An organic electroluminescent device

Abstract

The application provides an organic electroluminescent device, which comprises a substrate, an anode, an organic layer and a cathode. The organic electroluminescent device contains a star-shaped amine derivative represented by formula I as a hole transport layer material. The structure is centered on benzene, three triarylamines are connected, and at least one of the three triarylamines is bridged with the central benzene, so that the compound has good hole transport performance and thermal stability. Meanwhile, the deuterium atoms contained in the structure can effectively adjust the HOMO energy level of the molecule, better match the adjacent functional layer, and be more conducive to improving the carrier mobility, further improving the luminous efficiency of the device, and specifically, the driving voltage is reduced, the luminous efficiency is increased, and the service life is prolonged.

Description

TECHNICAL FIELD

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

[0002] In recent years, the organic electroluminescence device (OLED) is widely researched as a new generation of display technology, and the OLED as the core of the display technology has unlimited development prospects. Compared with the traditional technology, the OLED technology has more excellent characteristics such as thinner and lighter, self-luminescence, high brightness, wide viewing angle, fast response speed, high luminous efficiency, wide color gamut, low driving voltage, etc., and has an irreplaceable position in various display devices and solid-state lighting and other high-end product fields.

[0003] The organic electroluminescence device is generally a sandwich structure, that is, the organic functional layer is sandwiched between the anode and the cathode on both sides of the device, and the organic functional layer includes, for example, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc. The light-emitting process of the organic electroluminescence device is essentially a process of realizing photoelectric conversion, and the light-emitting principle can be explained as follows: under the driving of an applied voltage, electrons enter the electron transport layer from the cathode, and holes enter the hole transport layer from the anode, and the two recombine in the light-emitting layer to generate excitons, and the excitons radiate back to the ground state and emit light. Organic electroluminescence materials can be roughly divided into electrode materials, electrode modification materials, charge transport materials and light-emitting materials. According to the properties of the transported charge, the charge transport material can be divided into hole transport material and electron transport material. The hole transport material is an important functional material in the organic electroluminescence device, which can effectively improve the injection efficiency and transport efficiency of the hole in the device, so that the hole transport rate and the electron transport rate are balanced. As a hole transport material with excellent performance must have the following points: (1) high hole mobility to ensure good hole transport performance; (2) good film-forming property to form a uniform and amorphous film without pinholes; (3) the amorphous film formed has good thermal stability; (4) has a suitable HOMO orbital energy level to ensure that the hole can be effectively injected and transported. The improvement and perfection of the performance of the hole transport material can directly and effectively improve the luminous brightness and efficiency of the light-emitting device, and its stability has a great influence on the service life of the device.

[0004] At present, the functional layer materials of most organic electroluminescence devices cannot meet the standards, especially the hole transport region materials, which generally have the problems of low hole mobility, poor film-forming property and poor thermal stability, thereby affecting the efficiency and service life of the device, so it is necessary to develop a hole transport material with higher performance in order to continuously improve the performance of the organic electroluminescence device. SUMMARY

[0005] In order to solve the problems in the prior art, the present application provides an organic electroluminescent device, which comprises a substrate, an anode, an organic layer and a cathode, wherein the organic layer comprises a hole transport layer containing a star-shaped amine derivative represented by Formula I,

[0006]

[0007] L0 to L3 are the same or different and selected from any one of a single bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C2-C30 heteroarylene group, a substituted or unsubstituted fused ring group of C3-C30 alicyclic and C6-C30 aromatic rings, and a combination thereof, and L1 to L3 are not simultaneously selected from a single bond;

[0008] x1 to x3 are the same or different and selected from 1, 2, 3, 4 or 5;

[0009] Ar1 to Ar6 are the same or different and selected from any one of a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 heteroaryl group, a substituted or unsubstituted fused ring group of C3-C30 alicyclic and C6-C30 aromatic rings, a substituted or unsubstituted fused ring group of C1-C25 aliphatic heterocyclic and C6-C30 aromatic rings, and when at least one of Ar1 and Ar2 is selected from a substituted or unsubstituted C2-C30 heteroaryl group or / and at least one of L0 connected to Ar1 and Ar2 is selected from a substituted or unsubstituted C2-C30 heteroarylene group, L1 is selected from a single bond, when at least one of Ar3 and Ar4 is selected from a substituted or unsubstituted C2-C30 heteroaryl group or / and at least one of L0 connected to Ar3 and Ar4 is selected from a substituted or unsubstituted C2-C30 heteroarylene group, L2 is selected from a single bond, and when at least one of Ar5 and Ar6 is selected from a substituted or unsubstituted C2-C30 heteroaryl group or / and at least one of L0 connected to Ar5 and Ar6 is selected from a substituted or unsubstituted C2-C30 heteroarylene group, L3 is selected from a single bond;

[0010] R is the same or different and selected from any one of hydrogen, deuterium, a cyano group, a halogen, a substituted or unsubstituted C1-C25 alkyl group, a substituted or unsubstituted C2-C25 alkenyl group, a substituted or unsubstituted C3-C25 cycloalkyl group, a substituted or unsubstituted C3-C25 cycloalkenyl group, a substituted or unsubstituted C1-C25 heterocycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted fused ring group of C3-C30 alicyclic and C6-C30 aromatic rings, a substituted or unsubstituted fused ring group of C1-C25 aliphatic heterocyclic and C6-C30 aromatic rings, and a substituted or unsubstituted C2-C30 heteroaryl group;

[0011] provided that at least one of the hydrogen atoms in Formula I is replaced by deuterium.

[0012] Beneficial effects: The organic electroluminescent device provided by the present application contains a star-shaped amine derivative represented by Formula I as a hole transport layer material, the structure of which is centered on benzene, connecting three triarylamines, and at least one of the three triarylamines is bridged to the central benzene, so that the compound has good hole transport performance and thermal stability; at the same time, the deuterium atoms contained in the structure can effectively adjust the HOMO energy level of the molecule, better match the adjacent functional layers, and more conducive to improving the carrier mobility, further improving the luminous efficiency of the device, specifically manifested as lower driving voltage, higher luminous efficiency, and longer service life. DETAILED DESCRIPTION

[0013] The present application will be further illustrated below in conjunction with specific examples, which should be understood as merely illustrating the present application but not limiting the scope of the present application. After reading the present application, those skilled in the art can make various equivalent modifications to the present application, which all fall within the scope of the present application.

[0014] 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.

[0015] In the compounds of the present application, the "substituted with deuterium" means that the hydrogen atoms in the compound or group are replaced by deuterium. "Partially substituted with deuterium" means that part of the hydrogen atoms in the compound or group are replaced by deuterium; "completely substituted with deuterium" means that all the hydrogen atoms in the compound or group are replaced by deuterium.

[0016] In the compounds of the present application, the hydrogen on the aromatic ring or aromatic group refers only to the hydrogen directly connected to the carbon / nitrogen of the aromatic ring, but does not include the hydrogen on the substituent of the aromatic ring. For example, the hydrogen on the benzene ring refers only to the hydrogen directly connected to the carbon of the benzene ring. Similarly.

[0017] The "*" appearing in the present application indicates the connection position with another substituent. When the position of the substituent on the aromatic ring is not fixed, it means that it can be connected to any one of the corresponding optional sites of the aromatic ring. For example, may represent Similarly.

[0018] In the present specification, when the bond where the substituent or the connection site passes through two or more rings, it means that it can be connected to any one of the two or two rings, and specifically can be connected to any one of the corresponding optional sites of the ring. For example, may represent may be represented by and so on.

[0019] The halogen includes fluorine, chlorine, bromine, iodine.

[0020] The alkyl group refers to a group obtained by removing one hydrogen atom from an alkane molecule, and can be a straight-chain alkyl group or a branched-chain alkyl group, preferably has 1 to 25 carbon atoms, more preferably has 1 to 15 carbon atoms, and further preferably has 1 to 6 carbon atoms. Specific examples can include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-methylpentyl, 2-ethylbutyl, and the like, but are not limited thereto.

[0021] The alkenyl group refers to a group obtained by removing one hydrogen atom from an alkene molecule, and can be a straight-chain alkenyl group or a branched-chain alkenyl group, preferably has 2 to 25 carbon atoms, more preferably has 2 to 15 carbon atoms, and further preferably has 2 to 6 carbon atoms. Specific examples can include ethenyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, 1-phenylethenyl-1-yl, 2-phenylethenyl-1-yl, and the like, but are not limited thereto.

[0022] The cycloalkyl group refers to a group obtained by removing one hydrogen atom from a cycloalkane molecule, and preferably has 3 to 25 carbon atoms, more preferably has 3 to 15 carbon atoms, and further preferably has 3 to 10 carbon atoms. Specific examples can include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, norbornyl, camphanyl, and the like, but are not limited thereto.

[0023] The cycloalkenyl group refers to a group obtained by removing one hydrogen atom from a cycloalkene molecule, and preferably has 3 to 25 carbon atoms, more preferably has 3 to 15 carbon atoms, and further preferably has 3 to 10 carbon atoms. Specific examples can include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, and the like, but are not limited thereto.

[0024] The heterocycloalkyl group refers to a group obtained by removing one hydrogen atom from a heterocycloalkane molecule, and the heteroatom includes, but is not limited to, S, O, N, Si, P, B, Se, preferably has 1 to 25 carbon atoms, more preferably has 3 to 15 carbon atoms, and further preferably has 2 to 7 carbon atoms. Specific examples can include aziridinyl, azetidinyl, tetrahydropyrrolyl, tetrahydropyridyl, piperidyl, azacycloheptyl, and the like, but are not limited thereto.

[0025] The aryl group refers to a group obtained by removing one hydrogen atom from the aromatic ring carbon of an aromatic hydrocarbon molecule, which can be a monocyclic aryl group, a polycyclic aryl group or a fused ring aryl group, preferably having 6-30 carbon atoms, more preferably 6-18 carbon atoms, further more preferably 6-14 carbon atoms, particularly preferably 6-12 carbon atoms, and specific examples can include a phenyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, a quinquephenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a fluorenyl group, a methylfluorenyl group, a phenylfluorenyl group, a spirobifluorenyl group, a triphenylenyl group, a benzofluorenyl group, etc., but are not limited thereto.

