An organic electroluminescent device

Abstract

The application provides an organic electroluminescent device, and particularly relates to the technical field of organic electroluminescence. In order to solve the problem of low light extraction efficiency of the covering layer material in the prior art, the application provides an organic electroluminescent device, wherein the covering layer material of the device is a core with central benzene or N heterobenzene, and is connected with at least one benzene five-membered heterocycle and an N heterobridging group; the covering layer material has a strong rigid structure, a high glass transition temperature, and good thermal stability and is not easy to decompose at high temperature; when the covering layer material is applied to the organic electroluminescent device as a covering layer, the light extraction effect can be effectively improved, the total reflection of light in the device and the generation of Joule heat are reduced, and therefore the luminous efficiency and service life of the device are increased.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic electroluminescence, in particular to an organic electroluminescence device. BACKGROUND

[0002] Organic Light-Emitting Diode (OLED) refers to a phenomenon that organic semiconductor materials and light-emitting materials emit light by carrier injection and recombination under the drive of an external electric field, which can directly convert electric energy into light energy. Due to its advantages of ultra-thin, full solidification, low power consumption, self-luminescence, fast response speed, wide color gamut, good temperature characteristics and flexible display, it is widely used in the fields of information display and solid-state lighting.

[0003] In OLED, under the action of an external electric field, electrons from the cathode and holes from the anode enter the organic layer to recombine and release energy, which is transferred to the organic light-emitting compound to make it transition from the ground state to the excited state. The excited molecules return to the ground state in the form of light, forming a luminescent phenomenon. OLED is a sandwich structure, usually composed of an anode, a cathode and an organic layer formed between the two electrodes. At present, the organic layer involved in OLED includes a hole injection layer, a hole transport layer, a hole blocking layer, a light-emitting layer, an electron blocking layer, an electron transport layer, an electron injection layer and a cover layer. Although the OLED manufacturing process is constantly innovated and reformed, there are still many problems in commercialization for its large-scale application, which is due to the fact that the development of organic light-emitting materials is not perfect at this stage.

[0004] For the cover layer material, most of the traditional cover layer materials are inorganic materials, which have certain disadvantages. On the one hand, the evaporation temperature of inorganic materials is relatively high, and the deformation of the device caused by high temperature makes the cover layer unable to be precisely evaporated. On the other hand, due to the waveguide effect, the internal light of the device increases the total reflection phenomenon, which reduces the light extraction efficiency. In addition, the cathode of the OLED device is mostly a metal with relatively active chemical properties, which is easily eroded in an environment containing oxygen, especially in an air containing water vapor, which causes electrochemical corrosion, causing great harm to the device and reducing the service life of the device. In order to improve the light extraction efficiency of the organic light-emitting device and improve the service life of the device, it is essential to develop a cover layer material with low absorption in the visible light region, high refractive index, excellent thin film stability and good durability. SUMMARY

[0005] The present application provides an organic electroluminescence device to solve the problem of affecting the luminous efficiency and service life of the organic electroluminescence device in the prior art.

[0006] In detail, the present application provides an organic electroluminescent device, comprising an anode, a cathode, and an organic layer, wherein the organic layer comprises a cover layer, and the cover layer has a structure as shown in Formula I,

[0007]

[0008] In Formula I, Ar1-Ar3 are the same as or different from each other, wherein at least one is selected from a group as shown in Formula II, and the rest are the same as or different from each other, and are selected from any one of a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 heteroaryl group, and a fused ring group of a substituted or unsubstituted C6-C30 aromatic ring and a C3-C30 aliphatic ring;

[0009]

[0010] In Formula II, L0 is selected from any one of a group as shown below and a combination thereof;

[0011]

[0012] Z is the same as or different from each other, and is selected from a CH or N atom, and at least one Z in each group is selected from an N atom; when Z is bonded to other groups, Z is selected from a C atom;

[0013] R1 is the same as or different from each other, and is selected from any one of hydrogen, deuterium, a cyano group, a trifluoromethyl group, a halogen, 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 C6-C30 aryl group, and a substituted or unsubstituted C2-C30 heteroaryl group;

[0014] a1 is selected from 0, 1, 2, or 3, and a2 is selected from 0, 1, 2, 3, 4, or 5; when there are two or more R1, the two or more R1 are the same as or different from each other, or adjacent two R1 can be connected to each other to form a substituted or unsubstituted ring;

[0015] x1 is selected from any one of O, S, NR a ; and R a is selected from any one of hydrogen, deuterium, 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 C6-C30 aryl group, and a substituted or unsubstituted C2-C30 heteroaryl group;

[0016] Y is the same as or different from each other, and is selected from a CH or N atom;

[0017] The R and R' may be the same as or different from each other, and are selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl.

[0018] The m is selected from 0, 1, 2, 3 or 4; when there are two or more R, the two or more R are the same or different from each other, or two adjacent R can be connected to each other to form a substituted or unsubstituted ring;

[0019] The m' is selected from 0, 1, or 2;

[0020] The x atoms may be the same as or different from each other, and are selected from CH or N atoms. When x is bonded to other groups, the x atoms are selected from C atoms.

[0021] The R2 is selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl.

[0022] The value of n is selected from 0, 1, 2, or 3;

[0023] The L1 to L3 may be the same as or different from each other, and are selected from any one of the following: single bond, substituted or unsubstituted C6 to C30 arylene, substituted or unsubstituted C2 to C30 heteroarylene, divalent substituted or unsubstituted C6 to C30 aromatic ring and C3 to C30 aliphatic ring fused ring group.

[0024] Beneficial effects: The Formula I compound provided by this invention has a central benzene or N-heterobenzene as the core, connected with at least one benzo5-membered heterocyclic ring and an N-heterobridging group. It has strong rigidity, and after the material is deposited, it forms a highly dense film layer, thereby giving the film layer high stability. At the same time, the Formula I compound has a high glass transition temperature and good thermal stability, and is not easily decomposed at high temperatures. When applied as a capping layer in organic electroluminescent devices, it can effectively improve the light extraction effect, reduce total internal reflection of light inside the device, and reduce the generation of Joule heat inside the device, thereby increasing the luminous efficiency and lifespan of the device. Detailed Implementation

[0025] The technical solutions of the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments of the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.

[0026] In the compounds of the present application, 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 non-natural abundance.

[0027] In the present application, “*” means a moiety connected to another substituent.

[0028] In the present application, when the position of a substituent on a ring is not fixed, it means that it can be connected to any one of the corresponding optional sites of the ring. For example, may mean and the like. In this way.

[0029] In the present specification, when a substituent or a connecting site is a bond that penetrates through two or more rings, it means that it can be connected to any one of the two or more rings, and specifically can be connected to any one of the corresponding optional sites of the ring. For example, may mean may mean In this way.

[0030] Examples of the halogen atom described in the present application can include fluorine, chlorine, bromine, or iodine.

[0031] The alkyl group described in the present application refers to a monovalent group obtained by removing one hydrogen atom from an alkane molecule, which can be a straight-chain alkyl group or a branched-chain alkyl group, preferably has 1 to 12 carbon atoms, more preferably has 1 to 8 carbon atoms, and particularly preferably has 1 to 6 carbon atoms. The alkyl group can be substituted or unsubstituted. Specific examples can include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, and the like, but are not limited thereto.

[0032] The alkenyl group described in the present application refers to a monovalent group obtained by removing one hydrogen atom from an alkene molecule, which can be a straight-chain alkenyl group or a branched-chain alkenyl group, preferably has 2 to 12 carbon atoms, more preferably has 2 to 8 carbon atoms, and particularly preferably has 2 to 6 carbon atoms. The alkenyl group can be substituted or unsubstituted. Specific examples can include ethenyl, 1-propenyl, isopropenyl, butenyl, pentenyl, 3-methyl-1-butenyl, allyl, 1-phenylethenyl-1-yl, phenethyl, and the like, but are not limited thereto.

[0033] The cycloalkyl group according to the present application refers to a monovalent group obtained by removing one hydrogen atom from a cyclic alkane molecule, preferably 3 to 12 carbon atoms, and particularly preferably 3 to 6 carbon atoms. The cycloalkyl group can be substituted or unsubstituted. The cycloalkyl group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, a norbornyl group, and the like, but is not limited thereto.

[0034] The aryl group according to the present application refers to a monovalent group obtained by removing one hydrogen atom from an aromatic nucleus carbon of an aromatic compound molecule, which can be a monocyclic aryl group, a polycyclic aryl group, or a fused ring aryl group, preferably has 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms, and most preferably 6 to 12 carbon atoms. The aryl group can be substituted or unsubstituted. The monocyclic aryl group refers to an aryl group having only one aromatic ring in a molecule, for example, a phenyl group, and the like, but is not limited thereto; the polycyclic aryl group refers to an aryl group having two or more independent aromatic rings in a molecule, for example, a biphenyl group, a terphenyl group, a quaterphenyl group, and the like, but is not limited thereto; and the fused ring aryl group refers to an aryl group having two or more aromatic rings in a molecule and being fused to each other by sharing two adjacent carbon atoms, for example, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a triphenylenyl group, a fluoranthenyl group, a 9,9-dimethylfluorenyl group, a 9,9-diphenylfluorenyl group, a 9-methyl-9-phenylfluorenyl group, a benzofluorenyl group, a 9,9'-spirobifluorenyl group, and the like, but is not limited thereto.

