CN114621181B

CN114621181B - Star-shaped tetramine derivative and organic electroluminescent device thereof

Info

Publication number: CN114621181B
Application number: CN202210360107.1A
Authority: CN
Inventors: 陆影; 郭建华; 刘小婷; 杜明珠
Original assignee: Changchun Hyperions Technology Co Ltd
Current assignee: Changchun Hyperions Technology Co Ltd
Priority date: 2022-04-06
Filing date: 2022-04-06
Publication date: 2023-02-28
Anticipated expiration: 2042-04-06
Also published as: CN114621181A

Abstract

The invention provides a star-shaped tetramine derivative and an organic electroluminescent device thereof, and relates to the technical field of organic electroluminescence. In order to solve the problems of low luminous efficiency, short service life and the like of a device caused by poor performance of a hole transport material, the invention provides a derivative which takes benzene as a center and is connected with three triarylamines, wherein one branch of one triarylamine is connected with the other triarylamine through bridged benzo or naphthofuran and thiophene, and the structure of the derivative has certain electron donating capability and higher HOMO energy level, so that the energy barrier of hole transport is reduced, and the mobility of holes is increased; meanwhile, the star-shaped tetramine derivative has good thermal stability and film forming property, and can be used as a first hole transport material or a second hole transport material to be applied to an organic electroluminescent device, so that the luminous efficiency of the device can be effectively improved, and the service life of the device can be effectively prolonged.

Description

Star-shaped tetramine derivative and organic electroluminescent device thereof

Technical Field

The invention relates to the technical field of organic electroluminescent materials, in particular to a star-shaped tetramine derivative and an organic electroluminescent device thereof.

Background

An organic electroluminescent device (OLED) is an all-solid-state light emitting device in which holes are injected from an anode and electrons are injected from a cathode by applying a voltage across the anode and the cathode, and the holes and the electrons are combined in a light emitting layer after passing through respective organic functional layers to form excitons, which are in an excited state and cannot exist stably, and which are transitioned from the excited state back to a ground state to emit light by radiation. Because the organic light emitting diode display has the advantages of being thinner and lighter, wide in visual angle, high in brightness, high in contrast, high in definition, stable in image, rich in color, fast in response, low in energy consumption, low in temperature, excellent in anti-seismic performance, flexible and low in manufacturing cost, the Organic Light Emitting Diode (OLED) becomes a new generation of flat panel display which is very popular at present, and is increasingly applied to various flat panel display devices, such as electronic products of smart phones, smart watches, flat computers, televisions, vehicle-mounted displays, visual wearable devices and the like.

The organic electroluminescent device adopts "sandwich" structure at first, along with the continuous perfect of technique, the luminous efficacy of organic electroluminescent ware promotes gradually, and the device structure is continuous perfect, and organic electroluminescent device includes positive pole, negative pole, each organic functional layer between and outside two electrodes at present, and wherein, each organic functional layer includes: a hole injection layer, a hole transport layer, a hole assist layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, a capping layer, and the like. Organic electroluminescent devices can be classified into: bottom emitting devices, top emitting devices.

The performance of the organic electroluminescent device is mainly determined by the following indexes: luminous efficiency and service life. Among them, the luminous efficiency mainly depends on the following two aspects: the carrier injection in the device is balanced, and the light extraction efficiency of the device structure is improved.

The hole transport layer in the organic electroluminescent device has the main functions of enhancing the injection of holes into the light-emitting layer and improving the recombination probability of the holes and electrons in the light-emitting layer, thereby improving the luminous efficiency and prolonging the service life of the device. The excellent hole transport material has the advantages of high thermal stability, good hole mobility, difficult crystallization, good film forming property, small potential barrier with an anode and the like.

With the increasing market demand and the continuous progress of industrial technology, in the future, an organic electroluminescent device is required to have higher luminous efficiency and longer service life, and therefore, the development of a carrier transport material which has good thermal stability and can promote carrier injection balance becomes an urgent problem to be solved, so that the luminous efficiency of the device is improved, and the service life of the device is prolonged.

Disclosure of Invention

In order to solve the problems, the invention provides the star-shaped tetramine derivative and the organic electroluminescent device thereof, and the star-shaped tetramine derivative is applied to a hole transport layer or a second hole transport layer of the organic electroluminescent device, so that the luminous efficiency and the service life of the organic electroluminescent device can be effectively improved.

The invention provides a star-shaped tetramine derivative, which has a structure shown as a formula I,

in formula I, ar ₁ ～Ar ₇ Any one selected from the group consisting of substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C6-C30 aromatic ring, and C3-C30 aliphatic ring fused ring, which may be the same or different from each other;

x is selected from any one of O or S;

said L ₁ ～L ₉ Any one selected from the group consisting of a single bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C2-C30 heteroarylene group, a substituted or unsubstituted divalent C6-C30 aromatic ring and C3-C30 aliphatic ring fused ring group, and a combination thereof, which may be the same or different from each other;

the R is ₀ 、R ₁ 、R ₂ Identical or different from each other, selected from any one of hydrogen, deuterium, tritium, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C2-C12 alkenyl group, a substituted or unsubstituted C3-C12 cycloalkyl group, a substituted or unsubstituted C3-C12 cycloalkenyl group, a substituted or unsubstituted C2-C12 heterocycloalkyl 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,or two adjacent R ₀ Can be connected with each other to form a substituted or unsubstituted ring;

n is selected from 0, 1,2 or 3, when n is more than 1, two or more R ₁ Identical to or different from each other, or two adjacent R ₁ Can be connected with each other to form a substituted or unsubstituted ring;

m is selected from 0, 1,2, 3 or 4, when m is more than 1, two or more R ₂ Identical to or different from each other, or two adjacent R ₂ Can be connected with each other to form a substituted or unsubstituted ring;

the substituted group in the above "substituted or unsubstituted" is selected from one or more of the following groups: deuterium, tritium, cyano, a halogen atom, amino, nitro, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl, a fused ring group of a substituted or unsubstituted C6-C30 aromatic ring and a C3-C30 aliphatic ring, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C2-C30 heteroaryl group; in the case of substitution with a plurality of substituents, the plurality of substituents may be the same as or different from each other, or adjacent substituents may be bonded to form a ring.

The invention also provides an organic electroluminescent device which comprises an anode, an organic layer and a cathode, wherein the organic layer is positioned between the anode and the cathode or positioned on the side of the cathode away from the anode, and the organic layer comprises any one or more than one of the star-shaped tetramine derivatives.

Advantageous effects

The star-shaped tetramine derivative shown in the formula I is formed by connecting three triarylamines by taking benzene as a center, wherein one branch of one triarylamine is connected with the other triarylamine through bridging benzo or naphthofuran and thiophene. Compared with a simple star-shaped compound, the introduction of bridging and the addition of a triarylamine improve the electron donating capability of the compound, increase the HOMO energy level of molecules, reduce the energy barrier of hole transmission between an anode and a hole transmission layer, and effectively improve the mobility of holes; meanwhile, the star-shaped tetramine derivative has high glass transition temperature and low molecular crystallization capacity, so that the material has good thermal stability and film forming property; the star-shaped tetramine derivative is used as a hole transport material to be applied to an organic electroluminescent device, so that the luminous efficiency of the device can be effectively improved, and the service life of the device can be effectively prolonged.

Detailed Description

The following description will clearly and completely describe the technical solutions of the specific embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of protection 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 their natural isotopic abundance and unnatural abundance.

In the present specification, "+" means a moiety linked to another substituent.

In the present specification, when the position of a substituent on an aromatic ring is not fixed, it means that it can be attached to any of the respective optional positions of the aromatic ring. For example,

can represent

And the like. And so on.

Examples of halogen atoms described herein may include fluorine, chlorine, bromine or iodine.

The alkyl group in the present invention refers to a monovalent group obtained by removing one hydrogen atom from an alkane molecule, and may be a straight-chain or branched-chain alkyl group, preferably having 1 to 12 carbon atoms, more preferably having 1 to 8 carbon atoms, and particularly preferably having 1 to 6 carbon atoms. The alkyl group 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.

The alkenyl group in the present invention means a monovalent group obtained by removing one hydrogen atom from an olefin molecule, and may be a straight alkenyl group or a branched alkenyl group, preferably having 2 to 15 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 6 carbon atoms. Alkenyl groups may be substituted or unsubstituted. Specific examples may include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-diphenylvinyl-1-yl, 2-phenyl-2- (naphthalen-1-yl) vinyl-1-yl, 2-bis (diphenyl-1-yl) vinyl-1-yl, styryl, and the like, but are not limited thereto.

The cycloalkyl group in the present invention means a monovalent group obtained by removing one hydrogen atom from a cyclic alkane molecule, and preferably has 3 to 18 carbon atoms, more preferably 3 to 12 carbon atoms, and particularly 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.

The cycloalkenyl group in the present invention refers to a monovalent group obtained by removing one hydrogen atom from a cycloolefin molecule, and is a cyclic hydrocarbon group having a carbon-carbon double bond inside the ring, and includes cyclic monoolefin, cyclic polyene and the like. Preferably from 3 to 15 carbon atoms, more preferably from 3 to 12 carbon atoms, and particularly preferably from 3 to 6 carbon atoms. Cycloalkenyl groups may be substituted or unsubstituted. Examples of the cycloalkenyl group include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclobutadienyl, cyclopentadienyl, cyclohexadienyl and the like, but are not limited thereto.

The heterocycloalkyl group in the present invention refers to a general term of a group obtained by replacing one or more carbon atoms in a cycloalkyl group with a heteroatom, including but not limited to O, S, N, si or P atom, preferably having 2 to 15 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 6 carbon atoms. Heterocycloalkyl groups may be substituted or unsubstituted. Specific examples may include, but are not limited to, tetrahydropyrrolyl, piperidinyl, furanyl, thienyl, and the like.

