CN116143739A

CN116143739A - Diamine compound and organic light-emitting device thereof

Info

Publication number: CN116143739A
Application number: CN202310066143.1A
Authority: CN
Inventors: 韩春雪; 刘小婷; 陆影; 周雯庭
Original assignee: Changchun Hyperions Technology Co Ltd
Current assignee: Changchun Hyperions Technology Co Ltd
Priority date: 2023-01-17
Filing date: 2023-01-17
Publication date: 2023-05-23

Abstract

The invention provides a diamine compound and an organic light-emitting device thereof, and relates to the technical field of organic photoelectric materials. The compound of the invention improves the glass transition temperature (Tg) of the material and the evaporation temperature, and effectively prolongs the service life of the organic light-emitting device. On one hand, the material serving as the hole transport layer is applied to devices, and has the advantages of high luminous efficiency and long service life. On the other hand, the light extraction efficiency can be improved when the light extraction efficiency is applied to a device as a coating material, thereby improving the luminous efficiency and the service life of the device. The method has good application effect and industrialization prospect, and 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, signs, signal lamps and the like.

Description

Diamine compound and organic light-emitting device thereof

Technical Field

The invention relates to the technical field of organic photoelectric materials, in particular to a diamine compound and an organic light-emitting device thereof.

Background

Organic electroluminescence has the characteristics of low driving voltage, magneto luminescence, light weight, thinness, wide viewing angle, quick response and the like, and has gradually developed into the most advantageous technology in the field of new generation flat panel display. The conventional OLED device generally includes an anode, a cathode, and organic layers such as a hole injection layer, a hole transport layer, a hole auxiliary layer, a light emitting auxiliary layer, an electron blocking layer, a light emitting layer, an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a capping layer disposed between the anode and the cathode on a substrate.

An organic light emitting device is generally composed of an anode and a cathode with an organic layer material therebetween. The organic layer adjacent to the anode contains a hole transporting substance and has a function of mainly transporting holes to the light emitting layer in the organic light emitting device apparatus. Similarly, the organic layer adjacent to the cathode contains an electron mediator, and has a function of mainly transporting electrons in the organic light-emitting device. Holes and electrons injected from the anode and the cathode are recombined in the light-emitting layer, and then the excited state is converted to the ground state, thereby emitting light.

In the organic light-emitting device, when light emitted from the light-emitting layer is incident on other films, if the light is incident at a certain angle or more, total reflection occurs at the interface between the light-emitting layer and the other films. Therefore, only a part of the emitted light can be utilized. Recently, an organic light emitting device has been proposed in which a high refractive index coating layer is formed on the outer side of a low refractive index semitransparent electrode in order to improve light extraction efficiency. However, so far, there has been little research on compounds suitable for use as a cover material.

Accordingly, in order to improve light emission characteristics such as a driving voltage and light emission efficiency of the organic light emitting device, and in order to extend the life of the device, organic layer materials used in the organic light emitting device, for example, hole transport layer materials, capping layer materials, and the like, have been continuously researched and developed.

Disclosure of Invention

The invention aims to provide a diamine compound and an organic light-emitting device thereof based on the prior art and aiming at industrialization, and the organic light-emitting device prepared by using the diamine compound has the advantages of high efficiency and long service life, and the molecular structural general formula of the diamine compound is shown as formula I:

wherein the Ar is ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ Are identical or different from each other, and at least one is selected from the group represented by formula a, the rest is independently selected from one of the groups represented by formula b, formula c and formula d,

in formula a, X is selected from O or S;

the z are the same or different and are each independently selected from CH or N; when z is bonded to other groups, the z is selected from C;

the R is _b The same or different, each independently selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl; or optionally adjacent two R _b The groups may be bonded together to form a substituted or unsubstituted cyclic structure;

the R is _a Identical or different, each independently selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, One of a substituted or unsubstituted C6 to C25 aryl group and a substituted or unsubstituted C2 to C20 heteroaryl group;

the a is selected from 0, 1 or 2; said b is selected from 0, 1, 2, 3 or 4;

in formula b, the R ₁ One selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl;

said n ₁ Selected from 0, 1, 2, 3, 4 or 5; when n is ₁ Above 1, each R ₁ Identical or different, adjacent two R' s ₁ The groups may be bonded together to form a substituted or unsubstituted cyclic structure;

in formula c, the X ₀ Selected from O, S, C (R) _e )(R _f ) Any one of N (R);

the R is _e 、R _f The same or different, each independently selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, 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 R _e 、R _f Can be combined with each other to form a substituted or unsubstituted spiro ring; or R is _e 、R _f Any one of them can be directly connected with L ₁ 、L ₂ 、L ₃ Or L ₄ Bonding;

r is selected from any one of 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, or R can be directly combined with L ₁ 、L ₂ 、L ₃ Or L ₄ Bonding;

the R is ₂ 、R ₃ The same or different, each independently selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl;

said n ₂ Selected from 0, 1, 2, 3 or 4; when n is ₂ Above 1, each R ₂ Identical or different, adjacent two R' s ₂ The groups may be bonded together to form a substituted or unsubstituted cyclic structure; said n ₃ Selected from 0, 1, 2, 3 or 4; when n is ₃ Above 1, each R ₃ Identical or different, adjacent two R' s ₃ The groups may be bonded together to form a substituted or unsubstituted cyclic structure;

in the formula d, y is the same or different and is selected from CH or N, and at least one y is selected from N; when y is bonded to other groups, the y is selected from C;

the R is ₄ The same or different, each independently selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl;

Said n ₄ Selected from 0, 1, 2, 3 or 4; when n is ₄ Above 1, each R ₄ Identical or different, adjacent two R' s ₄ The groups may be bonded together to form a substituted or unsubstituted cyclic structure;

said V is selected from O, S or NR _y The R is _y Aryl selected from substituted or unsubstituted C6 to C25;

the R is _c 、R _d The same or different, each independently selected from one of hydrogen, deuterium, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted n-propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthylOf a species, or of two adjacent R _c Bonded together to form a substituted or unsubstituted cyclic structure, or two adjacent R' s _d Bonded together to form a substituted or unsubstituted cyclic structure;

said c is selected from 0, 1, 2 or 3; said d is selected from 0, 1, 2 or 3;

the L is _c 、L _d The same or different, each independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C2-C30 heteroarylene group;

The L is ₁ 、L ₂ 、L ₃ 、L ₄ And the two substituents are the same or different and are each independently selected from one of single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C2-C30 heteroarylene or adjacent two substituents are bonded to form a substituted or unsubstituted cyclic structure.

The invention also provides an organic light-emitting device, which comprises an anode, a cathode and an organic layer, wherein the organic layer is positioned between the anode and the cathode or outside one or more than one of the anode and the cathode, and the organic layer contains any one or a combination of at least two of the diamine compounds.

The invention has the beneficial effects that:

the invention provides a diamine compound and an organic light-emitting device thereof, wherein the compound improves the glass transition temperature (Tg) and evaporation temperature of materials, and effectively prolongs the service life of the organic light-emitting device. On the one hand, the material serving as the hole transport layer is applied to a device, can improve the transport efficiency of holes in the device, simultaneously reduces the energy barrier of the holes in the injection process, improves the injection efficiency of the holes, and has the advantages of high luminous efficiency and long service life. On the other hand, the material serving as a coating layer is applied to a device, so that the total emission of an interface between an ITO film and a glass substrate and an interface between the glass substrate and air can be effectively solved, the total reflection loss and waveguide loss in an OLED device are reduced, the light extraction efficiency is improved, and the luminous efficiency and the service life of the organic light-emitting device are improved.

Detailed Description

The following description of embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is shown, however, only some, but not all embodiments of the invention are shown. 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 invention, the use of "H" and "hydrogen" means that the hydrogen atoms in the chemical structure contain no more than the natural abundance of deuterium or tritium atoms, for example, no more than 0.0156 atomic% deuterium. "D" and "deuterium" refer to any value where the abundance of deuterium content is above natural abundance, e.g., above 0.1 atomic%, above 1 atomic%, above 10 atomic%, e.g., where about 95 atomic% is deuterium. In the present invention, the omitted hydrogen atom represents "H" or "hydrogen".

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->

And so on. />

Halogen in the present invention means fluorine, chlorine, bromine and iodine.

The alkyl group according to the present invention is a hydrocarbon group having at least one hydrogen atom in the alkane molecule, and may be a straight chain alkyl group or a branched chain alkyl group, and preferably has 1 to 15 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms. The straight-chain alkyl group includes, but is not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl and the like; the branched alkyl group includes, but is not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, an isomeric group of n-pentyl, an isomeric group of n-hexyl, an isomeric group of n-heptyl, an isomeric group of n-octyl, an isomeric group of n-nonyl, an isomeric group of n-decyl, and the like. The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.

The chain alkyl group having more than three carbon atoms according to the present invention includes isomers thereof, for example, propyl group includes n-propyl group, isopropyl group, butyl group includes n-butyl group, sec-butyl group, isobutyl group, tert-butyl group. And so on.

Cycloalkyl as used herein refers to a hydrocarbon group having at least one hydrogen atom in the cycloparaffin molecule, preferably having 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, particularly preferably 3 to 6 carbon atoms, and examples may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, camphene, norbornyl, etc., but are not limited thereto. The cycloalkyl group is preferably a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, a 2-adamantyl group, or a norbornyl group.

