Diamine derivative and organic electroluminescent device thereof

Abstract

The invention provides a diamine derivative and an organic electroluminescent device thereof, and particularly relates to the technical field of organic electroluminescence. The diamine derivative provided by the invention has good hole transport capacity and appropriate HOMO energy level, is beneficial to hole injection and transport, increases effective recombination of excitons, reduces energy barriers needing to be overcome in hole transport and injection processes, reduces generation of Joule heat in a device, has relatively high thermal stability, is not easy to crystallize, and has a good application prospect. And when the compound is applied to an organic electroluminescent device as a hole transport layer material, the luminous efficiency of the device can be improved, and the service life of the device can be prolonged.

Description

[0001] This application is a divisional application of the Chinese patent application filed on July 18, 2023, with the invention name “A diamine derivative and its organic electroluminescent device” and application number 202310883474.4. Technical Field

[0002] The invention relates to the technical field of organic electroluminescence, and in particular to a diamine derivative and an organic electroluminescent device thereof. Background Art

[0003] Organic Light-Emitting Diode (OLED). Compared with traditional liquid crystal display (LCD), OLED display technology has the advantages of self-luminescence, wide viewing angle, high resolution, low power consumption, and extremely high response speed. It has broad application prospects in the new generation of display and lighting products.

[0004] Organic electroluminescent devices are driven by an external voltage. Electrons and holes are injected from the cathode and anode into the organic layer, and injected and migrate in the organic layer. Then, the electrons and holes are recombined in the light-emitting layer to generate excitons. When the excitons release energy in the form of light radiation, it is the electroluminescence of the organic light-emitting device. The classic sandwich structure of organic electroluminescent devices is composed of cathode, anode, and organic layer. The organic functional layers mainly include: hole injection layer (HIL), hole transport layer (HTL), electron blocking layer (EBL), light-emitting layer (EML), hole blocking layer (HBL), electron transport layer (ETL), electron injection layer (EIL) and capping layer (CPL).

[0005] With the continuous development of science and technology, the performance requirements of organic electroluminescent devices are constantly increasing. As an important component of hole transfer, hole transport layer materials have a position that cannot be ignored in organic electroluminescent devices. However, the HOMO value and triplet energy level of hole transport layer materials at this stage are low, and holes require a larger energy barrier during the transmission process; the hole mobility is low, resulting in an unbalanced transmission of holes and electrons, reducing the recombination probability of excitons in the light-emitting layer and the luminous efficiency of the device; the glass transition temperature is low, which reduces the service life of the device; it is easy to crystallize and has poor film-forming properties; therefore, it is particularly important to develop a hole transport material with high hole mobility, good film-forming properties and thermal stability, suitable HOMO energy level and easy carrier transmission, so as to achieve high efficiency and long life performance of the device. Summary of the invention

[0006] In order to solve the problem of poor performance of devices in the prior art, the present invention provides a diamine derivative and an organic electroluminescent device thereof, which can effectively improve the luminous efficiency of the device and extend its service life by applying the diamine derivative to the hole transport region.

[0007] The present invention provides a diamine derivative having a structure as shown in Formula I.

[0008]

[0009] In formula I, the Ar1 to Ar4, L1 to L4, and L contain at least one group represented by formula II-1 or formula II-2, and the Ar1 to Ar4 are the same or different from each other, at least one of which is selected from the group represented by formula III, and the rest are the same or different from each other and are selected from any one of the groups represented by formula V-1 to formula V-4;

[0010]

[0011] The R1 is selected from deuterium, substituted or unsubstituted C2-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, Any of the following:

[0012] The a is selected from 1, 2, 3, 4 or 5; when there are two or more R1, the two or more R1 are the same or different from each other;

[0013] The R2 is selected from hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, Any of the following:

[0014] The d1 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, and the d2 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; when there are two or more R2, the two or more R2 are the same or different from each other;

[0015]

[0016] Said p1 is selected from 1, 2, 3, 4 or 5, and said p2 is selected from 1, 2, 3 or 4;

[0017] The L is selected from the following groups:

[0018]

[0019] The R is selected from hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, Any of the following:

[0020] The m1 is selected from 0, 1, 2, 3 or 4, the m2 is selected from 0, 1, 2 or 3, the m3 is selected from 0, 1, 2, 3, 4, 5 or 6, and when two or more R are present, the two or more R are the same as or different from each other.

[0021] The L1 to L4 are the same or different from each other and are selected from single bonds or groups substituted or unsubstituted by R4 as shown below: phenylene, biphenylene, terphenylene or

[0022] The R4 is selected from hydrogen, deuterium, cyano, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C12-C30 aryl, Any of the following:

[0023] The R5 and R6 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 C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl;

[0024] The f1 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, and the f2 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0025] The present invention also provides an organic electroluminescent device, comprising an anode, an organic layer, and a cathode, wherein the organic layer is located between the anode and the cathode or outside any one of the anode and the cathode, and the organic layer comprises any one or more of the diamine derivatives.

[0026] Beneficial effects: The diamine derivatives shown in Formula I of the present invention have suitable HOMO energy levels, good hole transport capabilities, and high thermal stability, which are beneficial to hole injection and transport, increase the effective recombination of excitons in the light-emitting layer, and reduce the energy barrier that needs to be overcome during hole injection and transport. Using it as a hole transport layer material in an organic electroluminescent device can effectively improve the luminous efficiency of the device and extend its service life. In addition, the triarylamine derivatives shown in Formula IV have a high refractive index and a high glass transition temperature, which can improve the light extraction efficiency of the device. When it is used in an organic electroluminescent device simultaneously with the diamine derivatives shown in Formula I, the device performance is further improved. DETAILED DESCRIPTION

[0027] The following will be described clearly and completely in conjunction with the technical solutions of the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present invention.

[0028] In the compounds of the present invention, any atom not designated as a particular isotope is included as any stable isotope of that atom, and includes the atom in both its natural isotopic abundance and unnatural abundance.

[0029] In the present invention, "D" is deuterium, an isotope of hydrogen.

[0030] In the present invention, "*" means a portion connecting to another substituent.

[0031] In this specification, 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 positions of the ring. For example, Can be expressed Can be expressed For example, Can be expressed And so on.

[0032] In this specification, when a substituent or a bond at a connection site runs through two or more rings, it indicates that it can be connected to any of the two or more rings, specifically, it can be connected to any of the corresponding optional sites of the ring. For example, Can be expressed Can be expressed And so on.

[0033] Examples of the halogen atom described in the present invention may include fluorine, chlorine, bromine or iodine.

[0034] The alkyl group of the present invention refers to a monovalent group obtained by removing a hydrogen atom from an alkane molecule, which may be a straight chain alkyl group or a branched chain alkyl group, preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms. The alkyl group may be substituted or unsubstituted. Specific examples may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc., but are not limited thereto.

[0035] The alkenyl group of the present invention refers to a monovalent group obtained by removing a hydrogen atom from an olefin molecule, which can be a straight chain alkenyl group or a branched chain alkenyl group, preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms. The alkenyl group can be substituted or unsubstituted. Specific examples may include vinyl, 1-propenyl, isopropenyl, butenyl, pentenyl, 3-methyl-1-butenyl, allyl, 1-phenylvinyl-1-yl, styryl, etc., but are not limited thereto.