[0026] The heteroaryl group refers to a group obtained by replacing one or more aromatic ring carbons in an aryl group with a heteroatom, and the heteroatom includes but is not limited to S, O, N, Si, P, B, Se, and can be a monocyclic heteroaryl group or a fused ring heteroaryl group, preferably having 2-30 carbon atoms, more preferably 2-16 carbon atoms, further more preferably 3-9 carbon atoms. Specific examples can include a pyrrolyl group, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a triazinyl group, a thiophenyl group, a furanyl group, an oxazolyl group, a thiazolyl group, an imidazolyl group, a triazolyl group, an indolyl group, a quinolyl group, an isoquinolyl group, a benzothiophenyl group, a benzofuranyl group, a benzoxazolyl group, a benzothiazolyl group, a benzimidazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, a benzocarbazolyl group, a phenoxazinyl group, a quinoxazinyl group, a quinazolinyl group, etc., but are not limited thereto.

[0027] The fused ring group of aliphatic and aromatic rings refers to a group obtained by removing one hydrogen atom from the aliphatic ring and aromatic ring fused together, preferably having 7-30 carbon atoms, more preferably 7-18 carbon atoms, further more preferably 7-13 carbon atoms. Specific examples can include a benzocyclopropyl group, a benzocyclobutyl group, a benzocyclopentyl group, a benzocyclohexyl group, a benzocycloheptyl group, a benzocyclopentenyl group, a benzocyclohexenyl group, a benzocycloheptenyl group, a naphthocyclopropyl group, a naphthocyclobutyl group, a naphthocyclopentyl group, a naphthocyclohexyl group, etc., but are not limited thereto.

[0028] The fused ring group of aliphatic and aromatic rings refers to a group obtained by removing one hydrogen atom from the aliphatic ring and aromatic ring fused together, preferably having 7-30 carbon atoms, more preferably 7-18 carbon atoms, further more preferably 7-13 carbon atoms. Specific examples can include a benzocyclopropyl group, a benzocyclobutyl group, a benzocyclopentyl group, a benzocyclohexyl group, a benzocycloheptyl group, a benzocyclopentenyl group, a benzocyclohexenyl group, a benzocycloheptenyl group, a naphthocyclopropyl group, a naphthocyclobutyl group, a naphthocyclopentyl group, a naphthocyclohexyl group, etc., but are not limited thereto.

[0029] The aryl group refers to a group obtained by removing one hydrogen atom from the aromatic ring carbon of an aromatic hydrocarbon molecule, which can be a monocyclic aryl group, a polycyclic aryl group or a fused ring aryl group, preferably having 6-30 carbon atoms, more preferably 6-18 carbon atoms, further more preferably 6-14 carbon atoms, particularly preferably 6-12 carbon atoms, and specific examples can include a phenyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, a quinquephenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a fluorenyl group, a methylfluorenyl group, a phenylfluorenyl group, a spirobifluorenyl group, a triphenylenyl group, a benzofluorenyl group, etc., but are not limited thereto.

[0030] The divalent alicyclic and aromatic fused ring group means a group obtained by removing two hydrogen atoms from an alicyclic and aromatic fused ring, preferably having 7 to 30 carbon atoms, more preferably 7 to 18 carbon atoms, further preferably 7 to 13 carbon atoms. Specific examples include divalent benzocyclopropyl, divalent benzocyclobutyl, divalent benzocyclopentyl, divalent benzocyclohexyl, divalent benzocycloheptyl, divalent benzocyclopentenyl, divalent benzocyclohexenyl, divalent benzocycloheptenyl, divalent naphthocyclopentyl, divalent naphthocyclohexyl, and the like, but are not limited thereto.

[0031] The "substituted or unsubstituted" means unsubstituted or substituted with one or more selected from the group consisting of deuterium, a cyano group, a halogen atom, an amino group, a nitro group, a substituted or unsubstituted C1 to C25 alkyl group, a substituted or unsubstituted C2 to C25 alkenyl group, a substituted or unsubstituted C3 to C25 cycloalkyl group, a substituted or unsubstituted C3 to C25 cycloalkenyl group, a substituted or unsubstituted C1 to C25 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 alicyclic and C6 to C30 aromatic fused ring group, a substituted or unsubstituted C1 to C25 aliphatic and C6 to C30 aromatic fused ring group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C3 to C25 alicyclic and C2 to C30 heteroaromatic fused ring group, a substituted or unsubstituted C6 to C30 arylamine group, a substituted or unsubstituted C6 to C30 aryloxy group; preferably deuterium, fluorine, chlorine, bromine, iodine, a cyano group, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a cyclopropyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-pentenyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cyclopentadienyl group, a cyclohexadienyl group, an adamantyl group, a norbornyl group, a camphorinyl group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a triphenylenyl group, a perylenyl group, a pyrenyl group, a benzyl group, a benzocyclopropyl group, a benzocyclobutyl group, a benzocyclopentyl group, a benzocyclohexyl group, a benzocycloheptyl group, a benzocyclopentenyl group, a benzocyclohexenyl group, a benzocycloheptenyl group, a naphthocyclopropyl group, a naphthocyclobutyl group, a naphthocyclopentyl group, a naphthocyclohexyl group, a 9,9-dimethylfluorenyl group, a 9,9-diphenylfluorenyl group, a 9-methyl-9-phenylfluorenyl group, a spirobifluorenyl group, a diphenylamine group, a carbazolyl group, an acridinyl group, a furanyl group, a thienyl group, a dibenzofuranyl group, a dibenzothienyl group, a phenothiazinyl group, a phenoxazinyl group, an indolyl group, an aziridinyl group, an azetidinyl group, a pyrrolidinyl group, a piperidinyl group, an azepanyl group, and the like, and the above substituents can be further substituted with deuterium, an alkyl group, an alicyclic group, an aliphatic heterocyclic group, an aryl group, an alicyclic and aromatic fused ring group, an aliphatic and aromatic fused ring group, and the like, and in the case of being substituted with a plurality of substituents, the plurality of substituents are the same as or different from each other.

[0032] The "connection to form a ring" means that two groups are connected to each other by a chemical bond and optionally aromatized. Examples are as follows:

[0033]

[0034] In the present application, 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 both, and 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. Specific examples can include benzene, naphthalene, indene, cyclopentene, cyclopentane, cyclopentane benzene, cyclohexene, cyclohexane, cyclohexane benzene, fluorene, pyridine, quinoline, isoquinoline, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, phenanthrene, pyrene, etc., but are not limited thereto.

[0035] The present application provides an organic electroluminescent device, comprising a substrate, an anode, an organic layer, and a cathode, wherein the organic layer comprises a hole transport layer, and the hole transport layer contains a star-shaped amine derivative represented by Formula I,

[0036]

[0037] L0 to L3 are the same or different and are selected from any one of a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, a substituted or unsubstituted divalent C3 to C30 alicyclic ring and C6 to C30 aromatic ring fused ring group, and a combination thereof, and L1 to L3 are not simultaneously selected from a single bond;

[0038] x1 to x3 are the same or different and are selected from 1, 2, 3, 4, or 5;

[0039] Ar1 to Ar6 are the same or different and are selected from any one of a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C3 to C30 alicyclic ring and C6 to C30 aromatic ring fused ring group, a substituted or unsubstituted C1 to C25 aliphatic heterocyclic ring and C6 to C30 aromatic ring fused ring group, and when at least one of Ar1 and Ar2 is selected from a substituted or unsubstituted C2 to C30 heteroaryl group or / and at least one of L0 connected to Ar1 and Ar2 is selected from a substituted or unsubstituted C2 to C30 heteroarylene group, L1 is selected from a single bond, when at least one of Ar3 and Ar4 is selected from a substituted or unsubstituted C2 to C30 heteroaryl group or / and at least one of L0 connected to Ar3 and Ar4 is selected from a substituted or unsubstituted C2 to C30 heteroarylene group, L2 is selected from a single bond, and when at least one of Ar5 and Ar6 is selected from a substituted or unsubstituted C2 to C30 heteroaryl group or / and at least one of L0 connected to Ar5 and Ar6 is selected from a substituted or unsubstituted C2 to C30 heteroarylene group, L3 is selected from a single bond;

[0040] said R, the same or different, is selected from any one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C2-C25 alkenyl, substituted or unsubstituted C3-C25 cycloalkyl, substituted or unsubstituted C3-C25 cycloalkenyl, substituted or unsubstituted C1-C25 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 alicyclo and C6-C30 aryl fused ring group, substituted or unsubstituted C1-C25 alicyclo and C6-C30 aryl fused ring group, substituted or unsubstituted C2-C30 heteroaryl;

[0041] with the proviso that at least one deuterium atom is contained in formula I.

[0042] Preferably, said formula I is selected from any one of formula I-A to formula I-C,

[0043]

[0044] Preferably, said R, the same or different, in the present application is selected from any one of hydrogen, deuterium, cyano, halogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, adamantyl, norbornyl, bornyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylenyl, fluorenyl, benzocyclopropyl, benzocyclobutyl, benzocyclopentyl, benzocyclohexyl, benzocycloheptyl, benzocyclopentenyl, benzocyclohexenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl;

[0045] said R can be unsubstituted by deuterium, partially substituted by deuterium, fully substituted by deuterium.

[0046] Preferably, said R, the same or different, in the present application is selected from any one of hydrogen, deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, phenyl, biphenyl, deuterated methyl, deuterated ethyl, deuterated n-propyl, deuterated isopropyl, deuterated n-butyl, deuterated tert-butyl, deuterated pentyl, deuterated hexyl, deuterated cyclopropyl, deuterated cyclobutyl, deuterated cyclopentyl, deuterated cyclohexyl, deuterated cycloheptyl, deuterated adamantyl, deuterated norbornyl, deuterated phenyl, deuterated biphenyl.