The aryl group in the present invention refers to a monovalent group obtained by removing one hydrogen atom from an aromatic nucleus carbon of an aromatic compound molecule, and may be a monocyclic aryl group, a polycyclic aryl group or a condensed ring aryl group, and preferably has 6 to 60 carbon atoms, more preferably 6 to 30 carbon atoms, particularly preferably 6 to 18 carbon atoms, and most preferably 6 to 12 carbon atoms. The aryl group may be substituted or unsubstituted. The monocyclic aryl group means an aryl group having only one aromatic ring in the molecule, for example, phenyl group and the like, but is not limited thereto; the polycyclic aromatic group means an aromatic group having two or more independent aromatic rings in a molecule, for example, biphenyl, terphenyl, quaterphenyl, etc., but is not limited thereto; the condensed ring aryl group means an aryl group having two or more aromatic rings in a molecule and condensed by sharing two adjacent carbon atoms with each other, and is exemplified by naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, perylene, and the like,

A group, 9-dimethylfluorenyl group, 9-diphenylfluorenyl group, 9-methyl-9-phenylfluorenyl group, benzofluorenyl group, triphenylenyl group, fluoranthenyl group, 9' -spirobifluorenyl group and the like, but are not limited thereto.

The heteroaryl group in the present invention refers to a general term of a group in which one or more of the aromatic nucleus carbon atoms in the aryl group is replaced with a heteroatom, including but not limited to O, S, N, si or P atom, preferably having 2 to 60 carbon atoms, more preferably 2 to 30 carbon atoms, particularly preferably 2 to 18 carbon atoms, and most preferably 2 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 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 pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl and the like, but is not limited thereto; the polycyclic heteroaryl group includes bipyridyl, phenylpyridyl, and the like, but is not limited thereto; the fused ring heteroaryl group includes, but is not limited to, quinolyl, isoquinolyl, benzoquinolyl, benzoisoquinolyl, quinazolinyl, quinoxalinyl, benzoquinazolinyl, benzoquinoxalinyl, phenanthrolinyl, naphthyridinyl, indolyl, benzothienyl, benzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, dibenzothienyl, dibenzooxazolyl, dibenzoimidazolyl, dibenzothiazolyl, carbazolyl, benzocarbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenoxathinyl, spirofluorene xanthyl, spirofluorene thioxanthyl, etc.

The alicyclic ring in the present invention refers to a cyclic hydrocarbon having an aliphatic property, and contains a closed carbon ring in a molecule, and preferably has 3 to 60 carbon atoms, more preferably 3 to 30 carbon atoms, further preferably 3 to 18 carbon atoms, more preferably 3 to 12 carbon atoms, and most preferably 3 to 7 carbon atoms. They may form monocyclic or polycyclic hydrocarbons and may be fully or partially unsaturated. The aliphatic ring may be substituted or unsubstituted. Specific examples may include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclobutene, cyclopentene, cyclohexene, cycloheptene, and the like, but are not limited thereto. Multiple monocyclic hydrocarbons can also be linked in a variety of ways: two rings in the molecule can share one carbon atom to form a spiro ring; two carbon atoms on the ring can be connected by a carbon bridge to form a bridged 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 containing one or more aromatic rings in a molecule and 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 6 to 18 carbon atoms, most preferably 6 to 12 carbon atoms, the aliphatic ring preferably has 3 to 30 carbon atoms, more preferably C3 to C18 carbon atoms, more preferably 3 to 12 carbon atoms, most preferably 3 to 7 carbon atoms. The fused ring of the aromatic ring and the aliphatic ring may be substituted or unsubstituted. Examples include benzocyclopropane group, benzocyclobutane group, benzocyclopentane group, benzocyclocyclohexane group, benzocycloheptane group, benzocyclobutene group, benzocyclopentenyl group, benzocyclocyclohexenyl group, benzocycloheptenyl group, naphthocyclopropanyl group, naphthocyclobutane group, naphthocyclopentyl group, naphthocyclohexane group, naphthocyclopentenyl group, naphthocyclohexenyl group, and the like, but are not limited thereto.

The arylene group in the present invention is a general term of a divalent group remaining after two hydrogen atoms are removed from an aromatic core 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, and as the above-mentioned arylene group, as the monocyclic arylene group, a phenylene group or the like may be mentioned, but not limited thereto. The arylene group may be substituted or unsubstituted. The polycyclic arylene group may be, but is not limited to, biphenylene, terphenylene, tetraphenylene, and the like. Examples of the fused ring arylene group include a naphthylene group, an anthracenylene group, a phenanthrenylene group, a pyrenylene group, a fluorenylene group, a spirofluorenylene group, a triphenylene group, a peryleneene group, a fluorenylene group, and a fluorenylene group

And the like, but not limited thereto.

The heteroarylene group in the present invention refers to a general term in which two hydrogen atoms are removed from the nuclear carbon of an aromatic heterocyclic ring composed of carbon and hetero atoms, leaving a divalent group, the hetero atoms may be one or more of N, O, S, si, and P, and may be a monocyclic heteroarylene group, a polycyclic heteroarylene group, or a fused ring heteroarylene group, preferably having 2 to 30 carbon atoms, more preferably having 2 to 22 carbon atoms, still more preferably having 2 to 20 carbon atoms, and most preferably 3 to 12 carbon atoms, and the heteroarylene group may be substituted or unsubstituted. Examples may include, but are not limited to, pyridylene, pyrimidylene, pyrazinylene, pyridazinylene, triazinylene, thiophenylene, pyrrolylene, furanylene, pyranylene, oxazolylene, thiazolyl ene, imidazolyl, benzoxazolyl, benzothiazylene, benzimidazolylene, carbazolyl, benzocarbazolyl, acridinylene, oxaanthylene, thiaanthylene, phenazinylene, phenothiazinylene, phenoxazinyl, indolyl, quinolylene, isoquinolylene, benzothiophenylene, benzofuranylene, dibenzofuranylene, dibenzothiophenylene, quinoxalylene, quinazolinylene, naphthyridinylene, purinylene, phenanthrolinylene, and the like.

The term "unsubstituted" in the "substituted or unsubstituted" as used herein means that a hydrogen atom on the group is not substituted with any substituent; "substituted" means that at least one hydrogen atom on the group is substituted by 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.

In the "substituted or unsubstituted" of the present invention, the substituent may be independently selected from any one of deuterium, tritium, cyano, nitro, amino, a halogen atom, a substituted or unsubstituted C1 to C12 alkyl group, a substituted or unsubstituted C2 to C12 alkenyl group, a substituted or unsubstituted C3 to C12 cycloalkyl group, a substituted or unsubstituted C1 to C12 alkylamino group, a substituted or unsubstituted C6 to C30 arylamine group, a substituted or unsubstituted C2 to C12 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted fused ring group of a C6 to C30 aromatic ring and a C3 to C30 aliphatic ring, and a substituted or unsubstituted C1 to C30 silyl group, preferably deuterium, tritium, cyano, halogen atom, amino, C1-C12 alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, C6-C30 aryl, C2-C30 heteroaryl, and specific examples thereof may include deuterium, tritium, fluorine, chlorine, bromine, iodine, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, tolyl, pentadeuterated phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, triphenylene, and the like,

The term "linked to form a 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 a fusion of the two, 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, a seven-membered ring, or a fused ring, such as benzene, naphthalene, indene, cyclopentene, cyclopentane, cyclopentobenzene, cyclohexene, cyclohexane, cyclohexanebenzone, pyridine, quinoline, isoquinoline, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, phenanthrene, or pyrene, but not limited thereto.

in formula I, ar ₁ ～Ar ₇ Any one selected from the group consisting of substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C6-C30 aromatic ring and C3-C30 aliphatic ring fused ring, which may be the same or different from each other;

x is selected from any one of O or S;

said R is ₀ 、R ₁ 、R ₂ The same or different from each other, and is selected from any one of hydrogen, deuterium, tritium, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C2-C12 alkenyl group, a substituted or unsubstituted C3-C12 cycloalkyl group, a substituted or unsubstituted C3-C12 cycloalkenyl group, a substituted or unsubstituted C2-C12 heterocycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 heteroaryl group, a substituted or unsubstituted condensed ring group of an aromatic ring of C6-C30 and an aliphatic ring of C3-C30, or two adjacent R groups ₀ Can be connected with each other to form a substituted or unsubstituted ring;

n is selected from 0, 1,2 or 3, when n is more than 1, two or more R ₁ Two R's, equal to or different from each other, or adjacent ₁ Can be connected with each other to form a substituted or unsubstituted ring;

m is selected from 0, 1,2, 3 or 4, when m is more than 1, two or more R ₂ Two R's, equal to or different from each other, or adjacent ₂ Can be connected with each other to form a substituted or unsubstituted ring.

Preferably, the substituted group in the above "substituted or unsubstituted" is selected from one or more of the following groups: deuterium, tritium, cyano, halogen atoms, amino, nitro, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl, substituted or unsubstituted fused ring groups of C6-C30 aromatic rings and C3-C30 aliphatic rings, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl; in the case of being substituted with a plurality of substituents, the plurality of substituents may be the same as or different from each other, or adjacent substituents may be bonded to form a ring.

Preferably, the star tetraamine derivative is selected from any one of the structures shown in the following,

preferably, said R is ₁ 、R ₂ The same or different from each other, and is selected from any one of hydrogen, deuterium, tritium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C12 heteroaryl, substituted or unsubstituted C6-C30 aromatic ring and C3-C30 aliphatic ring fused ring group, or two adjacent R ₁ Two adjacent R ₂ Can be mutually connected to form one or more than one substituted or unsubstituted C6-C10 ring;

n is selected from 0, 1,2 or 3, and m is selected from 0, 1,2, 3 or 4.