[0036] The cycloalkyl group of the present invention refers to a monovalent group obtained by removing a hydrogen atom from a cyclic alkane molecule, preferably 3 to 12 carbon atoms, more preferably 3 to 10 carbon atoms, and particularly preferably 3 to 6 carbon atoms. The cycloalkyl group may be substituted or unsubstituted. The cycloalkyl group includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, etc., but is not limited thereto.

[0037] The aryl group described in the present invention refers to a monovalent group obtained by removing a hydrogen atom from the aromatic carbon of the aromatic compound molecule, which can be a monocyclic aromatic group, a polycyclic aromatic group or a condensed aromatic group, preferably having 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 12 carbon atoms. The aryl group can be substituted or unsubstituted. The monocyclic aromatic group refers to an aromatic group with only one aromatic ring in the molecule, for example, phenyl, etc., but not limited thereto; the polycyclic aromatic group refers to an aromatic group containing two or more independent aromatic rings in the molecule, for example, biphenyl, terphenyl, quaterphenyl, etc., but not limited thereto; the condensed aromatic group refers to an aromatic group containing two or more aromatic rings in the molecule and fused to each other by sharing two adjacent carbon atoms, for example, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, perylenyl, The invention also includes, but is not limited to, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, benzofluorenyl, 9,9'-spirobifluorenyl and the like.

[0038] The heteroaryl group of the present invention refers to a general term for a group obtained by replacing one or more aromatic carbon atoms in an aromatic group with a heteroatom, wherein the heteroatom includes but is not limited to an O, S, N, Si or P atom, preferably having 2 to 30 carbon atoms, particularly preferably 2 to 18 carbon atoms, and most preferably 2 to 12 carbon atoms. The attachment site of the heteroaryl group may be located on a ring-forming carbon atom or on a ring-forming heteroatom, and the heteroaryl group may be a monocyclic heteroaryl group, a polycyclic heteroaryl group or a condensed ring heteroaryl group. The heteroaryl group may be substituted or unsubstituted. The monocyclic heteroaryl groups include pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furanyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, etc., but are not limited thereto; the polycyclic heteroaryl groups include bipyridyl, bipyrimidinyl, phenylpyridinyl, phenylpyrimidinyl, etc., but are not limited thereto; the condensed ring heteroaryl groups include quinolyl, isoquinolyl, benzoquinolyl, benzoisoquinolyl, quinazolinyl, quinoxalinyl, benzoquinazolinyl, benzoquinoxalinyl, The invention also includes benzophenone, phenanthroline, naphthyridinyl, indolyl, benzothiophenyl, benzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, benzodibenzofuranyl, dibenzothiophenyl, benzodibenzothiophenyl, dibenzoxazolyl, dibenzimidazolyl, dibenzothiazolyl, carbazolyl, benzocarbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenoxathiyl, spirofluorenyloxanthryl, spirofluorenylthioanthryl and the like, but is not limited thereto.

[0039] The aliphatic ring described in the present invention refers to a cyclic hydrocarbon with 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, and more preferably 3 to 7 carbon atoms. It can form a monocyclic hydrocarbon or a polycyclic hydrocarbon, which can be completely unsaturated or partially unsaturated. The aliphatic ring can be substituted or unsubstituted. Specific examples may include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclobutene, cyclopentene, cyclohexene, cycloheptene, etc., but are not limited thereto. Multiple monocyclic hydrocarbons can also be connected in a variety of ways: two rings in the molecule can share a carbon atom to form a spirocycle; 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.

[0040] The fused ring of the aromatic ring and the aliphatic ring of the present invention refers to a ring formed by condensing one or more aromatic rings and one or more aliphatic rings in a molecule 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 benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexane, benzocycloheptane, benzocyclobutenyl, benzocyclopentenyl, benzocyclohexenyl, benzocycloheptenyl, naphthocyclopropane, naphthocyclobutane, naphthocyclopentane, naphthocyclohexane, naphthocyclopentenyl, naphthocyclohexenyl, etc., but are not limited thereto.

[0041] The arylene group described in the present invention refers to the general term for the divalent group left after two hydrogen atoms are removed from the aromatic core carbon of the aromatic hydrocarbon molecule. It can be a monocyclic arylene group, a polycyclic arylene group or a condensed ring arylene group, preferably having 6 to 30 carbon atoms, more preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and most preferably 6 to 12 carbon atoms. Regarding the above-mentioned arylene groups, as a monocyclic arylene group, it can be a phenylene group, etc., but it is not limited to this. The arylene group can be substituted or unsubstituted. As the above-mentioned polycyclic arylene group, it can be a biphenylene group, a terphenylene group, a quaterphenylene group, etc., but it is not limited to this. As the above-mentioned condensed ring arylene group, it can be a naphthylene group, anthrylene group, phenanthrenyl group, pyrenyl group, fluorenyl group, spirofluorenyl group, triphenylene group, perylene group, fluoranthenyl group, fluoranthene group, etc. etc., but not limited thereto.

[0042] The heteroarylene group described in the present invention refers to a general term for a divalent group remaining after removing two hydrogen atoms from the core carbon of an aromatic heterocycle composed of carbon and heteroatoms. The heteroatom may be one or more of N, O, S, Si, and P. It may be a monocyclic heteroarylene group, a polycyclic heteroarylene group, or a condensed-ring heteroarylene group, preferably having 2 to 30 carbon atoms, more preferably 2 to 22 carbon atoms, further preferably 2 to 20 carbon atoms, and most preferably 3 to 12 carbon atoms. The heteroarylene group may be substituted or unsubstituted. Examples may include pyridylene, pyrimidylene, pyrazinylene, pyridazinylene, triazinylene, thienylene, pyrrolylene, furanylene, pyranylene, oxazolylene, thiazolylene, imidazolylene, benzoxazolylene, benzothiazolylene, benzimidazolylene, carbazolylene, benzocarbazolylene, acridinylene, xanthrenylene, thioanthrenylene, phenazinylene, phenothiazinylene, phenoxazinylene, indolylene, quinolylene, isoquinolylene, benzothienylene, benzofuranylene, dibenzofuranylene, dibenzothienylene, quinoxalylene, quinazolinylene, naphthyridinylene, purinylene, o-phenanthrolineylene, and the like, but are not limited thereto.

[0043] The divalent fused ring group of an aromatic ring and an aliphatic ring described in the present invention refers to a fused ring group of an aromatic ring and an aliphatic ring having two linking positions, i.e., a divalent group. Except that they are divalent groups, the description of the fused ring group of an aromatic ring and an aliphatic ring described above can be applied.

[0044] In the "substituted or unsubstituted" of the present invention, "unsubstituted" means that the hydrogen atom on the group is not replaced by any substituent; "substituted" means that at least one hydrogen atom on the group is replaced by a substituent, and the position of the substitution is not limited. When multiple hydrogen atoms are replaced by multiple substituents, the multiple substituents may be the same or different.

[0045] The substituents in the "substituted or unsubstituted" of the present invention may be the same or different from each other, and are selected from any of deuterium, cyano, nitro, trifluoromethyl, halogen atoms, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C6-C30 aromatic ring and C3-C30 aliphatic ring fused ring One, preferably deuterium, cyano, halogen atoms, trifluoromethyl, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C2-C30 heteroaryl, specific examples may include deuterium, fluorine, chlorine, bromine, iodine, cyano, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, deuterated methyl, deuterated isopropyl, deuterated tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, tolyl, pentadeuterated phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, triphenylene, 1,2-dimethyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1,2-diphenyl-1 The invention also includes oxadiazole, oxazolyl, thiazolyl, benzothiazolyl, benzotriazolyl, benzoimidazolyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, phenothiazinyl, phenoxazinyl, and the like, but is not limited thereto.