Aryl in the present invention refers to the generic term for monovalent radicals remaining after removal of one hydrogen atom from the aromatic nucleus carbon of an aromatic compound molecule, which may be a monocyclic aryl, polycyclic aryl or fused ring aryl, preferably having from 6 to 25 carbon atoms, more preferably from 6 to 20 carbon atoms, particularly preferably from 6 to 14 carbon atoms, and most preferably from 6 to 12 carbon atoms. 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, etc., but is not limited thereto; the condensed ring aryl group refers to an aryl group having two or more aromatic rings in the molecule and condensed by sharing two adjacent carbon atoms with each other, for example, but not limited to, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluorenyl, benzofluorenyl, triphenylenyl, fluoranthryl, spirobifluorenyl, and the like. The aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group (preferably a 2-naphthyl group), an anthryl group (preferably a 2-anthryl group), a phenanthryl group, a pyrenyl group, a perylenyl group, a fluorenyl group, a benzofluorenyl group, a triphenylenyl group, or a spirobifluorenyl group.

Heteroaryl according to the present invention refers to the generic term for groups in which one or more aromatic nucleus carbon atoms in the aryl group are replaced by heteroatoms, including but not limited to oxygen, sulfur, nitrogen or phosphorus atoms, preferably having 1 to 25 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 3 to 15 carbon atoms, most preferably 3 to 12 carbon atoms, the attachment site of the heteroaryl group may be located on a ring-forming carbon atom, or on a ring-forming nitrogen atom, and the heteroaryl group may be a monocyclic heteroaryl, polycyclic heteroaryl or fused ring heteroaryl. The monocyclic heteroaryl group includes, but is not limited to, pyridyl, pyrimidinyl, triazinyl, furyl, thienyl, pyrrolyl, imidazolyl, and the like; the polycyclic heteroaryl group includes bipyridyl, bipyrimidinyl, phenylpyridyl, etc., but is not limited thereto; the fused ring heteroaryl group includes, but is not limited to, quinolinyl, isoquinolinyl, indolyl, benzothienyl, benzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, benzodibenzofuranyl, dibenzothiophenyl, benzodibenzothiophenyl, carbazolyl, benzocarbazolyl, acridinyl, 9, 10-dihydroacridinyl, phenoxazinyl, phenothiazinyl, phenoxathiazinyl, and the like. The heteroaryl group is preferably a pyridyl group, a pyrimidyl group, a thienyl group, a furyl group, a benzothienyl group, a benzofuryl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a dibenzofuryl group, a dibenzothienyl group, a benzodibenzothienyl group, a benzodibenzofuryl group, a carbazolyl group, an acridinyl group, a phenoxazinyl group, a phenothiazinyl group, or a phenoxathiazide group.

The arylene group according to the present invention means a generic term for divalent groups remaining after removal of two hydrogen atoms from the aromatic nucleus carbon of an aromatic compound molecule, which may be a monocyclic arylene group, a polycyclic arylene group or a condensed ring arylene group, preferably having 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms. The monocyclic arylene group includes phenylene and the like, but is not limited thereto; the polycyclic arylene group includes biphenylene, terphenylene, etc., but is not limited thereto; the condensed ring arylene includes, but is not limited to, naphthylene, anthrylene, phenanthrylene, fluorenylene, pyreylene, triphenylene, fluoranthenylene, phenylenedenyl, and the like. The arylene group is preferably phenylene, biphenylene, terphenylene, naphthylene, fluorenylene, or phenylenediyl.

Heteroaryl, as used herein, refers to the generic term for groups in which one or more of the aromatic nucleus carbons in the arylene group is replaced with a heteroatom, including but not limited to oxygen, sulfur, nitrogen, or phosphorus atoms. Preferably having 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 3 to 12 carbon atoms, the heteroarylene group may be attached at a ring-forming carbon atom or at a ring-forming nitrogen atom, and the heteroarylene group may be a monocyclic heteroarylene group, a polycyclic heteroarylene group, or a fused ring heteroarylene group. The monocyclic heteroarylene group includes, but is not limited to, a pyridylene group, a pyrimidinylene group, a triazinylene group, a furanylene group, a thienyl group, and the like; the polycyclic heteroarylene group includes bipyridylene group, bipyrimidiylene group, phenylpyridylene group, etc., but is not limited thereto; the condensed ring heteroarylene group includes quinolinylene, isoquinolylene, indolylene, benzothienyl, benzofuranylene, benzoxazolylene, benzimidazolylene, benzothiazolylene, dibenzofuranylene, benzodibenzofuranylene, dibenzothiophenylene, benzodithiorenylene, carbazolylene, benzocarbazolylene, acridinylene, 9, 10-dihydroacridinylene, phenoxazinylene, phenothiazinylene, phenoxazinylene, and the like, but is not limited thereto. The heteroaryl group is preferably a pyridyl group, a pyrimidylene group, a thienyl group, a furanylene group, a benzothienyl group, a benzofuranylene group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a dibenzodibenzothiophenyl group, a benzodibenzofuranyl group, a carbazolyl group, an acridinyl group, a phenoxazinyl group, a phenothiazinyl group, or a phenoxathiazide group.

The term "unsubstituted …" as used herein, such as unsubstituted alkyl, unsubstituted cycloalkyl, unsubstituted aryl, unsubstituted heteroaryl, unsubstituted arylene, unsubstituted heteroarylene, and the like, means that the "hydrogen" (H) in the group is not replaced with other groups including deuterium.

"substituted …" as used herein, such as substituted alkyl, substituted cycloalkyl, substituted aryl, substituted heteroaryl, substituted arylene, substituted heteroarylene, and the like, means mono-or poly-substituted with groups independently selected from deuterium, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C2-C15 heteroaryl, substituted or unsubstituted amine, and the like, but not limited thereto, preferably with groups selected from deuterium, halogen, cyano, methyl, ethyl, isopropyl, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, camphene, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, benzophenanthryl, perylene, pyrenyl, benzyl, tolyl, fluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, dimethylamino, dicarbazolyl, 9-phenylfluorenyl, benzoxazolyl, oxazolyl, benzofuranyl, thienyl, pyrrolyl, thienyl, or the like. In addition, the substituent may be substituted with one or more substituents selected from deuterium, halogen atom, cyano, alkyl, cycloalkyl and aryl.

The term "bonded to form a cyclic structure" as used herein means that two groups are attached 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, such as benzene, naphthalene, fluorene, cyclopentene, cyclohexene, cyclopentane, cyclohexane acene, pyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquinoline, dibenzothiophene, phenanthrene or pyrene, but is not limited thereto.

The two adjacent groups described herein may be bonded together to form a cyclic structure, preferably, the two adjacent groups may be bonded together to form a benzene ring, naphthalene ring, pyridine ring, or pyrimidine ring.

More preferably, two adjacent groups may be bonded together to form a benzene ring or naphthalene ring.

Most preferably, two adjacent groups may be bonded together to form a benzene ring.

The invention provides a diamine compound, the molecular structural general formula of which is shown as formula I:

in formula a, X is selected from O or S;

the R is _a The same or different, each independently selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen,One of a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C6-C25 aryl group, and a substituted or unsubstituted C2-C20 heteroaryl group;

the a is selected from 0, 1 or 2; said b is selected from 0, 1, 2, 3 or 4;

In formula c, the X ₀ Selected from O, S, C (R) _e )(R _f ) Any one of N (R);

the R is ₂ 、R ₃ The same or different, each independently selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substitutedOr any one of unsubstituted C6 to C25 aryl groups;

The R is _c 、R _d The same or different, each independently selected from hydrogen, deuterium, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted n-propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstitutedOne of norbornyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, or two adjacent R' s _c Bonded together to form a substituted or unsubstituted cyclic structure, or two adjacent R' s _d Bonded together to form a substituted or unsubstituted cyclic structure;

said c is selected from 0, 1, 2 or 3; said d is selected from 0, 1, 2 or 3;

Preferably Ar ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ At least one group selected from the group consisting of a group of formula a, including Ar ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ One, two, three or four of the groups of formula a; in Ar ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ Ar is selected from the group represented by formula a ₁ 、Ar ₂ 、Ar ₃ Or Ar ₄ Selected from the group represented by formula a; in Ar ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ Ar is selected from the group represented by formula a ₁ And Ar is a group ₂ Or Ar ₁ And Ar is a group ₃ Selected from the group represented by formula a; in Ar ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ Ar is selected from the group represented by formula a ₁ 、Ar ₂ And Ar is a group ₃ Selected from the group represented by formula a; in Ar ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ Ar is selected from the group consisting of four of the groups of formula a ₁ 、Ar ₂ 、Ar ₃ And Ar is a group ₄ Selected from the group represented by formula a.