Preferably, the

Selected from any one of the structures shown below,

the R is ₁ 、R ₂ Any one selected from the group consisting of hydrogen, deuterium, tritium, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, phenyl, pentadeuterated phenyl, naphthyl, deuterated naphthyl, tolyl, biphenyl, deuterated biphenyl, terphenyl, anthracenyl, phenanthrenyl, triphenylenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirobifluorenyl, carbazolyl, 9-phenylcarbazolyl, dibenzofuranyl, dibenzothienyl, benzocyclopropyl, benzocyclobutenyl, benzocyclopentyl, benzocycloheteroalkyl, benzocycloheptyl, benzocyclobutenyl, benzocycloheptenyl, naphthocyclopentyl, naphthocyclohexenyl, naphthocycloheptanyl, naphthocyclopentenyl, naphthocyclohexenyl, and naphthocycloheptenyl, which are the same or different from each other;

n is ₁ Is selected from 0, 1,2 or 3, the n ₂ Is selected from 0, 1 or 2, the n ₃ Is selected from 0, 1,2, 3 or 4, the n ₄ Is selected from 0, 1,2, 3, 4, 5, 6, 7, 8 or 9, said n ₅ Selected from 0, 1,2, 3, 4 or 5, said n ₆ Is selected from 0, 1,2, 3, 4, 5, 6 or 7, said n ₇ Is selected from 0, 1,2, 3, 4, 5, 6, 7 or 8, the n ₈ Selected from 0, 1,2, 3, 4, 5 or 6;

m is ₁ Is selected from 0, 1,2 or 3, m ₂ Is selected from 0, 1,2, 3, 4, 5, 6, 7, 8 or 9, m ₃ Is selected from 0, 1,2, 3, 4 or 5, m ₄ Is selected from 0, 1,2, 3, 4, 5, 6 or 7, m ₅ Is selected from 0, 1,2, 3 or 4, m ₆ Is selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9 or 10, said m ₇ Is selected from 0, 1,2, 3, 4, 5 or 6, m ₈ Selected from 0, 1,2, 3, 4, 5, 6, 7 or 8.

More preferably, the

Is selected from the followingAny one of the structures shown in the figures,

preferably, ar is ₁ ～Ar ₇ The same or different from each other, selected from any one of the groups shown below,

z is ₁ Selected from the group consisting of a single bond, O, S, C (R) _x R _y ) Or N (R) _z ) Any one of, the Z ₂ Selected from O, S, C (R) _x R _y ) Or N (R) _z ) Any one of the above;

said R is _x 、R _y The same or different from each other, selected from any one of hydrogen, deuterium, tritium, 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 _x 、R _y May be a position linked to another substituent, or R _x 、R _y Can be connected with each other to form a substituted or unsubstituted ring;

said R is _z Any one selected from hydrogen, deuterium, tritium, 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 _z May be a position to which another substituent is attached;

said R is ₃ The same or different from each other, and is selected from any one of hydrogen, deuterium, tritium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, condensed ring group of substituted or unsubstituted C6-C30 aromatic ring and C3-C30 aliphatic ring, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or two adjacent R ₃ Can be connected with each other to form a substituted or unsubstituted ring;

said p is ₁ Is selected from 0, 1,2, 3, 4 or 5, the p ₂ Is selected from 0, 1,2, 3 or 4, the p ₃ Selected from 0, 1,2, 3, 4, 5, 6 or 7, said p ₄ Is selected from 0, 1,2, 3, 4, 5, 6, 7, 8 or 9, said p ₅ Selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9,10 or 11, said p ₆ Selected from 0, 1,2 or 3.

Preferably, said R is _x 、R _y Can be mutually connected to form a substituted or unsubstituted ring selected from any one of the structures shown in the specification,

the R is ₅ The same or different from each other, and is selected from any one of hydrogen, deuterium, tritium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, condensed ring group of substituted or unsubstituted C6-C30 aromatic ring and C3-C30 aliphatic ring, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or two adjacent R ₅ Can be connected with each other to form a substituted or unsubstituted ring;

a is a ₁ Selected from 0, 1,2, 3 or 4, said a ₂ Selected from 0, 1,2, 3, 4, 5 or 6, said a ₃ Independently selected from 0, 1,2, 3, 4, 5, 6, 7 or 8, said a ₄ Independently selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9 or 10,a is a mentioned ₅ Selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9,10, 11 or 12, said a ₆ Selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9,10, 11, 12, 13 or 14.

Preferably, the adjacent two R ₃ Can be mutually connected to form any one or more than one of substituted or unsubstituted benzene ring, naphthalene ring, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclobutene, cyclopentene, cyclohexene and cycloheptene.

Preferably, ar is ₁ ～Ar ₇ Identical to or different from each other, selected from any one of the following substituted or unsubstituted groups,

the "substituted" group is selected from any one or more of deuterium, tritium, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, phenyl, deuterated phenyl, naphthyl, deuterated naphthyl, biphenyl, deuterated biphenyl, terphenyl, anthracenyl, phenanthrenyl, triphenylenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirobifluorenyl, carbazolyl, 9-phenylcarbazolyl, dibenzofuranyl, dibenzothienyl, benzocyclopropyl, benzocyclobutenyl, benzocyclopentyl, benzocycloheteroalkyl, benzocycloheptyl, benzocycloheptenyl, benzocyclopentyl, naphthocyclopentyl, naphthocyclohexyl, naphthocycloheptanyl, naphthocyclopentenyl, naphthocyclohexenyl, naphthocycloheptenyl, or adjacent substituents may be linked to each other to form a substituted or unsubstituted ring;

q is a radical of ₁ Selected from 0, 1,2, 3, 4 or 5, said q ₂ Selected from 0,1.2, 3 or 4, said q ₃ Selected from 0, 1,2, 3, 4, 5, 6 or 7, said q ₄ Selected from 0, 1,2, 3, 4, 5 or 6, said q ₅ Selected from 0, 1,2, 3, 4, 5, 6, 7, 8 or 9, said q ₆ Selected from 0, 1,2 or 3.

Preferably, said L ₁ ～L ₉ The same or different from each other, selected from a single bond or any one of the structures shown below,

preferably, said R is ₄ Identical to or different from each other, any one selected from deuterium, tritium, methyl, deuterated methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, deuterated tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, phenyl, pentadeuterated phenyl, naphthyl, deuterated naphthyl, biphenyl, terphenyl, anthracenyl, phenanthrenyl, triphenylene, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirobifluorenyl, carbazolyl, 9-phenylcarbazolyl, dibenzofuranyl, dibenzothienyl, benzocyclopropyl, benzocyclobutane, benzocyclopentane, benzocyclocyclohexane, benzocycloheptane, benzocyclopentenyl, benzocycloheptenyl, naphthocyclopentyl, naphthocyclohexane, naphthocycloheptanyl, naphthocyclopentenyl, naphthocyclohexenyl, naphthocycloheptanyl, naphthocyclohexenyl, or two adjacent R groups, or two R groups ₄ Can be connected with each other to form a substituted or unsubstituted ring;

said x ₁ Selected from 1,2, 3 or 4, said x ₂ Selected from 1,2, 3, 4, 5, 6, 7 or 8, said x ₃ Selected from 1,2, 3, 4, 5, 6, 7, 8, 9,10, 11 or 12, said x ₄ Selected from 1,2, 3, 4, 5 or 6, said x ₅ Selected from 1,2, 3, 4, 5, 6, 7, 8, 9 or 10, said x ₆ Selected from 1,2, 3, 4 or 5, said x ₇ Is selected from 1 or 2, x ₈ Selected from 1,2 or 3, said x ₉ Selected from 1,2, 3, 4, 5, 6, 7, 8, 9,10, 11 or 12.

Most preferably, the star tetraamine derivative is selected from any one of the following structures,

some specific structural forms of the star-shaped tetraamine derivative represented by formula I of the present invention are listed above, but the present invention is not limited to these listed chemical structures, and all the groups in which the substituents are as defined above are included based on the structure represented by formula I.

The invention also provides an organic electroluminescent device which comprises an anode, an organic layer and a cathode, wherein the organic layer is positioned between the anode and the cathode or positioned on the outer side of any one of the cathode and the anode, and the organic layer comprises any one or more than one star-shaped tetraamine derivatives.

Preferably, the organic layer is located between the anode and the cathode, and includes at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

Preferably, the organic layer is located outside the anode and the cathode, and includes a capping layer.

Preferably, the hole transport layer comprises 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 the star tetraamine derivatives of the present invention.

Preferably, the organic layer may have a single-layer structure, a double-layer structure, or a multi-layer structure. However, the structure of the organic electroluminescent device is not limited thereto.

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

The anode material of the present invention preferably uses a material having a high functional function and improving the 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 multi-layer structure including two or more layers, for example, the anode may have a single layer structure of Al or a triple layer structure of ITO/Ag/ITO, but is not limited thereto.

The hole injection layer material of the present invention is preferably a material having a good hole accepting ability. Can be selected from any one or more than one of the following structures: metalloporphyrin, oligothiophene, arylamine derivatives, perylene derivatives, hexanitrile hexaazatriphenylene compounds, phthalocyanine compounds, polycyanoconjugated organic materials, quinacridone compounds, anthraquinone compounds, polyaniline-based and polythiophene-based conductive polymers, and the like, but are not limited thereto.

The hole transport layer material of the present invention is preferably a material having high hole mobility. Can be selected from any one or more than one of the following structures: carbazole derivatives, triarylamine derivatives, biphenyldiamine derivatives, fluorene derivatives, stilbene derivatives, hexacarbonitrile hexaazatriphenylene 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' -dimethylbiphenyldiamine (HMTPD), and the like. The star tetraamine derivatives according to the invention are preferred.