[0046] Unless otherwise specified, the term "ring" used herein refers to a condensed ring consisting of an aliphatic ring having 3 to 30 carbon atoms, an aromatic ring having 6 to 30 carbon atoms, or a heterocyclic ring having 2 to 60 carbon atoms, or a combination thereof, which includes a saturated or unsaturated ring.

[0047] The term "connected to form a ring" used in the present invention refers to two groups connected to each other by a chemical bond and optionally aromatized. For example:

[0048]

[0049] In the present specification, the ring formed by connection can be an aromatic ring or a non-aromatic ring, and can be a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring, an eight-membered ring, a condensed ring, etc., for example, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclopentene, cyclohexene, adamantane, norbornane, benzene, naphthalene, phenanthrene, triphenylene, pyridine, pyrimidine, pyridazine, pyrazine, quinoline, isoquinoline, quinazoline, quinoxaline, fluorene, dibenzofuran, dibenzothiophene, carbazole, etc., but are not limited to these.

[0050] The “at least one” mentioned in the present invention includes one, two, three, four or more.

[0051] The present invention provides a diamine derivative having a structure as shown in Formula I.

[0052]

[0053] In formula I, the Ar1 to Ar4, L1 to L4, and L contain at least one group represented by formula II-1 or formula II-2, and the Ar1 to Ar4 are the same or different from each other, at least one of which is selected from the group represented by formula III, and the rest are the same or different from each other and are selected from any one of the groups represented by formula V-1 to formula V-4;

[0054]

[0055] The R1 is selected from deuterium, substituted or unsubstituted C2-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, Any of the following:

[0056] The a is selected from 1, 2, 3, 4 or 5; when there are two or more R1, the two or more R1 are the same or different from each other;

[0057] The R2 is selected from hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, Any of the following:

[0058] The d1 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, and the d2 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; when there are two or more R2, the two or more R2 are the same or different from each other;

[0059]

[0060] Said p1 is selected from 1, 2, 3, 4 or 5, and said p2 is selected from 1, 2, 3 or 4;

[0061] The L is selected from the following groups:

[0062]

[0063] The R is selected from hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, Any of the following:

[0064] The m1 is selected from 0, 1, 2, 3 or 4, the m2 is selected from 0, 1, 2 or 3, the m3 is selected from 0, 1, 2, 3, 4, 5 or 6, and when two or more R are present, the two or more R are the same as or different from each other.

[0065] The L1 to L4 are the same or different from each other and are selected from single bonds or groups substituted or unsubstituted by R4 as shown below: phenylene, biphenylene, terphenylene or

[0066] The R4 is selected from hydrogen, deuterium, cyano, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C12-C30 aryl, Any of the following:

[0067] The R5 and R6 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 C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl;

[0068] The f1 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, and the f2 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0069] Preferably, at least one of Ar1 to Ar4 is selected from the group shown in Formula III, including one, two, three or four of Ar1 to Ar4 selected from the group shown in Formula III.

[0070] Preferably, Ar1, Ar2, Ar3 or Ar4 is selected from the group represented by formula III.

[0071] Preferably, Ar1 and Ar2, or Ar1 and Ar4 are selected from the group represented by formula III.

[0072] Preferably, Ar1, Ar2 and Ar4 are selected from the group represented by formula III.

[0073] Preferably, Ar1, Ar2, Ar3 and Ar4 are selected from the group represented by formula III.

[0074] Preferably, the formula III is selected from any one of the groups shown below;

[0075]

[0076] The R a selected from deuterium, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted cyclopropanyl, substituted or unsubstituted cyclobutanyl, substituted or unsubstituted cyclopentanyl, substituted or unsubstituted cyclohexanyl, substituted or unsubstituted cycloheptyl, substituted or unsubstituted cyclooctyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornyl, substituted or unsubstituted camphenyl, Any of the following:

[0077] a1 is selected from 1, 2, 3, 4 or 5, a2 is selected from 0, 1, 2, 3 or 4, and a3 is selected from 0, 1, 2 or 3; when there are two or more R a When two or more R a the same as or different from one another;

[0078] The R b are the same as or different from each other and are selected from any one of hydrogen, deuterium, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted cyclopropanyl, substituted or unsubstituted cyclobutanyl, substituted or unsubstituted cyclopentanyl, substituted or unsubstituted cyclohexanyl, substituted or unsubstituted cycloheptyl, substituted or unsubstituted cyclooctyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornyl, substituted or unsubstituted camphenyl, substituted or unsubstituted phenyl, and substituted or unsubstituted biphenyl;

[0079] The b1 is selected from 0, 1, 2, 3, 4 or 5, and the b2 is selected from 0, 1, 2, 3 or 4; when there are two or more R b When two or more R b The same as or different from each other.

[0080] Preferably, the formula III is selected from any one of the groups shown below;

[0081]

[0082] s1 is selected from 1, 2, 3, 4, or 5, s2 is selected from 0, 1, 2, 3, or 4, s3 is selected from 0, 1, 2, 3, 4, or 5, s4 is selected from 0, 1, 2, 3, 4, 5, 6, or 7, s5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, s7 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13, s8 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15, s9 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, s 10 Selected from 0, 1, 2 or 3.

[0083] Preferably, Ar1 to Ar4, L1 to L4, and L contain at least one group shown in formula II-1 or formula II-2, including Ar1 to Ar4, L1 to L4, and L containing one, two, three, four, five, six, seven, eight, nine or more groups shown in formula II-1 or formula II-2.

[0084] Preferably, Ar1, Ar2, Ar3 or Ar4 is selected from the group shown in formula II-1.

[0085] Preferably, Ar1 and Ar2, or Ar1 and Ar4 are selected from the group shown in formula II-1.

[0086] Preferably, Ar1, Ar2 and Ar4 are selected from the group shown in formula II-1.

[0087] Preferably, L1, L2, L3 or L4 is selected from the group shown in formula II-2.

[0088] Preferably, L1 and L2, or L1 and L4 are selected from the group shown in formula II-2.

[0089] Preferably, L1, L2 and L4 are selected from the group shown in formula II-2.

[0090] Preferably, L1, L2, L3 and L4 are selected from the group shown in formula II-2.

[0091] Preferably, the L contains at least one group of formula II-2. More preferably, the L is selected from the group of formula II-2.

[0092] Preferably, at least one of Ar1 to Ar4 is selected from the group shown in formula II-1, or at least one of L1 to L4 is selected from the group shown in formula II-2, or L contains at least one group shown in formula II-2.

[0093] Preferably, at least one of Ar1 to Ar4 is selected from the group represented by formula II-1, and at least one of L1 to L4 is selected from the group represented by formula II-2.

[0094] Preferably, at least one of Ar1 to Ar4 is selected from the group shown in formula II-1 and L contains at least one group shown in formula II-2. More preferably, at least one of Ar1 to Ar4 is selected from the group shown in formula II-1 and L is selected from the group shown in formula II-2.

[0095] Preferably, at least one of L1 to L4 is selected from the group shown in formula II-2 and L contains at least one group shown in formula II-2. More preferably, at least one of L1 to L4 is selected from the group shown in formula II-2 and L is selected from the group shown in formula II-2.