[0035] The heteroaryl group according to the present application refers to the group of radicals obtained by replacing one or more aromatic ring carbon atoms in an aryl group with a heteroatom, including but not limited to O, S, N, Si or P atom, preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, further preferably having 3 to 12 carbon atoms. The connecting site of the heteroaryl group can be located on the ring carbon atom or on the ring heteroatom, and the heteroaryl group can be monocyclic, polycyclic or fused ring heteroaryl group. The heteroaryl group can be substituted or unsubstituted. The monocyclic heteroaryl group includes pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, triazinyl, furanyl, thiophenyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, etc., but is not limited thereto; the polycyclic heteroaryl group includes bipyridyl, bipyrimidyl, phenylpyridyl, phenylpyrimidyl, etc., but is not limited thereto; the fused ring heteroaryl group includes quinolyl, isoquinolyl, benzoquinolyl, benzoisoquinolyl, quinazolyl, quinoxalyl, benzoquinazolyl, benzoquinoxalyl, phenanthrolinyl, naphthylidinyl, indolyl, benzothiophenyl, benzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, N-heterobenzoxazolyl, N-heterobenzimidazolyl, N-heterobenzothiazolyl, dibenzofuranyl, benzdibenzofuranyl, dibenzothiophenyl, benzdibenzothiophenyl, dibenzoxazolyl, dibenzimidazolyl, dibenzothiazolyl, carbazolyl, benzocarbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenoxathiazinyl, spirofluorene xanthene, spirofluorene thioxanthene, etc., but is not limited thereto.

[0036] The aliphatic ring according to the present application refers to a cyclic hydrocarbon having aliphatic properties, containing a closed carbon ring in the molecule, preferably having 3 to 30 carbon atoms, more preferably 3 to 18 carbon atoms, further preferably 3 to 12 carbon atoms, more preferably 3 to 7 carbon atoms. It can form a monocyclic hydrocarbon or a polycyclic hydrocarbon, and can be completely unsaturated or partially unsaturated. The aliphatic ring can be substituted or unsubstituted. Specific examples can include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclobutene, cyclopentene, cyclohexene, cycloheptene, etc., but are not limited thereto. Multiple monocyclic hydrocarbons can also be connected in various ways: two rings in the molecule can share a 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 can also be connected to each other to form a cage structure.

[0037] The fused ring of the aromatic ring and the aliphatic ring according to the present application refers to a ring in which one or more aromatic rings and one or more aliphatic rings are 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, and most preferably 6 to 12 carbon atoms, and the aliphatic ring preferably has 3 to 30 carbon atoms, more preferably C3 to C18 carbon atoms, more preferably 3 to 12 carbon atoms, and most preferably 3 to 7 carbon atoms. The fused ring of the aromatic ring and the aliphatic ring can be substituted or unsubstituted. Examples include benzocyclopropanyl, benzocyclobutanyl, benzocyclopentanyl, benzocyclohexanyl, benzocycloheptanyl, benzocyclobutenyl, benzocyclopentenyl, benzocyclohexenyl, benzocycloheptenyl, naphthocyclopropanyl, naphthocyclobutanyl, naphthocyclopentanyl, naphthocyclohexanyl, naphthocyclopentenyl, naphthocyclohexenyl, and the like, but are not limited thereto.

[0038] The arylene group according to the present application refers to a general term for a divalent group obtained by removing two hydrogen atoms from the aromatic nucleus carbon of an aromatic hydrocarbon molecule, and can be a monocyclic arylene group, a polycyclic arylene group, or a fused ring arylene group, preferably has 6 to 30 carbon atoms, more preferably has 6 to 22 carbon atoms, more preferably has 6 to 18 carbon atoms, and most preferably has 6 to 12 carbon atoms. As the monocyclic arylene group, phenylene and the like can be used, but are not limited thereto. The arylene group can be substituted or unsubstituted. As the polycyclic arylene group, biphenylene, terphenylene, quaterphenylene, and the like can be used, but are not limited thereto. As the fused ring arylene group, naphthylene, anthracenylene, phenanthrenylene, pyrenylene, fluorenylene, spirofluorenylene, triphenylenylene, perylenylene, fluoranthenylene, and the like can be used, but are not limited thereto.

[0039] ​The heteroarylene group according to the present application refers to a general term of divalent group obtained by removing two hydrogen atoms from the core carbon of the aromatic heterocycle composed of carbon and heteroatom, and the heteroatom can be one or more of N, O, S, Si, P, and can be monocyclic heteroarylene, polycyclic heteroarylene or fused ring heteroarylene, 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 can be substituted or unsubstituted. Examples can include pyridylene, pyrimidylene, pyrazylene, pyridazylene, triazylene, thiophenylene, pyrrolylene, furanylene, pyranylene, oxazolyiene, thiazolyiene, imidazolyiene, benzoxazolyiene, benzothiazolyiene, benzimidazolyiene, carbazolyiene, benzocarbazolyiene, azidylene, xanthylene, thianthrene, phenazinylene, phenothiazinylene, phenoxazinylene, indolyiene, quinolyiene, isoquinolyiene, benzothiophenylene, benzofuranylene, dibenzofuranylene, dibenzothiophenylene, quinoxalyiene, quinazolyiene, naphtholyiene, purinylene, phenanthrolinylene, and the like, but are not limited thereto.

[0040] The divalent aromatic ring and aliphatic ring fused ring group according to the present application refers to a divalent group having two linking positions on the aromatic ring and aliphatic ring fused ring group. They can be applicable to the above description of the aromatic ring and aliphatic ring fused ring group except that they are divalent groups, respectively.

[0041] The "unsubstituted" in the "substituted or unsubstituted" according to the present application means that the hydrogen atom on the group is not substituted by 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 by a plurality of substituents, the plurality of substituents can be the same or different.

[0042] The substituents described in the "substituted or unsubstituted" of this invention may be the same as or different from each other, and are selected from deuterium, cyano, nitro, trifluoromethyl, halogen atoms, substituted or unsubstituted C1-C12 alkyl groups, substituted or unsubstituted C2-C12 alkenyl groups, substituted or unsubstituted C3-C12 cycloalkyl groups, substituted or unsubstituted C2-C12 heterocycloalkyl groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C2-C30 heteroaryl groups, substituted or unsubstituted C6-C30 aromatic rings and C3-C30 aliphatic rings. The fused cyclic group can be any one of the following, preferably deuterium, cyano, halogen atom, trifluoromethyl, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, or C2-C30 heteroaryl. Specific examples may include deuterium, fluorine, chlorine, bromine, iodine, cyano, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornel, phenyl, biphenyl, terphenyl, tolyl, pentadeuterated phenyl, naphthyl, anthracene, phenanthryl, pyrene, or triphenylene. alkyl, peryl, fluoranyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, spirofluorenyl, carbazole, 9-phenylcarbazole, 9,9'-spirodifluorenyl, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexane, benzocycloheptane, benzocyclobutenyl, benzocyclopentenyl, benzocyclohexenyl, benzocycloheptenyl, naphthocyclopentane, naphthocyclohexane, naphthocycloheptane, naphthalene The compounds include, but are not limited to, cyclopentenyl, naphthocyclohexenyl, naphthocycloheptenyl, pyrroleyl, furanyl, thiophenyl, benzofuranyl, benzothiophenyl, dibenzofuranyl, dibenzothiophenyl, pyridinyl, pyrimidinyl, pyrazinyl, pyrazinyl, triazinyl, oxazolyl, thiazolyl, imidazolyl, benzooxazolyl, benzothiazolyl, benzotriazolyl, benzoimidazolyl, quinolinyl, isoquinolinyl, quinoxolinyl, quinazolinyl, phenothiazinyl, phenothiazinyl, acridineyl, etc.

[0043] The "linked ring formation" described in this invention refers to two groups being linked together by chemical bonds and optionally undergoing aromatization. Examples are shown below:

[0044]

[0045] In this invention, the ring formed by the connection can be an aromatic ring system, an aliphatic ring system, or a ring system formed by the fusion of the two. The ring formed by the connection can be a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, or a fused ring, such as benzene, naphthalene, indene, cyclopentene, cyclopentane, cyclopentanophenene, cyclohexene, cyclohexane, cyclohexanophenene, pyridine, quinoline, isoquinoline, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, naphthalene, phenanthrene, or pyrene, but is not limited thereto.

[0046] The present application provides an organic electroluminescent device, comprising an anode, a cathode, an organic layer, the organic layer comprising a cover layer, the cover layer having a structure as shown in Formula I,

[0047]

[0048] In Formula I, the Ar1~Ar3 are the same as or different from each other, at least one of which is selected from the group shown in Formula II, and the rest are the same as or different from each other, selected from any one 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 of fused ring group;

[0049]

[0050] In Formula II, the L0 is selected from any one of the following groups and combinations thereof;

[0051]

[0052] The Z is the same as or different from each other, selected from CH or N atom, and at least one Z in each group is selected from N atom; when Z is bonded to other groups, the Z is selected from C atom;

[0053] The R1 is the same as or different from each other, selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1~C12 alkyl, substituted or unsubstituted C2~C12 alkenyl, substituted or unsubstituted C3~C12 cycloalkyl, substituted or unsubstituted C6~C30 aryl, substituted or unsubstituted C2~C30 heteroaryl;

[0054] The a1 is selected from 0, 1, 2 or 3, and the a2 is selected from 0, 1, 2, 3, 4 or 5; when there are two or more R1, the two or more R1 are the same as or different from each other, or adjacent two R1 can be connected to each other to form a substituted or unsubstituted ring;

[0055] The x1 is selected from any one of O, S, NR a ; the R a is selected from any one of hydrogen, deuterium, substituted or unsubstituted C1~C12 alkyl, substituted or unsubstituted C2~C12 alkenyl, substituted or unsubstituted C3~C12 cycloalkyl, substituted or unsubstituted C6~C30 aryl, substituted or unsubstituted C2~C30 heteroaryl;

[0056] The Y is the same as or different from each other, selected from CH or N atom;

[0057] R, R' are the same as or different from each other, and are selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl;

[0058] m is selected from 0, 1, 2, 3 or 4; when there are two or more R, the two or more R are the same as or different from each other, or adjacent two R can be connected to each other to form a substituted or unsubstituted ring;

[0059] m' is selected from 0, 1 or 2;

[0060] x is the same as or different from each other, and is selected from CH or N atom, when x is bonded with other groups, x is selected from C atom;

[0061] R2 is selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl;

[0062] n is selected from 0, 1, 2 or 3;

[0063] L1-L3 are the same as or different from each other, and are selected from any one of single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C2-C30 heteroarylene, divalent substituted or unsubstituted C6-C30 aromatic ring and C3-C30 aliphatic ring fused ring group.