Preferably, the group of formula a is selected from one of the following groups:

the X is selected from O or S;

the R is _a The same or different, each independently selected from one or more of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted: one or more of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, biphenyl, terphenyl, naphthyl, phenyl-naphthyl, naphthyl-phenyl, pyridinyl, pyrimidinyl, pyridazine, pyrazine, triazinyl; wherein the substituent in the "substituted or unsubstituted" is selected from one or more of deuterium, cyano, trifluoromethyl, halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, phenyl, biphenyl, naphthyl, and in the case of being substituted with a plurality of substituents, the plurality of substituents are the same as or different from each other;

The a is selected from 0, 1 or 2;

the R is _b The same or different, each independently selected from one or more of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted: one or more of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, biphenyl, terphenyl, naphthyl, phenyl-naphthyl, naphthyl-phenyl, pyridinyl, pyrimidinyl, pyridazine, pyrazine, triazinyl; wherein the substituent in the "substituted or unsubstituted" is selected from one or more of deuterium, cyano, trifluoromethyl, halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, phenyl, biphenyl, naphthyl, and in the case of being substituted with a plurality of substituents, the plurality of substituents are the same as or different from each other; or optionally adjacent two R _b The groups may be bonded to form substituted or unsubstituted benzene rings, substituted or unsubstituted benzene ringsOne of an unsubstituted naphthalene ring, a substituted or unsubstituted pyridine ring, a substituted or unsubstituted pyrimidine ring, and a substituted or unsubstituted pyrazine ring;

said b ₁ Selected from 0, 1, 2, 3 or 4; said b ₂ Selected from 0, 1, 2 or 3; said b ₃ Selected from 0, 1 or 2; said b ₄ Selected from 0 or 1.

More preferably, the group of formula a is selected from one of the following groups:

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further preferably, the Ar ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ Are identical or different from each other, and at least one is selected from the group represented by formula a, and the others are each independently selected from one of the following groups:

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the R is ₁ One selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, and substituted or unsubstituted naphthyl;

the R is ₂ 、R ₃ Independently selected from hydrogen, deuteriumCyano, trifluoromethyl, halogen, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, tolyl, biphenyl, terphenyl, anthryl, phenanthryl, triphenylene, spirofluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, dibenzofuranyl, dibenzothienyl, 9-phenylcarbazolyl, carbazolyl, and R ₂ 、R ₃ May also be substituted with one or more of deuterium, cyano, trifluoromethyl, halogen, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, phenyl, deuterated phenyl, naphthyl, deuterated naphthyl, tolyl, biphenyl, deuterated biphenyl, terphenyl, anthryl, phenanthryl, triphenylene, and where substituted with multiple substituents, the multiple substituents may be the same or different from each other; or any two adjacent R ₂ Are combined with each other to form a substituted or unsubstituted benzene ring or naphthalene ring; or any two adjacent R ₃ Are combined with each other to form a substituted or unsubstituted benzene ring or naphthalene ring;

the R is _c 、R _d 、R ₅ Independently selected from any of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted: C1-C6 alkyl, C3-C6 cycloalkyl, adamantyl, norbornyl, C6-C12 aryl, C2-C12 heteroaryl; the substituent of the substituent is any one or more of deuterium, C1-C12 alkyl and C3-C12 cycloalkyl;

the R is selected from deuterium or substituted or unsubstituted groups as follows: one of methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, anthryl, phenanthryl, triphenylene, dibenzofuranyl, dibenzothienyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirofluorenyl, 9-phenylcarbazolyl;

The R is ₄ Selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-one of a C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group;

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

More preferably, the Ar ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ Are identical or different from each other, and at least one is selected from the group represented by formula a, and the others are each independently selected from one of the following groups:

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the R is ₁ 、R ₂ 、R ₃ 、R ₄ 、R ₆ Are the same or different from each other and are independently selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen or one of the following substituted or unsubstituted groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl Triphenylene; wherein the substituent in the "substituted or unsubstituted" is selected from one or more of deuterium, cyano, trifluoromethyl, halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, norbornyl, phenyl, biphenyl, naphthyl, and in the case of being substituted with a plurality of substituents, the plurality of substituents are the same or different from each other;

the R is selected from deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tertiary butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, anthryl, phenanthryl, triphenylene, dibenzofuranyl, dibenzothienyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirofluorenyl, 9-phenylcarbazolyl, and the above groups may also be substituted with one or more of deuterium, cyano, trifluoromethyl, halogen, methyl, ethyl, n-propyl, n-butyl, isopropyl, tertiary butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, tolyl, biphenyl, terphenyl, deuterated isopropyl, deuterated tertiary butyl, deuterated cyclohexyl, deuterated cyclopentyl, deuterated cyclobutyl, deuterated cyclopropyl, deuterated adamantyl, deuterated norbornyl, deuterated phenyl, deuterated naphthyl, deuterated biphenyl;

Most preferably, the Ar ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ Are identical or different from each other and at least one selected from the group represented by formula a, whichThe remainder are each independently selected from one of the following groups:

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preferably, the said

One selected from the group consisting of:

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more preferably, the

One selected from the group consisting of:

preferably, the L ₁ 、L ₂ 、L ₃ 、L ₄ The same or different are each independently selected from the group consisting of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted carbazolylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted pyrimidylene group, a substituted or unsubstituted triazinylene group, a substituted or unsubstituted pyridazinylene group, a substituted or unsubstituted pyrazinylene group, a substituted or unsubstituted quinolinylene group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted quinazolinylene group, a substituted or unsubstituted phthalazinylene group, a substituted or unsubstituted naphthyridine group, a substituted or unsubstituted cyclopentylene group, and a combination thereof.

Further preferably, the L ₁ 、L ₂ 、L ₃ 、L ₄ The same or different, each independently selected from a single bond or one of the following groups:

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the R is _q Selected from hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-to-CAny of the heteroaryl groups of C30;

the Y is the same or different and is selected from CR' or N;

r' is selected from any one of hydrogen, deuterium, methyl, ethyl, isopropyl, tertiary butyl, cyclopentyl, cyclohexyl, phenyl, biphenyl, naphthyl, deuterated phenyl, deuterated biphenyl and deuterated naphthyl;

the q is ₀ Selected from 0, 1, 2 or 3; the q is ₁ Selected from 0, 1, 2, 3 or 4; the q is ₂ Selected from 0, 1, 2, 3, 4, 5 or 6; the q is ₃ Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

More preferably, the L ₁ 、L ₂ 、L ₃ 、L ₄ The same or different, each independently selected from a single bond or one of the following groups:

the above is bridged by L ₁ 、L ₂ The radicals may be further substituted by one or more of deuterium, cyano, fluoro, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, biphenyl, naphthyl, deuterated phenyl, deuterated biphenyl, deuterated naphthyl, pyridine, pyrimidine, one or more,

R' is selected from any one of hydrogen, deuterium, methyl, ethyl, isopropyl, tertiary butyl, phenyl, biphenyl, naphthyl, deuterated phenyl, deuterated biphenyl and deuterated naphthyl.

The L is _c 、L _d The same or different, each independently selected from a single bond or one of the following groups:

most preferably, the diamine compound is selected from any one of the chemical structures shown below:

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

the compound of the invention can be obtained by obtaining an intermediate A through suzuki reaction, then carrying out Buch-Wald reaction with an amine compound to obtain a target compound shown in a chemical formula I, namely, adding raw materials, a catalyst, alkali, a ligand and a solution in a nitrogen atmosphere, and reacting at a corresponding temperature to obtain the compound, wherein X ₀ 、X ₁ 、X ₂ 、X ₃ Selected from the same or different halogens, such as Cl, br, I.

The source of the raw materials used in the above-mentioned various reactions is not particularly limited, and can be obtained using commercially available raw materials or by using a preparation method well known to those skilled in the art.

Preferably, the organic layer is located between the anode and the cathode, and the organic layer comprises a hole transport region, a light emitting layer, and an electron transport region, and the hole transport region and/or the light emitting layer contains any one or a combination of at least two of the diamine compounds described in the present invention.

Preferably, the organic layer comprises a hole transport region between the anode and the light emitting layer, and the hole transport region contains any one or a combination of at least two of the diamine compounds according to the present invention.

More preferably, the hole transport layer contains any one or a combination of at least two of the diamine compounds according to the present invention.

Preferably, the organic layer comprises a light-emitting layer, the light-emitting layer is positioned between the hole transport region and the electron transport region, and the light-emitting layer contains any one or a combination of at least two of the diamine compounds.

Preferably, the light-emitting layer comprises a host material and/or a doping material, and the host material contains any one or a combination of at least two of the diamine compounds.

More preferably, the organic layer is located outside any one of the anode and the cathode, and the organic layer includes a coating layer containing any one or a combination of at least two of the diamine compounds of the present invention.

The anode can be made of high-power functional electrode material, can be of a single-layer structure or a multi-layer composite structure, for example, can be made of transparent materials such as Indium Tin Oxide (ITO), indium Zinc Oxide (IZO) and the like, can also be made of metal materials with good conductivity between two layers of Indium Tin Oxide (ITO), and can be any one of aluminum (Al), silver (Ag), titanium (Ti) and molybdenum (Mo) or any alloy of a plurality of the above materials.

The cathode may be made of a metal material, for example, any one of lithium (Li), aluminum (Al), magnesium (Mg), silver (Ag), or the like, or an alloy of any of the above materials.