[0096] Preferably, at least one of Ar1 to Ar4 is selected from the group shown in formula II-1, at least one of L1 to L4 is selected from the group shown in formula II-2, and L contains at least one group shown in formula II-2. More preferably, at least one of Ar1 to Ar4 is selected from the group shown in formula II-1, at least one of L1 to L4 is selected from the group shown in formula II-2, and L is selected from the group shown in formula II-2.

[0097] Preferably, the formula II-1 is selected from any one of the groups shown below;

[0098]

[0099] The e1 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, the e2 is selected from 0, 1, 2, 3, 4, or 5, the e3 is selected from 0, 1, 2, 3, 4, 5, 6, or 7, the e4 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, and the e5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15.

[0100] Preferably, the formula II-2 is selected from any one of the groups shown below;

[0101]

[0102] Preferably, L is selected from any one of the following groups:

[0103]

[0104] The R's are the same as or different from each other and are selected from any one of hydrogen, deuterium, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted cycloheptyl, substituted or unsubstituted cyclooctyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornyl, substituted or unsubstituted camphenyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, and substituted or unsubstituted naphthyl;

[0105] The n1 is selected from 0, 1, 2, 3 or 4, the n2 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, the n3 is selected from 0, 1, 2, 3, 4, 5 or 6, and when two or more R are present, the two or more R are the same as or different from each other.

[0106] Preferably, L is selected from any one of the following groups:

[0107]

[0108]

[0109]

[0110]

[0111] The R's are the same as or different from each other and are selected from any one of hydrogen, deuterium, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornyl, substituted or unsubstituted camphenyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, and substituted or unsubstituted naphthyl;

[0112] The n1 is selected from 0, 1, 2, 3 or 4, the n2 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, the n3 is selected from 0, 1, 2, 3, 4, 5 or 6, and when two or more R are present, the two or more R are the same as or different from each other.

[0113] Preferably, L1 to L4 are the same or different from each other and are selected from a single bond or any one of the groups shown below;

[0114]

[0115] R4 is selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, methyl, deuterated methyl, ethyl, isopropyl, deuterated isopropyl, tert-butyl, deuterated tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, and norbornyl;

[0116] The q1 is selected from 0, 1, 2, 3 or 4, and the q2 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0117] Preferably, the diamine derivative is selected from any one of the structures shown below:

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133] Some specific chemical structures of the diamine derivatives represented by Chemical Formula I of the present invention are listed above, but the present invention is not limited to these listed chemical structures, and all chemical structures based on the structure shown in Chemical Formula I and having substituents as defined above should be included.

[0134] The present invention also provides an organic electroluminescent device, comprising an anode, an organic layer, and a cathode, wherein the organic layer is located between the anode and the cathode or outside any one of the anode and the cathode, and the organic layer contains any one or more of the diamine derivatives.

[0135] Preferably, the organic layer is located between the anode and the cathode, and includes at least one layer of a hole transport region, a light emitting layer, and an electron transport region.

[0136] Preferably, the hole transport region described in the present invention comprises at least one of a hole injection layer, a hole transport layer, and an electron blocking layer. More preferably, the hole transport region described in the present invention comprises at least one of a hole injection layer and a hole transport layer. More preferably, the hole transport region described in the present invention comprises a hole transport layer, and the hole transport layer comprises any one or more of the diamine derivatives described in the present invention.

[0137] Preferably, the hole transport layer of the present invention comprises a first hole transport layer and a second hole transport layer.

[0138] Preferably, the electron transport region described in the present invention comprises at least one layer of an electron injection layer, an electron transport layer, and a hole blocking layer. More preferably, the electron transport region described in the present invention comprises at least one layer of an electron transport layer and a hole blocking layer. More preferably, the electron transport region described in the present invention comprises an electron transport layer.

[0139] Preferably, the light-emitting layer of the present invention comprises a host material and a guest material; preferably, the host material of the present invention comprises a single host material or a dual host material.

[0140] Preferably, the organic layer of the present invention is located on the outside of any one of the anode and the cathode, and includes a covering layer.

[0141] Preferably, the covering layer of the present invention comprises any one or more of the structures shown in Formula IV,

[0142]

[0143] In formula IV, X is selected from O or S;

[0144] The ring M and the ring N are the same as or different from each other, and are selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted phenanthrene ring, or a substituted or unsubstituted triphenylene ring, and the ring M and the ring N are not simultaneously selected from a substituted or unsubstituted benzene ring;

[0145] The x1 is selected from any one of O, S, and N(R3);

[0146] The R3 is selected from any one of 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 R3 can be directly combined with L b Bonding;

[0147] The z are the same as or different from each other and are selected from CH or N atoms. When z is bonded to other groups, the z is selected from C atoms;

[0148] Ar5 is selected from any one of a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 heteroaryl group, and a substituted or unsubstituted C6-C30 aromatic ring and a C3-C30 aliphatic ring fused ring.

[0149] The L a , L b , L c are the same as or different from each other and are 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 divalent substituted or unsubstituted C6-C30 aromatic ring and a C3-C30 aliphatic ring fused ring, and combinations thereof;

[0150] The R 11 , R 12 , R 13 , R 14 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, and substituted or unsubstituted C2-C30 heteroaryl;

[0151] The c1 is selected from 0, 1, 2, 3 or 4, the c2 is selected from 0, 1, 2 or 3, and the c3 is selected from 0, 1 or 2. When there are two or more R 11 , R 12 , R 13 , R 14 When two or more R 11 , R 12 , R 13 , R 14 Same or different from each other, or two adjacent R 14 They may be linked to each other to form a substituted or unsubstituted ring.

[0152] Preferably, in the formula I Select any one of the following structures,

[0153]

[0154]

[0155] The R 11 , R 12 The same as or different from each other, and selected from hydrogen, deuterium, cyano, halogen, trifluoromethyl, or any one or more of the following groups which are substituted or unsubstituted by one or more deuterium, cyano, trifluoromethyl, halogen, C1-C6 alkyl: methyl, ethyl, propyl, isopropyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, adamantyl, norbornane, phenyl, biphenyl, naphthyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl or naphthyridinyl;

[0156] The f1 is selected from 0, 1, 2, 3, 4, 5 or 6, the f2 is selected from 0, 1, 2 or 3, the f3 is selected from 0, 1, 2, 3, 4 or 5, the f4 is selected from 0, 1, 2, 3 or 4, and the f5 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0157] Preferably, in the formula I Any one selected from the following groups,

[0158]

[0159]

[0160] The x1 is selected from any one of O, S, and N(R3);

[0161] The R3 is selected from any one or more of the following groups substituted or unsubstituted by one or more deuteriums or C1-C6 alkyl groups: methyl, ethyl, propyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylene, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl or naphthyridinyl;

[0162] The R 13 , R 14The same as or different from each other, and selected from hydrogen, deuterium, cyano, halogen, trifluoromethyl, or any one or more of the following groups which are substituted or unsubstituted by one or more deuterium, cyano, trifluoromethyl, halogen, C1-C6 alkyl: methyl, ethyl, propyl, isopropyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, adamantyl, norbornane, phenyl, biphenyl, naphthyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl or naphthyridinyl;

[0163] The g1 is selected from 0, 1, 2, 3 or 4, the g2 is selected from 0, 1 or 2, the g3 is selected from 0, 1, 2 or 3, the g4 is selected from 0 or 1, the g5 is selected from 0, 1, 2, 3, 4, 5 or 6, the g6 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, the g7 is selected from 0, 1, 2, 3, 4 or 5, and the g8 is selected from 0, 1, 2, 3, 4, 5, 6 or 7.