[0064] Preferably, the groups of Ar1-L1-*, Ar2-L2-*, and Ar3-L3- in formula I are connected to the central ring in the meta position.

[0065] Preferably, all x on the central ring in formula I are selected from CH, and the central ring is selected from benzene ring.

[0066] Preferably, 1, 2 or 3 x on the central ring in formula I are selected from N atom, and the rest are selected from CH. More preferably, the central ring is selected from any one of pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, and triazine ring.

[0067] Preferably, one of Ar1-Ar3 is selected from the group represented by formula II, and more preferably, Ar1, Ar2 or Ar3 is selected from the group represented by formula II.

[0068] Preferably, two of Ar1to Ar3are selected from the group of Formula II, more preferably, Ar1and Ar2, Ar1and Ar3, or Ar2and Ar3are selected from the group of Formula II.

[0069] Preferably, Ar1to Ar3are all selected from the group of Formula II.

[0070] Preferably, L0is selected from any one of the following groups:

[0071]

[0072] Z are the same or different from each other, selected from CH or N atom, and at least one Z in each group is selected from N atom; when Z is bonded to other groups, the Z is selected from C atom;

[0073] R1are the same or different from each other, selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen, or any one of the following groups substituted or unsubstituted with one or more deuterium, C1-C12alkyl: methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, pyridyl, or pyrimidyl;

[0074] a1is selected from 0, 1, 2, or 3, a2is selected from 0, 1, 2, 3, 4, or 5, a3is selected from 0, 1, 2, 3, or 4, and a4is selected from 0, 1, 2, 3, 4, 5, or 6.

[0075] Preferably, L0is selected from any one of the following groups:

[0076]

[0077]

[0078] Preferably, L0is selected from any one of the following groups: Preferably, L0is selected from any one of the following groups:

[0079]

[0080] R, R' are the same or different from each other, selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen, or any one of the following groups substituted or unsubstituted with one or more deuterium, C1-C12alkyl: methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, pyridyl, pyrimidyl, quinolyl, isoquinolyl, quinazolyl, or quinoxalyl;

[0081] said ml is selected from 0, 1, 2, 3 or 4, said m2 is selected from 0, 1, 2 or 3, said m3 is selected from 0, 1 or 2, said m4 is selected from 0 or 1, when two or more R are present, the two or more R are the same or different from each other, or two adjacent R can be connected to each other to form a substituted or unsubstituted ring;

[0082] said m' is selected from 0, 1 or 2, said m" is selected from 0 or 1.

[0083] Preferably, said is selected from any one of the following groups:

[0084]

[0085]

[0086] said xl is the same or different from each other, selected from O, S or NR a is selected from any one of the following groups:

[0087] said R a is selected from hydrogen, deuterium or any one of the following groups substituted or unsubstituted with one or more deuterium, C1-C12 alkyl group: methyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl, cyclopropane group, cyclobutane group, cyclopentane group, cyclohexane group, cycloheptane group, adamantane group, norbornane group, phenyl group, biphenyl group, naphthyl group, anthracene group, phenanthrene group, triphenylene group, pyridyl group or pyrimidyl group;

[0088] said bl is selected from 0, 1, 2, 3, 4 or 5, said b2 is selected from 0, 1, 2, 3 or 4, said b3 is selected from 0, 1, 2, 3, 4, 5, 6 or 7.

[0089] Preferably, said Ar1-Ar3 are the same or different from each other, wherein at least one is selected from the group represented by Formula II, and the rest are the same or different from each other, selected from any one of the following groups:

[0090]

[0091] said R3 is the same or different from each other, selected from any one of the following groups: hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C12 alkyl group, substituted or unsubstituted C3-C12 cycloalkyl group, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C2-C30 heteroaryl group;

[0092] said c1 is selected from 0, 1, 2, 3, 4 or 5, said c2 is selected from 0, 1, 2, 3, 4, 5, 6 or 7, said c3 is selected from 0, 1, 2, 3 or 4, said c4 is selected from 0, 1, 2, 3, 4, 5 or 6; when there are two or more R3, the two or more R3 are the same as or different from each other, or adjacent two R3 can be connected to each other to form a substituted or unsubstituted ring;

[0093] said Q is selected from any one of O, S, C(R b )(R c ), N(R d );

[0094] said R b , R c , R d are the same as or different from each other, and are 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 b , R c may be connected to each other to form a substituted or unsubstituted ring, or R b , R c , R d may be directly bonded to any one of L1-L3;

[0095] said t is the same as or different from each other, and is selected from a CH or N atom, and 1, 2, 3 or 4 t in formula III-4 is selected from a N atom, and 1, 2, 3, 4, 5 or 6 t in formula III-5 is selected from a N atom; when t is bonded to other groups, said t is selected from a C atom;

[0096] said z1 is selected from O, S or C(R e ); said z2 is selected from C(R f ) or N;

[0097] said R e , R f are the same as or different from each other, and are selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl.

[0098] Preferably, said R3, equal to or different from each other, are selected from hydrogen, deuterium or any one of the following groups, substituted or unsubstituted, with one or more deuterium, C1-C12 alkyl groups: methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, adamantane, norbornane, phenyl, biphenyl, naphthyl, anthryl, phenanthryl, triphenylene, pyridyl or pyrimidyl.

[0099] Preferably, when two or more R3are present, two or more R3, equal to or different from each other, or adjacent two R3may be connected to each other to form any one of the following groups, substituted or unsubstituted: three-membered ring, four-membered ring, five-membered ring, six-membered ring, benzene ring, naphthalene ring.

[0100] Preferably, said Ar1-Ar3, equal to or different from each other, wherein at least one is selected from the group of formula II, the remaining ones, equal to or different from each other, are selected from any one of the following groups:

[0101]

[0102]

[0103] said R4, equal to or different from each other, are selected from hydrogen, deuterium or any one of the following groups, substituted or unsubstituted, with one or more deuterium, C1-C12 alkyl groups: methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, adamantane, norbornane, phenyl, biphenyl, naphthyl, pyridyl or pyrimidyl;

[0104] said d1 is selected from 0, 1, 2, 3, 4 or 5, said d2 is selected from 0, 1, 2, 3 or 4, said d3 is selected from 0, 1, 2, 3, 4, 5, 6 or 7, said d4 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, said d5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, said d6 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said d7 is selected from 0, 1, 2, 3, 4, 5 or 6, said d8 is selected from 0, 1, 2 or 3;

[0105] said R b , R c , R d , equal to or different from each other, are selected from hydrogen, deuterium or any one of the following groups, substituted or unsubstituted, with one or more deuterium, C1-C12 alkyl groups: methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, adamantane, norbornane, phenyl, biphenyl, naphthyl, pyridyl or pyrimidyl;

[0106] said La , L b , L each other, are selected from any one of a single bond, substituted or unsubstituted phenylene, biphenylene, naphthylene, pyridylene, or pyrimidylene;

[0107] said ring A is selected from a spirocyclic structure selected from any one of the following groups:

[0108]

[0109] said R5, equal to or different from each other, is selected from any one of hydrogen, deuterium, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, cyclopropanyl, cyclobutanyl, cyclopentanoyl, cyclohexanoyl, cycloheptanoyl, adamantyl, norbornanyl, phenyl, biphenyl, naphthyl;

[0110] said e1 is selected from 0, 1, 2, 3 or 4, said e2 is selected from 0, 1, 2, 3, 4, 5 or 6, said e3 is independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said e4 is independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, said e5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, said e6 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14.

[0111] Preferably, said Ar1 to Ar3, equal to or different from each other, wherein at least one is selected from a group of formula II, the rest, equal to or different from each other, are selected from any one of the following groups:

[0112]

[0113]

[0114]

[0115]

[0116]

[0117] Preferably, said L1 to L3, equal to or different from each other, are selected from a single bond or any one of the following groups:

[0118]

[0119] The R6 may be the same as or different from each other, and are selected from any one of hydrogen, deuterium or C1-C12 alkyl groups substituted or unsubstituted with one or more deuterium groups, substituted or unsubstituted C3-C12 cycloalkyl groups, substituted or unsubstituted C6-C30 aryl groups, and substituted or unsubstituted C2-C30 heteroaryl groups.

[0120] The s1 is selected from 0, 1, 2, 3 or 4; the s2 is selected from 0, 1, 2, 3, 4 or 5; the s3 is selected from 0, 1, 2 or 3; the s4 is selected from 0, 1 or 2; and the s5 is selected from 0, 1, 2, 3, 4, 5 or 6.

[0121] The R x R y R z They may be the same as or different from each other, selected from any one of hydrogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or R x R y They can connect with each other to form substituted or unsubstituted rings;

[0122] The V atoms may be the same or different from each other, and are selected from CH or N atoms, with at least one V in each group being selected from N atoms; when V is bonded to other groups, the V is selected from C atoms;

[0123] The ring B is selected from substituted or unsubstituted C3 to C7 aliphatic rings.