The hole transport region may include at least one selected from a hole injection layer, a hole transport layer, a hole buffer layer, and an electron blocking layer. The hole transport region may have a single layer structure (such as a hole injection layer and/or a hole transport layer) or a single layer formed using a hole injection material and a hole transport material. In some embodiments, the hole transport region may have, without limitation, a single layer formed using a plurality of different materials, or a multi-layered laminated structure of a hole injection layer/hole transport layer, a hole injection layer/hole transport layer/hole buffer layer, a hole injection layer/hole buffer layer, a hole transport layer/hole buffer layer, or a hole injection layer/hole transport layer/electron blocking layer laminated from the anode (e.g., on or over the anode). The hole transport region may have a thickness of about 100nm to about 150nm.

The hole injection layer is a layer for injecting holes from the electrode, and as the hole injection material, a metal porphyrin, an oligothiophene, an arylamine-based organic material, a hexanitrile hexaazabenzophenanthrene-based organic material, a quinacridone-based organic material, a perylene-based organic material, anthraquinone, polyaniline, and a polythiophene-based conductive polymer are preferable, but not limited thereto.

The hole-transporting layer is a layer that receives holes from the hole-injecting layer and transports the holes to the light-emitting layer, and is preferably a substance having high hole mobility. Specifically, the hole transport layer material may be selected from polymer materials such as aromatic amine derivatives, carbazole derivatives, stilbene derivatives, triphenyldiamine derivatives, styrene compounds, butadiene compounds, and the like, and polymer materials such as polyparaphenylene derivatives, polyaniline and its derivatives, polythiophene and its derivatives, polyvinylcarbazole and its derivatives, polysilane and its derivatives, and the like, but is not limited thereto.

The light emitting layer may include a host material and a dopant material. The host material includes aromatic condensed ring derivatives, heterocyclic compounds, polymers, and the like. Specifically, examples of the aromatic condensed ring derivative include compounds having a condensed aromatic ring such as anthracene, phenanthrene, pyrene, benzophenanthrene, naphthacene, perylene, benzo [9, 10] phenanthrene, fluoranthene, fluorene, indene, and the like, and examples of the heterocyclic compound include carbazole derivatives, dibenzofuran derivatives, indolocarbazole derivatives, triazine derivatives, and the like, and as the polymer, polyphenylene vinylene derivatives, polyparaphenylene derivatives, polyfluorene derivatives, polyvinylcarbazole derivatives, polythiophene derivatives, and the like can be used. But is not limited thereto. The host material may be a single structure formed by a single substance, a single layer structure formed by different substances, or a multi-layer structure, and the host material may include a single layer, a light-emitting layer formed by a first host material and a second host material, or more.

Examples of the doping material include aromatic amine derivatives, styryldiamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is an aromatic condensed ring derivative having a substituted or unsubstituted arylamine group, and there are pyrene, anthracene, bisindenopyrene, etc. having an arylamine group, and the styryldiamine compound is a compound in which at least 1 arylvinyl group is substituted on a substituted or unsubstituted arylamine group, and is substituted or unsubstituted with 1 or 2 or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamine group. Specifically, there are styrylamine, styrylenediamine, styrylenetriamine, styrylenetetramine, and the like, but not limited thereto. Further, as the metal complex, there are iridium complex, platinum complex, and the like, but not limited thereto. The doping material can be a single structure formed by a single substance, or can be a single-layer structure or a multi-layer structure formed by different substances.

The electron transport region may include at least one of an electron injection layer, an electron transport layer, a buffer layer, and a hole blocking layer. The electron transport layer may be a single structure formed of a single material, a single layer structure formed of different materials, or a multi-layer structure, and the electron transport layer may include a single layer, or may include a first electron transport layer and a second electron transport layer or more. The type of the electron transport region may be an electron injection layer/electron transport layer structure, an electron injection layer/electron transport layer/buffer layer structure, an electron injection layer/buffer layer structure, or an electron injection layer/electron transport layer/hole blocking layer structure, in which layers of the respective structures are stacked one after another in the stated order from the cathode, but the structure of the electron transport region is not limited thereto.

The electron transporting layer is a layer that receives electrons from the electron injecting layer and transports the electrons to the light emitting layer, and the electron transporting material is a material that can well receive electrons from the cathode and transfer the electrons to the light emitting layer, and is preferably a material having high electron mobility. Specifically, there is an Al complex of 8-hydroxyquinoline containing Alq ₃ But not limited to, complexes of (c) and (d), organic radical compounds, hydroxyflavone-metal complexes, and the like. In particular, examples of suitable cathode materials are the usual materials having a low work function accompanied by an aluminum layer or a silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium are each accompanied by an aluminum layer or a silver layer.

The electron injection layer is a layer that injects electrons from the electrode, and is preferably the following compound: alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides, alkaline earth metal halides, and the like, but are not limited thereto. Examples of the metal complex include, but are not limited to, lithium 8-hydroxyquinoline, zinc bis (8-hydroxyquinoline), copper bis (8-hydroxyquinoline), manganese bis (8-hydroxyquinoline), aluminum tris (2-methyl-8-hydroxyquinoline), gallium tris (8-hydroxyquinoline), beryllium bis (10-hydroxybenzo [ h ] quinoline), zinc bis (10-hydroxybenzo [ h ] quinoline), gallium bis (2-methyl-8-quinoline) chloride, gallium bis (2-methyl-8-quinoline) (o-cresol), gallium bis (2-methyl-8-quinoline) (1-naphthol) aluminum, and the like.

The hole blocking layer is a layer that prevents holes from reaching the cathode, and can be formed generally under the same conditions as the hole injection layer. Specifically, there are diazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes, and the like, but not limited thereto.

The coating layer has a thiophene structure, a thiazole structure, a thiadiazole structure, a furan structure, an oxazole structure, an oxadiazole structure or a pyrrole structure, and other known materials suitable for the coating layer can be selected, and the diamine compound can be selected.

The method for preparing and forming each layer in the organic light emitting device is not particularly limited, and may be formed by vacuum evaporation, spin coating, vapor deposition, knife coating, langerhans inkjet printing, laser Induced Thermal Imaging (LITI) method.

The organic light-emitting 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.

Description of the starting materials, reagents and characterization equipment:

the source of the raw materials used in the following examples is not particularly limited and may be commercially available products or prepared by a preparation method 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 was carried out using a Vario EL cube organic elemental analyzer from Elementar, germany, and the sample mass was 5 to 10mg.

Synthesis example 1: preparation of Compound 8

Preparation of intermediate A-8:

under nitrogen, a-8 (24.58 g,90.00 mmol), b-8 (8.38 g,90.00 mmol), sodium tert-butoxide (12.97 g,135.00 mmol) were added to 400ml toluene and Pd (dppf) Cl was added with stirring ₂ (0.66 g,0.90 mmol) and the mixture of the above reactants was heated under reflux for 4h. After the reaction, cooling to room temperature, adding distilled water, extracting with dichloromethane, standing for liquid separation, collecting an organic layer, drying with anhydrous magnesium sulfate, filtering, concentrating the filtrate by reduced pressure distillation, cooling for crystallization, suction filtering, and recrystallizing the obtained solid with ethyl acetate to obtain an intermediate A-8 (21.83 g, 85%), wherein the HPLC purity is not less than 99.78%. Mass spectrum m/z:285.1169 (theory: 285.1154).

Preparation of Compound 8:

under the protection of nitrogen, raw material g-8 (9.78 g,30.00 mmol), intermediate A-8 (18.83 g,66.00 mmol) and sodium tert-butoxide (5.77 g,60.00 mmol) were added to 100ml toluene, pd was added under stirring ₂ (dba) ₃ (0.33 g,0.36 mmol) and BINAP (0.45 g,0.72 mmol), and the mixture of the above-mentioned reactants was heated under reflux for 5 hours. After the reaction, cooling to room temperature, adding distilled water, extracting with dichloromethane, standing for liquid separation, collecting an organic layer, drying with anhydrous magnesium sulfate, filtering, concentrating the filtrate by reduced pressure distillation, cooling for crystallization, suction-filtering, and recrystallizing the obtained solid with toluene to obtain a compound 8 (17.20 g, yield 78%), wherein the HPLC purity is not less than 99.95%. Mass spectrum m/z:734.2551 (theory: 734.2569). Theoretical element content (%) C ₅₂ H ₃₄ N ₂ O ₃ : c,84.99; h,4.66; n,3.81. Measured element content (%): c,84.95; h,4.69; n,3.86.

Synthesis example 2: preparation of Compound 10

According to the same manner as that for Compound 8 of Synthesis example 1, equimolar amounts of a-8 and g-8 were replaced with equimolar amounts of a-10 and g-10, respectively, to obtain Compound 10 (16.75 g), which had an HPLC purity of ≡ 99.93%. Mass spectrum m/z:734.2586 (theory: 734.2569). Theoretical element content (%) C ₅₂ H ₃₄ N ₂ O ₃ : c,84.99; h,4.66; n,3.81. Measured element content (%): c,84.94; h,4.68; n,3.79.

Synthesis example 3: preparation of Compound 15

According to the same manner as that for Compound 8 of Synthesis example 1, equimolar amounts of b-8 and g-8 were replaced with equimolar amounts of b-15 and g-10, respectively, to give Compound 15 (19.69 g) having an HPLC purity of ≡ 99.91%. Mass spectrum m/z:874.4121 (theory: 874.4134). Theoretical element content (%) C ₆₂ H ₅₄ N ₂ O ₃ : c,85.09; h,6.22; n,3.20. Measured element content (%): c,85.12; h,6.26; n,3.18.