[0164] Preferably, Ar5 is selected from any one of the following groups:

[0165]

[0166]

[0167] The v's are the same or different from each other and are selected from CH or N atoms. When v is bonded to other groups, the v's are selected from C atoms;

[0168] The t1 is selected from O, S, N (R 16 ), wherein t2 is selected from any one of CH or N atoms;

[0169] The T is selected from O, S, N (R z )、C(R x R y )

[0170] The R x , R y 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, and a fused ring of a substituted or unsubstituted C6-C30 aromatic ring and a C3-C30 aliphatic ring; or R x , R y They may be connected to each other to form a substituted or unsubstituted ring, or R x , R y Any one of them can be directly connected with L cBonding;

[0171] The R z Any one selected from 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 a fused ring of a substituted or unsubstituted C6-C30 aromatic ring and a C3-C30 aliphatic ring; or R z Can be directly with L c Bonding;

[0172] The R 15 any one or more of the following groups selected from hydrogen, deuterium, cyano, halogen, trifluoromethyl, or substituted or unsubstituted by one or more deuterium, cyano, trifluoromethyl, halogen, C1-C6 alkyl: methyl, ethyl, propyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, triphenylene, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, naphthyridinyl, trimethylsilyl, triethylsilyl, triisopropylsilyl, tri-tert-butylsilyl, or triphenylsilyl;

[0173] wherein h1 is selected from 0, 1, 2, 3, 4, or 5, wherein h2 is selected from 0, 1, 2, 3, or 4, wherein h3 is selected from 0, 1, 2, 3, 4, 5, 6, or 7, wherein h4 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, wherein h5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, wherein h6 is selected from 0, 1, 2, 3, 4, 5, or 6, wherein h7 is selected from 0, 1, 2, 3, 4, 5, 6, 7, or 8, wherein h8 is selected from 0, 1, 2, 3, 4, 5, 6, 7, or 8, wherein h9 is selected from 0, 1, 2, or 3, wherein h 10 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13;

[0174] The R 16 Any one or more of the following groups selected from the group consisting of methyl, ethyl, propyl, isopropyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, adamantyl, norbornane, phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylene, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl or naphthyridinyl.

[0175] Preferably, Ar5 is selected from any one of the following groups:

[0176]

[0177]

[0178]

[0179]

[0180] The t1 is selected from O, S, N (R 16 ), wherein t2 is selected from any one of CH or N atoms;

[0181] The T is selected from O, S, N (R z )、C(R x R y )

[0182] The R x , R y are the same as or different from each other and are selected from any one of the following groups which are substituted or unsubstituted by one or more deuteriums, C1 to C6: methyl, ethyl, propyl, isopropyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, adamantyl, norbornane, phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylene, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl or naphthyridinyl, or R x , R y They may be connected to each other to form a substituted or unsubstituted ring, or R x , R y Any one of them can be directly connected with L c Bonding;

[0183] The R z Any one of the following groups which are substituted or unsubstituted by one or more deuterium, C1-C6: methyl, ethyl, propyl, isopropyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, adamantyl, norbornyl, phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylene, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl or naphthyridinyl, or R z Can be directly with L c Bonding;

[0184] Preferably, the R x , R y They can be connected to each other to form a substituted or unsubstituted ring structure as follows:

[0185]

[0186] The R17 Any one or more of the following groups selected from hydrogen, deuterium or substituted or unsubstituted by one or more deuterium groups: methyl, ethyl, propyl, isopropyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, phenyl, biphenyl, naphthyl, pyridyl or pyrimidinyl;

[0187] The j1 is selected from 0, 1, 2, 3 or 4, the j2 is selected from 0, 1, 2, 3, 4, 5 or 6, the j3 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, the j4 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, and the j5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14.

[0188] Preferably, the L a , L b , L c are the same as or different from each other and are selected from a single bond or any one of the groups shown below,

[0189]

[0190] The R 18 are the same as or different from each other and are selected from any one of the following groups which are substituted or unsubstituted by one or more deuterium, cyano, trifluoromethyl, or C1-C6 alkyl groups: methyl, ethyl, isopropyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, adamantyl, norbornane, phenyl, biphenyl, naphthyl, pyridyl, pyrimidinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, naphthyridinyl, benzocyclopropane, benzocyclobutane, benzocyclopentane, or benzocyclohexane;

[0191] The k1 is selected from 0, 1, 2, 3 or 4, the k2 is selected from 0, 1, 2 or 3, the k3 is selected from 0, 1 or 2, the k4 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, and the k5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0192] Preferably, the triarylamine derivative of formula IV is selected from any one of the following structures,

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210] Some specific chemical structures of the derivatives represented by Formula IV of the present invention are listed above, but the present invention is not limited to these listed chemical structures. All derivatives based on the structure represented by Formula IV and having substituents as defined above should be included.

[0211] The present invention has no particular limitation on the materials of the thin films in the organic electroluminescent device, and materials known in the art can be used. The organic functional layers of the organic electroluminescent device mentioned above and the electrodes on both sides of the device are introduced below:

[0212] The organic electroluminescent device of the present invention is usually formed on a substrate. The substrate may be any substrate that does not change when forming electrodes or organic layers, for example, glass, plastic, polymer film, silicon, etc.

[0213] The anode material of the present invention preferably uses a material with high functional function to improve hole injection efficiency. The anode material that can be used in the present invention is selected from the following: 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 multilayer 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.

[0214] The hole injection layer material of the present invention is preferably a material with good hole acceptance ability, and can be selected from any one or more of the following structures: metal porphyrin, oligothiophene, arylamine derivatives, perylene derivatives, hexanitrile hexaazatriphenylene compounds, phthalocyanine compounds, polycyano conjugated organic materials, quinacridone compounds, anthraquinone compounds, and conductive polymers based on polyaniline and polythiophene, etc., but not limited thereto.

[0215] The hole transport layer material of the present invention preferably has a material with high hole mobility, and can be selected from any one or more of the following structures: carbazole derivatives, triarylamine derivatives, diphenylene diamine derivatives, fluorene derivatives, stilbene derivatives, hexanitrile hexaazatriphenylene compounds, quinacridone compounds, anthraquinone compounds, 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-methylbenzene)-3, 3'-dimethylbenzenediamine (HMTPD), etc., but are not limited thereto. The diamine derivatives described in the present invention are preferred.

[0216] The light-emitting layer material of the present invention comprises a main material and a doping material. The main material of the light-emitting layer can be selected from 4,4'-di(9-carbazole)biphenyl (CBP), 9,10-di(2-naphthyl)anthracene (ADN), 4,4-di(9-carbazolyl)biphenyl (CPB), 9,9'-(1,3-phenyl)di-9H-carbazole (mCP), 4,4',4"-tri(carbazole-9-yl)triphenylamine (TCTA), 9,10-di(1-naphthyl)anthracene (α-AND), N,N'-di-(1-naphthyl)- N,N'-diphenyl-[1,1':4',1":4",1"'-quadrphenyl]-4,4"'-diamino (4PNPB), 1,3,5-tri(9-carbazolyl)benzene (TCP), etc. In addition to the above materials and their combinations, the main material of the light-emitting layer may also include other known materials suitable for the light-emitting layer, but is not limited thereto. The light-emitting layer doping materials of the present invention are divided into blue light-emitting materials, green light-emitting materials and red light-emitting materials. The light-emitting layer doping materials 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)phenylvinyl]biphenyl (BDAVBi), 4,4'-bis[4-(di-p-tolylamino)phenylvinyl]biphenyl (DPAVBi), bis(2-hydroxyphenylpyridinium)beryllium (Bepp2), bis(4,6-difluorophenylpyridinium-C2,N)picolinyliridium (FIrpic), tris(2-phenylpyridinium)iridium (Ir( ppy)3), bis(2-phenylpyridine)iridium acetylacetonate (Ir(ppy)2(acac)), 9,10-bis[N-(p-tolyl)anilino]anthracene (TPA), 4-(dicyanomethylidene)-2-methyl-6-(4-dimethylaminophenylvinyl)-4H-pyran (DCM), tris[1-phenylisoquinoline-C2,N]iridium (III) (Ir(piq)3), bis(1-phenylisoquinoline)(acetylacetonate)iridium (Ir(piq)2(acac)), etc., but are not limited thereto.