[0047] Preferably, said R, the same or different, in the present application is selected from any one of deuterium or the following groups:

[0048]

[0049] Preferably, L0to L3are the same or different and are selected from any one of a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted anthracenylene, substituted or unsubstituted phenanthrenylene, substituted or unsubstituted triphenylenylene, substituted or unsubstituted pyrenylene, substituted or unsubstituted fluorenylene, substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted dibenzothiophenylene, substituted or unsubstituted carbazolylene, substituted or unsubstituted benzocyclopropylene, substituted or unsubstituted benzocyclobutylene, substituted or unsubstituted benzocyclopentylene, substituted or unsubstituted benzocyclohexylene, substituted or unsubstituted benzocycloheptylene, substituted or unsubstituted benzocyclobutendiyl, substituted or unsubstituted benzocyclopentadiyl, substituted or unsubstituted benzocyclohexadiyl, substituted or unsubstituted benzocycloheptadiyl, and combinations thereof, and L1to L3are not simultaneously selected from a single bond.

[0050] Preferably, L0to L3are the same or different and are selected from any one of a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted anthracenylene, substituted or unsubstituted phenanthrenylene, substituted or unsubstituted triphenylenylene, substituted or unsubstituted pyrenylene, substituted or unsubstituted fluorenylene, substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted dibenzothiophenylene, substituted or unsubstituted carbazolylene, substituted or unsubstituted benzocyclopropylene, substituted or unsubstituted benzocyclobutylene, substituted or unsubstituted benzocyclopentylene, substituted or unsubstituted benzocyclohexylene, substituted or unsubstituted benzocycloheptylene, substituted or unsubstituted benzocyclobutendiyl, substituted or unsubstituted benzocyclopentadiyl, substituted or unsubstituted benzocyclohexadiyl, substituted or unsubstituted benzocycloheptadiyl, and combinations thereof, and L1to L3are not simultaneously selected from a single bond.

[0051]

[0052]

[0053] R1is selected from any one of hydrogen, deuterium, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, propenyl, butenyl, pentenyl, hexenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, or adjacent two R1s are connected to each other to form a substituted or unsubstituted ring;

[0054] R1may be unsubstituted, partially substituted, or fully substituted with deuterium.

[0055] m1is selected from 0, 1, 2, 3, or 4; m2is selected from 0, 1, or 2; m3is selected from 0, 1, 2, 3, 4, or 5; m4is selected from 0, 1, 2, 3, 4, 5, or 6; m5is selected from 0, 1, 2, 3, 4, 5, 6, 7, or 8; m6is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; m7is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; m8is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14; m9is selected from 0, 1, 2, 3, 4, 5, 6, or 7; m 10 is selected from 0, 1, 2, or 3.

[0056] Preferably, Ar1 to Ar6 are selected from any one of the following groups:

[0057]

[0058]

[0059] The R2s, whether identical or different, are selected from any one of hydrogen, deuterium, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornel, camphenyl, aziridinyl, aziridine, azircyclobutyl, pyrrolyl, piperidinyl, azircycloheptyl, phenyl, naphthyl, anthracene, phenanthrene, triphenylene, biphenyl, terphenyl, benzocyclopentyl, benzocyclohexyl, benzocyclopentenyl, benzocyclohexenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, dibenzofuranyl, dibenzothiopheneyl, 9-phenylcarbazoyl, or adjacent R2s connected to each other to form substituted or unsubstituted rings;

[0060] The R2 may be unreplaced by deuterium, partially replaced by deuterium, or completely replaced by deuterium;

[0061] The n1 is selected from 0, 1, 2, 3, 4, or 5; the n2 is selected from 0, 1, 2, 3, or 4; the n3 is selected from 0, 1, 2, or 3; the n4 is selected from 0, 1, or 2; the n5 is selected from 0, 1, 2, 3, 4, 5, or 6; the n6 is selected from 0, 1, 2, 3, 4, 5, 6, 7, or 8; the n7 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; the n8 is selected from 0 or 1; the n9 is selected from 0, 1, 2, 3, 4, 5, 6, or 7; the n 10 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9;

[0062] The R a R b R c R d The same or different from any one selected from hydrogen, deuterium, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornel, substituted or unsubstituted camphenyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracene, substituted or unsubstituted biphenyl, substituted or unsubstituted phenanthrene, substituted or unsubstituted triphenylene, or R a R b They connect with each other to form substituted or unsubstituted rings.

[0063] Preferably, Ar1 to Ar6 are selected from any one of the following groups,

[0064]

[0065]

[0066]

[0067]

[0068] Preferably, at least one of Ar1, Ar2, Ar3, Ar4, Ar5, and Ar6 is substituted with a deuterium atom.

[0069] Preferably, at least one of Ar1, Ar2, Ar3, Ar4, Ar5, and Ar6 is substituted with one, two, three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty, twenty-one, twenty-two, twenty-three, twenty-four, or twenty-five deuterium atoms.

[0070] Preferably, at least one of L0, L1, L2, and L3 is substituted with a deuterium atom.

[0071] Preferably, at least one of L0, L1, L2, and L3 is substituted with one, two, three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty, twenty-one, or twenty-two deuterium atoms.

[0072] Preferably, at least one of R is selected from deuterium or a deuterated group.

[0073] Preferably, at least one of the deuterated groups of R is substituted with one, two, three, four, five, six, seven, eight, nine, ten, eleven, or twelve deuterium atoms.

[0074] Preferably, at least one of the rings directly connected to the N atom (connected to L0) in the structure of Formula I is substituted with more than two deuterium atoms; more preferably, at least three, at least four, or at least five deuterium atoms; and still more preferably, all the hydrogens on the ring that are not substituted by other groups are substituted with deuterium. Here, the hydrogens on the ring refer to the hydrogens connected to the ring carbon atoms of the ring, and the hydrogens on the substituents of the ring are not specifically limited.

[0075] In the present application, the ring directly connected to the N atom (connected to L0) in the structure of Formula I includes at least one of the following:

[0076] i. L0, in the case of not being a bond, the ring directly connected to the N atom;

[0077] ii. Ar1, Ar2, Ar3, Ar4, Ar5 or Ar6, in the case of L0 connected thereto being a bond, the ring directly connected to the N atom;

[0078] iii. L1, L2 or L3, in the case of not being a bond, the ring directly connected to the N atom.

[0079] In the present application, the ring directly connected to the N atom (connected to L0) in the structure of Formula I refers to a monocyclic ring, and the monocyclic ring directly connected to the N atom in a fused ring and a spiro ring.

[0080] Preferably, the ring directly connected to the N atom (connected to L0) in the structure of Formula I is selected from a benzene ring.

[0081] Therefore, preferably, in the benzene ring directly connected to the N atom (connected to L0) in the structure of Formula I, at least one benzene ring has two or more deuteriums substituted thereon; more preferably, at least three, at least four or five deuteriums are substituted thereon; and still more preferably, all the hydrogens on the benzene ring which are not substituted by other groups are substituted by deuteriums. Here, the hydrogens on the benzene ring refer only to the hydrogens connected to the ring carbon atoms of the benzene ring, and the hydrogens on the substituents of the benzene ring are not specifically limited.

[0082] Further preferably, in the aromatic group directly connected to the N atom (connected to L0) in the structure of Formula I, at least one aromatic group has all the hydrogens thereon which are not substituted by other groups substituted by deuteriums.

[0083] In the present application, the aromatic group directly connected to the N atom (connected to L0) in the structure of Formula I includes at least one of the following:

[0084] i. L0, in the case of not being a bond, the aromatic group in L0 connected to the N atom;

[0085] ii. Ar1, Ar2, Ar3, Ar4, Ar5 or Ar6, in the case of L0 connected thereto being a bond, the aromatic group in Ar1, Ar2, Ar3, Ar4, Ar5 or Ar6 connected to the N atom;

[0086] iii. L1, L2 or L3, in the case of not being a bond, the ring directly connected to the N atom.

[0087] Most preferably, Formula I is selected from any one of the following groups,

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108] The above lists some specific structural forms of the star-shaped amine derivatives of formula I according to the present application, but the present application is not limited to these listed chemical structures, and any structure based on the structure of formula I and having substituents as defined above should be included.

[0109] The organic electroluminescent device according to the present application can further comprise a light-emitting layer, a hole-injection layer, an electron-transporting layer, an electron-injection layer, a hole-blocking layer, an electron-blocking layer, and a cover layer, in addition to the hole-transporting layer, and each of the organic layers can be formed as a single layer or as a plurality of layers stacked together, and each of the organic layers can comprise one or more materials.

[0110] Preferably, the hole transport layer comprises a first hole transport layer and / or a second hole transport layer, the second hole transport layer being located between the first hole transport layer and the cathode.

[0111] Preferably, the first hole transport layer is located between the anode and the light-emitting layer, and the second hole transport layer is located between the first hole transport layer and the light-emitting layer.

[0112] The materials of each layer in the organic electroluminescent device are not particularly limited in the present application, and the materials known in the art can be used. The following describes each organic functional layer of the organic electroluminescent device mentioned above and the electrodes on both sides of the device, respectively:

[0113] The substrate is the connection point of the organic electroluminescent device and the external circuit, and a material with good stability is preferred. Common substrate materials include glass, resin, silicon, metal foil, etc., but are not limited thereto.

[0114] The anode is preferably a material with good conductivity and a high work function, including conductive oxides, metals, etc. The conductive oxides include indium tin oxide (ITO), indium zinc oxide (IZO), indium oxide (InO), zinc oxide (ZnO), etc., and the metals include silver (Ag), aluminum (Al), platinum (Pt), gold (Au), palladium (Pd), nickel (Ni), etc. The anode can also be composed of multiple materials stacked together, such as zinc oxide / aluminum (ZnO / Al), silver / indium tin oxide (Ag / ITO), aluminum / nickel (Al / Ni), aluminum / platinum (Al / Pt), etc., but the anode materials are not limited thereto.

