). Theoretical element content (%) C ₅₅ H ₃₂ N ₂ O ₂ : c,87.74; h,4.28; n,3.72. Measured element content (%): c,87.77; h,4.23; n,3.71.

Synthesis example 40 Synthesis of Compounds 2-309

Following the procedure for the preparation of Synthesis example 34 substituting f-90 with equimolar f-309 and g-90 with equimolar g-309, compound 2-309 (19.02 g) was obtained; HPLC purity is more than or equal to 99.98%. Mass spectrum m/z:696.2788 (theory: 696.2777). Theoretical element content (%) C ₅₀ H ₃₆ N ₂ O ₂ : c,86.18; h,5.21; n,4.02. Measured element content (%): c,86.23; h,5.23; n,4.00.

Device example 1

Firstly, the ITO substrate is washed 3 times in distilled water, ultrasonic washing is carried out for 15 minutes, after the distilled water washing is finished, solvents such as isopropanol, acetone, methanol and the like are sequentially ultrasonic washed, and then the ITO substrate is dried at 120 ℃.

Evaporating HT-1:P-1=97:3 (doping mass ratio) with the thickness of 10nm on the cleaned ITO substrate by adopting a vacuum evaporation method to serve as a hole injection layer material; evaporating compounds 1-8 with the thickness of 80nm on the hole injection layer to serve as a hole transport layer material; vapor deposition of CDBP: ir (ppy) on the hole transport layer ₂ (acac) =92:8 (mass ratio) as a light-emitting layer, the vapor deposition thickness was 35nm; evaporating 2-158 on the light-emitting layer to serve as a hole blocking layer material, wherein the evaporating thickness is 30nm; evaporating TPyQB and Liq (doping mass ratio is 1:1) on the hole blocking layer to serve as electron transport layer materials, wherein the evaporating thickness is 25nm; evaporating LiF as an electron injection layer on the electron transport layer, wherein the evaporating thickness is 1.0nm; then, al is evaporated on the electron injection layer to serve as a cathode, and the evaporation thickness is 120nm, so that the organic electroluminescent device is prepared.

Device examples 2 to 25

In addition to the above, the device of examples 1-10 and 2-90, 1-12 and 2-140, 1-35 and 2-421, 1-36 and 2-335, 1-62 and 2-225, 1-66 and 2-138, 1-111 and 2-421, 1-115 and 2-349, 1-120 and 2-482, 1-126 and 2-29, 1-132 and 2-277, 1-149 and 2-309, 1-151 and 2-76, 1-170 and 2-101, 1-229 and 2-29, 1-292 and 2-188, 1-299 and 2-496, 1-314 and 2-101, 1-358 and 2-371, 1-141 and 2-349, 1-141 and 1-35 and 2-395 are prepared as described in the device of examples 1-132 and 2-277, and 1-35, and the device of examples 1-35 and 1-35 are used as devices.

Comparative device examples 1 to 12

The same procedure as in device example 1 was used to prepare an organic electroluminescent device except that compounds 1 to 2-309, compounds 2 to 2-349, compounds 3 to 2-277, compounds 1 to 151 to 4, compounds 1 to 115 to 5, compounds 1 to 229 to 6, compounds 1 to 111 to BAlq, compounds 1 to 314 to BAlq, compounds 1 to 299 to BAlq, HMTPD to 2-101, HMTPD to 2-76, and HMTPD to 2-496 were used instead of compounds 1 to 8 and compounds 2 to 158 in device example 1.

Comparative device example 13

Evaporating HT-1:P-1=97:3 (doping mass ratio) with the thickness of 10nm on the cleaned ITO substrate by adopting a vacuum evaporation method to serve as a hole injection layer material; evaporating compounds 1-10 with the thickness of 80nm on the hole injection layer to serve as a hole transport layer material; vapor deposition of CDBP: ir (ppy) on the hole transport layer ₂ (acac) =92:8 (mass ratio) as a light emitting layer, the vapor deposition thickness was 35nm; evaporating TPyQB and Liq (doping mass ratio is 1:1) on the luminescent layer as electron transport layer materials, wherein the evaporating thickness is 55nm; evaporating LiF as an electron injection layer on the electron transport layer, wherein the evaporating thickness is 1.0nm; then, al is evaporated on the electron injection layer to serve as a cathode, and the evaporation thickness is 120nm, so that the organic electroluminescent device is prepared.

Comparative device examples 14 to 18

An organic electroluminescent device was produced by the same procedure as in comparative device example 13, except that compounds 1 to 36, compounds 1 to 66, compounds 1 to 132, compounds 1 to 292 or compounds 1 to 501 were used in place of the compounds 1 to 10 in device example 1, respectively.