[0217] The doping ratio of the host material and the guest material in the light-emitting layer of the present invention is determined according to the materials used. The amount of the doping material is preferably 0.1 to 70% by mass, more preferably 0.1 to 30% by mass, further preferably 1 to 30% by mass, further preferably 1 to 20% by mass, and particularly preferably 1 to 10% by mass.

[0218] The hole blocking layer material described in the present invention is preferably a material that can effectively block hole transmission and allow excitons to recombine in the light-emitting layer rather than in the electron transport layer. In addition to the nitrogen-containing heterocyclic derivatives provided by the present invention, any one or more of the following structures can be selected: phenanthroline derivatives, rare earth derivatives, imidazole derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, triazine derivatives, quinoline derivatives, diazine derivatives, azobenzene derivatives, anthrone derivatives, etc., but not limited thereto.

[0219] The electron transport layer material of the present invention is preferably a material with high electron mobility. It 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), di(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), etc., but not limited thereto.

[0220] The electron injection layer material described in the present invention is preferably a material having a smaller difference in potential barrier with the adjacent organic layer material. Specific examples may include: alkali metal compounds (such as lithium oxide, lithium fluoride, cesium carbonate, cesium fluoride, 8-hydroxyquinoline cesium, 8-hydroxyquinoline aluminum), organic metal salts (metal acetates, metal benzoates or metal stearates), molybdenum trioxide, metal aluminum, etc., but are not limited thereto.

[0221] The cathode material of the present invention preferably uses a material with a low work function that can promote electron injection into the organic layer to reduce the electron injection barrier. It 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 thereof, or mixtures thereof (e.g., a mixture of Ag and Mg), but is not limited thereto.

[0222] The covering layer of the present invention is provided on the outside of any one or more electrodes of the anode and the cathode to reduce the total reflection loss of light and improve the light extraction efficiency. It 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, diamine derivatives, porphyrin derivatives, phthalocyanine derivatives, Alq3, TPBi or mixtures thereof, but not limited thereto. The derivative of formula IV of the present invention is preferred.

[0223] The organic electroluminescent device of the present invention can be manufactured by sequentially stacking the above-mentioned structures. The manufacturing method can use a known method such as a wet film forming method and a dry film forming method. Specific examples of the wet film forming method include various coating methods such as a spin coating method, a dipping method, a casting method, and an inkjet method. Specific examples of the dry film forming method include a vacuum evaporation method, a sputtering method, a plasma method, an ion plating method, etc., but are not limited thereto.

[0224] The organic light-emitting device of the present invention can be widely used in the fields of panel display, lighting source, flexible OLED, electronic paper, organic solar cell, organic photoreceptor or organic thin film transistor, signboard, signal lamp, etc.

[0225] By the following examples, the present invention is explained in more detail, but it is not intended to limit the present invention. On the basis of this description, those of ordinary skill in the art will be able to implement the present invention and prepare other compounds and devices according to the present invention within the entire disclosed range without paying creative work.

[0226] The present invention provides a method for preparing compounds represented by Formula I and Formula IV, but the preparation method of the present invention is not limited thereto. The specific synthetic route is as follows:

[0227] [Synthetic route of formula I]

[0228] Preparation of intermediate M-1:

[0229]

[0230] Preparation of intermediate N-1:

[0231]

[0232] Preparation of compounds of formula I:

[0233]

[0234] Among them, X a They are the same as or different from each other and are selected from any one of Cl, Br, and I; the definitions of Ar1 to Ar4, L1 to L4, and L are the same as above.

[0235] [Synthetic route of Formula IV]

[0236] Preparation of raw material A-2:

[0237]

[0238] Preparation of compounds of formula IV:

[0239]

[0240] Among them, Xa are the same or different from each other and are selected from any one of Cl, Br, I; X, z, Ar1, L a ~L c , R 11 ~R 14 The limitations of c1 to c3, ring M, and ring N are the same as above.

[0241] The present invention can bond the above-mentioned substituents by methods known in the art, and the type and position of the substituents or the number of the substituents can be changed according to techniques known in the art.

[0242] Description of raw materials, reagents and characterization equipment:

[0243] The present invention has no particular limitation on the sources of the raw materials and reagents used in the following examples. The raw materials and reagents may be commercially available products or prepared by methods well known to those skilled in the art.

[0244] Mass spectrometry was performed using a British Waters G2-Si quadrupole tandem time-of-flight high-resolution mass spectrometer, with chloroform as the solvent;

[0245] The elemental analysis was performed using a Vario EL cube organic element analyzer from Elementar, Germany, with a sample mass of 5 to 10 mg.

[0246] Synthesis Example 1: Preparation of Compound 1-5

[0247]

[0248] Preparation of intermediate M-1-5:

[0249] Under nitrogen protection, a-1-5 (24.59 g, 90 mmol), b-1-5 (15.23 g, 90 mmol), sodium tert-butoxide (15.38 g, 160 mmol) were added to 400 ml of toluene, and palladium acetate (0.22 g, 1.00 mmol) and tri-tert-butylphosphine (4.0 mL of 0.50 M toluene solution, 2.00 mmol) were added under stirring, and the mixed solution of the above reactants 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 the liquid was separated by standing. The organic layer was collected and dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure. The temperature was lowered for crystallization, and suction was filtered. The obtained solid was recrystallized with ethyl acetate to obtain intermediate M-1-5 (26.03 g, 80%), with HPLC purity ≧99.81%. Mass spectrum m / z: 361.1815 (theoretical value: 361.1830).

[0250] Preparation of compound 1-5:

[0251] Under nitrogen protection, M-1-5 (16.27 g, 45 mmol), e-1-5 (6.24 g, 20 mmol), sodium tert-butoxide (5.77 g, 60 mmol) were added to 150 ml of toluene, and Pd2(dba)3 (0.23 g, 0.25 mmol) and BINAP (0.31 g, 0.50 mmol) were added under stirring, and the mixed solution of the above reactants was heated to reflux for 5.0 h. After the reaction was completed, it was cooled to room temperature, distilled water was added, extracted with dichloromethane, and the liquid was separated by standing. The organic layer was collected and dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. The temperature was lowered for crystallization, and suction was filtered. The obtained solid was recrystallized from toluene to obtain compound 1-5 (13.27 g, yield 76%), HPLC purity ≧99.93%. Mass spectrum m / z: 872.4115 (theoretical value: 872.4130). Theoretical element content (%) C 66 H 52 N2: C, 90.79; H, 6.00; N, 3.21. Measured element content (%): C, 90.80; H, 6.02; N, 3.19.