The light-emitting layer material comprises a host material AND a doping material, wherein the light-emitting layer host material can be selected from 4,4' -di (9-Carbazole) Biphenyl (CBP), 9, 10-di (2-naphthyl) Anthracene (ADN), 4-di (9-carbazolyl) biphenyl (CPB), 9' - (1, 3-phenyl) di-9H-carbazole (mCP) AND 4,4',4 "-tris (carbazol-9-yl) triphenylamine (TCTA), 9, 10-bis (1-naphthyl) anthracene (α -AND), N ' -bis- (1-naphthyl) -N, N ' -diphenyl- [1,1':4',1":4",1" ' -tetrabiphenyl ] -4,4"' -diamino (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 also include other known materials suitable for use as a light emitting layer. The doping materials of the luminescent layer are divided into blue luminescent materials, green luminescent materials and red luminescent materials. 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-t-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) picolinoyiridyinium (FIrpic), tris (2-phenylpyridine) iridium (Ir (ppy) 3), bis (2-phenylpyridine) iridium acetylacetonate (Ir (ppy) 2 (acac)), 9, 10-bis [ N- (p-tolyl) anilinyl ] anthracene (TPA), 4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminophenylvinyl) -4H-phenylpyrane (DCM), tris [ 1-diphenylpyrene-C) (Ir (p-isoquinoxalinyl) iridium (iryl)) and bis [ 3- (p-phenylpyridine (picc) iridium (irq) (Ir (picc) 3), iridium (acetylacetonate) and the like, but is not limited thereto.

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, even more preferably 1 to 20% by mass, and particularly preferably 1 to 10% by mass.

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), and 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 with an adjacent organic layer material, and specific examples thereof may include: alkali metal compounds (for example, lithium oxide, lithium fluoride, cesium carbonate, cesium fluoride, cesium 8-hydroxyquinoline, aluminum 8-hydroxyquinoline), organic metal salts (metal acetate, metal benzoate, or metal stearate), molybdenum trioxide, aluminum metal, 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 facilitate electron injection into the organic layer to reduce an 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/Al, mo, ti, compounds including them, or mixtures thereof (e.g., a mixture of Ag and Mg), but is not limited thereto.

The covering layer is provided outside more than one of the anode and the cathode, so that the light extraction efficiency is improved. Can be selected from any one or more than one of the following structures: an arylamine derivative, a biscarbazole derivative, a benzimidazole derivative, a benzoxazole derivative, a benzothiazole derivative, a triazole derivative, a benzidine derivative, a porphyrin derivative, a phthalocyanine derivative, a naphthalocyanine derivative, or a mixture thereof, but is not limited thereto.

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

The organic electroluminescent device according to the present invention can be manufactured by sequentially laminating the above-described structures. The production method may employ a known method such as a wet film formation method or a dry film formation method. Specific examples of the wet film formation method include various coating methods such as a spin coating method, a dipping method, a casting method, and an ink jet method, and specific examples of the dry film formation method include, but are not limited to, a vacuum deposition method, a sputtering method, a plasma method, and an ion plating method.

The organic light-emitting device can be widely applied to the fields of panel display, lighting sources, flexible OLEDs, electronic paper, organic solar cells, organic photoreceptors or organic thin film transistors, signs, signal lamps and the like.

The invention is explained in more detail by the following examples, without wishing to restrict the invention accordingly. 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 inventive effort.

The invention provides a synthesis method of a compound represented by a formula I, and a specific synthetic route is as follows:

[ synthetic route ]

Preparation of intermediate a:

preparation of intermediate B:

preparation of intermediate C:

the raw materials a to f can be commercial products or can be prepared by a synthesis method commonly used in the field, and the raw materials a, b and c can be prepared by the following preparation methods:

preparation of raw material a:

preparation of raw material b:

preparation of raw material c:

preparation of Compounds of formula I:

1. when intermediate a, intermediate B and intermediate C are different from each other:

2. when intermediate B and intermediate C are identical to each other:

wherein, X _a 、X ₁ ～X ₃ The same or different from each other, and is selected from any one of Cl, br and I; ar (Ar) ₁ ～Ar ₇ 、L ₁ ～L ₉ 、R ₀ ～R ₂ X, m and n are as defined above.

The invention synthesizes star-shaped tetramine derivatives through Suzuki coupling reaction and Buchwald coupling reaction.

The substituents described above for the present invention may be bonded via methods known in the art, and the kind and position of the substituent or the number of the substituent may be changed according to techniques known in the art.

Description of raw materials, reagents and characterization equipment:

the present invention is not particularly limited to the starting materials and sources of reagents used in the following examples, and they may be commercially available products or prepared by methods known to those skilled in the art.

The mass spectrum uses a British Watts G2-Si quadrupole tandem time-of-flight high-resolution mass spectrometer, and chloroform is used as a solvent;

elemental analysis was carried out by using a Vario EL cube type organic element analyzer manufactured by Elementar, germany, and the sample mass was 5 to 10mg.

Synthesis example 1: preparation of intermediate A1-2

Under the protection of nitrogen, p-2 (14.72g, 150mmol), q-2 (25.93g, 160mmol), sodium tert-butoxide (23.06g, 240mmol) and Pd (dppf) Cl were added in sequence to a reaction flask ₂ (1.10 g, 1.50mmol), followed by addition of 900ml of toluene to dissolve it, and heating and refluxing the reaction for 4 hours. After the reaction is finished, cooling to room temperature, adding distilled water, extracting with dichloromethane, standing for liquid separation, collecting an organic phase, drying with anhydrous magnesium sulfate, filtering, distilling and concentrating the filtrate under reduced pressure, cooling for crystallization, performing suction filtration, recrystallizing the obtained solid with ethyl acetate to obtain an intermediate A1-2 (22.05 g, the yield is 82%), and the HPLC purity is not less than 99.53%. Mass spectrum m/z:179.1534 (theoretical value: 179.1519).

The following intermediate A1 was synthesized according to the above procedure, substituting starting material p and starting material q in equimolar amounts:

synthetic example 2: preparation of intermediate d-61

Preparation of intermediate N-61:

adding n into a reaction bottle under the protection of nitrogen ₁ -61 (51.61g, 300.00mmol), pinacol diboron (81.26g, 320.00mmol), pd (dppf) Cl ₂ (2.20g, 3.00mmol), KOAc (44.16g, 450.00mmol) and DMF (600 mL), refluxing and heating for reaction for 4 hours, adding distilled water after the reaction is finished, extracting with dichloromethane, washing an organic phase with distilled water for three times, standing and separating, collecting the organic phase, drying with anhydrous magnesium sulfate, filtering, distilling and concentrating the filtrate under reduced pressure, cooling and crystallizing, carrying out suction filtration, and recrystallizing the obtained solid with toluene to obtain an intermediate N-61 (52.58 g, yield 80%); purity by HPLC ≧ 98.68%. Mass spectrum m/z:219.1413 (theoretical value: 219.1431).

Preparation of intermediate d-61:

under the protection of nitrogen, N-61 (48.20g, 220mmol) and N are added into a reaction bottle in sequence ₂ -61 (55.93g, 260mmol), potassium carbonate (45.61g, 330mmol), pd (PPh) ₃ ) ₄ (2.54g, 2.20mmol), 500mL of a toluene/ethanol/water (3. After the reaction was completed, the reaction mixture was cooled to room temperature, toluene was added to separate each phase, the toluene phase was washed three times with distilled water, dried over anhydrous magnesium sulfate, the solvent was concentrated by rotary evaporation, cooled to crystallize, suction-filtered, and the resulting solid was recrystallized from toluene to obtain intermediate d-61 (39.01 g, yield 78%). HPLC purity ≧ 99.71%. Mass spectrum m/z:227.1601 (theoretical value: 227.1612).

Synthetic example 3: preparation of intermediate d-487

According to the same preparation method as that of intermediate d-61 in Synthesis example 2, intermediate d-487 (38.19 g) was obtained by replacing n1-61 and n2-61 with n1-487 and q-2 in equal moles, respectively, and the HPLC purity was ≧ 99.73%. Mass spectrum m/z:214.1533 (theoretical value: 214.1518).

Synthetic example 4: preparation of intermediates A2-529

Under the protection of nitrogen, x-529 (41.29g, 200mmol), y-529 (80.14g, 206mmol), potassium carbonate (48.37g, 350mmol), pd (PPh) were added to the reaction flask ₃ ) ₄ (2.31g, 2.00mmol), 600mL of a toluene/ethanol/water (3. After the reaction is finished, cooling to room temperature, adding toluene, separating each phase, washing the toluene phase with distilled water for three times, drying with anhydrous magnesium sulfate, filtering, distilling and concentrating the filtrate under reduced pressure, cooling, crystallizing, filtering, recrystallizing the obtained solid with toluene, and obtaining an intermediate A2-529 (66.11 g, the yield is 78%), wherein the HPLC purity is not less than 99.54%. Mass spectrum m/z:421.9521 (theoretical 421.9532).

Synthetic example 5: preparation of intermediates A2-550

According to the same production method as that for intermediates A2 to 529 of Synthesis example 4, equimolar amounts of x-529 and y-529 were replaced with equimolar amounts of x-550 and y-550, respectively, to obtain intermediates A2 to 550 (54.97 g), each having an HPLC purity of 99.58% or higher. Mass spectrum m/z:359.9873 (theoretical value: 359.9855).

Synthetic example 6: preparation of intermediate B-61

Under the protection of nitrogen, the mixture is turned to the reverse directionA flask was charged with q-76 (12.56g, 80mmol), d-61 (18.19g, 80mmol), sodium tert-butoxide (14.42g, 150mmol), pd (dppf) Cl ₂ (0.59g, 0.8mmol), and then 400ml of toluene was added thereto to dissolve it, followed by heating and refluxing for 5 hours. After the reaction is finished, cooling to room temperature, adding dichloromethane and distilled water into the mixture for extraction, standing for liquid separation, collecting an organic phase, drying with anhydrous magnesium sulfate, filtering, distilling and concentrating the filtrate under reduced pressure, cooling for crystallization, performing suction filtration, recrystallizing the obtained solid with ethyl acetate to obtain an intermediate B-61 (20.15 g, yield of 83%), and the HPLC purity being not less than 99.49%. Mass spectrum m/z:303.1936 (theoretical value: 303.1925).