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 testing the light emitting characteristics of the organic electroluminescent devices obtained in comparative examples 1 to 18, which were devices 1 to 25 in the device examples according to the present invention, are shown in table 1 below.

As can be seen from table 1, the organic electroluminescent device of the present invention can effectively improve the recombination probability of holes and electrons in the light-emitting layer, and improve the light-emitting efficiency and the service life of the device.

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. An organic electroluminescent device comprises an anode, an organic layer and a cathode, wherein the organic layer comprises a hole transmission region, a luminescent layer, an electron transmission region and a covering layer, and is characterized in that the hole transmission region comprises a structure shown in a formula I, and the electron transmission region comprises a structure shown in a formula II;

the R is ₂ 、R ₃ Are the same or different from each other, and are selected from any one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 aromatic ring and C3-C30 aliphatic ring condensed ring base;

said n ₄ Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, when two or more R's are present ₃ When two or more R' s ₃ Identical to or different from each other, orTwo adjacent R ₃ May be linked to each other to form a substituted or unsubstituted ring;

the saidAt least one deuterium;

said n ₂ Selected from 1, 2 or 3;

the X is ₁ Selected from O, S, N (R) _e ) Any one of them;

the R is _c Are identical or different from each other and are selected from hydrogen, deuterium, cyano, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted CAny one of aryl groups of 6 to C30, substituted or unsubstituted heteroaryl groups of 2 to C30, substituted or unsubstituted aromatic rings of 6 to C30 and condensed ring groups of aliphatic rings of 3 to C30;

the a' is selected from 0, 1, 2 or 3;

2. An organic electroluminescent device as claimed in claim 1, wherein theAny one selected from the following groups;

the R is ₀ 、R ₈ Identical to or different from each other, selected from hydrogen, deuterium, cyano, halogen or any one of the following groups substituted or unsubstituted by one or more deuterium, C1-C12 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, tert-butyl, cyclopropanyl, cyclobutylalkyl, cyclopentanyl, cyclohexenyl, cycloheptanyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl or naphthyl, and said R ₀ At least one deuterium;

3. An organic electroluminescent device as claimed in claim 1, wherein theAny one selected from the following groups;

the s is ₁ Selected from 0, 1, 2 or 3, said s ₂ Selected from 0, 1, 2, 3 or 4, said s ₃ Selected from the group consisting of0. 1, 2, 3, 4 or 5, said s ₄ Selected from 0, 1, 2, 3, 4, 5, 6 or 7, said s ₅ Selected from 0, 1 or 2, said s ₆ Selected from 0, 1, 2, 3, 4, 5 or 6, said s ₇ Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said s ₈ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

4. An organic electroluminescent device as claimed in claim 1, wherein Ar ₁ 、Ar ₂ Are the same or different from each other, and are selected from any one of the following groups;

the c ₁ Selected from 0, 1, 2, 3, 4 or 5, said c ₂ Selected from 0, 1, 2, 3 or 4, said c ₃ Selected from 0, 1, 2, 3, 4, 5, 6 or 7, said c ₄ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, said c ₅ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, said c ₆ Selected from 0, 1, 2 or 3, said c ₉ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, said c ₁₀ Selected from 0, 1, 2, 3, 4, 5 or6, said c ₁₁ Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said c ₁₂ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, said c ₁₃ Selected from 0, 1 or 2.

5. An organic electroluminescent device as claimed in claim 1, wherein theAny one selected from the following groups;

6. An organic electroluminescent device as claimed in claim 1, wherein the L ₁ 、L ₂ Are identical or different from each other and are selected from single bonds or groups as shown below, and groups thereofAny one of the combinations;

7. An organic electroluminescent device as claimed in claim 1, wherein theAny one selected from the following groups;

the R is _a 、R _b 、R _x 、R _y 、R _z 、R _d Are the same or different from each other, and are selected from any one of hydrogen, deuterium, or a group as described below which is substituted or unsubstituted by one or more deuterium, C1-C12 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, naphthyl, benzocyclopentyl or benzocyclohexenyl; or said R _a 、R _b Any one of them can be directly connected with L _a Bonding;

8. An organic electroluminescent device as claimed in claim 1, wherein the organic electroluminescent device comprisesAny one selected from the following groups;

the X is ₁ Selected from O, S, N (R) _e ) Any one of them;

said f ₁ Selected from 0, 1, 2, 3 or 4, said f ₂ Selected from 0, 1, 2, 3, 4 or 5。

9. An organic electroluminescent device according to claim 1, wherein the structure of formula I is selected from any one of the following structures;

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10. an organic electroluminescent device according to claim 1, wherein the structure of formula II is selected from any one of the following structures;

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