[0124] Preferably, ring B is selected from any one of the following groups, either substituted or unsubstituted:

[0125]

[0126] In this context, "*" represents a loop connection site; dashed lines indicate single or double bonds.

[0127] Preferably, L1 to L3 are the same or different from each other, and are selected from single bonds or any one of the following groups;

[0128]

[0129] Preferably, the covering layer is selected from any one of the structures shown below;

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158] The above lists some specific structural forms of the compound of formula I according to the present application, but the present application is not limited to the listed chemical structures, and any structure based on the structure shown in formula I and having substituents as defined above should be included.

[0159] The present application provides a preparation method of the compound represented by formula I, but the preparation method of the present application is not limited thereto, and the specific synthesis route is as follows: preparation of formula I.

[0160] 1. When Ar1-L1-*, Ar2-L2-*, Ar3-L3-* are the same as each other,

[0161]

[0162] 2. When Ar1-L1-*, Ar2-L2-*, Ar3-L3-* are the same as each other,

[0163]

[0164] 3. When Ar1-L1-*, Ar2-L2-*, Ar3-L3-* are different from each other,

[0165]

[0166] Preparation of formula II:

[0167]

[0168] wherein X a , X b are the same or different from each other and are selected from any one of Cl, Br, and I; Ar1-Ar3, L0-L3, x, x1, R, R', R2, Y, n, m, and m' are defined as above; the raw materials used in the above preparation route can be commercially available products or can be prepared by methods well known to those skilled in the art.

[0169] The organic electroluminescent device according to the present application comprises an anode, a hole transport region, a light-emitting layer, an electron transport region, a cathode, and a cover layer. Each functional layer can be composed of a single layer, a double layer, or a plurality of layers, and each layer can be composed of one material or two or more materials, but the structure of the organic electroluminescent device is not limited thereto.

[0170] Preferably, the hole transport region according to the present application comprises at least one of a hole injection layer, a hole transport layer, and an electron blocking layer.

[0171] Preferably, the hole transport layer according to the present application comprises a first hole transport layer and / or a second hole transport layer.

[0172] Preferably, the electron transport region according to the present application comprises at least one of an electron injection layer, an electron transport layer, and a hole blocking layer.

[0173] Preferably, the electron transport layer according to the present application comprises a first electron transport layer and / or a second electron transport layer.

[0174] Preferably, the capping layer according to the present application comprises any one or more of the compounds of formula I according to the present application.

[0175] Preferably, the capping layer according to the present application comprises a first capping layer and / or a second capping layer, which comprises any one or more of the compounds of formula I according to the present application.

[0176] The organic electroluminescent device according to the present application is generally formed on a substrate. The substrate described above can be any substrate that does not change when electrodes and organic layers are formed, such as a glass, a plastic, a polymer film, silicon, and the like.

[0177] The anode material according to the present application preferably uses a material having a high functional function to improve the hole injection efficiency. The anode material that can be used in the present application is selected from the group consisting of indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), 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 can have a single layer structure or a multi-layer structure including two or more layers, for example, the anode can have a single layer structure of Al or a three-layer structure of ITO / Ag / ITO, but is not limited thereto.

[0178] The hole injection layer material according to the present application preferably has a material having a suitable HOMO value to facilitate the injection and transport of holes. It can be selected from any one or more of the following structures: metalloporphyrin, oligothiophene, arylamine derivative, hexacyno hexaazatriphenylene compound, phthalocyanine compound, polycyano conjugated organic material, quinacridone compound, anthraquinone compound, and conductive polymer based on polyaniline and polystyrene, and the like, but is not limited thereto.

[0179] The hole transport layer material according to the present application is preferably a material having a high hole mobility. It can be selected from any one or more of the following structures: carbazole derivatives, triarylamine derivatives, diphenylamine derivatives, fluorene derivatives, stilbene derivatives, hexacyno hexaazatriphenylene derivatives, quinacridone derivatives, anthraquinone derivatives, polyaniline, polythiophene, polyvinylcarbazole, etc. Examples of the hole transport layer material include the following materials: N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), 4-[1-[4-[di(4-methylphenyl)amino]phenyl]cyclohexyl]-N-(3-methylphenyl)-N-(4-methylphenyl)aniline (TAPC), N,N,N',N'-tetrakis(3-methylphenyl)-3,3'-dimethylbiphenyl diamine (HMTPD), etc., but is not limited thereto.

[0180] The light emitting layer material according to the present application comprises a host material and a dopant material. The light emitting layer host material can be selected from 4,4'-bis(9-carbazolyl)biphenyl (CBP), 9,10-di(2-naphthyl)anthracene (ADN), 9,9'-(1,3-phenyl)bis-9H-carbazole (mCP), 4,4',4"-tris(carbazol-9-yl)triphenylamine (TCTA), 9,10-di(1-naphthyl)anthracene (a-AND), N,N'-di-(1-naphthyl)-N,N'-diphenyl-[1,1':4',1":4",1"'-terphenyl]-4,4"-diamine (4PNPB), 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 can also include other known materials suitable for use in a light emitting layer, without being limited thereto. The light emitting layer dopant material according to the present application is classified into a blue light emitting material, a green light emitting material, and a red light emitting material. The light emitting layer dopant material can be selected from (6-(4-(diphenylamino(phenyl)-N,N-diphenylpyrene-1-amine) (DPAP-DPPA), 2,5,8,11-tetra-tert-butylperylene (TBPe), 4,4'-bis[4-(diphenylamino)styryl]biphenyl (BDAVBi), 4,4'-bis[4-(di-p-tolylamino)styryl]biphenyl (DPAVBi), bis(2-hydroxyphenylpyridine)beryllium (Bepp2), bis(4,6-difluorophenylpyridine-C2,N)picolatoiridium (FIrpic), tris(2-phenylpyridine)iridium (Ir(ppy)3), bis(2-phenylpyridine)iridium (Ir(ppy)2(acac)), 9,10-di[N-(p-tolyl)anilino]anthracene (TPA), 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM), tris[1-phenylisoquinoline-C2,N]iridium(III) (Ir(piq)3), bis(1-phenylisoquinoline)(acetylacetonate)iridium (Ir(piq)2(acac)), and the like, without being limited thereto.

[0181] The doping ratio of the host material and the guest material in the light emitting layer according to the present application is determined according to the materials used. The amount of the dopant material is preferably selected from 0.1 to 70 mass%, more preferably from 0.1 to 30 mass%, further preferably from 1 to 30 mass%, more further preferably from 1 to 20 mass%, and particularly preferably from 1 to 10 mass%.

[0182] The hole blocking layer material according to the present application is preferably a material capable of effectively blocking the hole transport, and making the exciton recombine in the light emitting layer rather than in the electron transport layer. In addition to the nitrogen-containing heterocyclic derivative provided by the present application, the hole blocking layer material can also be selected from any one or more of the following structures: phenanthroline derivatives, rare earth derivatives, imidazole derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, triazine derivatives, quinoline derivatives, diazaphen derivatives, azaphen derivatives, anthrone derivatives, and the like, but is not limited thereto.

[0183] The electron transport layer material according to the present application is preferably a material having a high electron mobility. The electron transport layer material 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) (Alq3), 8-hydroxyquinoline-lithium (Liq), bis(2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (BAlq), 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), 4,7-diphenyl-1,10-phenanthroline (Bphen), and the like, but is not limited thereto.

[0184] The electron injection layer material according to the present application is preferably a material having a small potential barrier difference with the adjacent organic layer material. Specific examples of the electron injection layer material can include: alkali metal compounds (e.g., lithium oxide, lithium fluoride, cesium carbonate, cesium fluoride, cesium 8-hydroxyquinolate, aluminum 8-hydroxyquinolate), organic metal salts (metal acetate, metal benzoate, or metal stearate), molybdenum trioxide, metallic aluminum, and the like, but is not limited thereto.

[0185] The cathode material according to the present application is preferably a material having a low work function, which can facilitate the electron injection into the organic layer, so as to reduce the electron injection barrier. The cathode material can be selected from any one or more of the following materials: Ag, Mg, Cu, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF / Ca, LiF / Al, Mo, Ti, compounds including the above, or mixtures thereof (e.g., a mixture of Ag and Mg), but is not limited thereto.

[0186] The cover layer according to the present application is provided outside any one or more of the anode and the cathode, so as to reduce the total reflection loss of light and improve the light extraction efficiency. The cover layer can be selected from any one or more of the following structures: arylamine derivatives, biscarbazole derivatives, benzimidazole derivatives, benzoxazole derivatives, benzothiazole derivatives, triazole derivatives, benzofuran derivatives, bisamine derivatives, porphyrin derivatives, phthalocyanine derivatives, Alq3, TPBi, or mixtures thereof, but is not limited thereto. Preferably, the compound of Formula I according to the present application is used as the cover layer.

[0187] The thickness of each organic layer of the organic electroluminescent device is not particularly limited, and a thickness commonly used in the art can be used.

[0188] The organic electroluminescent device described in the present application can be manufactured by sequentially laminating the above-described structure. The manufacturing method can use a known method such as a wet film forming method, a dry film forming method, etc. As specific examples of the wet film forming method, various coating methods such as a spin coating method, a dip coating method, a flow coating method, an inkjet method, etc. are used, and as specific examples of the dry film forming method, a vacuum evaporation method, a sputtering method, a plasma method, an ion plating method, etc. are used, but the present application is not limited thereto.