The following intermediate B was synthesized according to the above procedure, substituting starting material q-76 and starting material d-61, respectively, in equimolar amounts:

synthetic example 7: preparation of intermediate C-281

Under the protection of nitrogen, e-281 (18.65g, 80mmol), p-48 (7.44g, 80mmol), sodium tert-butoxide (14.42g, 150mmol), pd (dppf) Cl were added to the reaction flask ₂ (0.59g, 0.8mmol), and then 400ml of toluene was added thereto to dissolve it, and the reaction was refluxed for 5.5 hours. After the reaction is finished, cooling to room temperature, adding dichloromethane and distilled water into the mixture for extraction, standing for liquid separation, collecting an organic phase, drying the organic phase by using anhydrous magnesium sulfate, filtering, distilling and concentrating the filtrate under reduced pressure, cooling, performing suction filtration, and recrystallizing by using ethyl acetate to obtain an intermediate C-281 (15.70 g, yield 80%), wherein the HPLC purity is not less than 99.89%. Mass spectrum m/z:245.1218 (theoretical value: 245.1204).

Synthetic example 8: preparation of intermediate C-330

According to the preparation method of intermediate C-281 of synthetic example 7, replacing equimolar e-281 with C-330 provides intermediate C-330 (11.75 g) with HPLC purity ≧ 99.79%. Mass spectrum m/z:179.1320 (theoretical value: 179.1303).

Synthetic example 9: preparation of Compound 2

Preparation of intermediate a-2:

a1-2 (21.51g, 120mmol), y-2 (35.71g, 120mmol), palladium acetate (0.27g, 1.20 mmol), sodium tert-butoxide (23.06g, 240mmol), and tri-tert-butylphosphine (4.80 mL of a 0.50M solution in toluene, 2.40 mmol) were added in this order to a reaction flask under nitrogen atmosphere, followed by addition of 600mL of toluene to dissolve the components and heating and refluxing for 6 hours. After the reaction is stopped, the reaction mixture is cooled to room temperature, dichloromethane and distilled water are added into the mixture for extraction, an organic phase is collected, dried by anhydrous magnesium sulfate, filtered, the filtrate is concentrated by reduced pressure distillation, and after cooling and suction filtration, the mixture is recrystallized by toluene/methanol (10. Mass spectrum m/z:395.1331 (theoretical value: 395.1320).

Preparation of intermediate A-2:

a-2 (31.68g, 80mmol), p-48 (7.46g, 80mmol), palladium acetate (0.18g, 0.80mmol), sodium tert-butoxide (14.42g, 150mmol), tri-tert-butylphosphine (3.20 mL of a 0.50M solution in toluene, 1.60 mmol) were sequentially added to a reaction flask under nitrogen atmosphere to dissolve the components, and then 400mL of toluene was added thereto and the reaction was refluxed for 7 hours. After the reaction was terminated, the reaction mixture was cooled to room temperature, dichloromethane and distilled water were added to the mixture to extract, the mixture was allowed to stand for liquid separation, the organic phase was collected, dried over anhydrous magnesium sulfate, filtered, the filtrate was concentrated by distillation under reduced pressure, and recrystallized from toluene/methanol (10) after cooling and suction filtration to obtain intermediate a-2 (26.07 g, yield 72%), and HPLC purity ≧ 99.79%. Mass spectrum m/z:452.2123 (theoretical value: 452.2131).

Preparation of intermediate I-2:

under nitrogen protection, g-2 (19.04g, 60mmol), intermediate A1-76 (10.15g, 60mmol), sodium tert-butoxide (11.53g, 120mmol), palladium acetate (0.13g, 0.6 mmol), and tri-tert-butylphosphine (2.4 mL of a 0.5M solution in toluene, 1.2 mmol) were added to a reaction flask, and then dissolved in 500mL of toluene, and the mixture was stirred and heated under reflux for 7 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, dichloromethane and distilled water were added to the mixture to extract, the mixture was allowed to stand for liquid separation, the organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure and purified by column chromatography (petroleum ether/dichloromethane = 10) to obtain intermediate I-2 (17.65 g, yield 82%) having an HPLC purity of 99.81% or more. Mass spectrum m/z:356.9932 (theoretical value: 356.9920).

Synthesis of intermediate II-2

Under the protection of nitrogen, I-2 (14.35g, 40mmol), intermediate A1-2 (7.17g, 40mmol), sodium tert-butoxide (7.69g, 80mmol), pd were added to a reaction flask ₂ (dba) ₃ (0.37g, 0.40mmol) x-phos (0.38g, 0.80mmol) was dissolved by adding 300mL toluene, and the mixture was stirred and heated under reflux for 7 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, dichloromethane and distilled water were added to the mixture to extract, the mixture was allowed to stand for liquid separation, the organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure and purified by column chromatography (n-hexane/ethyl acetate = 10) to obtain intermediate II-2 (13.71 g, yield 75%) having an HPLC purity of 99.86% or more. Mass spectrum m/z:456.2157 (theoretical value: 456.2177).

Preparation of compound 2:

under the protection of nitrogen, II-2 (9.14g, 20mmol), A-2 (9.05g, 20mmol), sodium tert-butoxide (3.84g, 40mmol) and Pd were added to a reaction flask in this order ₂ (dba) ₃ (0.18g, 0.20mmol) and BINAP (0.25g, 0.40mmol), and then 200ml of toluene was added to dissolve them, and the mixture was stirred and heated under reflux for 6 hours. After the reaction, the mixture was cooled to room temperature, dichloromethane and distilled water were added to the mixture to extract the mixture, the mixture was allowed to stand for liquid separation, and the organic phase was collected over anhydrous magnesium sulfateDrying, filtering, distilling and concentrating the filtrate under reduced pressure, cooling, crystallizing, filtering, recrystallizing the obtained solid with toluene to obtain the compound 2 (12.75 g, yield 73%), and the HPLC purity is not less than 99.91%. Mass spectrum m/z:872.4542 (theoretical value: 872.4542). Theoretical element content (%) C ₆₀ H ₂₄ D ₂₀ N ₄ S: c,82.53; h,7.38; and N,6.42. Measured elemental content (%): c,82.49; h,7.41; and N,6.38.

Synthesis example 10: preparation of Compound 48

Preparation of intermediate A-48:

according to the same production method as that of intermediate A-2 of Synthesis example 9, equimolar amounts of A1-2 and y-2 were replaced with equimolar amounts of A1-48 and y-48, respectively, to obtain intermediate A-48 (31.62 g, yield 69%), and HPLC purity ≧ 99.76%. Mass spectrum m/z:572.2240 (theoretical value: 572.2224).

Preparation of intermediate II-48:

under nitrogen protection, g-48 (8.11g, 30mmol), A1-76 (10.15g, 60mmol), sodium tert-butoxide (16.73g, 70mmol), palladium acetate (0.07g, 0.30mmol) and x-phos (0.14g, 0.60mmol) were added to a reaction flask in this order, and then 500mL of toluene was added to dissolve them, the mixture was stirred, and the reaction was refluxed for 8.5 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, dichloromethane and distilled water were added to the mixture to extract the mixture, the mixture was allowed to stand for liquid separation, the organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure and purified by column chromatography (petroleum ether/ethyl acetate = 10) to obtain intermediate II-48 (10.86 g, yield 81%) with an HPLC purity of 99.82% or more. Mass spectrum m/z:446.1561 (theoretical value: 446.1550).

Preparation of compound 48:

under the protection of nitrogen, II-48 (8.94g, 20mmol), A-48 (11.46, 20 mmol), sodium tert-butoxide (3.84g, 40mmol) and Pd were added into a reaction bottle in sequence ₂ (dba) ₃ (0.18g, 0.20mmol) and BINAP (0.25g, 0.40mmol), followed by addition of 200ml of toluene to dissolve them, followed by stirring and mixingThe mixture was heated under reflux for 6 hours. After the reaction is finished, cooling to room temperature, adding dichloromethane and distilled water into the mixture for extraction, standing for liquid separation, collecting an organic phase, drying with anhydrous magnesium sulfate, filtering, distilling and concentrating the filtrate under reduced pressure, cooling for crystallization, performing suction filtration, and recrystallizing the obtained solid with toluene to obtain compound 48 (13.77 g, the yield is 70%), wherein the HPLC purity is not less than 99.95%. Mass spectrum m/z:982.4018 (theoretical value: 982.4007). Theoretical element content (%) C ₇₀ H ₄₆ D ₄ N ₄ S: c,85.51; h,5.53; and N,5.70. Measured elemental content (%): c,85.48; h,5.49; and N,5.75.

Synthetic example 11: preparation of Compound 61

According to the same production method as that for the synthesis of Compound 2 of EXAMPLE 9, equimolar amounts of A1-2, y-2 and A1-2 were replaced with equimolar amounts of A1-76, y-61 and B-61, respectively, to give Compound 61 (13.62 g) with an HPLC purity ≧ 99.94%. Mass spectrum m/z:986.4331 (theoretical value: 986.4320). Theoretical element content (%) C ₇₀ H ₅₀ D ₄ N ₄ S: c,85.16; h,5.92; n,5.67. Measured elemental content (%): c,85.20; h,5.89; and N,5.70.

Synthetic example 12: preparation of Compound 75

According to the same production method as that for the synthesis of Compound 2 of EXAMPLE 9, equimolar amounts of A1-2, y-2 and A1-2 were replaced with equimolar amounts of A1-76, y-75 and B-75, respectively, to give Compound 75 (13.45 g) with an HPLC purity of 99.96% or higher. Mass spectrum m/z:946.4051 (theoretical value: 946.4069). Theoretical element content (%) C ₆₇ H ₅₄ N ₄ S: c,84.95; h,5.75; and N,5.91. Measured elemental content (%): c,84.97; h,5.72; and N,5.88.