[0115] The cathode is preferably a material with good conductivity and a low work function, including metals, metal alloys, etc. The metals include aluminum (Al), silver (Ag), gold (Au), lead (Pb), lithium (Li), magnesium (Mg), and the metal alloys include magnesium-silver alloy (Mg / Al), lithium-aluminum alloy (Li / Al), calcium / silver (Ca / Ag), etc., but the cathode materials are not limited thereto.

[0116] The hole injection layer is preferably a material with a NOMO energy level matching the anode, including metal compounds, arylamine derivatives, phthalocyanine compounds, arylamine compounds, polymers, etc. The metal compounds include molybdenum trioxide (MoO3), vanadium pentoxide (V2O5), tungsten trioxide (WO3), nickel oxide (NiO), titanium dioxide (TiO2), etc., the phthalocyanine compounds include copper phthalocyanine (CuPc), titanium oxide phthalocyanine (TiOPC), etc., the arylamine compounds generally include 4,4',4"-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (m-MTDATA), 4,4',4"-tris[2-naphthylphenylamino]triphenylamine (2T-NATA), etc., and the polymers include poly(3,4-ethylenedioxythiophene) / poly(styrenesulfonic acid) (PEDOT / PSS), etc., but the hole injection material is not limited thereto.

[0117] The hole transport layer is preferably a material with high hole mobility, including arylamine derivatives, polymers, etc. The arylamine derivatives include N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), N4,N4,N4',N4'-tetra([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine, 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline] (TAPC), N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), 2,2,7,7-tetrakis(diphenylamino)-9,9-spirobifluorene (Spiro-TAD), 4,4',4"-tris(carbazol-9-yl)triphenylamine (TCTA), etc., and the polymers include polyvinylcarbazole (PVCA), etc., but the hole transport material is not limited thereto.

[0118] The light-emitting layer contains a host material and a plurality of guest materials. The light-emitting layer can be a single light-emitting layer or a composite light-emitting layer stacked laterally or longitudinally. The host material can be an anthracene derivative, a pyrene derivative, a naphthalene derivative, a pentacene derivative, a phenanthrene derivative, a fluoranthene derivative, a carbazole derivative, a dibenzofuran derivative, a dibenzothiophene derivative, a pyrimidine derivative, or the like. Specific examples include 4,4'-bis(9-carbazolyl)biphenyl (CBP), 9,10-di(2-naphthyl)anthracene (ADN), 4,4-bis(9-carbazolyl)-biphenyl (CPB), 9,9'-(1,3-phenyl)di-9H-carbazole (mCP), 4,4',4"-tris(carbazol-9-yl)triphenylamine (TCTA), 9,10-di(1-naphthyl)anthracene (a-ADN), N,N'-di-(1-naphthyl)-N,N'-diphenyl-[1,1':4',1":4",1"'-quaterphenyl]-4,4"-diamine (4PNPB), 1,3,5-tris(9-carbazolyl)benzene (TCP), and the like, but is not limited thereto. The guest material can be a fused polycyclic aromatic derivative, a styrylamine derivative, a fused ring amine derivative, a boron-containing compound, a pyrrole derivative, an indole derivative, a carbazole derivative, a heavy metal complex, a phosphorescent rare earth metal complex, or the like. Specific examples include 6-(4-(diphenylamino(phenyl)-N,N-diphenylpyren-1-ylamine) (DPAP-DPPA), 2,5,8,11-tetra-t-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)picolato-iridium (FIrpic), tris(2-phenylpyridine)iridium (Ir(ppy)3), bis(2-phenylpyridine)iridium acetylacetonate (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, but is not limited thereto.

[0119] The electron transport layer preferably has a material with high electron affinity and electron transport capacity, including quinoline, imidazole, phenanthroline derivative, triazole, metal complex, triazine, pyridine, etc. Quinoline includes 8-hydroxyquinoline-lithium (LiQ), etc., imidazole includes 1,3,5-tris(1-phenyl-1H-benzimidazole-2-yl)benzene (TPBi), etc., phenanthroline derivative includes 2,9-(dimethyl)-4,7-diphenyl-1,10-phenanthroline (BCP), 2-(naphthalene-2-yl)-4,7-(diphenyl)-1,10-phenanthroline (HNBphen), etc., triazole includes 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), etc., metal complex includes tris(8-hydroxyquinoline)aluminum (III) (Alq3), etc., triazine includes 4,4'-bis(4,6-diphenyl-1,3,5-triazinyl)diphenyl (BTB), etc., pyridine includes 1,3,5-tris[(3-pyridyl)-phenyl]benzene (TmPyPB), etc., but the electron transport material is not limited thereto.

[0120] The electron injection layer preferably has a material with good electron injection capacity to reduce the interface barrier between the cathode and the electron transport layer, including metal salt, metal oxide, metal, etc. Metal salt includes lithium fluoride (LiF), lithium 8-hydroxyquinolate (Liq), sodium fluoride (NaF), rubidium fluoride (RbF), cesium fluoride (CsF), magnesium phosphide (MgP), cesium carbonate (Cs2CO3), etc., metal oxide includes lithium oxide (Li2O), lithium boron oxide (LiBO2), aluminum oxide (Al2O3), vanadium oxide (V2O5), etc., metal includes lithium (Li), cesium (Cs), etc., but the electron injection material is not limited thereto.

[0121] The cover layer preferably has a material with high glass transition temperature and excellent light extraction performance, including metal compound, arylamine derivative, carbazole derivative, etc. Metal compound includes tris(8-hydroxyquinoline)aluminum (III) (Alq3), etc., arylamine derivative includes N,N'-di(naphthalene-1-yl)-N,N'-di(phenyl)-2,2'-dimethylbenzidine (NPD), etc., carbazole derivative includes 4,4'-di(9-carbazole)biphenyl (CBP), etc., but the cover layer material is not limited thereto.

[0122] The present application does not have special restrictions on the thickness of each organic layer of the organic electroluminescent device, and the thickness commonly used in the art can be used.

[0123] The preparation method of the organic electroluminescent device of the present application is not particularly limited, and vacuum evaporation, spin coating, vapor deposition, blade coating, laser thermal transfer printing, electrostatic spraying, sputtering, screen printing, slot coating, dip coating, etc. can be used, but are not limited thereto.

[0124] The organic electroluminescent device described in the present application can be widely applied in the fields of panel display, lighting source, flexible OLED, electronic paper, organic solar cell, organic photoreceptor or organic thin film transistor, indicator, signal lamp, etc., but is not limited thereto.

[0125] The present application is explained in more detail by the following examples, but is not intended to be limited thereby. On the basis of 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 inventive labor.

[0126] Synthetic examples

[0127] The method for preparing the compound represented by Formula 1 of the present application is not particularly limited, and can be prepared by a method well known to those skilled in the art. The star-shaped amine derivative of Formula 1 of the present application can be prepared by the synthetic routes listed below.

[0128]

[0129] wherein each X n is the same or different, selected from Cl, Br, I; each B n is the same or different, selected from or a hydrogen atom.

[0130] Raw materials and reagents: The present application does not have a particular limitation on the raw materials or reagents used in the following synthetic examples, which can be commercially available products or prepared by a method well known to those skilled in the art. The raw materials and reagents are all reagent pure.

[0131] Instrument: Mass spectrometer is G2-Si quadrupole tandem time-of-flight high-resolution mass spectrometer produced by Waters Company in the UK; elemental analyzer is Vario EL cube type organic elemental analyzer produced by Elementar Company in Germany.

[0132] Synthesis of intermediate c-6 in [Example 1]

[0133]

[0134] To the reaction flask was added a-6 (23.56 g, 240.00 mmol), b-6 (68.93 g, 240.00 mmol), Pd(dppf)Cl2(1.76 g, 2.40 mmol), NaOt-Bu (46.13 g, 480.00 mmol), toluene (600 ml) under nitrogen protection, heated reaction for 3.5 hours. After the reaction was completed, it was cooled to room temperature, water was added, extracted with dichloromethane, the organic layer was dried over anhydrous magnesium sulfate, filtered, the solvent was removed under reduced pressure, recrystallized with ethyl acetate to obtain intermediate c-6 (61.38 g, yield 84%), the solid purity was ≥ 99.43% detected by HPLC. Mass spectrum m / z: 304.1972 (theoretical value: 304.1988).

[0135] According to the above method, the raw material a and the raw material b were replaced with equal moles to synthesize the following intermediate c:

[0136]

[0137]

[0138]

[0139] Synthesis of intermediate g-6

[0140]

[0141] Synthesis of intermediate f-6

[0142] To the reaction flask was added d-6 (26.14 g, 150.00 mmol), e-6 (28.72 g, 150.00 mmol), Pd(OAc)2(0.34 g, 1.50 mmol), P(t-Bu)3(0.91 g, 4.50 mmol), NaOt-Bu (28.83 g, 300.00 mmol), toluene (450 ml) under nitrogen protection, heated reaction for 4.5 hours. After the reaction was completed, it was cooled to room temperature, water was added, extracted with dichloromethane, the organic layer was dried over anhydrous magnesium sulfate, filtered, the solvent was removed under reduced pressure, recrystallized with ethyl acetate to obtain intermediate f-6 (35.03 g, yield 82%), the solid purity was ≥ 99.58% detected by HPLC. Mass spectrum m / z: 284.1138 (theoretical value: 284.1129).

[0143] Synthesis of intermediate g-6

[0144] To a reaction flask, under nitrogen protection, were added intermediate f-6 (34.18 g, 120.00 mmol), B2Pin2 (30.47 g, 120.00 mmol), Pd(dppf)Cl2(2.63 g, 3.60 mmol), KOAc (35.33 g, 360.00 mmol), DMF (400 mL), heated to react for 5.5 hours, after the reaction was completed, distilled water was added, extracted with dichloromethane, the organic phase was separated and washed with distilled water three times, dried over anhydrous magnesium sulfate, concentrated by rotary evaporation, crystallized by cooling, suction filtered, and the obtained solid was recrystallized with toluene to obtain intermediate g-6 (37.93 g, yield 84%); HPLC purity ≥ 99.66%. Mass spectrum m / z: 376.2381 (theoretical value: 376.2370).