[0189] The organic electroluminescent device described in the present application can be widely used in the fields of panel display, illumination light source, flexible OLED, electronic paper, organic solar cell, organic photoreceptor or organic thin film transistor, signboard, signal lamp, etc.

[0190] The present application is explained more in detail by the following examples, but the present application is not intended to be limited thereto. Based on this description, a person of ordinary skill in the art will be able to implement the present application and prepare other compounds and devices according to the present application within the entire scope disclosed without any creative effort.

[0191] Preparation and characterization of compounds

[0192] Explanation of raw materials, reagents and characterization equipment:

[0193] The present application does not have a particular limitation on the source of raw materials used in the following examples, and can be a commercially available product or prepared by a preparation method well known to those skilled in the art.

[0194] Mass spectrometry uses a Waters G2-Si quadrupole tandem time-of-flight high-resolution mass spectrometer in the United Kingdom, chloroform as the solvent;

[0195] Elemental analysis uses a Vario EL cube organic elemental analyzer of Elementar Company in Germany, and the sample mass is 5-10 mg;

[0196] Synthesis Example 1: Preparation of intermediate M-1:

[0197]

[0198] Preparation of intermediate M1-1:

[0199] The starting material m-1 (34.64 g, 180.00 mmol), pinacol diborane (50.79 g, 200.00 mmol), K2CO3 (74.63 g, 540.00 mmol), Pd(PPh3)4 (6.24 g, 5.40 mmol) were added to DMF (850 mL) under nitrogen protection, and the mixed solution of the above reaction was heated to reflux for 6 h. After the reaction was completed, the reaction mixture was cooled to room temperature, distilled water was added, extracted with dichloromethane, and separated by standing. The organic layer was collected and dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The obtained solid was recrystallized with ethyl acetate and dried to obtain the intermediate M1-1 (37.94 g, 88%); HPLC purity ≧ 98.81%. Mass spectrum m / z: 239.0871 (theoretical value: 239.0884).

[0200] Preparation of intermediate M2-1:

[0201] The starting material n-1 (31.52 g, 160.00 mmol), the intermediate M1-1 (35.93 g, 150.00 mmol), K2CO3 (41.46 g, 300.00 mmol), Pd(PPh3)4 (3.47 g, 3.00 mmol) were added to 570 mL of toluene, 190 mL of ethanol, and 190 mL of water under nitrogen protection, and the mixed solution of the above reaction was heated to reflux for 5 h. After the reaction was completed, it was cooled to room temperature, and the filter cake was obtained by suction filtration. The filter cake was recrystallized with toluene / ethanol = 4:1 and dried to obtain the intermediate M2-1 (28.25 g, 82%); HPLC purity ≧ 99.87%. Mass spectrum m / z: 229.0284 (theoretical value: 229.0294).

[0202] Preparation of intermediate M-1:

[0203] The intermediate M2-1 (27.56 g, 120.00 mmol), pinacol diborane (33.52 g, 132.00 mmol), K2CO3 (49.75 g, 360.00 mmol), Pd(PPh3)4 (4.16 g, 3.60 mmol) were added to DMF (560 mL) under nitrogen protection, and the mixed solution of the above reaction was heated to reflux for 3.5 h. After the reaction was completed, the reaction mixture was cooled to room temperature, distilled water was added, extracted with dichloromethane, and separated by standing. The organic layer was collected and dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The obtained solid was recrystallized with ethyl acetate and dried to obtain the intermediate M-1 (33.15 g, 86%); HPLC purity ≧ 98.83%. Mass spectrum m / z: 321.1545 (theoretical value: 321.1536).

[0204] The starting materials were replaced accordingly, and the preparation method of intermediate M-1 in Synthesis Example 1 was followed to prepare intermediate M. The starting materials are shown in the following table:

[0205]

[0206]

[0207]

[0208] Synthesis Example 2: Preparation of compound 1:

[0209]

[0210] Under nitrogen protection, g-1 (9.44 g, 30.00 mmol), M-1 (30.51 g, 95.00 mmol), K2CO3 (14.51 g, 105.00 mmol) were added to 240 ml of tetrahydrofuran and 60 ml of distilled water, Pd(PPh3)4 (0.52 g, 0.45 mmol) was added under stirring, the mixture was heated to reflux for 5 h, after the reaction was completed, it was cooled to room temperature, distilled water was added, extracted with dichloromethane, separated by standing, the organic layer was collected and dried over anhydrous magnesium sulfate, filtered, the filtrate was concentrated by reduced pressure distillation, crystallized by cooling, filtered under suction, the obtained solid was recrystallized with toluene to obtain compound 1 (15.00 g, 76%), HPLC purity ≧ 99.97%. Mass spectrum m / z: 657.2069 (theoretical value: 657.2052). Theoretical elemental content (%) 45 H 27 N3O3: C, 82.18; H, 4.14; N, 6.39. Measured elemental content (%): C, 82.21; H, 4.11; N, 6.43.

[0211] Synthesis Example 3: Preparation of compound 89:

[0212]

[0213] Preparation of intermediate I-89:

[0214] Under nitrogen protection, g-89 (11.29 g, 50.00 mmol), A-89 (12.40 g, 50.00 mmol), KOAc (9.81 g, 100.00 mmol) were added into 400 ml tetrahydrofuran and 100 ml distilled water, Pd(dppf)Cl2(0.37 g, 0.50 mmol) was added under stirring, the mixture solution of the above reaction was heated to reflux for 3 h, after the reaction was completed, it was cooled to room temperature, distilled water was added, extracted with dichloromethane, separated by standing, the organic layer was collected and dried over anhydrous magnesium sulfate, filtered, the filtrate was concentrated by distillation under reduced pressure, crystallized by cooling, the obtained solid was recrystallized with ethyl acetate to obtain intermediate I-89 (13.97 g, 80%), HPLC purity≧99.84%. Mass spectrum m / z: 348.0465 (theoretical value: 348.0473).

[0215] Preparation of compound 89:

[0216] Under nitrogen protection, I-89 (10.48 g, 30.00 mmol), M-1 (20.23 g, 63.00 mmol), K2CO3(10.37 g, 75.00 mmol) were added into 240 ml tetrahydrofuran and 60 ml distilled water, Pd(PPh3)4(0.35 g, 0.30 mmol) was added under stirring, the mixture solution of the above reaction was heated to reflux for 4.5 h, after the reaction was completed, it was cooled to room temperature, distilled water was added, extracted with dichloromethane, separated by standing, the organic layer was collected and dried over anhydrous magnesium sulfate, filtered, the filtrate was concentrated by distillation under reduced pressure, crystallized by cooling, filtered, the obtained solid was recrystallized with toluene to obtain compound 89 (15.60 g, 78%), HPLC purity≧99.92%. Mass spectrum m / z: 666.2322 (theoretical value: 666.2307). Theoretical elemental content (%) 48 H 30 N2O2: C, 86.46; H, 4.54; N, 4.20. Found elemental content (%): C, 86.50; H, 4.59; N, 4.17.

[0217] Synthesis example 4: Preparation of compound 96:

[0218]

[0219] According to the same preparation method as synthesis example 3, A-89 was replaced by equimolar A-96, M-1 was replaced by equimolar M-96 to obtain compound 96 (13.81 g), HPLC purity≧99.95%. Mass spectrum m / z: 597.2424 (theoretical value: 597.2434). Theoretical elemental content (%) 42 H 19D7N2O2: C, 84.40; H, 5.56; N, 4.69. Found: C, 84.37; H, 5.59; N, 4.73.

[0220] Synthesis Example 5: Preparation of Compound 97:

[0221]

[0222] Following the same preparation method as in Synthesis Example 3, A-89 was replaced with an equivalent molar of A-97, M-1 was replaced with an equivalent molar of M-97, to give Compound 97 (14.60 g) with HPLC purity > 99.97%. Mass spectrum m / z: 648.2538 (theoretical value: 648.2525). Theoretical elemental content (%) C 44 H 32 N4O2: C, 81.46; H, 4.97; N, 8.64. Found: C, 81.50; H, 4.94; N, 8.66.

[0223] Synthesis Example 6: Preparation of Compound 98:

[0224]

[0225] Following the same preparation method as in Synthesis Example 3, A-89 was replaced with an equivalent molar of A-98, M-1 was replaced with an equivalent molar of M-98, to give Compound 98 (15.91 g) with HPLC purity > 99.91%. Mass spectrum m / z: 716.2450 (theoretical value: 716.2464). Theoretical elemental content (%) C 52 H 32 N2O2: C, 87.13; H, 4.50; N, 3.91. Found: C, 87.09; H, 4.47; N, 3.96.

[0226] Synthesis Example 7: Preparation of Compound 110:

[0227]

[0228] Following the same preparation method as in Synthesis Example 3, A-89 was replaced with an equivalent molar of A-110, M-1 was replaced with an equivalent molar of M-110, to give Compound 110 (15.48 g) with HPLC purity > 99.94%. Mass spectrum m / z: 716.2479 (theoretical value: 716.2464). Theoretical elemental content (%) C 52 H 32 N2O2: C, 87.13; H, 4.50; N, 3.91. Found: C, 87.16; H, 4.55; N, 3.88.