Synthetic example 13: preparation of Compound 76

According to the same production method as that of Compound 48 of Synthesis example 10, compound 76 (12.63 g) was obtained by substituting equimolar amounts of A1-48, y-48 and g-48 for equimolar amounts of A1-76, y-2 and g-76, respectively, and its HPLC purity was ≧ 99.99%. Mass spectrum m/z:852.3298 (theoretical value: 852.3287). Theoretical element content (%) C ₆₀ H ₄₄ N ₄ S: c,84.48; h,5.20; and N,6.57. Measured elemental content (%): c,84.51; h,5.17; and N,6.60.

Synthesis example 14: preparation of Compound 87

According to the same production method as that of Compound 48 of Synthesis example 10, except for replacing equimolar amounts of g-48, A1-76 and A-48 with equimolar amounts of g-76, B-87 and A-61, compound 87 (13.85 g) was obtained with an HPLC purity ≧ 99.92%. Mass spectrum m/z:1032.5655 (theoretical value: 1032.5670). Theoretical element content (%) C ₇₂ H ₂₄ D ₂₈ N ₄ S: c,83.68; h,7.80; n,5.42. Measured elemental content (%): c,83.72; h,7.79; n,5.38.

Synthetic example 15: preparation of Compound 88

According to the same production method as that of Compound 48 of Synthesis example 10, compound 88 (12.97 g) was obtained by substituting equimolar amounts of A1-2, y-88, p-2, g-76 and A1-2 for equimolar amounts of A1-48, y-48, p-48, g-48 and A1-76, respectively, and had an HPLC purity ≧ 99.98%. Mass spectrum m/z:887.5493 (theoretical value: 887.5484). Theoretical element content (%) C ₆₀ H ₉ D ₃₅ N ₄ S: c,81.13; h,8.96; and N,6.31. Measured elemental content (%): c,81.09; h,8.99; and N,6.29.

Synthetic example 16: preparation of Compound 120

According to the same production method as that of Compound 48 of Synthesis example 10, equimolar amounts of A1-48, y-48, g-48 and A1-76 were replaced with equimolar amounts of A1-76, y-120, g-76 and B-120, respectively, to give Compound 120 (13.67 g) in an HPLC purity of 99.93% or more. Mass spectrum m/z:1004.3928 (theoretical value: 1004.3913). Theoretical element content (%) C ₇₂ H ₅₂ N ₄ S: c,86.02; h,5.21; n,5.57. Measured elemental content (%): c,86.05; h,5.19; and N,5.59.

Synthetic example 17: preparation of Compound 158

According to the same production method as that for the synthesis of Compound 2 of EXAMPLE 9, equimolar amounts of A1-2, y-2 and A1-76 were replaced with equimolar amounts of A1-76, y-158 and B-158, respectively, to give Compound 158 (13.61 g) with an HPLC purity ≧ 99.92%. Mass spectrum m/z:1014.4526 (theoretical: 1014.4540). Theoretical element content (%) C ₇₂ H ₄₂ D ₁₀ N ₄ S: c,85.17; h,6.15; n,5.52. Measured elemental content (%): c,85.20; h,6.12; and N,5.49.

Synthetic example 18: preparation of Compound 184

According to the same production method as that of Compound 48 of Synthesis example 10, equimolar amounts of A1-48, y-48, g-48 and A1-76 were replaced with equimolar amounts of A1-76, y-184, g-76 and B-184, respectively, to give Compound 184 (13.51 g) in an HPLC purity of not less than 99.95%. Mass spectrum m/z:964.4550 (theoretical value: 964.4539). Theoretical element content (%) C ₆₈ H ₆₀ N ₄ S：C,84.61；H,6.27；N,5.80. Measured elemental content (%): c,84.58; h,6.30; n,5.78.

Synthetic example 19: preparation of Compound 185

According to the same production method as that of Compound 48 of Synthesis example 10, equimolar amounts of A1-48, y-48, g-48 and A1-76 were replaced with equimolar amounts of A1-2, y-185, g-76 and A1-203, respectively, to give Compound 185 (13.30 g) with an HPLC purity of 99.97% or higher. Mass spectrum m/z:922.4682 (theoretical value: 922.4699). Theoretical element content (%) C ₆₄ H ₂₆ D ₂₀ N ₄ S: c,83.26; h,7.20; and N,6.07. Measured elemental content (%): c,83.23; h,7.19; and N,6.09.

Synthetic example 20: preparation of Compound 188

According to the same production method as that of Compound 48 of Synthesis example 10, equimolar amounts of A1-48, y-48, g-48 and A1-76 were replaced with equimolar amounts of A1-76, y-188, g-76 and B-188, respectively, to give Compound 188 (13.11 g) in an HPLC purity of 99.96% or more. Mass spectrum m/z:922.4684 (theoretical value: 922.4699). Theoretical element content (%) C ₆₄ H ₂₆ D ₂₀ N ₄ S: c,83.26; h,7.20; and N,6.07. Measured elemental content (%): c,83.30; h,7.18; and N,6.10.

Synthetic example 21: preparation of Compound 203

According to the same production method as that used for the synthesis of Compound 2 of EXAMPLE 9, equimolar amounts of A1-2, y-2, A1-76 and A1-2 were replaced with equimolar amounts of A1-203, y-203, A1-203 and B-203, respectively, to give Compound 203 (13.83 g) with an HPLC purity ≧ 99.94%. Mass spectrum m/z:1001.5340 (theoretical value): 1001.5324). Theoretical element content (%) C ₇₀ H ₄₃ D ₁₅ N ₄ S: c,83.87; h,7.34; and N,5.59. Measured elemental content (%): c,83.90; h,7.29; and N,5.61.

Synthetic example 22: preparation of Compound 207

According to the same production method as that used for the synthesis of Compound 2 of EXAMPLE 9, equimolar amounts of A1-2, y-2, p-48 and I-2 were replaced with equimolar amounts of A1-76, y-207, b-207 and I-203, respectively, to give Compound 207 (13.60 g) with an HPLC purity of 99.97% or higher. Mass spectrum m/z:943.4554 (theoretical value: 943.4541). Theoretical element content (%) C ₆₆ H ₃₃ D ₁₅ N ₄ S: c,83.95; h,6.72; and N,5.93. Measured elemental content (%): c,83.99; h,6.69; and N,5.89.

Synthetic example 23: preparation of Compound 218

According to the same production method as that of Compound 48 of Synthesis example 10, equimolar amounts of A1-48, y-48, p-48 and II-48 were replaced with equimolar amounts of A1-76, y-218, b-207 and II-76, respectively, to give Compound 218 (13.15 g) with an HPLC purity of 99.97% or higher. Mass spectrum m/z:912.3815 (theoretical value: 912.3828). Theoretical element content (%) C ₆₆ H ₄₈ N ₄ O: c,86.81; h,5.30; and N,6.14. Measured elemental content (%): c,86.78; h,5.27; and N,6.16.

Synthetic example 24: preparation of Compound 237

According to the same preparation method as that used for synthesizing Compound 48 of Synthesis example 10, equimolar amounts of A1-48, y-218, p-48 and II-48 were replaced with equimolar amounts of A1-2,y-218, b-237 and II-88 to obtain the compound 237 (13.52 g), with HPLC purity ≧ 99.96%. Mass spectrum m/z:951.6263 (theoretical value: 951.6276). Theoretical element content (%) C ₆₆ H ₉ D ₃₉ N ₄ O: c,83.24; h,9.20; and N,5.88. Measured elemental content (%): c,83.26; h,9.17; n,5.92.

Synthetic example 25: preparation of Compound 240

According to the same production method as that of Compound 48 of Synthesis example 10, by substituting equimolar amounts of A1-48, y-48 and II-48 for equimolar amounts of A1-240, y-240 and II-185, compound 240 (13.15 g) was obtained with an HPLC purity ≧ 99.97%. Mass spectrum m/z:912.4087 (theoretical value: 912.4071). Theoretical element content (%) C ₆₄ H ₃₆ D ₁₀ N ₄ S: c,84.18; h,6.18; n,6.14. Measured elemental content (%): c,84.21; h,6.20; and N,6.10.

Synthetic example 26: preparation of Compound 244

According to the same production method as that for the synthesis of Compound 2 of EXAMPLE 9, equimolar amounts of A1-2, y-2 and II-2 were replaced with equimolar amounts of A1-244, y-244 and II-207, respectively, to give 244 (13.11 g) of Compound 99.94% or higher in HPLC purity. Mass spectrum m/z:977.4940 (theoretical value: 977.4926). Theoretical element content (%) C ₇₀ H ₃₅ D ₁₅ N ₄ O: c,85.94; h,6.69; n,5.73. Measured elemental content (%): c,85.89; h,6.72; and N,5.69.

Synthesis example 27: preparation of Compound 278

Compound 48 was the same as in Synthesis example 10The method (1) is characterized in that equimolar A1-48, equimolar y-48 and equimolar II-48 are respectively replaced by equimolar A1-76, equimolar y-278 and equimolar II-120, so as to obtain 278 (13.54 g), and the HPLC purity is ≧ 99.93%. Mass spectrum m/z:994.4500 (theoretical value: 994.4518). Theoretical element content (%) C ₇₂ H ₄₆ D ₆ N ₄ O: c,86.89; h,5.87; and N,5.63. Measured elemental content (%): c,86.91; h,5.90; and N,5.59.

Synthetic example 28: preparation of Compound 281

According to the same production method as that of Compound 2 of Synthesis example 9, equimolar a-2, A1-76 and A1-2 were replaced with equimolar a-218, B-281 and C-281, respectively, to give 281 (13.04 g) having an HPLC purity of 99.92% or higher. Mass spectrum m/z:1002.3918 (theoretical value: 1002.3934). Theoretical element content (%) C ₇₂ H ₅₀ N ₄ O ₂ : c,86.20; h,5.02; n,5.58. Measured elemental content (%): c,86.18; h,5.05; and N,5.61.