Synthesis example 4: preparation of Compound 16

According to the same manner as that for Compound 8 of Synthesis example 1, equimolar amounts of b-8 and g-8 were replaced with equimolar amounts of b-16 and g-10, respectively, to give Compound 16 (20.33 g), which had an HPLC purity of ≡ 99.94%. Mass spectrum m/z:846.3839 (theory: 846.3821). Theoretical element content (%) C ₆₀ H ₅₀ N ₂ O ₃ : c,85.08; h,5.95; n,3.31. Measured element content (%): c,85.04; h,5.98; n,3.29.

Synthesis example 5: preparation of Compound 22

According to the same manner as that for Compound 8 of Synthesis example 1, equimolar amounts of b-8 and g-8 were replaced with equimolar amounts of b-22 and g-10, respectively, to give Compound 22 (22.27 g), which had an HPLC purity of ≡ 99.96%. Mass spectrum m/z:1002.4771 (theory: 1002.4760). Theoretical element content (%) C ₇₂ H ₆₂ N ₂ O ₃ : c,86.19; h,6.23; n,2.79. Measured element content (%): c,86.15; h,6.28; n,2.76.

Synthesis example 6: preparation of Compound 26

According to the same manner as that for Compound 8 of Synthesis example 1, equimolar amounts of b-8 and g-8 were replaced with equimolar amounts of b-26 and g-10, respectively, to give Compound 26 (19.28 g), which had an HPLC purity of ≡ 99.97%. Mass spectrum m/z:904.4312 (theory: 904.4325). Theoretical element content (%) C ₆₄ H ₂₄ D ₁₈ N ₂ O ₃ : c,84.92; h,6.68; n,3.09. Measured element content (%): c,84.95; h,6.65; n,3.07.

Synthesis example 7: preparation of Compound 39

According to the same manner as that for Compound 8 of Synthesis example 1, equimolar amounts of a-8, b-8 and g-8 were replaced with equimolar amounts of a-39, b-39 and g-39, respectively, to give Compound 39 (16.31 g) having an HPLC purity of > 99.95%. Mass spectrum m/z:744.3213 (theory: 744.3197). Theoretical element content (%) C ₅₂ H ₂₄ D ₁₀ N ₂ O ₃ : c,83.84; h,5.95; n,3.76. Measured element content (%): c,83.81; h,5.93; n,3.79.

Synthesis example 8: preparation of Compound 47

Preparation of intermediate A-47:

under nitrogen, a-47 (19.18 g,90.00 mmol), b-16 (13.43 g,90.00 mmol), sodium tert-butoxide (12.97 g,135.00 mmol) were added to 400ml toluene and Pd (dppf) Cl was added with stirring ₂ (0.66 g,0.90 mmol) and the mixture of the above reactants was heated under reflux for 4h. After the reaction, cooling to room temperature, adding distilled water, extracting with dichloromethane, standing for liquid separation, collecting an organic layer, drying with anhydrous magnesium sulfate, filtering, concentrating the filtrate by reduced pressure distillation, cooling for crystallization, suction filtering, and recrystallizing the obtained solid with ethyl acetate to obtain an intermediate A-47 (21.28 g, 84%), wherein the HPLC purity is not less than 99.75%. Mass spectrum m/z:281.2131 (theory: 281.2143).

Preparation of intermediate B-47:

under nitrogen, c-47 (24.58 g,90.00 mmol), d-47 (18.83 g,90.00 mmol), sodium tert-butoxide (12.97 g,135.00 mmol) were added to 400ml toluene and Pd (dppf) Cl was added with stirring ₂ (0.66 g,0.90 mmol) and the mixture of the above reactants was heated under reflux for 4.5h. After the reaction, cooling to room temperature, adding distilled water, extracting with dichloromethane, standing for liquid separation, collecting an organic layer, drying with anhydrous magnesium sulfate, filtering, concentrating the filtrate by reduced pressure distillation, cooling for crystallization, filtering, and recrystallizing the obtained solid with ethyl acetate to obtain an intermediate B-47 (28.18 g, 78%), wherein the HPLC purity is not less than 99.67%. Mass spectrum m/z:401.1406 (theory: 401.1416).

Preparation of intermediate C-47:

under nitrogen, raw material g-47 (19.71 g,70.00 mmol), intermediate A-47 (19.71 g,70.00 mmol) and sodium tert-butoxide (12.11 g,126.00 mmol) were added to 300ml toluene and Pd (OAc) was added under stirring ₂ (0.19g，0.84mmol)、P(t-Bu) ₃ (3.36 mL of a 0.5M toluene solution, 1.68 mmol) and the mixture of the above reactants were heated under reflux for 5h. After the reaction, cooling to room temperature, adding distilled water, extracting with dichloromethane, standing for separating liquid, collecting organic layer, drying with anhydrous magnesium sulfate, filtering, distilling under reduced pressure to concentrate filtrate, and cooling Crystallization, suction filtration and recrystallization of the obtained solid from toluene/ethanol=5/1 gave intermediate C-47 (25.98 g, 77%) with HPLC purity ≡99.84%. Mass spectrum m/z:481.2188 (theory: 481.2172).

Preparation of compound 47:

intermediate C-47 (17.35 g,36.00 mmol), B-47 (15.90 g,39.60 mmol) and sodium tert-butoxide (6.92 g,72.00 mmol) were added to 200ml toluene under nitrogen and Pd was added with stirring ₂ (dba) ₃ (0.49 g,0.54 mmol) and BINAP (0.67 g,1.08 mmol), and the mixture of the above reactants was heated under reflux for 6h. After the reaction, cooling to room temperature, adding distilled water, extracting with dichloromethane, standing for liquid separation, collecting an organic layer, drying with anhydrous magnesium sulfate, filtering, concentrating the filtrate by distillation under reduced pressure, cooling for crystallization, suction-filtering, and recrystallizing the obtained solid with toluene to obtain a compound 47 (22.87 g, yield 75%), wherein the HPLC purity is not less than 99.94%. Mass spectrum m/z:846.3807 (theory: 846.3821). Theoretical element content (%) C ₆₀ H ₅₀ N ₂ O ₃ : c,85.08; h,5.95; n,3.31. Measured element content (%): c,85.05; h,5.99; n,3.34.

Synthesis example 9: preparation of Compound 55

Preparation of intermediate a-55:

a reaction flask was charged with a '-55 (27.57 g,144.00 mmol), b' -55 (29.41 g,120.00 mmol), potassium carbonate (24.88 g,180.00 mmol), pd (PPh) under nitrogen ₃ ) ₄ (1.39 g,1.20 mmol) was added 300mL of toluene/ethanol/water (2:1:1) mixed solvent, and the mixture was stirred and the above reactant system was heated under reflux for 4 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, toluene was added and the phases were separated, the toluene phase was washed three times with distilled water, dried over anhydrous magnesium sulfate, concentrated solvent was rotary evaporated, cooled and crystallized, and the obtained solid was recrystallized from toluene to give intermediate a-55 (22.88 g, yield 83%); HPLC purity ∈ 99.72%. Mass spectrum m/z:229.0386 (theoretical value)：229.0405)。

Preparation of intermediate A-55:

under nitrogen, a-55 (20.67 g,90.00 mmol), b-8 (8.38 g,90.00 mmol), sodium tert-butoxide (12.97 g,135.00 mmol) were added to 400ml toluene and Pd (dppf) Cl was added with stirring ₂ (0.66 g,0.90 mmol) and the mixture of the above reactants was heated under reflux for 4h. After the reaction, cooling to room temperature, adding distilled water, extracting with dichloromethane, standing for liquid separation, collecting an organic layer, drying with anhydrous magnesium sulfate, filtering, concentrating the filtrate by reduced pressure distillation, cooling for crystallization, filtering, and recrystallizing the obtained solid with ethyl acetate to obtain an intermediate A-55 (20.10 g, 78%), wherein the HPLC purity is not less than 99.68%. Mass spectrum m/z:286.1201 (theory: 286.1216).

Preparation of compound 55:

under the protection of nitrogen, raw material g-55 (9.96 g,30.00 mmol), intermediate A-55 (18.90 g,66.00 mmol) and sodium tert-butoxide (5.77 g,60.00 mmol) were added to 100ml toluene, pd was added under stirring ₂ (dba) ₃ (0.33 g,0.36 mmol) and BINAP (0.45 g,0.72 mmol), and the mixture of the above-mentioned reactants was heated under reflux for 5.5 hours. After the reaction, cooling to room temperature, adding distilled water, extracting with dichloromethane, standing for liquid separation, collecting an organic layer, drying with anhydrous magnesium sulfate, filtering, concentrating the filtrate by distillation under reduced pressure, cooling for crystallization, suction-filtering, and recrystallizing the obtained solid with toluene to obtain a compound 55 (16.27 g, yield 73%) with HPLC purity of 99.95%. Mass spectrum m/z:742.3089 (theory: 742.3072). Theoretical element content (%) C ₅₂ H ₂₆ D ₈ N ₂ O ₃ : c,84.07; h,5.70; n,3.77. Measured element content (%): c,84.03; h,5.74; n,3.79.