[0229] Synthesis Example 8: Preparation of Compound 124:

[0230]

[0231] Preparation of Intermediate I-124:

[0232] Under nitrogen protection, g-124 (25.39 g, 80.00 mmol), A-124 (16.57 g, 80.00 mmol), KOAc (15.70 g, 160.00 mmol) were added into 640 ml of tetrahydrofuran and 160 ml of distilled water, Pd(dppf)Cl2(0.59 g, 0.80 mmol) was added under stirring, the mixed solution of the above reaction was heated to reflux for 3.5 h, after the reaction was completed, it was cooled to room temperature, distilled water was added, extracted with dichloromethane, and separated by standing, the organic layer was collected and dried over anhydrous magnesium sulfate, filtered, the filtrate was concentrated by distillation under reduced pressure, and the crystals were precipitated by cooling, the obtained solid was recrystallized with ethyl acetate to obtain intermediate I-124 (22.29 g, 79%), HPLC purity ≧ 99.83%. Mass spectrum m / z: 351.0366 (theoretical value: 351.0376).

[0233] Preparation of Intermediate II-124:

[0234] Under nitrogen protection, I-124 (17.64 g, 50.00 mmol), M-1 (16.06 g, 50.00 mmol), KOAc (9.81 g, 100 mmol) were added into 400 ml of tetrahydrofuran and 100 ml of distilled water, Pd(OAc)2(0.11 g, 0.50 mmol) was added under stirring, the mixed solution of the above reaction was heated to reflux for 3 h, after the reaction was completed, it was cooled to room temperature, distilled water was added, extracted with dichloromethane, and separated by standing, the organic layer was collected and dried over anhydrous magnesium sulfate, filtered, the filtrate was concentrated by distillation under reduced pressure, and the crystals were precipitated by cooling, the obtained solid was recrystallized with ethyl acetate to obtain intermediate II-124 (17.75 g, 76%), HPLC purity ≧ 99.87%. Mass spectrum m / z: 466.1782 (theoretical value: 466.1798).

[0235] Preparation of Compound 124:

[0236] Under nitrogen protection, II-124 (14.01 g, 30.00 mmol), M-124 (11.13 g, 33.00 mmol), K2CO3 (8.29 g, 60.00 mmol) were added into 240 ml of tetrahydrofuran and 60 ml of distilled water, Pd(PPh3)4 (0.35 g, 0.30 mmol) was added under stirring, the mixture solution of the above reaction was heated to reflux for 4 h. After the reaction was completed, it was cooled to room temperature, distilled water was added, extracted with dichloromethane, and separated by standing. The organic layer was collected, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure. The product was crystallized by cooling, filtered, and the obtained solid was recrystallized with toluene to obtain compound 124 (13.48 g, 70%), HPLC purity ≧ 99.98%. Mass spectrum m / z: 641.2496 (theoretical value: 641.2487). Theoretical elemental content (%) C 44 H 19 D9N2OS: C, 82.34; H, 5.81; N, 4.36. Measured elemental content (%) C, 82.31; H, 5.77; N, 4.38.

[0237] Synthesis Example 9: Preparation of compound 160:

[0238]

[0239] According to the same preparation method as synthesis example 3, A-89 was replaced with an equal mole of A-160, and M-1 was replaced with an equal mole of M-160 to obtain compound 160 (17.44 g), HPLC purity ≧ 99.93%. Mass spectrum m / z: 818.2947 (theoretical value: 818.2933). Theoretical elemental content (%) C 60 H 38 N2O2: C, 88.00; H, 4.68; N, 3.42. Measured elemental content (%) C, 88.03; H, 4.72; N, 3.38.

[0240] Synthesis Example 10: Preparation of compound 168:

[0241]

[0242] According to the same preparation method as synthesis example 3, A-89 was replaced with an equal mole of A-168, and M-1 was replaced with an equal mole of M-168 to obtain compound 168 (16.05 g), HPLC purity ≧ 99.96%. Mass spectrum m / z: 742.2355 (theoretical value: 742.2369). Theoretical elemental content (%) C 52 H 30N4O2: C, 82.62; H, 4.22; N, 8.38. Found: C, 82.57; H, 4.25; N, 8.40.

[0243] Synthesis Example 11: Preparation of Compound 173:

[0244]

[0245] Compound 173 (14.85 g) was obtained according to the same preparation method as in Synthesis Example 3, replacing A-89 with an equivalent molar of A-173, and replacing M-1 with an equivalent molar of M-173, with an HPLC purity of > 99.92%. Mass spectrum m / z: 668.2228 (theoretical value: 668.2212). Theoretical elemental content (%) C 46 H 28 N4O2: C, 82.62; H, 4.22; N, 8.38. Found: C, 82.57; H, 4.25; N, 8.40.

[0246] Synthesis Example 12: Preparation of Compound 180:

[0247]

[0248] Compound 180 (15.07 g) was obtained according to the same preparation method as in Synthesis Example 3, replacing g-89 with an equivalent molar of g-180, and replacing A-89 with an equivalent molar of A-180, with an HPLC purity of > 99.91%. Mass spectrum m / z: 727.3289 (theoretical value: 727.3278). Theoretical elemental content (%) C 52 H 37 D3N2O2: C, 85.80; H, 5.95; N, 3.85. Found: C, 85.78; H, 5.98; N, 3.89.

[0249] Synthesis Example 13: Preparation of Compound 187:

[0250]

[0251] Compound 187 (15.69 g) was obtained according to the same preparation method as in Synthesis Example 3, replacing A-89 with an equivalent molar of A-187, and replacing M-1 with an equivalent molar of M-187, with an HPLC purity of > 99.92%. Mass spectrum m / z: 768.2516 (theoretical value: 768.2525). Theoretical elemental content (%) C 54 H 32N4O2: C, 84.36; H, 4.20; N, 7.29. Found ( % ): C, 84.40; H, 4.17; N, 7.31.

[0252] Synthesis Example 14: Preparation of Compound 223:

[0253]

[0254] Compound 223 (15.41 g) was obtained according to the same preparation method as in Synthesis Example 3, replacing A-89 with an equivalent molar of M-96, and replacing M-1 with an equivalent molar of A-223, with an HPLC purity of > 99.97%. Mass spectrum m / z: 675.2550 (theoretical value: 675.2562). Theoretical elemental content (%) C 51 H 33 NO: C, 90.64; H, 4.92; N, 2.07. Found ( % ): C, 90.66; H, 4.89; N, 2.11.

[0255] Synthesis Example 15: Preparation of Compound 276:

[0256]

[0257] Compound 276 (14.83 g) was obtained according to the same preparation method as in Synthesis Example 3, replacing A-89 with an equivalent molar of M-276, and replacing M-1 with an equivalent molar of A-276, with an HPLC purity of > 99.94%. Mass spectrum m / z: 641.2185 (theoretical value: 641.2177). Theoretical elemental content (%) C 47 H 31 NS: C, 87.95; H, 4.87; N, 2.18. Found ( % ): C, 87.91; H, 4.90; N, 2.20.

[0258] Synthesis Example 16: Preparation of Compound 288:

[0259]

[0260] Compound 288 (13.73 g) was obtained according to the same preparation method as in Synthesis Example 8, replacing A-124 with an equivalent molar of A-288, replacing M-1 with an equivalent molar of B-288, and replacing M-124 with an equivalent molar of M-288, with an HPLC purity of > 99.93%. Mass spectrum m / z: 635.3141 (theoretical value: 635.3126). Theoretical elemental content (%) C 47 H 33D4NO: C, 88.78; H, 6.50; N, 2.20. Found (mass %): C, 88.81; H, 6.46; N, 2.15.

[0261] Synthesis Example 17: Preparation of Compound 291:

[0262]

[0263] According to the same preparation method as in Synthesis Example 8, A-124 was replaced with an equivalent molar amount of A-291, M-1 was replaced with an equivalent molar amount of B-291, and M-124 was replaced with an equivalent molar amount of M-291 to obtain Compound 291 (13.56 g) with an HPLC purity of > 99.91%. Mass spectrum m / z: 645.2798 (theoretical value: 645.2780). Theoretical elemental content (%) C 46 H 35 N3O: C, 85.55; H, 5.46; N, 6.51. Found (mass %): C, 85.58; H, 5.50; N, 6.49.

[0264] Synthesis Example 18: Preparation of Compound 330:

[0265]

[0266] According to the same preparation method as in Synthesis Example 8, A-124 was replaced with an equivalent molar amount of A-223, M-1 was replaced with an equivalent molar amount of B-330, and M-124 was replaced with an equivalent molar amount of M-1 to obtain Compound 330 (15.11 g) with an HPLC purity of > 99.94%. Mass spectrum m / z: 689.2341 (theoretical value: 689.2355). Theoretical elemental content (%) C 51 H 31 NO2: C, 88.80; H, 4.53; N, 2.03. Found (mass %): C, 88.77; H, 4.49; N, 2.08.

[0267] Synthesis Example 19: Preparation of Compound 476:

[0268]

[0269] According to the same preparation method as in Synthesis Example 3, A-89 was replaced with an equivalent molar amount of M-1, and M-1 was replaced with an equivalent molar amount of A-476 to obtain Compound 476 (14.99 g) with an HPLC purity of > 99.98%. Mass spectrum m / z: 703.2130 (theoretical value: 703.2147). Theoretical elemental content (%) C 51 H 29NO3: C, 87.04; H, 4.15; N, 1.99. Found (%): C, 87.08; H, 4.12; N, 1.94.

[0270] Synthesis Example 20: Preparation of compound 499:

[0271]

[0272] Following the same preparation method as synthesis example 3, g-89 was replaced with equimolar of g-499, A-89 was replaced with equimolar of M-499, M-1 was replaced with equimolar of A-499, to give compound 499 (17.37 g) with HPLC purity > 99.95%. Mass spectrum m / z: 863.2076 (theoretical value: 863.2065). Theoretical elemental content (%) C 59 H 33 N3OS2: C, 82.01; H, 3.85; N, 4.86. Found (%): C, 82.04; H, 3.81; N, 4.90.