[0145] According to the above method, the raw material c / d and the raw material e were replaced with equal moles to synthesize the following intermediate g:

[0146]

[0147]

[0148]

[0149]

[0150]

[0151] [Example 3] Synthesis of compound 6

[0152]

[0153] Synthesis of intermediate B-6

[0154] To a reaction flask, under nitrogen protection, were added A-6 (24.33 g, 90.00 mmol), c-6 (56.17 g, 184.50 mmol), Pd(OAc)2(0.20 g, 0.90 mmol), BINAP (1.68 g, 2.70 mmol), NaOt-Bu (17.30 g, 180.00 mmol), then 300 mL of toluene was added, heated to reflux for 7 hours, after the reaction was completed. Naturally cooled to room temperature, filtered with diatomite, concentrated the filtrate by distillation under reduced pressure, purified by column chromatography (n-hexane: ethyl acetate = 10:1) to obtain intermediate B-6 (48.43 g, yield 75%), HPLC detected solid purity ≥ 99.84%. Mass spectrum m / z: 716.3754 (theoretical value: 716.3742).

[0155] Synthesis of compound 6

[0156] To a reaction flask, under nitrogen protection, were added intermediate B-6 (46.63 g, 65.00 mmol), intermediate g-6 (25.68 g, 68.25 mmol), K2CO3 (26.95 g, 195.00 mmol), Pd(PPh3)4 (0.75 g, 0.65 mmol) in sequence, 250 mL of tetrahydrofuran was added, the mixture was stirred, the above reaction system was heated to reflux for 9.5 hours. After the reaction was completed, it was cooled to room temperature, toluene was added, and the phases were separated, the toluene phase was washed with distilled water three times, dried over anhydrous magnesium sulfate, the solvent was concentrated by rotary evaporation, crystallization was performed by cooling, suction filtration was performed, the obtained solid was recrystallized with toluene, to obtain compound 6 (41.77 g, yield 69%). The solid purity was detected by HPLC to be ≥99.95%. Mass spectrum m / z: 930.5482 (theoretical value: 930.5494). Theoretical elemental content (%) 68 H 42 D 15 N3: C, 87.70; H, 7.79; N, 4.51. Measured elemental content (%): C, 87.73; H, 7.76; N, 4.53.

[0157] [Example 4] Synthesis of compound 33

[0158]

[0159] Synthesis of intermediate B-33

[0160] To a reaction flask, under nitrogen protection, were added A-33 (31.73 g, 100.00 mmol), d-33 (25.04 g, 100.00 mmol), Pd(OAc)2 (0.22 g, 1.00 mmol), P(t-Bu)3 (0.61 g, 3.00 mmol), NaOt-Bu (19.22 g, 200.00 mmol), then 300 mL of toluene was added, the reaction was heated to reflux for 6.5 hours, after the reaction was completed. It was naturally cooled to room temperature, filtered with diatomite, the filtrate was concentrated by distillation under reduced pressure, purified by column chromatography (n-hexane: ethyl acetate = 20: 1) to obtain intermediate B-33 (32.54 g, yield 74%), the solid purity was detected by HPLC to be ≥99.76%. Mass spectrum m / z: 438.0555 (theoretical value: 438.0547).

[0161] Synthesis of intermediate C-33

[0162] To a reaction flask, under nitrogen protection, were added intermediate B-33 (30.79 g, 70.00 mmol), intermediate g-33 (34.43 g, 73.50 mmol), K2CO3 (29.02 g, 210.00 mmol), Pd(PPh3)4 (0.81 g, 0.70 mmol) in sequence, 250 mL of tetrahydrofuran was added, the mixture was stirred, the above reaction system was heated to reflux for 8 hours. After the reaction was completed, it was cooled to room temperature, toluene was added and the phases were separated, the toluene phase was washed with distilled water three times, dried over anhydrous magnesium sulfate, the solvent was concentrated by rotary evaporation, crystallization was performed by cooling, the obtained solid was recrystallized with toluene / ethanol (10 / 1) to obtain intermediate C-33 (34.37 g, yield 70%). The solid purity was ≥99.82% detected by HPLC. Mass spectrum m / z: 700.3438 (theoretical value: 700.3429).

[0163] Synthesis of compound 33

[0164] To a reaction flask, under nitrogen protection, were added intermediate C-33 (31.56 g, 45.00 mmol), intermediate g1-33 (23.27 g, 47.25 mmol), KOAc (13.25 g, 135.00 mmol), Pd(dppf)Cl2 (0.33 g, 0.45 mmol) in sequence, 200 mL of tetrahydrofuran was added, the mixture was stirred, the above reaction system was heated to reflux for 10.5 hours. After the reaction was completed, it was cooled to room temperature, toluene was added and the phases were separated, the toluene phase was washed with distilled water three times, dried over anhydrous magnesium sulfate, the solvent was concentrated by rotary evaporation, crystallization was performed by cooling, the obtained solid was recrystallized with toluene to obtain compound 33 (31.10 g, yield 67%). The solid purity was ≥99.96% detected by HPLC. Mass spectrum m / z: 1030.5818 (theoretical value: 1030.5807). Theoretical elemental content (%) 76 H 46 D 15 N3: C, 88.50; H, 7.42; N, 4.07. Found elemental content (%): C, 88.52; H, 7.39; N, 4.09.

[0165] [Example 5] Synthesis of compound 62

[0166]

[0167] According to the method of Example 3, c-6 was replaced by equimolar d-6, g-6 was replaced by equimolar g-62 to obtain compound 62 (35.81 g), the solid purity was ≥99.91% detected by HPLC. Mass spectrum m / z: 786.4568 (theoretical value: 786.4555). Theoretical elemental content (%) 57H 30 D 15 N3: C, 86.98; H, 7.68; N, 5.34. Found (%): C, 86.95; H, 7.69; N, 5.32.

[0168] [Example 6] Synthesis of compound 97

[0169]

[0170] According to the method of Example 3, replace A-6 with equal molar of A-97, c-6 with equal molar of d-97, g-6 with equal molar of g-97, to obtain compound 97 (36.56 g), solid purity ≥ 99.92% by HPLC. Mass m / z: 814.4039 (theoretical value: 814.4053). Theoretical elemental content (%) C 60 H 38 D7N3: C, 88.42; H, 6.43; N, 5.16. Found (%): C, 88.44; H, 6.41; N, 5.13.

[0171] [Example 7] Synthesis of compound 114

[0172]

[0173] According to the method of Example 3, replace c-6 with equal molar of c-114, g-6 with equal molar of g-114, to obtain compound 114 (40.28 g), solid purity ≥ 99.97% by HPLC. Mass m / z: 910.5637 (theoretical value: 910.5621). Theoretical elemental content (%) C 66 H 22 D 27 N3: C, 86.99; H, 8.40; N, 4.61. Found (%): C, 86.97; H, 8.43; N, 4.63.

[0174] [Example 8] Synthesis of compound 128

[0175]

[0176] According to the method of Example 3, replace c-6 with equal molar of c-128, g-6 with equal molar of g-128, to obtain compound 128 (37.64 g), solid purity ≥ 99.96% by HPLC. Mass m / z: 838.5819 (theoretical value: 838.5807). Theoretical elemental content (%) C 60 H 46 D 15N3: C, 85.87; H, 9.12; N, 5.01. Found (mass %): C, 85.85; H, 9.13; N, 5.03.

[0177] [Example 9] Synthesis of compound 144

[0178]

[0179] According to the method of Example 3, c-6 was replaced with an equimolar amount of d-144 and g-6 was replaced with an equimolar amount of g-144 to obtain compound 144 (43.59 g) with a solid purity > 99.92% as determined by HPLC. Mass spectrum m / z: 985.4320 (theoretical value: 985.4334). Theoretical elemental content (%) C 74 H 47 D4N3: C, 90.12; H, 5.62; N, 4.26. Found elemental content (%) C, 90.15; H, 5.64; N, 4.24.

[0180] [Example 10] Synthesis of compound 151

[0181]

[0182] Synthesis of intermediate B-151

[0183] According to the method of synthesis of intermediate B-33, d-33 was replaced with an equimolar amount of d-6 to obtain intermediate B-151 (26.19 g, yield 72%) with a solid purity > 99.79% as determined by HPLC. Mass spectrum m / z: 362.0245 (theoretical value: 362.0234).

[0184] Synthesis of intermediate C-151

[0185] According to the method of synthesis of intermediate C-33, B-33 was replaced with an equimolar amount of B-151 and g-33 was replaced with an equimolar amount of g-151 to obtain intermediate C-151 (32.86 g, yield 69%). HPLC determined a solid purity > 99.85%. Mass spectrum m / z: 679.2811 (theoretical value: 679.2803).

[0186] Synthesis of compound 151

[0187] To a reaction flask was added intermediate C-151 (27.21 g, 40.00 mmol), c-151 (11.94 g, 40.00 mmol), Pd2(dba)3(0.37 g, 0.40 mmol), P(t-Bu)3(0.24 g, 1.20 mmol), NaOt-Bu (7.69 g, 80.00 mmol) under nitrogen protection, then 200 mL of toluene was added, heated to reflux for 7 hours, after the reaction was completed. Naturally cooled to room temperature, filtered with diatomite, concentrated the filtrate by distillation under reduced pressure, recrystallized with toluene to obtain compound 151 (24.88 g, yield 66%), the solid purity was ≥ 99.94% detected by HPLC. Mass m / z: 941.4568 (theoretical value: 941.4554). Theoretical elemental content (%) C 70 H 39 D 10 N3: C, 89.23; H, 6.31; N, 4.46. Found elemental content (%) C, 89.21; H, 6.32; N, 4.49.