Synthesis example 10: preparation of Compound 70

According to the same manner as in Compound 8 of Synthesis example 1, equimolar amounts of a-8, b-8 and g-8 were replaced with equimolar amounts of a-70, b-70 and g-10, respectively, to give a compoundProduct 70 (22.48 g) had an HPLC purity of > 99.92%. Mass spectrum m/z:998.4458 (theory: 998.4447). Theoretical element content (%) C ₇₂ H ₅₈ N ₂ O ₃ : c,86.54; h,5.85; n,2.80. Measured element content (%): c,86.51; h,5.81; n,2.82.

Synthesis example 11: preparation of Compound 87

According to the same manner as that for Compound 8 of Synthesis example 1, except that equimolar g-8 was replaced with equimolar g-87, compound 87 (20.49 g) was obtained, which had an HPLC purity of ≡99.94%. Mass spectrum m/z:886.3181 (theory: 886.3195). Theoretical element content (%) C ₆₄ H ₄₂ N ₂ O ₃ : c,86.66; h,4.77; n,3.16. Measured element content (%): c,86.69; h,4.74; n,3.18.

Synthesis example 12: preparation of Compound 88

According to the same manner as that for Compound 8 of Synthesis example 1, except that equimolar g-8 was replaced with equimolar g-88, compound 88 (19.22 g) was obtained, which had an HPLC purity of ≡99.96%. Mass spectrum m/z:810.2899 (theory: 810.2882). Theoretical element content (%) C ₅₈ H ₃₈ N ₂ O ₃ : c,85.90; h,4.72; n,3.45. Measured element content (%): c,85.93; h,4.71; n,3.43.

Synthesis example 13: preparation of Compound 89

According to the same manner as that for Compound 8 of Synthesis example 1, equimolar amounts of a-8, b-8 and g-8 were replaced with equimolar amounts of a-89, b-89 and g-89, respectively, to give Compound 89 (21.92 g) in HPLC purity99.94%. Mass spectrum m/z:986.3521 (theory: 986.3508). Theoretical element content (%) C ₇₂ H ₄₆ N ₂ O ₃ : c,87.60; h,4.70; n,2.84. Measured element content (%): c,87.56; h,4.73; n,2.88.

Synthesis example 14: preparation of Compound 98

According to the same manner as that for Compound 8 of Synthesis example 1, equimolar amounts of b-8 and g-8 were replaced with equimolar amounts of b-98 and g-10, respectively, to give Compound 98 (20.89 g) with an HPLC purity of ≡ 99.95%. Mass spectrum m/z:966.3082 (theory: 966.3094). Theoretical element content (%) C ₆₈ H ₄₂ N ₂ O ₅ : c,84.45; h,4.38; n,2.90. Measured element content (%): c,84.48; h,4.36; n,2.95.

Synthesis example 15: preparation of Compound 102

According to the same manner as that for Compound 8 of Synthesis example 1, equimolar amounts of a-8, b-8 and g-8 were replaced with equimolar amounts of a-102, b-102 and g-102, respectively, to obtain Compound 102 (19.87 g) having an HPLC purity of ≡99.91%. Mass spectrum m/z:882.2181 (theory: 882.2197). Theoretical element content (%) C ₆₀ H ₃₈ N ₂ S ₃ : c,81.60; h,4.34; n,3.17. Measured element content (%): c,81.54; h,4.31; n,3.19.

Synthesis example 16: preparation of Compound 154

According to the same manner as in Compound 55 of Synthesis example 9, equimolar amounts of b '-55, a-55, b-8 and g-55 were replaced with equimolar amounts of b' -154, a-154, b-55, g-8 to give compound 154 (20.17 g), HPLC purity. Mass spectrum m/z:920.2658 (theory: 920.2644). Theoretical element content (%) C ₆₂ H ₄₀ N ₄ OS ₂ : c,80.84; h,4.38; n,6.08. Measured element content (%): c,80.82; h,4.41; n,6.05.

Synthesis example 17: preparation of Compound 159

According to the same manner as that for Compound 8 of Synthesis example 1, equimolar amounts of a-8, b-8 and g-8 were replaced with equimolar amounts of a-159, b-159 and g-159, respectively, to give Compound 159 (23.75 g) with an HPLC purity of > 99.91%. Mass spectrum m/z:1146.3661 (theory: 1146.3678). Theoretical element content (%) C ₈₂ H ₅₄ N ₂ OS ₂ : c,85.83; h,4.74; n,2.44. Measured element content (%): c,85.88; h,4.76; n,2.41.

Synthesis example 18: preparation of Compound 186

According to the same manner as that for Compound 47 of Synthesis example 8, equimolar amounts of a-47, b-16, c-47, d-47 and g-47 were replaced with equimolar amounts of a-186, b-186, c-186, d-186 and g-186, respectively, to obtain Compound 186 (24.50 g) with an HPLC purity of ≡ 99.92%. Mass spectrum m/z:944.3578 (theory: 944.3566). Theoretical element content (%) C ₆₇ H ₃₆ D ₇ N ₃ OS: c,85.14; h,5.33; n,4.45. Measured element content (%): c,85.13; h,5.36; n,4.43.

Synthesis example 19: preparation of Compound 239

The compound according to synthesis example 955, and the equimolar amounts of a '-55, b' -55, a-55, b-8 and g-55 were replaced with equimolar amounts of a '-239, b' -239, a-239, b-239 and g-239, respectively, to give compound 239 (22.69 g) with an HPLC purity of 99.94%. Mass spectrum m/z:1064.4137 (theory: 1064.4124). Theoretical element content (%) C ₇₄ H ₅₆ N ₄ O ₂ S: c,83.43; h,5.30; n,5.26. Measured element content (%): c,83.47; h,5.33; n,5.22.

Synthesis example 20: preparation of Compound 319

According to the same manner as that for Compound 8 of Synthesis example 1, equimolar amounts of a-8, b-8 and g-8 were replaced with equimolar amounts of a-319, b-319 and g-319, respectively, to give Compound 319 (25.34 g) with an HPLC purity of ≡99.90%. Mass spectrum m/z:1205.5841 (theory: 1205.5859). Theoretical element content (%) C ₈₈ H ₇₅ N ₃ O ₂ : c,87.60; h,6.27; n,3.48. Measured element content (%): c,87.63; h,6.22; n,3.44.

Synthesis example 21: preparation of Compound 375

According to the same manner as that for Compound 8 of Synthesis example 1, equimolar amounts of a-8 and b-8 were replaced with equimolar amounts of a-375 and b-375, respectively, to obtain Compound 375 (19.81 g) with an HPLC purity of ≡ 99.96%. Mass spectrum m/z:868.2343 (theory: 868.2331). Theoretical element content (%) C ₅₈ H ₃₆ N ₄ OS ₂ : c,80.16; h,4.18; n,6.45. Measured element content (%): c,80.18; h,4.13; n,6.48.

Synthesis example 22: preparation of Compound 398

According to the same manner as that for Compound 47 of Synthesis example 8, equimolar amounts of a-47, b-16, c-47, d-47 and g-47 were replaced with equimolar amounts of a-8, b-98, c-398, b-98 and g-398, respectively, to give Compound 398 (25.97 g) having an HPLC purity of ≡ 99.95%. Mass spectrum m/z:1015.3429 (theory: 1015.3410). Theoretical element content (%) C ₇₂ H ₄₅ N ₃ O ₄ : c,85.10; h,4.46; n,4.14. Measured element content (%): c,85.06; h,4.49; n,4.18.

Synthesis example 23: preparation of Compound 500

According to the same manner as that for compound 55 of Synthesis example 9, equimolar amounts of a '-55, b' -55, a-55, b-8 and g-55 were replaced with equimolar amounts of a '-500, b' -500, a-500, b-500 and g-10, respectively, to give compound 500 (20.96 g) having an HPLC purity of ≡ 99.94%. Mass spectrum m/z:1026.3834 (theory: 1026.3847). Theoretical element content (%) C ₇₂ H ₃₀ D ₁₂ N ₂ O ₅ : c,84.19; h,5.30; n,2.73. Measured element content (%): c,84.21; h,5.34; n,2.71.

Synthesis example 24: preparation of Compound 510

According to the same manner as that for Compound 8 of Synthesis example 1, equimolar amounts of b-8 and g-8 were replaced with equimolar amounts of b-510 and g-10, respectively, to give Compound 510 (20.90 g), which had an HPLC purity of ≡ 99.96%. Mass spectrum m/z:928.3641 (theory: 928.3659). Theoretical element content (%) C ₆₄ H ₂₄ D ₁₄ N ₂ O ₅ ：C,8274; h,5.64; n,3.02. Measured element content (%): c,82.78; h,5.61; n,3.05.

Synthesis example 25: preparation of Compound 512

According to the same manner as that for Compound 8 of Synthesis example 1, equimolar amounts of a-8, b-8 and g-8 were replaced with equimolar amounts of a-512, b-98 and g-10, respectively, to give Compound 512 (23.45 g) with an HPLC purity of ≡99.93%. Mass spectrum m/z:1014.3106 (theory: 1014.3094). Theoretical element content (%) C ₇₂ H ₄₂ N ₂ O ₅ : c,85.19; h,4.17; n,2.76. Measured element content (%): c,85.14; h,4.19; n,2.79.