Synthetic example 29: preparation of Compound 303

According to the same production method as that for the synthesis of Compound 2 of EXAMPLE 9, equimolar amounts of A1-2, y-2 and A1-2 were replaced with equimolar amounts of A1-76, y-303 and B-303, respectively, to give Compound 303 (13.06 g) with an HPLC purity of 99.93% or higher. Mass spectrum m/z:988.4160 (theoretical value: 988.4141). Theoretical element content (%) C ₇₂ H ₅₂ N ₄ O: c,87.42; h,5.30; and N,5.66. Measured elemental content (%): c,87.38; h,5.27; and N,5.70.

Synthesis example 30: preparation of Compound 306

According to the same production method as that for the synthesis of Compound 2 of EXAMPLE 9, equimolar amounts of A1-2, y-2 and A1-2 were replaced with equimolar amounts of A1-76, y-306 and B-306, respectively, to give Compound 306 (13.60 g) with an HPLC purity of 99.94% or higher. Mass spectrum m/z:970.4622 (theoretical value: 970.4611). Theoretical element content (%) C ₇₀ H ₅₈ N ₄ O: c,86.56; h,6.02; n,5.77. Measured elemental content (%): c,86.60; h,6.06; and N,5.80.

Synthetic example 31: preparation of Compound 315

According to the same production method as that of Compound 48 of Synthesis example 10, compound 315 (13.55 g) was obtained by substituting equimolar amounts of A1-315, y-303, p-2, g-76 and B-315 for equimolar amounts of A1-48, y-48, p-48, g-48 and A1-76, respectively, and had an HPLC purity ≧ 99.97%. Mass spectrum m/z:924.4568 (theoretical value: 924.4581). Theoretical element content (%) C ₆₆ H ₃₆ D ₁₂ N ₄ O: c,85.68; h,6.53; and N,6.06. Measured elemental content (%): c,85.70; h,6.49; and N,6.10.

Synthetic example 32: preparation of Compound 330

According to the same production method as that used for the synthesis of Compound 2 of EXAMPLE 9, equimolar amounts of A1-2, y-2, A1-76 and A1-2 were replaced with equimolar amounts of A1-76, y-330, B-330 and C-330, respectively, to give Compound 330 (13.63 g) with an HPLC purity of 99.95% or higher. Mass spectrum m/z:972.4977 (theoretical value: 972.4964). Theoretical element content (%) C ₆₉ H ₄₂ T ₁₀ N ₄ O: c,85.15; h,7.45; and N,5.76. Measured elemental content (%): c,85.18; h,7.41; and N,5.80.

Synthetic example 33: preparation of Compound 359

According to the same production method as that of Compound 2 of Synthesis example 9, equimolar amounts of A1-2, y-2, I-2 and A1-2 were replaced with equimolar amounts of A1-203, y-218, I-203 and B-359, respectively, to give Compound 359 (13.12 g) with an HPLC purity of ≧ 99.96%. Mass spectrum m/z:963.5724 (theoretical value: 963.5709). Theoretical element content (%) C ₆₈ H ₄₅ D ₁₅ N ₄ O: c,84.69; h,7.84; and N,5.81. Measured elemental content (%): c,84.72; h,7.79; n,5.78.

Synthesis example 34: preparation of Compound 396

According to the same production method as that of Compound 48 in Synthesis example 10, equimolar amounts of A1-48, y-48 and II-48 were replaced with equimolar amounts of A1-396, y-396 and II-185, respectively, to give Compound 396 (15.22 g) having an HPLC purity ≧ 99.91%. Mass spectrum m/z:1086.5069 (theoretical value: 1086.5082). Theoretical element content (%) C ₇₉ H ₄₆ D ₁₀ N ₄ O: c,87.26; h,6.12; and N,5.15. Measured elemental content (%): c,87.30; h,6.09; and N,5.17.

Synthetic example 35: preparation of Compound 399

According to the same production method as that for Synthesis example 9, compound 2, in which I-2, A1-2 and A-2 were replaced with I-203, B-399 and A-330, respectively, in equimolar amounts, was synthesized to obtain 399 (13.19 g) with an HPLC purity of 99.96% or higher. Mass spectrum m/z:941.4151 (theoretical value: 941.4142). Theoretical element content (%) C ₆₈ H ₄₃ D ₅ N ₄ O: c,86.69; h,5.67; and N,5.95. Measured elemental content (%): c,86.72; h,5.70; n,5.92.

Synthetic example 36: preparation of Compound 446

According to the same production method as that for the synthesis of Compound 2 of EXAMPLE 9, equimolar amounts of A1-2, y-2, A1-76 and A1-2 were replaced with equimolar amounts of A1-76, y-446, B-446 and A1-48, respectively, to give compound 446 (13.78 g) with an HPLC purity of > 99.94%. Mass spectrum m/z:997.4723 (theoretical value: 997.4706). Theoretical element content (%) C ₇₂ H ₄₃ D ₉ N ₄ O: c,86.63; h,6.16; and N,5.61. Measured elemental content (%): c,86.59; h,6.19; and N,5.58.

Synthetic example 37: preparation of Compound 471

According to the same production method as that of Compound 48 of Synthesis example 10, equimolar amounts of A1-48, y-48, g-48 and A1-76 were replaced with equimolar amounts of A1-76, y-471, g-76 and A1-315, respectively, to give Compound 471 (14.19 g) with an HPLC purity of 99.91% or higher. Mass spectrum m/z:998.4759 (theoretical value: 998.4769). Theoretical element content (%) C ₇₂ H ₄₂ D ₁₀ N ₄ O: c,86.54; h,6.25; and N,5.61. Measured elemental content (%): c,86.49; h,6.28; and N,5.58.

Synthetic example 38: preparation of compound 487

According to the same production method as that for the synthesis of compound 2 of example 9, equimolar amounts of A1-2, y-2 and A1-2 were replaced with equimolar amounts of A1-76, y-487 and B-487, respectively, to give compound 487 (12.84 g) having an HPLC purity ≧ 99.92%. Mass spectrum m/z:957.4467 (theoretical value: 957.4455). Theoretical element content (%) C ₆₉ H ₄₇ D ₅ N ₄ O: c,86.49; h,6.00; and N,5.85. Measured elemental content (%): c,86.52; h,6.03；N,5.81。

Synthetic example 39: preparation of Compound 496

According to the same production method as that for the synthesis of Compound 2 of EXAMPLE 9, equimolar g-2, A1-76, A1-2 and A-2 were replaced with equimolar g-496, B-496, A1-203 and A-76, respectively, to give 496 (12.68 g) of a compound having an HPLC purity of 99.96% or more. Mass spectrum m/z:945.4675 (theoretical value: 945.4667). Theoretical element content (%) C ₆₆ H ₃₁ D ₁₇ N ₄ S: c,83.77; h,6.92; n,5.92. Measured elemental content (%): c,83.80; h,6.88; and N,5.89.

Synthetic example 40: preparation of Compound 504

According to the same production method as that of Compound 48 of Synthesis example 10, equimolar amounts of A1-48, y-48, g-48 and A1-76 were replaced with equimolar amounts of A1-203, y-303, g-504 and A1-203, respectively, to give Compound 504 (11.62 g) with an HPLC purity of 99.98% or higher. Mass spectrum m/z:893.4915 (theoretical value: 893.4926). Theoretical element content (%) C ₆₃ H ₃₅ D ₁₅ N ₄ O: c,84.62; h,7.32; and N,6.27. Measured elemental content (%): c,84.59; h,7.28; and N,6.30.

Synthesis example 41: preparation of Compound 506

According to the same preparation method as that for Synthesis example 9, compound 2, in which equimolar amounts of a-2, g-2 and A1-2 were replaced with equimolar amounts of a-207, g-496 and A1-244, respectively, was synthesized to give compound 506 (13.40 g) with an HPLC purity of 99.94% or higher. Mass spectrum m/z:970.4058 (theoretical value: 970.4069). Theoretical element content (%) C ₆₉ H ₅₄ N ₄ S: c,85.33; h,5.60; n,5.77. Measured elemental content (%): c,85.29; h,5.59; and N,5.80.

Synthesis example 42: preparation of Compound 522

According to the same production method as that of Compound 48 of Synthesis example 10, compound 522 (13.68 g) was obtained by substituting equimolar amounts of A1-48, y-48 and II-48 for equimolar amounts of A1-76, y-522 and II-76, respectively, and its HPLC purity was ≧ 99.96%. Mass spectrum m/z:936.3816 (theoretical value: 936.3828). Theoretical element content (%) C ₆₈ H ₄₈ N ₄ O: c,87.15; h,5.16; and N,5.98. Measured elemental content (%): c,87.18; h,5.20; and N,5.94.

Synthetic example 43: preparation of Compound 529

According to the same production method as that for the synthesis of Compound 2 of EXAMPLE 9, equimolar amounts of A1-2, y-2 and A1-2 were replaced with equimolar amounts of A1-76, A2-529 and A1-203, respectively, to give Compound 529 (13.39 g) having an HPLC purity of 99.93% or higher. Mass spectrum m/z:983.4082 (theoretical value: 983.4070). Theoretical element content (%) C ₇₀ H ₄₅ D ₅ N ₄ S: c,85.42; h,5.63; and N,5.69. Measured elemental content (%): c,85.39; h,5.59; n,5.73.

Synthetic example 44: preparation of Compound 550

According to the same production method as that used for the synthesis of Compound 2 of EXAMPLE 9, equimolar amounts of A1-2, y-2, I-2 and A1-2 were replaced with equimolar amounts of A1-76, A2-550, I-203 and B-550, respectively, to give Compound 550 (13.54 g) with an HPLC purity of 99.94% or higher. Mass spectrum m/z:980.5190 (theoretical value:980.5176). Theoretical element content (%) C ₇₀ H ₄₀ D ₁₄ N ₄ O: c,85.68; h,6.98; and N,5.71. Measured elemental content (%): c,85.71; h,7.01; and N,5.68.