[0188] [Example 11] Synthesis of compound 160

[0189]

[0190] According to the method of Example 3, c-6 was replaced with an equal mole of c-160, g-6 was replaced with an equal mole of g-160 to obtain compound 160 (45.09 g), the solid purity was ≥ 99.96% detected by HPLC. Mass m / z: 1004.5757 (theoretical value: 1004.5743). Theoretical elemental content (%) C 74 H 56 D9N3: C, 88.40; H, 7.42; N, 4.18. Found elemental content (%) C, 88.42; H, 7.43; N, 4.17.

[0191] [Example 12] Synthesis of compound 162

[0192]

[0193] According to the method of Example 3, c-6 was replaced with an equal mole of c-162, g-6 was replaced with an equal mole of g-162 to obtain compound 162 (42.98 g), the solid purity was ≥ 99.95% detected by HPLC. Mass m / z: 971.4980 (theoretical value: 971.4993). Theoretical elemental content (%) C 72 H 41 D 12N3: C, 87.67; H, 8.07; N, 4.26. Found: C, 87.69; H, 8.04; N, 4.29.

[0194] [Example 13] Synthesis of compound 185

[0195]

[0196] According to the method of Example 3, c-6 was replaced with an equivalent molar of c-185, g-6 was replaced with an equivalent molar of g-185, to obtain compound 185 (23.56 g) with solid purity > 99.94% as detected by HPLC. Mass spectrum m / z: 891.5878 (theoretical value: 891.5869). Theoretical elemental content (%) C 62 H 37 D 20 N5: C, 83.46; H, 8.69; N, 7.85. Found: C, 83.43; H, 8.71; N, 7.82.

[0197] [Example 14] Synthesis of compound 206

[0198]

[0199] According to the method of Example 3, c-6 was replaced with an equivalent molar of c-206, g-6 was replaced with an equivalent molar of g-206, to obtain compound 206 (44.24 g) with solid purity > 99.95% as detected by HPLC. Mass spectrum m / z: 985.6127 (theoretical value: 985.6119). Theoretical elemental content (%) C 72 H 59 D 10 N3: C, 87.67; H, 8.07; N, 4.26. Found: C, 87.69; H, 8.04; N, 4.29.

[0200] [Example 15] Synthesis of compound 224

[0201]

[0202] According to the method of Example 3, c-6 was replaced with an equivalent molar of c-224, g-6 was replaced with an equivalent molar of g-224, to obtain compound 224 (53.07 g) with solid purity > 99.98% as detected by HPLC. Mass spectrum m / z: 1199.6921 (theoretical value: 1199.6933). Theoretical elemental content (%) C 89 H 73D8N3: C, 89.03; H, 7.47; N, 3.50. Found (mass %): C, 89.00; H, 7.45; N, 3.53.

[0203] [Example 16] Synthesis of compound 243

[0204]

[0205] According to the method of Example 3, c-6 was replaced with an equimolar amount of d-243, and g-6 was replaced with an equimolar amount of g-243 to obtain compound 243 (48.87 g) with a solid purity > 99.97% as determined by HPLC. Mass m / z: 1088.6418 (theoretical value: 1088.6404). Theoretical elemental content (%) C 80 H 32 D 27 N3: C, 88.19; H, 7.95; N, 3.86. Found elemental content (%) C, 88.22; H, 7.94; N, 3.87.

[0206] [Example 17] Synthesis of compound 258

[0207]

[0208] According to the method of Example 3, c-6 was replaced with an equimolar amount of d-243, and g-6 was replaced with an equimolar amount of g-243 to obtain compound 243 (48.87 g) with a solid purity > 99.97% as determined by HPLC. Mass m / z: 1088.6418 (theoretical value: 1088.6404). Theoretical elemental content (%) C 78 H 42 D 13 N3O: C, 88.10; H, 6.44; N, 3.95. Found elemental content (%) C, 88.14; H, 6.41; N, 3.97.

[0209] [Example 18] Synthesis of compound 294

[0210]

[0211] According to the method of Example 4, A-33 was replaced with an equimolar amount of A-294, d-33 was replaced with an equimolar amount of d-294, g-33 was replaced with an equimolar amount of g-294, and g1-33 was replaced with an equimolar amount of g1-294 to obtain compound 294 (32.39 g) with a solid purity > 99.97% as determined by HPLC. Mass m / z: 1089.6636 (theoretical value: 1089.6621). Theoretical elemental content (%) C 80 H 51 D18 N3: C, 88.11 ; H, 8.04; N, 3.85. Found ( % ) : C, 88.08; H, 8.06; N, 3.83.

[0212] [Example 19] Synthesis of compound 297

[0213]

[0214] According to the method of Example 3, 184.50 mmol of c-6 was replaced by 90 mmol of c-297 and 68.25 mmol of g-6 was replaced by 133.25 mmol of g-297 to give compound 297 (46.52 g) with a solid purity > 99.96% as measured by HPLC. Mass spectrum m / z: 1051.5641 (theoretical: 1051.5650). Theoretical elemental content (%) C 78 H 53 D 10 N3: C, 89.02; H, 6.99; N, 3.99. Found ( % ) : C, 89.01 ; H, 7.01 ; N, 4.01.

[0215] [Example 20] Synthesis of compound 307

[0216]

[0217] According to the method of Example 3, 184.50 mmol of c-6 was replaced by 90 mmol of c-307 and 68.25 mmol of g-6 was replaced by 133.25 mmol of g-6 to give compound 307 (43.12 g) with a solid purity > 99.95% as measured by HPLC. Mass spectrum m / z: 960.5856 (theoretical: 960.5840). Theoretical elemental content (%) C 70 H 32 D 23 N3: C, 87.46; H, 8.17; N, 4.37. Found ( % ) : C, 87.49; H, 8.15; N, 4.39.

[0218] [Example 21] Synthesis of compound 327

[0219]

[0220] According to the method of Example 3, c-6 was replaced by 90 mmol of d-33, g-6 was replaced by 133.25 mmol of g-327, to obtain compound 327 (47.20 g) with a solid purity > 99.97% as determined by HPLC. Mass spectrum m / z: 1074.5482 (theoretical value: 1074.5494). Theoretical elemental content (%) C 80 H 42 D 15 N3: C, 88.35; H, 6.75; N, 3.91. Found elemental content (%) C, 88.32; H, 6.76; N, 3.93.

[0221] [Example 22] Synthesis of compound 361

[0222]

[0223] According to the method of Example 4, d-33 was replaced by an equimolar amount of d-6, intermediate g-33 was replaced by an equimolar amount of intermediate g-361, g1-33 was replaced by an equimolar amount of g1-361, to obtain compound 361 (30.86 g) with a solid purity > 99.96% as determined by HPLC. Mass spectrum m / z: 1022.5889 (theoretical value: 1022.5875). Theoretical elemental content (%) C 72 H 18 D 33 N3S: C, 84.50; H, 8.27; N, 4.11. Found elemental content (%) C, 84.55; H, 8.28; N, 4.09.

[0224] [Example 23] Synthesis of compound 374

[0225]

[0226] Synthesis of intermediate B-374

[0227] To a reaction flask, under nitrogen protection, were added A-374 (21.63 g, 80.00 mmol), intermediate g-6 (31.61 g, 84.00 mmol), K2CO3 (33.17 g, 240.00 mmol), Pd(PPh3)4 (0.92 g, 0.80 mmol) in sequence, 300 mL of tetrahydrofuran was added, the mixture was stirred, and the above reaction system was heated to reflux for 7 hours. After the reaction was completed, it was cooled to room temperature, toluene was added, and the phases were separated, the toluene phase was washed with distilled water three times, dried over anhydrous magnesium sulfate, the solvent was concentrated by rotary evaporation, crystallization was performed by cooling, suction filtration was performed, the obtained solid was recrystallized with toluene / ethanol (20 / 1), and intermediate B-374 (35.58 g, yield 73%) was obtained. The solid purity was detected by HPLC to be ≥ 99.78%. Mass spectrum m / z: 608.2815 (theoretical value: 608.2803).

[0228] Synthesis of compound 374

[0229] To a reaction flask, under nitrogen protection, were added intermediate B-374 (30.46 g, 50.00 mmol), intermediate g-374 (19.97 g, 52.50 mmol), KOAc (14.72 g, 150.00 mmol), Pd(dppf)Cl2 (0.37 g, 0.50 mmol) in sequence, 200 mL of tetrahydrofuran was added, the mixture was stirred, and the above reaction system was heated to reflux for 9.5 hours. After the reaction was completed, it was cooled to room temperature, toluene was added, and the phases were separated, the toluene phase was washed with distilled water three times, dried over anhydrous magnesium sulfate, the solvent was concentrated by rotary evaporation, crystallization was performed by cooling, suction filtration was performed, the obtained solid was recrystallized with toluene, and compound 374 (28.95 g, yield 70%) was obtained. The solid purity was detected by HPLC to be ≥ 99.92%. Mass spectrum m / z: 826.4815 (theoretical value: 826.4806). Theoretical elemental content (%) 60 H 26 D 19 N3: C, 87.12; H, 7.79; N, 5.08. Found elemental content (%): C, 87.09; H, 7.81; N, 5.06.

[0230]

[0231] To a reaction flask, under nitrogen protection, were added A-382 (9.44 g, 30.00 mmol), intermediate g-382 (42.54 g, 93.00 mmol), K2CO3(12.44 g, 90.00 mmol), Pd2(dba)3(0.27 g, 0.30 mmol) successively, 300 mL of tetrahydrofuran was added, the mixture was stirred, the above reaction system was heated to reflux for 9 hours. After the reaction was completed, it was cooled to room temperature, toluene was added, and the phases were separated, the toluene phase was washed with distilled water three times, dried over anhydrous magnesium sulfate, the solvent was concentrated by rotary evaporation, crystallization was performed by cooling, suction filtration was performed, the obtained solid was recrystallized with toluene, to obtain compound 382 (22.72 g, yield 71%). The solid purity was detected by HPLC to be ≥99.96%. Mass spectrum m / z: 1065.6423 (theoretical value: 1065.6436). Theoretical elemental content (%) 78 H 27 D 30 N3: C, 87.84; H, 8.22; N, 3.94. Actual elemental content (%): C, 87.82; H, 8.25; N, 3.96.