[0252] Synthesis Example 2: Preparation of Compound 1-31

[0253]

[0254] Preparation of intermediate M-1-31:

[0255] According to the preparation method of intermediate M-1-5 in Synthesis Example 1, a-1-5 was replaced with an equal mole of a-1-31, and b-1-5 was replaced with an equal mole of b-1-31 to obtain intermediate M-1-31 (28.19 g, 78%), HPLC purity ≧99.85%. Mass spectrum m / z: 401.2160 (theoretical value: 401.2143). Preparation of intermediate N-1-31:

[0256] According to the preparation method of intermediate M-1-5 in Synthesis Example 1, a-1-5 was replaced by an equal mole of a-1-31, and b-1-5 was replaced by an equal mole of d-1-31 to obtain intermediate N-1-31 (26.68 g, 82%), HPLC purity ≧99.82%. Mass spectrum m / z: 361.1812 (theoretical value: 361.1830).

[0257] Preparation of intermediate A-1-31:

[0258] Under nitrogen protection, A-1-31 (22.09 g, 55 mmol), g-1-31 (14.72 g, 55 mmol), sodium tert-butoxide (11.53 g, 120 mmol) were added to 400 ml of toluene, and Pd(OAc)2 (0.13 g, 0.60 mmol) and P(t-Bu)3 (2.4 mL of 0.5 M toluene solution, 1.20 mmol) were added under stirring, and the mixed solution of the above reactants was heated to reflux for 4.0 h. After the reaction was completed, it was cooled to room temperature, distilled water was added, extracted with dichloromethane, and the liquid was separated by standing. The organic layer was collected and dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure, cooled and crystallized, and filtered with suction. The obtained solid was recrystallized with toluene / ethanol = 8 / 1 to obtain intermediate A-1-31 (24.59 g, 76%), HPLC purity ≧99.87%. Mass spectrum m / z: 587.2361 (theoretical value: 587.2380).

[0259] Preparation of compound 1-31:

[0260] Under nitrogen protection, A-1-31 (17.65 g, 30 mmol), N-1-31 (10.84 g, 30 mmol), sodium tert-butoxide (7.21 g, 75 mmol) were added to 200 ml of toluene, and Pd2(dba)3 (0.27 g, 0.30 mmol) and P(t-Bu)3 (1.2 mL of 0.5 M toluene solution, 0.60 mmol) were added under stirring, and the mixed solution of the above reactants was heated to reflux for 6.0 h. After the reaction was completed, it was cooled to room temperature, distilled water was added, extracted with dichloromethane, and the liquid was separated by standing. The organic layer was collected and dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure. The temperature was lowered for crystallization, and suction was filtered. The obtained solid was recrystallized from toluene to obtain compound 1-31 (20.21 g, yield 74%), HPLC purity ≧99.90%. Mass spectrum m / z: 912.4455 (theoretical value: 912.4443). Theoretical element content (%) C 69 H 56 N2: C, 90.75; H, 6.18; N, 3.07. Measured element content (%): C, 90.74; H, 6.20; N, 3.08.

[0261] Synthesis Example 3: Preparation of Compound 1-55

[0262]

[0263] According to the same preparation method as compound 1-31 in Synthesis Example 2, a-1-31 was replaced by an equal mole of a-1-55, and b-1-31 was replaced by an equal mole of d-1-31 to obtain compound 1-55 (18.99 g), HPLC purity ≧99.93%. Mass spectrum m / z: 832.3830 (theoretical value: 832.3817). Theoretical element content (%) C 63 H 48 N2: C, 90.83; H, 5.81; N, 3.36. Measured element content (%): C, 90.82; H, 5.79; N, 3.37.

[0264] Synthesis Example 4: Preparation of Compound 1-63

[0265]

[0266] According to the same preparation method as compound 1-31 in Synthesis Example 2, a-1-31 was replaced with an equal mole of a-1-55, b-1-31 was replaced with an equal mole of d-1-31, a-1-31 was replaced with an equal mole of c-1-63, and e-1-31 was replaced with an equal mole of e-1-31 to obtain compound 1-63 (17.16 g), HPLC purity ≧99.91%. Mass spectrum m / z: 816.4369 (theoretical value: 816.4382). Theoretical element content (%) C 61 H 48 D4N2: C, 89.66; H, 6.91; N, 3.43. Measured element content (%): C, 89.67; H, 6.89; N, 3.42.

[0267] Synthesis Example 5: Preparation of Compound 1-80

[0268]

[0269] According to the same preparation method as compound 1-31 in Synthesis Example 2, a-1-31 was replaced with an equal mole of a-1-80, b-1-31 was replaced with an equal mole of d-1-31, a-1-31 was replaced with an equal mole of c-1-80, d-1-31 was replaced with an equal mole of d-1-80, and e-1-31 was replaced with an equal mole of e-1-80 to obtain compound 1-80 (17.85 g), HPLC purity ≧99.95%. Mass spectrum m / z: 837.4142 (theoretical value: 837.4131). Theoretical element content (%) C 63 H 43 D5N2: C, 90.28; H, 6.37; N, 3.34. Measured element content (%): C, 90.30; H, 6.36; N, 3.35.

[0270] Synthesis Example 6: Preparation of Compound 1-91

[0271]

[0272] According to the same preparation method as compound 1-5 in Synthesis Example 1, a-1-5 was replaced by an equal mole of a-1-31, and b-1-5 was replaced by an equal mole of d-1-31 to obtain compound 1-91 (14.49 g), HPLC purity ≧99.98%. Mass spectrum m / z: 872.4112 (theoretical value: 872.4130). Theoretical element content (%) C 66 H 52 N2: C, 90.79; H, 6.00; N, 3.21. Measured element content (%): C, 90.80; H, 6.02; N, 3.19.

[0273] Synthesis Example 7: Preparation of Compound 1-105

[0274]

[0275] According to the same preparation method as compound 1-5 in Synthesis Example 1, a-1-5 was replaced by an equal mole of a-1-105, and b-1-5 was replaced by an equal mole of b-1-105 to obtain compound 1-105 (13.97 g), HPLC purity ≧99.94%. Mass spectrum m / z: 872.4110 (theoretical value: 872.4130). Theoretical element content (%) C 66 H 52 N2: C, 90.79; H, 6.00; N, 3.21. Measured element content (%): C, 90.78; H, 6.01; N, 3.20.

[0276] Synthesis Example 8: Preparation of Compound 1-107

[0277]

[0278] According to the same preparation method as compound 1-5 in Synthesis Example 1, a-1-5 was replaced by an equal mole of a-1-107, and b-1-5 was replaced by an equal mole of b-1-105 to obtain compound 1-107 (13.92 g), HPLC purity ≧99.91%. Mass spectrum m / z: 880.4645 (theoretical value: 880.4633). Theoretical element content (%) C 66 H 44 D8N2: C, 89.96; H, 6.86; N, 3.18. Measured element content (%): C, 89.95; H, 6.87; N, 3.20.

[0279] Synthesis Example 9: Preparation of Compound 1-113

[0280]

[0281] According to the same preparation method as compound 1-5 in Synthesis Example 1, a-1-5 was replaced by an equal mole of a-1-31, and b-1-5 was replaced by an equal mole of b-1-113 to obtain compound 1-113 (14.13 g), HPLC purity ≧99.93%. Mass spectrum m / z: 882.4743 (theoretical value: 882.4758). Theoretical element content (%) C 66 H 42 D 10 N2: C, 89.75; H, 7.07; N, 3.17. Measured element content (%): C, 89.76; H, 7.10; N, 3.18.