[0273] Synthesis Example 21: Preparation of compound 508:

[0274]

[0275] Following the same preparation method as synthesis example 3, A-89 was replaced with equimolar of M-508, M-1 was replaced with equimolar of A-508, to give compound 508 (17.63 g) with HPLC purity > 99.91%. Mass spectrum m / z: 903.3268 (theoretical value: 903.3250). Theoretical elemental content (%) C 67 H 41 N3O: C, 89.01; H, 4.57; N, 4.65. Found (%): C, 89.03; H, 4.60; N, 4.61.

[0276] Synthesis Example 22: Preparation of compound 516:

[0277]

[0278] Following the same preparation method as synthesis example 3, A-89 was replaced with equimolar of M-516, M-1 was replaced with equimolar of M-124, to give compound 516 (15.48 g) with HPLC purity > 99.93%. Mass spectrum m / z: 706.1331 (theoretical value: 706.1320). Theoretical elemental content (%) C 44 H 26N4S3: C, 74.76; H, 3.71; N, 7.93. Found: C, 74.78; H, 3.68; N, 7.89.

[0279] Synthesis Example 23: Preparation of compound 538:

[0280]

[0281] Following the same preparation procedure as in Synthesis Example 3, A-89 was replaced with an equivalent molar of A-223, M-1 was replaced with an equivalent molar of M-538, to give compound 538 (15.73 g) with HPLC purity > 99.96%. Mass spectrum m / z: 698.1832 (calc. 698.1850). Theoretical elemental content (%) C 48 H 30 N2S2: C, 82.49; H, 4.33; N, 4.01. Found: C, 82.51; H, 4.30; N, 4.05.

[0282] Synthesis Example 24: Preparation of compound 552:

[0283]

[0284] Following the same preparation procedure as in Synthesis Example 3, A-89 was replaced with an equivalent molar of A-552, M-1 was replaced with an equivalent molar of M-552, to give compound 552 (17.28 g) with HPLC purity > 99.92%. Mass spectrum m / z: 822.2150 (calc. 822.2163). Theoretical elemental content (%) C 58 H 34 N2S2: C, 84.64; H, 4.16; N, 3.40. Found: C, 84.67; H, 4.20; N, 3.36.

[0285] Synthesis Example 25: Preparation of compound 580:

[0286]

[0287] Following the same preparation procedure as in Synthesis Example 8, A-124 was replaced with an equivalent molar of A-580, M-1 was replaced with an equivalent molar of B-580, M-124 was replaced with an equivalent molar of M-580, to give compound 580 (14.48 g) with HPLC purity > 99.94%. Mass spectrum m / z: 679.2091 (calc. 679.2082). Theoretical elemental content (%) C 48 H 29N3S: C, 84.80; H, 4.30; N, 6.18. Found: C, 84.77; H, 4.34; N, 6.20.

[0288] Synthesis Example 26: Preparation of compound 587:

[0289]

[0290] Following the same preparation procedure as in Synthesis Example 8, A-124 was replaced with an equivalent molar of A-587, M-1 was replaced with an equivalent molar of B-587, and M-124 was replaced with an equivalent molar of M-587 to give compound 587 (16.48 g) with HPLC purity > 99.97%. Mass spectrum m / z: 807.2945 (theoretical value: 807.2960). Theoretical elemental content (%) C 60 H 41 NS: C, 89.18; H, 5.11; N, 1.73. Found: C, 89.21; H, 5.07; N, 1.76.

[0291] Synthesis Example 27: Preparation of compound 588:

[0292]

[0293] Following the same preparation procedure as in Synthesis Example 3, g-89 was replaced with an equivalent molar of g-588, A-89 was replaced with an equivalent molar of A-588, and M-1 was replaced with an equivalent molar of M-538 to give compound 588 (15.78 g) with HPLC purity > 99.95%. Mass spectrum m / z: 710.1864 (theoretical value: 710.1850). Theoretical elemental content (%) C 49 H 30 N2S2: C, 82.79; H, 4.25; N, 3.94. Found: C, 82.82; H, 4.29; N, 3.92.

[0294] Synthesis Example 28: Preparation of compound 615:

[0295]

[0296] Following the same preparation procedure as in Synthesis Example 3, A-89 was replaced with an equivalent molar of M-124, and M-1 was replaced with an equivalent molar of A-223 to give compound 615 (15.57 g) with HPLC purity > 99.96%. Mass spectrum m / z: 691.2350 (theoretical value: 691.2334). Theoretical elemental content (%) C 51 H 33NS: C, 87.77; H, 4.75; N, 2.27. Found: C, 87.80; H, 4.71; N, 2.32.

[0297] Synthesis Example 29: Preparation of compound 621:

[0298]

[0299] Following the same preparation procedure as in Synthesis Example 3, A-89 was replaced with an equivalent molar of M-621, and M-1 was replaced with an equivalent molar of A-621 to give compound 621 (14.53 g) with HPLC purity > 99.91%. Mass spectrum m / z: 672.2588 (calcd: 672.2599). Theoretical elemental content (%) C 48 H 36 N2S: C, 85.68; H, 5.39; N, 4.16. Found: C, 85.71; H, 5.43; N, 4.11.

[0300] Synthesis Example 30: Preparation of compound 626:

[0301]

[0302] Following the same preparation procedure as in Synthesis Example 3, A-89 was replaced with an equivalent molar of M-626, and M-1 was replaced with an equivalent molar of A-626 to give compound 626 (13.49 g) with HPLC purity > 99.93%. Mass spectrum m / z: 615.2039 (calcd: 615.2021). Theoretical elemental content (%) C 45 H 29 NS: C, 87.77; H, 4.75; N, 2.27. Found: C, 87.80; H, 4.71; N, 2.32.

[0303] Synthesis Example 31: Preparation of compound 659:

[0304]

[0305] Following the same preparation procedure as in Synthesis Example 3, A-89 was replaced with an equivalent molar of A-659, and M-1 was replaced with an equivalent molar of M-538 to give compound 659 (15.40 g) with HPLC purity > 99.98%. Mass spectrum m / z: 712.1656 (calcd: 712.1643). Theoretical elemental content (%) C 48 H 28N2OS2: C, 80.87; H, 3.96; N, 3.93. Found (%,): C, 80.90; H, 3.91; N, 3.89.

[0306] Synthesis Example 32: Preparation of compound 669:

[0307]

[0308] Following the same preparation procedure as in Synthesis Example 3, replacing A-89 with an equivalent molar of A-669, M-1 with an equivalent molar of M-669, compound 669 (15.05 g) was obtained with HPLC purity ≧ 99.96%. Mass spectrum m / z: 716.1434 (calcd 716.1453). Theoretical elemental content (%) C 44 H 24 N6OS2: C, 73.72; H, 3.37; N, 11.72. Found (%,): C, 73.69; H, 3.40; N, 11.76.

[0309] Synthesis Example 33: Preparation of compound 670:

[0310]

[0311] Following the same preparation procedure as in Synthesis Example 3, replacing g-89 with an equivalent molar of g-670, A-89 with an equivalent molar of A-670, compound 670 (14.93 g) was obtained with HPLC purity ≧ 99.93%. Mass spectrum m / z: 681.2063 (calcd 681.2052). Theoretical elemental content (%) C 47 H 27 N3O3: C, 82.80; H, 3.99; N, 6.16. Found (%,): C, 82.76; H, 3.97; N, 6.21.

[0312] Synthesis Example 34: Preparation of compound 677:

[0313]

[0314] Following the same preparation procedure as in Synthesis Example 3, replacing A-89 with an equivalent molar of A-677, M-1 with an equivalent molar of M-538, compound 677 (14.91 g) was obtained with HPLC purity ≧ 99.94%. Mass spectrum m / z: 662.1471 (calcd 662.1487). Theoretical elemental content (%) C 44 H 26N2OS2: C, 79.73; H, 3.95; N, 4.23. Found (%,): C, 79.69; H, 3.98; N, 4.18.

[0315] Synthesis Example 35: Preparation of compound 709:

[0316]

[0317] Following the same preparation method as synthesis example 3, g-89 was replaced with equimolar of g-709, A-89 was replaced with equimolar of M-709, M-1 was replaced with equimolar of A-709, to give compound 709 (16.06 g) with HPLC purity > 99.97%. Mass spectrum m / z: 775.2142 (theoretical value: 775.2152). Theoretical elemental content (%) C 52 H 29 DN4O2S: C, 80.50; H, 4.03; N, 7.22. Found (%,): C, 80.47; H, 4.07; N, 7.18.

[0318] Synthesis Example 36: Preparation of compound 727:

[0319]

[0320] Following the same preparation method as synthesis example 3, A-89 was replaced with equimolar of M-124, M-1 was replaced with equimolar of B-330, to give compound 727 (15.33 g) with HPLC purity > 99.92%. Mass spectrum m / z: 719.1936 (theoretical value: 719.1919). Theoretical elemental content (%) C 51 H 29 NO2S: C, 85.09; H, 4.06; N, 1.95. Found (%,): C, 85.11; H, 4.02; N, 1.98.

[0321] Synthesis Example 37: Preparation of compound 734:

[0322]

[0323] Following the same preparation method as synthesis example 3, A-89 was replaced with equimolar of M-734, M-1 was replaced with equimolar of A-734, to give compound 734 (15.34 g) with HPLC purity > 99.95%. Mass spectrum m / z: 751.1451 (theoretical value: 751.1462). Theoretical elemental content (%) C 51 H 29NS3: C, 81.46; H, 3.89; N, 1.86. Found (mass %): C, 81.48; H, 3.93; N, 1.81.