[0232] [Example 25] Synthesis of compound 404

[0233]

[0234] Synthesis of intermediate B-404

[0235] To a reaction flask, under nitrogen protection, were added A-33 (34.91 g, 110.00 mmol), intermediate g-404 (63.82 g, 115.50 mmol), K2CO3(45.61 g, 330.00 mmol), Pd(PPh3)4(1.27 g, 1.10 mmol) successively, 400 mL of tetrahydrofuran was added, the mixture was stirred, the above reaction system was heated to reflux for 7 hours. After the reaction was completed, it was cooled to room temperature, toluene was added, and the phases were separated, the toluene phase was washed with distilled water three times, dried over anhydrous magnesium sulfate, the solvent was concentrated by rotary evaporation, crystallization was performed by cooling, suction filtration was performed, the obtained solid was recrystallized with toluene / ethanol (10 / 1) to obtain intermediate B-404 (50.14 g, yield 74%). The solid purity was detected by HPLC to be ≥99.72%. Mass spectrum m / z: 614.1184 (theoretical value: 614.1173).

[0236] Synthesis of intermediate C-404

[0237] To a reaction flask, under nitrogen protection, were added intermediate B-404 (49.28 g, 80.00 mmol), intermediate g1-404 (42.21 g, 84.00 mmol), KOAc (23.55 g, 240.00 mmol), Pd(dppf)Cl2(0.59 g, 0.80 mmol) successively, 300 mL of tetrahydrofuran was added, the mixture was stirred, the above reaction system was heated to reflux for 8.5 hours. After the reaction was completed, it was cooled to room temperature, toluene was added, and the phases were separated, the toluene phase was washed with distilled water three times, dried over anhydrous magnesium sulfate, the solvent was concentrated by rotary evaporation, crystallization was performed by cooling, suction filtration was performed, the obtained solid was recrystallized with toluene / ethanol (20 / 1), to obtain intermediate C-404 (50.32 g, yield 69%). The solid purity was detected by HPLC to be ≥ 99.86%. Mass spectrum m / z: 910.3889 (theoretical value: 910.3899).

[0238] Synthesis of compound 404

[0239] To a reaction flask, under nitrogen protection, were added intermediate C-404 (41.02 g, 45.00 mmol), intermediate g2-404 (21.38 g, 47.25 mmol), K2CO3(18.66 g, 135.00 mmol), Pd2(dba)3(0.41 g, 0.45 mmol) successively, 200 mL of tetrahydrofuran was added, the mixture was stirred, the above reaction system was heated to reflux for 10.5 hours. After the reaction was completed, it was cooled to room temperature, toluene was added, and the phases were separated, the toluene phase was washed with distilled water three times, dried over anhydrous magnesium sulfate, the solvent was concentrated by rotary evaporation, crystallization was performed by cooling, suction filtration was performed, the obtained solid was recrystallized with toluene, to obtain compound 404 (35.15 g, yield 65%). The solid purity was detected by HPLC to be ≥ 99.98%. Mass spectrum m / z: 1200.5954 (theoretical value: 1200.5964). Theoretical elemental content (%) 90 H 48 D 15 N3: C, 89.96; H, 6.54; N, 3.50. Found elemental content (%): C, 89.94; H, 6.53; N, 3.51.

[0240] [Example 26] Synthesis of compound 422

[0241]

[0242] According to the method of Example 25, intermediate g-404 is replaced with an equivalent molar amount of intermediate g-6, g1-404 is replaced with an equivalent molar amount of g-422, and g2-404 is replaced with an equivalent molar amount of g1-422 to give compound 422 (33.63 g) with a solid purity > 99.97% as determined by HPLC. Mass spectrum m / z: 1148.6447 (theoretical value: 1148.6435). Theoretical elemental content (%) C 85 H 36 D 25 N3: C, 88.81; H, 7.54; N, 3.66. Found elemental content (%) C, 88.84; H, 7.52; N, 3.68.

[0243] [Example 27] Synthesis of compound 437

[0244]

[0245] According to the method of Example 10, d-6 is replaced with an equivalent molar amount of d-33, g-151 is replaced with an equivalent molar amount of g-437, and c-151 is replaced with an equivalent molar amount of c-437 to give compound 437 (30.67 g) with a solid purity > 99.97% as determined by HPLC. Mass spectrum m / z: 1143.6265 (theoretical value: 1143.6276). Theoretical elemental content (%) C 85 H 61 D 10 N3: C, 89.20; H, 7.13; N, 3.67. Found elemental content (%) C, 89.18; H, 7.14; N, 3.69.

[0246] [Example 28] Synthesis of compound 449

[0247]

[0248] According to the method of Example 3, c-6 is replaced with an equivalent molar amount of d-33, and g-6 is replaced with an equivalent molar amount of g-449 to give compound 449 (54.35 g) with a solid purity > 99.98% as determined by HPLC. Mass spectrum m / z: 1228.7224 (theoretical value: 1228.7216). Theoretical elemental content (%) C 91 H 64 D 15 N3: C, 88.88; H, 7.70; N, 3.42. Found elemental content (%) C, 88.85; H, 7.72; N, 3.45.

[0249] [Example 29] Synthesis of compound 457

[0250]

[0251] According to the method of Example 3, c-6 is replaced with an equimolar amount of d-6, g-6 is replaced with an equimolar amount of g-457, to give compound 457 (38.85 g) with a solid purity > 99.97% as determined by HPLC. Mass spectrum m / z: 865.5043 (theoretical: 865.5056). Theoretical elemental content (%) C 63 H 31 D 18 N3: C, 87.36; H, 7.79; N, 4.85. Found elemental content (%) C, 87.34; H, 7.81; N, 4.87.

[0252] [Example 30] Synthesis of compound 522

[0253]

[0254] According to the method of Example 4, d-33 is replaced with an equimolar amount of c-522, g-33 is replaced with an equimolar amount of g-522, g1-33 is replaced with an equimolar amount of g1-522, to give compound 522 (34.42 g) with a solid purity > 99.97% as determined by HPLC. Mass spectrum m / z: 1140.6695 (theoretical: 1140.6686). Theoretical elemental content (%) C 84 H 32 D 29 N3: C, 88.38; H, 7.94; N, 3.68. Found elemental content (%) C, 88.40; H, 7.91; N, 3.66.

[0255] [Example 31] Synthesis of compound 553

[0256]

[0257] According to the method of Example 24, g-382 is replaced with an equimolar amount of intermediate g-553, to give compound 553 (26.05 g) with a solid purity > 99.99% as determined by HPLC. Mass spectrum m / z: 1315.6457 (theoretical: 1315.6467). Theoretical elemental content (%) C 99 H 54 D 15 N3: C, 90.37; H, 6.43; N, 3.19. Found elemental content (%) C, 90.40; H, 6.41; N, 3.17.

[0258] [Example 32] Synthesis of compound 599

[0259]

[0260] According to the method of Example 10, d-6 was replaced with an equimolar amount of c-607, g-6 was replaced with an equimolar amount of g-607, to give compound 607 (45.22 g) with a solid purity > 99.98% as determined by HPLC. Mass spectrum m / z: 1069.5013 (theoretical value: 1069.5022). Theoretical elemental content (%) C 66 H 31 D 14 N3OS: C, 84.13; H, 6.31; N, 4.46. Found elemental content (%) C, 84.15; H, 6.34; N, 4.43.

[0261] [Example 33] Synthesis of compound 607

[0262]

[0263] According to the method of Example 10, d-6 was replaced with an equimolar amount of c-607, g-6 was replaced with an equimolar amount of g-607, to give compound 607 (45.22 g) with a solid purity > 99.98% as determined by HPLC. Mass spectrum m / z: 1069.5013 (theoretical value: 1069.5022). Theoretical elemental content (%) C 78 H 55 D4N5: C, 87.52; H, 5.93; N, 6.54. Found elemental content (%) C, 87.50; H, 5.94; N, 6.56.

[0264] [Example 34] Synthesis of compound 608

[0265]

[0266] According to the method of Example 10, d-6 was replaced with an equimolar amount of c-607, g-6 was replaced with an equimolar amount of g-607, to give compound 607 (45.22 g) with a solid purity > 99.98% as determined by HPLC. Mass spectrum m / z: 1069.5013 (theoretical value: 1069.5022). Theoretical elemental content (%) C 58 H 31 D 10 N3O: C, 86.43; H, 6.38; N, 5.21. Found elemental content (%) C, 86.45; H, 6.36; N, 5.22.

[0267] [Example 35] Synthesis of compound 634

[0268]

[0269] According to the method of Example 10, d-6 was replaced with an equal molar amount of d-634, g-151 was replaced with an equal molar amount of g-634, and c-151 was replaced with an equal molar amount of c-634 to obtain compound 634 (29.89 g) with a purity of > 99.96% as determined by HPLC. Mass spectrum m / z: 1114.5430 (theoretical value: 1114.5443). Theoretical elemental content (%) C 82 H 42 D 15 N3O: C, 88.29; H, 6.50; N, 3.77. Actual elemental content (%) C, 88.27; H, 6.46; N, 3.80.

[0270] Blue organic light-emitting device (hole transport layer)

[0271] [Comparative Examples 1-2] Device preparation examples:

[0272] Comparative Example 1: An organic light-emitting device was prepared using a vacuum thermal evaporation method. The experimental procedure was as follows: an ITO / Ag / ITO glass substrate was cleaned in distilled water three times, and ultrasonically washed for 15 minutes. After the distilled water cleaning, the substrate was ultrasonically washed with isopropyl alcohol, acetone, and methanol in that order, and then dried at 120°C. The dried substrate was then placed in an evaporation machine.