Synthesis example 26: preparation of Compound 553

According to the same manner as that for Compound 8 of Synthesis example 1, equimolar amounts of a-8, b-8 and g-8 were replaced with equimolar amounts of a-553, b-553 and g-10, respectively, to obtain Compound 553 (25.74 g) with an HPLC purity of ≡99.94%. Mass spectrum m/z:1242.4016 (theory: 1242.4033). Theoretical element content (%) C ₉₀ H ₅₄ N ₂ O ₅ : c,86.94; h,4.38; n,2.25. Measured element content (%): c,86.98; h,4.39; n,2.22.

Synthesis example 27: preparation of Compound 565

According to the same manner as that for Compound 8 of Synthesis example 1, equimolar amounts of a-8, b-8 and g-8 were replaced with equimolar amounts of a-565, b-565 and g-10, respectively, to give Compound 565 (28.17 g) with an HPLC purity of ≡99.96%. Mass spectrum m/z:1234.6023 (theory: 1234.6012). Theoretical element content (%) C ₉₀ H ₇₈ N ₂ O ₃ : c,87.49; h,6.36; n,2.27. Measured element content (%): c,87.47; h,6.38; n,2.29.

Synthesis example 28: preparation of Compound 586

According to the same manner as that for Compound 8 of Synthesis example 1, equimolar amounts of a-8, b-8 and g-8 were replaced with equimolar amounts of a-586, b-98 and g-239, respectively, to give Compound 586 (24.05 g) with an HPLC purity of ≡99.93%. Mass spectrum m/z:1082.3162 (theory: 1082.3178). Theoretical element content (%) C ₇₆ H ₄₆ N ₂ O ₄ S: c,84.27; h,4.28; n,2.59. Measured element content (%): c,84.29; h,4.25; n,2.61.

Synthesis example 29: preparation of Compound 600

According to the same manner as that for Compound 47 of Synthesis example 8, equimolar amounts of a-47, b-16, c-47, d-47 and g-47 were replaced with equimolar amounts of a-8, b-600, c-600, b-98 and g-600, respectively, to give Compound 600 (26.25 g) having an HPLC purity of ≡ 99.91%. Mass spectrum m/z:1071.3785 (theory: 1071.3797). Theoretical element content (%) C ₇₆ H ₄₅ D ₄ N ₃ O ₂ S: c,85.13; h,4.98; n,3.92. Measured element content (%): c,85.10; h,4.94; n,3.95.

Synthesis example 30: preparation of Compound 609

According to the same manner as that of Compound 8 of Synthesis example 1, equimolar amounts of a-8, b-8 and g-8 were replaced with equimolar amounts of a-609, b-609 and g-102, respectively, to give Compound 609 [ 23.84 g) and HPLC purity. Mass spectrum m/z:1134.4237 (theory: 1134.4219). Theoretical element content (%) C ₈₂ H ₅₈ N ₂ O ₂ S: c,86.74; h,5.15; n,2.47. Measured element content (%): c,86.78; h,5.18; n,2.45.

Synthesis example 31: preparation of Compound 624

According to the same manner as that for Compound 8 of Synthesis example 1, equimolar amounts of a-8, b-8 and g-8 were replaced with equimolar amounts of a-624, b-565 and g-624, respectively, to obtain Compound 624 (26.71 g) having an HPLC purity of ≡99.95%. Mass spectrum m/z:1289.4904 (theory: 1289.4920). Theoretical element content (%) C ₉₆ H ₆₃ N ₃ O ₂ : c,89.34; h,4.92; n,3.26. Measured element content (%): c,89.39; h,4.95; n,3.22.

Synthesis example 32: preparation of Compound 632

According to the same manner as that for Compound 47 of Synthesis example 8, equimolar amounts of a-47, b-16, c-47, d-47 and g-47 were replaced with equimolar amounts of a-632, b-632, c-632, d-632 and g-398, respectively, to give Compound 632 (28.57 g) with an HPLC purity of ≡ 99.93%. Mass spectrum m/z:1183.3458 (theory: 1183.3444). Theoretical element content (%) C ₈₃ H ₄₉ N ₃ O ₄ S: c,84.17; h,4.17; n,3.55. Measured element content (%): c,84.12; h,4.19; n,3.52.

Synthesis example 33: preparation of Compound 661

Following the same procedure for the preparation of Compound 47 of Synthesis example 8Equimolar a-47, b-16, c-47, d-47, g-47 were replaced with equimolar a-8, b-98, c-661, d-661, g-186, respectively, to give compound 661 (28.72 g) with an HPLC purity of ≡99.90%. Mass spectrum m/z:1226.3887 (theory: 1226.3906). Theoretical element content (%) C ₉₀ H ₅₄ N ₂ O ₂ S: c,88.06; h,4.43; n,2.28. Measured element content (%): c,88.08; h,4.49; n,2.24.

Synthesis example 34: preparation of Compound 676

According to the same manner as in Compound 8 of Synthesis example 1, equimolar amounts of a-8 and b-8 were replaced with equimolar amounts of a-676 and b-676, respectively, to give Compound 676 (21.41 g) having an HPLC purity of ≡ 99.93%. Mass spectrum m/z:914.3497 (theory: 914.3508). Theoretical element content (%) C ₆₆ H ₄₆ N ₂ O ₃ : c,86.63; h,5.07; n,3.06. Measured element content (%): c,86.68; h,5.03; n,3.04.

Synthesis example 35: preparation of Compound 719

According to the same manner as that for preparing Compound 47 in Synthesis example 8, equimolar amounts of a-47, b-16, d-47 and g-47 were replaced with equimolar amounts of a-719, b-719, d-719 and g-398, respectively, to obtain Compound 719 (25.17 g), which has an HPLC purity of 99.94%. Mass spectrum m/z:1058.4009 (theory: 1058.3993). Theoretical element content (%) C ₇₄ H ₄₂ D ₅ N ₅ O ₃ : c,83.91; h,4.95; n,6.61. Measured element content (%): c,83.95; h,4.93; n,6.64.

Synthesis example 36: preparation of Compound 746

According to the same manner as that described in Synthesis example 8, compound 47 was obtained by substituting equimolar amounts of a-47, b-16, c-47 and g-47 with equimolar amounts of a-746, b-746, c-746 and g-398, respectively, to give compound 746 (27.91 g) having an HPLC purity of 99.96%. Mass spectrum m/z:1106.3388 (theory: 1106.3398). Theoretical element content (%) C ₇₆ H ₅₄ N ₂ OS ₃ : c,82.43; h,4.92; n,2.53. Measured element content (%): c,82.41; h,4.97; n,2.56.

Synthesis example 37: preparation of Compound 758

According to the same manner as that for preparing compound 55 of Synthesis example 9, equimolar amounts of a '-55, b' -55, a-55, b-8 and g-55 were replaced with equimolar amounts of a '-758, b' -758, a-758, b-758 and g-10, respectively, to obtain compound 758 (23.46 g) having an HPLC purity of ∈ 99.95%. Mass spectrum m/z:1100.3568 (theory: 1100.3583). Theoretical element content (%) C ₇₆ H ₅₂ N ₄ OS ₂ : c,82.88; h,4.76; n,5.09. Measured element content (%): c,82.90; h,4.72; n,5.12.

Synthesis example 38: preparation of Compound 803

According to the same manner as that for Compound 8 of Synthesis example 1, equimolar amounts of a-8, b-8 and g-8 were replaced with equimolar amounts of a-803, b-98 and g-10, respectively, to give Compound 803 (18.33 g) with an HPLC purity of ≡99.94%. Mass spectrum m/z:814.3182 (theory: 814.3195). Theoretical element content (%) C ₅₈ H ₄₂ N ₂ O ₃ : c,85.48; h,5.19; n,3.44. Measured element content (%): c,85.50; h,5.20; n,3.40.

Blue organic light emitting device (cover layer)

Comparative examples 1-2 device preparation examples:

comparative example 1: the organic light emitting device is prepared by utilizing a vacuum thermal evaporation method. The experimental steps are as follows: the ITO-Ag-ITO substrate is put in distilled water for 3 times, ultrasonic washing is carried out for 15 minutes, after the distilled water is washed, solvents such as isopropanol, acetone, methanol and the like are sequentially washed by ultrasonic waves, and then the substrate is dried and dried at 120 ℃ and is sent into an evaporator.

Evaporating a hole injection layer HAT-CN/20nm, an evaporating hole transport layer HT/60nm, an evaporating luminescent layer body BH+FIrpic (97% by mass: 3% mixture)/23 nm on the prepared ITO-Ag-ITO transparent electrode in a layer-by-layer vacuum evaporation mode, and then evaporating an electron transport layer ET: liq (doping ratio is 1:1)/30 nm, electron injection layer LiF/1nm, cathode Mg-Ag/17nm, and coating layer CP-1/70nm on cathode. And sealing the device in a glove box, thereby preparing an organic light emitting device. After the organic light-emitting device is manufactured according to the steps, the photoelectric property of the device is measured, and the molecular structural formula of the related material is shown as follows:

Comparative example 2: the organic light emitting device of comparative example 2 was prepared in the same manner as comparative example 1, except that the capping layer material CP-1 in comparative example 1 was replaced with CP-2.