Device example 1

Firstly, the ITO substrate is put into distilled water for cleaning for 3 times, ultrasonic cleaning is carried out for 15 minutes, after the cleaning of the distilled water is finished, solvents such as isopropanol, acetone, methanol and the like are sequentially subjected to ultrasonic cleaning, and then drying is carried out at 120 ℃.

Adopting a vacuum evaporation method to evaporate HATNA with the thickness of 20nm on the cleaned ITO substrate as a hole injection layer material; a compound 61 with a thickness of 70nm is vapor-plated on the hole injection layer as a hole transport layer material; a hole transport layer was deposited with a thickness of 25nm, wherein BH-1 bd-1=96 (mass ratio); depositing BTB and Liq (doping ratio 1) as an electron transport layer and a hole blocking layer on the light emitting layer, wherein the deposition thickness is 30nm; evaporating LiF as an electron injection layer on the electron transport layer and the hole blocking layer, wherein the evaporation thickness is 0.8nm; then, al (110 nm) was vapor-deposited on the electron injection layer as a cathode, thereby preparing an organic electroluminescent device.

Device examples 2 to 18

An organic electroluminescent device was produced by the same production method as that of device example 1 except that compound 75, compound 87, compound 120, compound 158, compound 185, compound 188, compound 218, compound 244, compound 281, compound 303, compound 306, compound 359, compound 396, compound 471, compound 496, compound 504, and compound 529 each were used as a hole transport layer instead of compound 61 in device example 1.

Comparative device examples 1 to 4

An organic electroluminescent device was produced by the same production method as that of device example 1 except that compound 61 in device example 1 was replaced with comparative compound 1, comparative compound 2, comparative compound 3 and comparative compound 4, respectively, as a hole transport layer.

The test software, computer, K2400 digital source meter manufactured by Keithley corporation, usa, and PR788 spectral scanning luminance meter manufactured by Photo Research corporation, usa were combined into a combined IVL test system to test the luminous efficiency of the organic electroluminescent device. The lifetime test was carried out using the McScience M6000 OLED lifetime test system. The environment for testing is atmospheric environment, and the temperature is room temperature.

The results of the light emission characteristic test of the obtained organic electroluminescent device are shown in table 1. Table 1 shows the results of the test of the light emitting characteristics of the compounds prepared in the inventive examples and the organic electroluminescent devices prepared from the comparative compounds.

Device example 19

Adopting a vacuum evaporation method to evaporate HATNA with the thickness of 20nm on the cleaned ITO substrate as a hole injection layer material; NPB with the thickness of 50nm is evaporated on the hole injection layer to be used as a first hole transport layer material; evaporating the compound 2 of the present invention as a second hole transporting material on the first hole transporting material to a thickness of 30nm; depositing a light-emitting layer of GH-1 GD-1= -95 (mass ratio) on the second hole transport layer, wherein the deposition thickness is 25nm; depositing BTB and Liq (doping ratio 1) as an electron transport layer and a hole blocking layer on the light emitting layer, wherein the deposition thickness is 30nm; evaporating LiF as an electron injection layer on the electron transport layer and the hole blocking layer, wherein the evaporation thickness is 0.8nm; then, al (110 nm) was vapor-deposited on the electron injection layer as a cathode, thereby preparing an organic electroluminescent device.

Device examples 20 to 36

An organic electroluminescent device was produced by the same production method as in device example 19 except that compound 48, compound 76, compound 88, compound 184, compound 203, compound 207, compound 237, compound 240, compound 278, compound 315, compound 330, compound 399, compound 446, compound 487, compound 506, compound 522, and compound 550 of the present invention were used as the second hole transporting layer in place of compound 2 in device example 19, respectively.

Comparative device examples 5 to 8

An organic electroluminescent device was produced by the same production method as that of device example 19 except that compound 2 in device example 19 was replaced with comparative compound 1, comparative compound 2, comparative compound 3 and comparative compound 4, respectively, as the second hole transporting layer.

The test software, computer, K2400 digital source manufactured by Keithley corporation, usa, and PR788 spectral scanning luminance meter manufactured by Photo Research corporation, usa were combined into a joint IVL test system to test the luminous efficiency of the organic electroluminescent device. The lifetime test was carried out using the McScience M6000 OLED lifetime test system. The environment of the test is atmospheric environment, and the temperature is room temperature.

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

As can be seen from the data in tables 1 and 2, compared with the comparative compounds 1-4, the star-shaped tetraamine derivative provided by the invention as a single hole transport layer or a second hole transport layer material can significantly improve the luminous efficiency and the service life of the device due to the fact that the material has good hole mobility, high glass transition temperature and excellent film-forming property when being applied to an organic electroluminescent device.

It should be understood that the present invention has been particularly described with reference to particular embodiments thereof, but that various changes in form and details may be made therein by those skilled in the art without departing from the principles of the invention and, therefore, within the scope of the invention.

Claims

1. A star-shaped tetramine derivative is characterized in that the star-shaped tetramine derivative has a structure shown as a formula I,

in formula I, ar ₁ ～Ar ₇ The same or different from each other, selected from any one of the groups shown below,

z is ₁ Selected from a single bond, said Z ₂ Selected from O, S or C (R) _x R _y ) Any one of the above;

the R is _x 、R _y Are the same or different from each other and are selected from any one of substituted or unsubstituted C1-C6 alkyl and substituted or unsubstituted phenyl, or R _x 、R _y May be a position to which another substituent is attached;

the R is ₃ The same or different from each other, and is selected from hydrogen, deuterium, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, and substituted or unsubstitutedAny one of substituted adamantyl and substituted or unsubstituted phenyl;

the R is ₃ 'the same or different from each other, is any one selected from hydrogen, deuterium, a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted adamantyl group, a substituted or unsubstituted norbornyl group, a substituted or unsubstituted phenyl group, or two adjacent R' s ₃ ' may be connected to each other to form a substituted or unsubstituted cyclopentane ring, a substituted or unsubstituted cyclohexane ring;

the R is ₃ "is the same as or different from each other, and is any one selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted adamantyl group, a substituted or unsubstituted norbornyl group, a substituted or unsubstituted phenyl group, and two adjacent R' s ₃ "can be mutually connected to form a substituted or unsubstituted benzene ring;

said p is ₁ Selected from 0, 1,2, 3, 4 or 5, said p ₂ Is selected from 0, 1,2, 3 or 4, the p ₃ Selected from 0, 1,2, 3, 4, 5, 6 or 7, said p ₄ Selected from 0, 1,2, 3, 4, 5, 6, 7, 8 or 9, said p ₆ Selected from 0, 1,2 or 3;

said L ₁ ～L ₉ Any one selected from the group consisting of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, and a substituted or unsubstituted biphenylene group, the same or different from each other;

the R is ₀ Identical to or different from each other, selected from hydrogen, deuterium, substituted or unsubstituted C1-C6 alkyl;

the above-mentioned

Any one selected from the structures shown below,

the R is ₁ 、R ₂ The same or different from each other, selected from any one of hydrogen and deuterium;

n is said ₁ Selected from 0, 1,2 or 3, said n ₂ Selected from 0, 1 or 2, said n ₃ Selected from 0, 1,2, 3 or 4, said n ₅ Selected from 0, 1,2, 3, 4 or 5;

m is said ₁ Is selected from 0, 1,2 or 3, m ₃ Selected from 0, 1,2, 3, 4 or 5, said m ₅ Is selected from 0, 1,2, 3 or 4, m ₇ Selected from 0, 1,2, 3, 4, 5 or 6;

the above "substituted or unsubstituted" substituent group is selected from: deuterium, and C1-C6 alkyl.

2. The star tetraamine derivative according to claim 1, wherein the star tetraamine derivative is characterized in that

Selected from any one of the structures shown below,

3. the star tetraamine derivative of claim 1, wherein Ar is selected from the group consisting of ₁ ～Ar ₇ The same or different from each other, selected from any one of the groups shown below,

q is a radical of ₁ Selected from 0,1.2, 3, 4 or 5, said q ₂ Selected from 0, 1,2, 3 or 4, q ₃ Selected from 0, 1,2, 3, 4, 5, 6 or 7, q ₄ Selected from 0, 1,2, 3, 4, 5 or 6, q ₅ Selected from 0, 1,2, 3, 4, 5, 6, 7, 8 or 9, said q ₆ Selected from 0, 1,2 or 3.

4. The star tetraamine derivative according to claim 1, wherein L is L ₁ ～L ₉ The same or different from each other, selected from a single bond or any one of the structures shown below,

said R is ₄ Identical to or different from each other, selected from deuterium, methyl;

said x ₁ Selected from 1,2, 3 or 4, said x ₂ Selected from 1,2, 3, 4, 5, 6, 7 or 8, said x ₄ Selected from 1,2, 3, 4, 5 or 6.

5. A star tetraamine derivative characterized in that the star tetraamine derivative is selected from any one of the following structures,

6. an organic electroluminescent device comprising an anode, an organic layer, and a cathode, wherein the organic layer is located between the anode and the cathode or outside any one of the cathode and the anode, and wherein the organic layer comprises any one or more of the star tetraamine derivatives according to any one of claims 1 to 5.

7. The device according to claim 6, wherein the organic layer is located between the anode and the cathode, and the organic layer comprises a hole transport layer, and the hole transport layer comprises any one or more of the star tetraamine derivatives of claims 1 to 5.

8. The organic electroluminescent device according to claim 6, wherein the hole transport layer comprises at least one of a first hole transport layer and a second hole transport layer, and the at least one of the first hole transport layer and the second hole transport layer comprises one or more star-shaped tetraamine derivatives according to any one of claims 1 to 5.