[0273] On the prepared ITO / Ag / ITO glass electrode, a hole injection layer of HI-1 / P-1 = 96 / 4 (mass ratio) was evaporated by vacuum evaporation layer by layer, with a thickness of 10 nm. A hole transport layer of compound A was evaporated, with a thickness of 80 nm. An emitting layer of BH / BD = 95 / 5 (mass ratio) was evaporated, with a thickness of 25 nm. An electron transport layer of ET-1 was evaporated, with a thickness of 35 nm. An electron injection layer of LiF was evaporated, with a thickness of 1.5 nm. A cathode of Mg / Ag = 1 / 9 (mass ratio) was evaporated, with a thickness of 12 nm. A cover layer of CP-1 was evaporated, with a thickness of 60 nm, thereby preparing an organic electroluminescent device.

[0274] After the organic light-emitting device was prepared according to the above procedure, the photoelectric performance of the device was measured. The molecular structures of the relevant materials are shown below:

[0275]

[0276] [Application Examples 1-27]

[0277] Application Examples 1 to 28: Application Examples 1 to 28 were produced in the same manner as in Comparative Example 1, except that the hole transport layer material compound A of Comparative Example 1 was replaced with the compounds 33, 62, 97, 114, 128, 144, 151, 160, 162, 185, 224, 243, 258, 294, 297, 327, 374, 382, 404, 422, 437, 449, 522, 553, 599, 607, 608 of the present application, respectively.

[0278] A combined IVL test system consisting of test software, a computer, a K2400 digital source meter produced by Keithley Company, USA, and a PR788 spectral scanning luminance meter of Photo Research Company, USA was used to test the driving voltage and luminous efficiency of the organic electroluminescent device. The test of the lifetime T98 (luminance decay to 98% of the initial luminance) was performed using an M6000 OLED lifetime test system of McScience Company. The test was performed in an atmospheric environment at room temperature, and the current density was 10 mA / cm 2 . The test results of the luminous characteristics of the obtained organic light-emitting device are shown in Table 1.

[0279] Table 1:

[0280]

[0281]

[0282] As can be seen from Table 1, the organic electroluminescent device of the present application not only reduces the driving voltage, but also has the advantages of high luminous efficiency and long lifetime compared with the comparative examples, because the star-shaped amine derivative contained in the organic electroluminescent device of the present application as the hole transport layer material can maximize the carrier mobility in the organic electroluminescent device, increase the probability of hole and electron recombination in the light-emitting layer, and ultimately improve the luminous efficiency of the organic electroluminescent device and prolong the service life of the device, while reducing the driving voltage of the device.

[0283] Green organic light-emitting device (second hole transport layer)

[0284] [Comparative Example 2] Device preparation example:

[0285] Comparative Example 2: An organic light-emitting device was prepared by a vacuum thermal evaporation method. The experimental steps were: the ITO / Ag / ITO glass substrate was cleaned in distilled water for 3 times, ultrasonic washing for 15 minutes, after the distilled water cleaning, isopropanol, acetone, methanol and other solvents were sequentially ultrasonic washed, and then dried at 120°C, and sent to the evaporation machine.

[0286] HI-2 was vacuum evaporated as a hole injection layer on the prepared ITO / Ag / ITO glass electrode in a layer-by-layer manner, with an evaporation thickness of 10 nm; HT-1 was evaporated as a first hole transport layer, with an evaporation thickness of 50 nm; compound A was evaporated as a second hole transport layer, with an evaporation thickness of 40 nm; GH / GD = 97 / 3 (mass ratio) was evaporated as a light-emitting layer, with an evaporation thickness of 20 nm; ET-2 was evaporated as an electron transport layer, with an evaporation thickness of 30 nm; LiF was evaporated as an electron injection layer, with an evaporation thickness of 1 nm; Mg / Ag = 1 / 9 (mass ratio) was evaporated as a cathode, with an evaporation thickness of 10 nm; and CP-1 was evaporated as a cover layer, with an evaporation thickness of 60 nm, thereby preparing an organic electroluminescent device.

[0287] After the preparation of the organic light-emitting device was completed according to the above steps, the photoelectric performance of the device was measured, and the molecular structural formula of the relevant material is shown below:

[0288]

[0289] [Application Examples 28-50]

[0290] Application Examples 29-50: Application Examples 29-53 were prepared by the same method as in Comparative Example 2, except that the second hole transport layer material compound A in Comparative Example 3 was replaced by the compounds 6, 62, 114, 128, 151, 160, 162, 206, 224, 243, 294, 297, 307, 327, 361, 374, 382, 404, 437, 449, 457, 608, 634 of the present application, respectively.

[0291] The test results of the light-emitting characteristics of the obtained organic light-emitting device are shown in Table 2.

[0292] Table 2:

[0293]

[0294]

[0295] As can be seen from the results in Table 2, the organic electroluminescent device of the present application has the characteristics of low driving voltage, high luminous efficiency, and long service life, etc. compared with the comparative examples, which is due to the introduction of the second hole transport layer, which reduces the energy gap between the hole transport layer and the light-emitting layer, and is more conducive to improving the mobility of the charge carriers, further improving the luminous efficiency of the device.

[0296] It should be noted that the present application is particularly described with individual embodiments, but those skilled in the art can make various forms or details of improvements to the present application without departing from the principles of the present application, and these improvements also fall within the scope of protection of the present application.

Claims

1. An organic electroluminescent device comprising a substrate, an anode, an organic layer, and a cathode, characterized in that, The organic layer comprises a hole transport layer containing a star-shaped amine derivative represented by Formula I, L0 is the same or different and is selected from a single bond or any one of the following groups, L1-L3 are the same or different and are selected from a single bond or any one of the following groups, and L1-L3 are not simultaneously selected from a single bond R1 is the same or different and is selected from any one of hydrogen, deuterium, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and pentyl; R1 can be unsubstituted, partially substituted, or fully substituted with deuterium; m1 is selected from 0, 1, 2, 3, or 4; m2 is selected from 0, 1, or 2; m3 is selected from 0, 1, 2, 3, 4, or 5; m4 is selected from 0, 1, 2, 3, 4, 5, or 6; m5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, or 8; m6 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; and m9 is selected from 0, 1, 2, 3, 4, 5, 6, or 7; x1-x3 are the same or different and are selected from 1; Ar1-Ar6 are selected from any one of the following groups, R2 is the same or different and is selected from any one of hydrogen, deuterium, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, camphanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, phenyl, naphthyl, and biphenyl, or adjacent two R2s are connected to each other to form a substituted or unsubstituted benzene ring; R2 can be unsubstituted, partially substituted, or fully substituted with deuterium; n1 is selected from 0, 1, 2, 3, 4, or 5; n2 is selected from 0, 1, 2, 3, or 4; n3 is selected from 0, 1, 2, or 3; n4 is selected from 0, 1, or 2; n5 is selected from 0, 1, 2, 3, 4, 5, or 6; n6 is selected from 0, 1, 2, 3, 4, 5, 6, 7, or 8; and n7 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; said R a , R b , R c , R d are the same or different and are selected from any one of hydrogen, deuterium, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, or R a , R b are connected to each other to form a substituted or unsubstituted: cyclopentane, cyclohexane, fluorene; said "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, methyl, ethyl, isopropyl, tert-butyl; and when at least one of Ar1 and Ar2 is selected from a substituted or unsubstituted C2-C30 heteroaryl group or / and at least one of L0 connected to Ar1 and Ar2 is selected from a substituted or unsubstituted C2-C30 heteroarylene group, L1 is selected from a single bond, when at least one of Ar3 and Ar4 is selected from a substituted or unsubstituted C2-C30 heteroaryl group or / and at least one of L0 connected to Ar3 and Ar4 is selected from a substituted or unsubstituted C2-C30 heteroarylene group, L2 is selected from a single bond, and when at least one of Ar5 and Ar6 is selected from a substituted or unsubstituted C2-C30 heteroaryl group or / and at least one of L0 connected to Ar5 and Ar6 is selected from a substituted or unsubstituted C2-C30 heteroarylene group, L3 is selected from a single bond; R is selected from the group consisting of hydrogen, deuterium, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-pentyl, i-pentyl, neopentyl, hexyl, heptyl, octyl, deuterated methyl, deuterated ethyl, deuterated n-propyl, deuterated i-propyl, deuterated n-butyl, deuterated t-butyl, deuterated pentyl, deuterated hexyl, and is the same or different; with the proviso that at least one ring of the ring directly connected to the N atom to which L0is attached in the structure of Formula I is substituted with at least three deuterium, and the ring carbon atoms of the ring to which the hydrogen not substituted with other groups are substituted with deuterium; the ring directly connected to the N atom to which L0is attached in the structure of Formula I includes at least one of the following: i. the ring directly connected to the N atom to which L0is attached in the structure of Formula I is a ring to which L0is not a bond; ii. the ring directly connected to the N atom to which L0is attached in the structure of Formula I is a ring to which L0is a bond; iii. the ring directly connected to the N atom to which L0is attached in the structure of Formula I is a ring to which L1, L2or L3is not a bond.

2. An organic electroluminescent device according to claim 1, characterized in that Formula I is selected from any one of the following Formula I-A to Formula I-C, R is selected from the group consisting of hydrogen, deuterium, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, and is the same or different; R can be unsubstituted, partially substituted or fully substituted with deuterium.

3. An organic electroluminescent device according to claim 1, characterized in that L1-L3are the same or different and are selected from a single bond or any one of the following groups, R1is selected from the group consisting of hydrogen, deuterium, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, and is the same or different; R1can be unsubstituted, partially substituted or fully substituted with deuterium.

4. An organic electroluminescent device according to claim 1, characterized in that Ar1-Ar6are selected from any one of the following groups, R2is selected from the group consisting of hydrogen, deuterium, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, camphanyl, phenyl, and is the same or different; R2can be unsubstituted, partially substituted or fully substituted with deuterium. R a , R b , R c , R d any one of which is the same or different selected from substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted phenyl.

5. The organic electroluminescent device according to claim 1, wherein Ar1-Ar6are selected from any one of the following groups, 。 6. An organic electroluminescent device according to claim 1, characterized in that Formula I is selected from any one of the following groups,

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