[0324] Synthesis Example 38: Preparation of compound 778:

[0325]

[0326] According to the same preparation method as in Synthesis Example 8, g-124 was replaced with an equimolar amount of g-778, A-124 was replaced with an equimolar amount of A-778, M-1 was replaced with an equimolar amount of B-778, and M-124 was replaced with an equimolar amount of M-778, to obtain compound 778 (17.39 g) with an HPLC purity of > 99.90%. Mass spectrum m / z: 864.3517 (theoretical value: 864.3504). Theoretical elemental content (%) C 66 H 44 N2: C, 91.63; H, 5.13; N, 3.24. Found elemental content (%): C, 91.60; H, 5.09; N, 3.25.

[0327] [Device Example 1]

[0328] First, the ITO / Ag / ITO substrate was cleaned in distilled water three times, and ultrasonically washed for 15 minutes. After the distilled water cleaning, the substrate was ultrasonically washed in the order of isopropyl alcohol, acetone, and methanol, and then dried at 120°C.

[0329] A vacuum evaporation method was used to evaporate HI-1:P-1 = 93:3 (doping mass ratio) as a hole injection layer material to a thickness of 35 nm on the cleaned ITO / Ag / ITO substrate; HT-1 as a hole transport layer material to a thickness of 80 nm on the hole injection layer; RH-1:RD-1 = 98:2 (mass ratio) as a light-emitting layer to a thickness of 40 nm on the hole transport layer; HB-1 as a hole blocking layer material to a thickness of 40 nm on the light-emitting layer;

[0330] ET-1 and Liq (doping mass ratio of 1:1) were evaporated as an electron transport layer material to a thickness of 30 nm on the hole blocking layer; LiF was evaporated as an electron injection layer to a thickness of 1.0 nm on the electron transport layer; then Mg:Ag = 1:9 (mass ratio of 1:1) was evaporated as a cathode to a thickness of 11 nm on the electron injection layer; and compound 1 was evaporated as a cover layer to a thickness of 70 nm on the cathode, thereby preparing an organic electroluminescent device.

[0331]

[0332] [Device Example 2-37]

[0333] An organic electroluminescence device was produced in the same manner as in Device Example 1, except that Compound 89, Compound 96, Compound 97, Compound 98, Compound 110, Compound 124, Compound 160, Compound 168, Compound 173, Compound 180, Compound 187, Compound 223, Compound 276, Compound 288, Compound 291, Compound 330, Compound 476, Compound 499, Compound 508, Compound 516, Compound 538, Compound 552, Compound 580, Compound 587, Compound 588, Compound 615, Compound 621, Compound 626, Compound 659, Compound 669, Compound 670, Compound 677, Compound 709, Compound 727, Compound 734, Compound 778 of the present application was used instead of Compound 1 as the cover layer.

[0334] [Comparative Device Examples 1-2]

[0335] An organic electroluminescence device was produced in the same manner as in Device Example 1, except that Comparative Compound 1 or Comparative Compound 2 was used instead of Compound 1 as the cover layer.

[0336] A combined IVL test system consisting of test software, a computer, a K2400 digital source meter manufactured by Keithley Corporation, USA, and a PR788 spectral scan luminance meter manufactured by Photo Research Corporation, USA was used to test the luminous efficiency of the organic electroluminescence device. The M6000 OLED lifetime test system manufactured by McScience Corporation was used to test the lifetime. The test environment was an atmospheric environment, and the temperature was room temperature.

[0337] The results of the luminous characteristic tests of the organic electroluminescence devices of Device Examples 1 to 37 and Comparative Examples 1 to 2 of the present application are shown in Table 1 below.

[0338]

[0339]

[0340] As can be seen from the data in Table 1, the use of the cover layer compounds of the present application as the cover layer material in the organic electroluminescence device can effectively improve the light extraction efficiency of the device, reduce the total reflection of light inside the device, and increase the luminous efficiency and lifetime of the organic electroluminescence device, as compared with Comparative Device Examples 1-2.

[0341] It should be noted that the present application has been described in particular detail with reference to certain embodiments thereof. However, it will be understood by those of ordinary skill in the art that various changes in form and details can be made therein without departing from the spirit and scope of the present application. Accordingly, although specific embodiments have been illustrated and described herein, it should be appreciated that the present application is not limited to the details of the above-described embodiments, but can be implemented with various changes and modifications, without departing from the spirit and scope of the present application.

Claims

1. An organic electroluminescent device comprising an anode, a cathode, an organic layer, the organic layer comprising a cover layer, characterized in that, The cover layer has a structure as shown in Formula I; In Formula I, Ar1~Ar3are the same as or different from each other, at least one of which is selected from the group consisting of Formula II, and the rest are the same as or different from each other, selected from any one of the following groups: ； The t is the same as or different from each other, selected from CH or N atom, and 1, 2 or 3 t is selected from N atom; The R4is the same as or different from each other, selected from hydrogen, deuterium or any one of the following groups substituted or unsubstituted by one or more deuterium, C1~C6alkyl: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, adamantyl, norbornane, phenyl; The d1is selected from 0, 1, 2, 3, 4 or 5, the d2is selected from 0, 1, 2, 3 or 4, the d3is selected from 0, 1, 2, 3, 4, 5, 6 or 7, the d4is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, the d5is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, the d7is selected from 0, 1, 2, 3, 4, 5 or 6, the d8is selected from 0, 1, 2 or 3; said R b , R c are the same or different from each other and are selected from any one of the following groups, substituted or unsubstituted, with one or more deuterium, C1-C6alkyl: methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, phenyl, biphenyl, naphthyl; said R d each independently of one another, selected from any one of the following groups, substituted or unsubstituted, by one or more deuterium, C1-C6alkyl: phenyl, biphenyl, naphthyl; said L a , L b are identical or different from each other and are selected from any one of the following groups: a single bond, substituted or unsubstituted phenylene; wherein the substituents in the substituted phenylene are identical or different from each other and are selected from the group consisting of deuterium, fluorine, chlorine, bromine, iodine, cyano, trifluoromethyl, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl; The ring A is selected from a spiro ring structure, the spiro ring structure is selected from any one of the following groups: ； The R5is the same as or different from each other, selected from any one of hydrogen, deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, adamantyl, phenyl; The e3is independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; In Formula II, the L0is selected from any one of the following groups: said x1is selected from O, S, NR a a selected from substituted or unsubstituted C6-C12 aryl; wherein the substituents in the substituted C6-C12 aryl group are the same or different from each other and are selected from deuterium, fluorine, chlorine, bromine, iodine, cyano, trifluoromethyl, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl;​ " in the formula II is selected from any one of the following groups: " is selected from any one of the following groups: ； The R, R' is the same as or different from each other, selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen or any one of the following groups substituted or unsubstituted by one or more deuterium, C1~C6alkyl: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, phenyl; The m1is selected from 0, 1, 2, 3 or 4, the m2is selected from 0, 1, 2 or 3, the m3is selected from 0, 1 or 2, when there are two or more R, the two or more R are the same as or different from each other, or adjacent two R can be connected to form a substituted or unsubstituted benzene ring; wherein the substituents in the substituted benzene ring are the same as or different from each other, selected from deuterium, fluorine, chlorine, bromine, iodine, cyano, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl; The m' is selected from 0, 1 or 2; The x is the same as or different from each other, selected from CH or N atom, when x is bonded to other groups, the x is selected from C atom; The R2is selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1~C6alkyl; wherein the substituents in the substituted C1~C6alkyl are the same as or different from each other, selected from deuterium, fluorine, chlorine, bromine, iodine; The n is selected from 0, 1, 2 or 3; The L1~L3is the same as or different from each other, selected from a single bond or any one of the following groups: The L1~L3connected with L0is selected from a single bond.

2. An organic electroluminescent device according to claim 1, characterized in that The L0is selected from any one of the following groups: The cover layer has a structure as shown in Formula I; 。 3. An organic electroluminescent device according to claim 1, characterized in that " in the formula II is selected from any one of the following groups: " is selected from any one of the following groups: ； R, R' are the same or different from each other and are selected from the group consisting of hydrogen, deuterium, cyano, trifluoromethyl, halogen or any one of the following groups unsubstituted or substituted by one or more deuterium: methyl, ethyl, isopropyl, tert-butyl, naphthyl.

4. An organic electroluminescent device according to claim 1, characterized in that " in the formula II is selected from any one of the following groups: " is selected from any one of the following groups: 。 5. An organic electroluminescent device according to claim 1, characterized in that Ar1~Ar3are the same or different from each other, wherein at least one is selected from the group consisting of the following formula II and the remaining ones are the same or different from each other and are selected from any one of the following groups: ； R4are the same or different from each other and are selected from the group consisting of hydrogen, deuterium or any one of the following groups unsubstituted or substituted by one or more deuterium: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl; R b , R c are identical or different from each other and are selected from any one of the following groups, substituted or unsubstituted by one or more deuterium: methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, phenyl, biphenyl, naphthyl; said R d each independently of one another, are selected from any one of the following groups, substituted or unsubstituted by one or more deuterium: phenyl, biphenyl, naphthyl.

6. An organic electroluminescent device according to claim 1, characterized in that Ar1~Ar3are the same or different from each other, wherein at least one is selected from the group consisting of the following formula II and the remaining ones are the same or different from each other and are selected from any one of the following groups: 。 7. The organic electroluminescent device according to claim 1, wherein L1~L3are the same or different from each other and are selected from the group consisting of a single bond or any one of the following groups: 。 8. An organic electroluminescence device comprising an anode, a cathode, an organic layer, the organic layer comprising a cover layer, the cover layer being selected from any one of the following structures: 。

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