Application examples 1 to 37

Application examples 1-37: the capping layer materials CP-1 of the organic light emitting devices were sequentially changed to the inventive compounds 8, 10, 15, 16, 22, 26, 39, 47, 55, 70, 87, 88, 89, 98, 102, 154, 159, 186, 239, 319, 375, 398, 500, 510, 512, 553, 565, 586, 600, 609, 624, 632, 661, 676, 719, 746, 758, and the other steps were the same as comparative example 1. The results of the light emission characteristics test of the obtained organic light emitting device are shown in table 1. Table 1 shows the results of the light emitting characteristics test of the light emitting devices prepared with the compounds prepared in the examples of the present invention and the comparative substances.

TABLE 1 test of light emitting characteristics of light emitting device

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Note that: t97 means that the current density is 10mA/cm ² In the case, the time taken for the device brightness to decay to 97%;

as can be seen from the results of table 1, the diamine compound of the present invention is applied to an organic light emitting device, and as a capping material, it is effective to improve light extraction efficiency, and thus light emission efficiency of the organic light emitting device, and further to improve life of the organic light emitting device, as compared with comparative examples 1 to 2, and is an organic light emitting device capping material having good performance.

Comparative example 3 device preparation example: (hole transporting layer)

Comparative example 3: the organic light emitting device is prepared by utilizing a vacuum thermal evaporation method. The experimental steps are as follows: the ITO transparent substrate is put in distilled water for 3 times, washed by ultrasonic waves for 15 minutes, washed by ultrasonic waves sequentially by solvents such as isopropanol, acetone, methanol and the like after the distilled water is washed, dried and dried at 120 ℃, and sent into an evaporator.

Evaporating a hole injection layer HAT-CN/20nm, an evaporating hole transmission layer HT1-1/60nm and an evaporating main body H-1 on the prepared ITO transparent substrate electrode in a layer-by-layer vacuum evaporation mode: h-2: ir doped (piq) ₂ acac (mass ratio 49%:49%:2% mixture)/26 nm, then evaporating the electron transport layer ET: liq (doping ratio is 1:1)/30 nm, liF/0.5nm of electron injection layer and Al/110nm of cathode. And sealing the device in a glove box, thereby preparing an organic light emitting device. After the organic light emitting device is manufactured according to the steps, the device is measuredThe molecular structural formula of the related material is shown as follows:

application examples 38 to 58

Device examples 38-58: the hole transport layer materials of the organic light-emitting device were changed to the inventive compounds 8, 10, 15, 16, 22, 26, 39, 70, 87, 88, 89, 98, 102, 510, 512, 586, 600, 609, 624, 746, 803 in this order, and the other steps were the same as in comparative example 3.

Test software, a computer, a K2400 digital source meter manufactured by Keithley company, U.S. and a PR788 spectral scanning luminance meter manufactured by Photoresearch company, U.S. are combined into a combined IVL test system to test the driving voltage and luminous efficiency of the organic light emitting device. Life testing an M6000OLED life test system from McScience was used. The environment tested was atmospheric and the temperature was room temperature. The results of the light emission characteristics test of the obtained organic light emitting device are shown in table 2. Table 2 shows the results of the light emitting characteristics test of the light emitting devices prepared with the compounds prepared in the examples of the present invention and the comparative substances.

TABLE 2 test of light emitting characteristics of light emitting device

as can be seen from the results of table 2, the diamine compound of the present invention was applied to an organic light emitting device, and as a hole transport layer material, it exhibited the advantages of high light emitting efficiency and long service life as compared with comparative example 3, and was an organic light emitting material having good performance.

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 diamine compound is characterized in that the molecular structure is shown as a formula I:

in formula a, X is selected from O or S;

the R is _a The same or different, each independently selected from one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl;

the a is selected from 0, 1 or 2; said b is selected from 0, 1, 2, 3 or 4;

In formula b, the R ₁ Selected from hydrogen, deuterium,Cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl;

in formula c, the X ₀ Selected from O, S, C (R) _e )(R _f ) Any one of N (R);

said n ₂ Selected from 0, 1, 2, 3 or 4; when n is ₂ Above 1, each R ₂ Identical or different, adjacent two R' s ₂ The groups may be bonded together to form a substituted or unsubstituted cyclic structure; said n ₃ Selected from 0, 1, 2, 3 or 4; when n is ₃ When the number of the components is more than 1,each R ₃ Identical or different, adjacent two R' s ₃ The groups may be bonded together to form a substituted or unsubstituted cyclic structure;

the R is _c 、R _d The same or different, each independently selected from one of hydrogen, deuterium, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted n-propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, or two adjacent R _c Bonded together to form a substituted or unsubstituted cyclic structure, or two adjacent R' s _d Bonded together to form a substituted or unsubstituted cyclic structure;

said c is selected from 0, 1, 2 or 3; said d is selected from 0, 1, 2 or 3;

2. The diamine compound of claim 1, wherein the group of formula a is selected from one of the following groups:

the X is selected from O or S;

The a is selected from 0, 1 or 2;

the R is _b The same or different, each independently selected from one or more of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptylOne or more of octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, biphenyl, terphenyl, naphthyl, phenyl-naphthyl, naphthyl-phenyl, pyridinyl, pyrimidinyl, pyridazine, pyrazine, triazinyl; wherein the substituent in the "substituted or unsubstituted" is selected from one or more of deuterium, cyano, trifluoromethyl, halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, phenyl, biphenyl, naphthyl, and in the case of being substituted with a plurality of substituents, the plurality of substituents are the same as or different from each other; or optionally adjacent two R _b The groups may be bonded to form one of a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted pyridine ring, a substituted or unsubstituted pyrimidine ring, and a substituted or unsubstituted pyrazine ring;

3. The diamine compound of claim 1, wherein the group of formula a is selected from one of the following groups:

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4. the diamine compound of claim 1, wherein Ar ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ Are identical or different from each other, andat least one of the groups is selected from the group represented by formula a, and the rest are each independently selected from one of the following groups:

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the R is ₂ 、R ₃ Independently selected from one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, tolyl, biphenyl, terphenyl, anthryl, phenanthryl, triphenylene, spirofluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, dibenzofuranyl, dibenzothiophenyl, 9-phenylcarbazolyl, carbazolyl, and R ₂ 、R ₃ May also be substituted with one or more of deuterium, cyano, trifluoromethyl, halogen, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, phenyl, deuterated phenyl, naphthyl, deuterated naphthyl, tolyl, biphenyl, deuterated biphenyl, terphenyl, anthryl, phenanthryl, triphenylene, and where substituted with multiple substituents, the multiple substituents may be the same or different from each other; or any two adjacent R ₂ Are combined with each other to form a substituted or unsubstituted benzene ring or naphthalene ring; or any two adjacent R ₃ Are combined with each other to form a substituted or unsubstituted benzene ring or naphthalene ring;

The R is ₄ One selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, and substituted or unsubstituted naphthyl;

5. The diamine compound of claim 1, wherein Ar ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ Are identical or different from each other, and at least one is selected from the group represented by formula a, and the others are each independently selected from one of the following groups:

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the R is ₁ 、R ₂ 、R ₃ 、R ₄ 、R ₆ Are the same or different from each other and are independently selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen or one of the following substituted or unsubstituted groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, triphenylenyl; wherein the substituent in the "substituted or unsubstituted" is selected from one or more of deuterium, cyano, trifluoromethyl, halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, norbornyl, phenyl, biphenyl, naphthyl, and in the case of being substituted with a plurality of substituents, the plurality of substituents are the same or different from each other;

6. The diamine compound of claim 1, wherein the amine compound is a compound having a chain-transfer moiety

One selected from the group consisting of:

7. the diamine compound of claim 1, wherein L ₁ 、L ₂ 、L ₃ 、L ₄ The same or different are each independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted pyrimidylene groupAn unsubstituted triazinylene group, a substituted or unsubstituted pyridazinylene group, a substituted or unsubstituted pyrazinylene group, a substituted or unsubstituted quinolinylene group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted quinazolinylene group, a substituted or unsubstituted quinoxalinylene group, a substituted or unsubstituted phthalazinylene group, a substituted or unsubstituted naphthyridine group, a substituted or unsubstituted benzocyclopentylene group, a substituted or unsubstituted benzocyclohexenylene group, a substituted or unsubstituted benzocyclopentenyl group, a substituted or unsubstituted benzocyclohexenylene group, or a combination thereof.

8. The diamine compound of claim 1, wherein the diamine compound of formula i is selected from any one of the chemical structures shown below:

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9. an organic light-emitting device comprising an anode, a cathode, and an organic layer located between the anode and the cathode or outside one or more of the anode and the cathode, wherein the organic layer contains any one or a combination of at least two of the diamine compounds according to any one of claims 1 to 8.

10. An organic light-emitting device according to claim 9, wherein the organic layer comprises a hole transport region, a light-emitting layer, an electron transport region, and a cover layer, and wherein at least one of the cover layers contains any one or a combination of at least two of the diamine compounds according to any one of claims 1 to 8.