[0282] Synthesis Example 10: Preparation of Compound 1-135

[0283]

[0284] According to the same preparation method as compound 1-5 in Synthesis Example 1, a-1-5 was replaced by an equal mole of a-1-135, and b-1-5 was replaced by an equal mole of d-1-31 to obtain compound 1-135 (11.82 g), HPLC purity ≧99.96%. Mass spectrum m / z: 720.3518 (theoretical value: 720.3504). Theoretical element content (%) C 54 H 44 N2: C, 89.96; H, 6.15; N, 3.89. Measured element content (%): C, 89.95; H, 6.16; N, 3.90.

[0285] Synthesis Example 11: Preparation of Compound 1-142

[0286]

[0287] According to the same preparation method as compound 1-5 in Synthesis Example 1, a-1-5 was replaced by an equal mole of a-1-80, and b-1-5 was replaced by an equal mole of b-1-142 to obtain compound 1-142 (14.56 g), HPLC purity ≧99.92%. Mass spectrum m / z: 944.6019 (theoretical value: 944.6009). Theoretical element content (%) C 70 H 76 N2: C, 88.93; H, 8.10; N, 2.96. Measured element content (%): C, 88.92; H, 8.09; N, 2.94.

[0288] Synthesis Example 12: Preparation of Compound 1-161

[0289]

[0290] According to the same preparation method as compound 1-5 in Synthesis Example 1, a-1-5 was replaced by an equal mole of a-1-161, and b-1-5 was replaced by an equal mole of b-1-161 to obtain compound 1-161 (11.6 g), HPLC purity ≧99.91%. Mass spectrum m / z: 766.4959 (theoretical value: 766.4947). Theoretical element content (%) C 56 H 30 D 18 N2: C, 87.68; H, 8.67; N, 3.65. Measured element content (%): C, 87.70; H, 8.68; N, 3.63.

[0291] Synthesis Example 13: Preparation of Compound 1-165

[0292]

[0293] According to the same preparation method as compound 1-5 in Synthesis Example 1, a-1-5 was replaced by an equal mole of a-1-165, and b-1-5 was replaced by an equal mole of d-1-31 to obtain compound 1-165 (14.32 g), HPLC purity ≧99.96%. Mass spectrum m / z: 872.4115 (theoretical value: 872.4130). Theoretical element content (%) C 66 H 52 N2: C, 90.79; H, 6.00; N, 3.21. Measured element content (%): C, 90.80; H, 6.02; N, 3.19.

[0294] Synthesis Example 14: Preparation of Compound 1-203

[0295]

[0296] According to the same preparation method as compound 1-5 in Synthesis Example 1, a-1-5 was replaced by an equal molar amount of a-1-31, b-1-5 was replaced by an equal molar amount of b-1-105, and e-1-5 was replaced by an equal molar amount of e-1-203 to obtain compound 1-203 (13.88 g), HPLC purity ≧99.90%. Mass spectrum m / z: 900.4455 (theoretical value: 900.4443). Theoretical element content (%) C 68 H 56 N2: C, 90.63; H, 6.26; N, 3.11. Measured element content (%): C, 90.62; H, 6.27; N, 3.09.

[0297] Synthesis Example 15: Preparation of Compound 1-208

[0298]

[0299] According to the same preparation method as compound 1-31 in Synthesis Example 2, a-1-31 was replaced with an equal molar amount of a-1-55 to obtain compound 1-208 (21.22 g), HPLC purity ≧99.97%. Mass spectrum m / z: 872.4113 (theoretical value: 872.4130). Theoretical element content (%) C 66 H 52 N2: C, 90.79; H, 6.00; N, 3.21. Measured element content (%): C, 90.80; H, 6.01; N, 3.19.

[0300] Synthesis Example 16: Preparation of Compound 1-231

[0301]

[0302] According to the same preparation method as compound 1-5 in Synthesis Example 1, a-1-5 was replaced by an equal mole of a-1-31, b-1-5 was replaced by an equal mole of b-1-31, and e-1-5 was replaced by an equal mole of e-1-231 to obtain compound 1-231 (14.49 g), HPLC purity ≧99.92%. Mass spectrum m / z: 952.4772 (theoretical value: 952.4756). Theoretical element content (%) C 72 H 60 N2: C, 90.72; H, 6.34; N, 2.94. Measured element content (%): C, 90.69; H, 6.35; N, 2.93.

[0303] Synthesis Example 17: Preparation of Compound 1-264

[0304]

[0305] According to the same preparation method as compound 1-31 in Synthesis Example 2, a-1-31 was replaced with an equal mole of a-1-264, b-1-31 was replaced with an equal mole of b-1-264, a-1-31 was replaced with an equal mole of c-1-264, d-1-31 was replaced with an equal mole of b-1-264, and e-1-31 was replaced with an equal mole of e-1-264 to obtain compound 1-264 (16.44 g), HPLC purity ≧99.91%. Mass spectrum m / z: 760.3742 (theoretical value: 760.3756). Theoretical element content (%) C 57 H 40D4N2: C, 89.96; H, 6.36; N, 3.68. Measured element content (%): C, 89.95; H, 6.37; N, 3.70.

[0306] Synthesis Example 18: Preparation of Compound 1-285

[0307]

[0308] According to the same preparation method as compound 1-31 in Synthesis Example 2, a-1-31 was replaced with an equal mole of a-1-285, b-1-31 was replaced with an equal mole of b-1-285, a-1-31 was replaced with an equal mole of a-1-105, d-1-31 was replaced with an equal mole of d-1-285, and e-1-31 was replaced with an equal mole of e-1-285 to obtain compound 1-285 (18.62 g), HPLC purity ≧ 99.93%. Mass spectrum m / z: 861.5018 (theoretical value: 861.5008). Theoretical element content (%) C 64 H 47 D9N2: C, 89.15; H, 7.60; N, 3.25. Measured element content (%): C, 89.16; H, 7.58; N, 3.24.

[0309] Synthesis Example 19: Preparation of Compound 1-319

[0310]

[0311] According to the same preparation method as compound 1-5 in Synthesis Example 1, a-1-5 was replaced by an equal molar amount of a-1-31, b-1-5 was replaced by an equal molar amount of d-1-31, and e-1-5 was replaced by an equal molar amount of e-1-319 to obtain compound 1-319 (14.03 g), HPLC purity ≧99.95%. Mass spectrum m / z: 922.4270 (theoretical value: 922.4287). Theoretical element content (%) C 70 H 54 N2: C, 91.07; H, 5.90; N, 3.03. Measured element content (%): C, 91.10; H, 5.89; N, 3.02.

[0312] Synthesis Example 20: Preparation of Compound 1-338

[0313]

[0314] According to the same preparation method as compound 1-5 in Synthesis Example 1, a-1-5 was replaced by an equal molar amount of a-1-31, b-1-5 was replaced by an equal molar amount of d-1-31, and e-1-5 was replaced by an equal molar amount of e-1-338 to obtain compound 1-338 (15.18 g), HPLC purity ≧99.94%. Mass spectrum m / z: 972.4432 (theoretical value: 972.4443). Theoretical element content (%) C 74 H 56 N2: C, 91.32; H, 5.80; N, 2.88. Measured element content (%): C, 91.31; H, 5.79; N, 2.90.

[0315] Synthesis Example 21: Preparation of Compound 1-394

[0316]

[0317] According to the same preparation method as compound 1-5 in Synthesis Example 1, a-1-5 was replaced by an equal mole of a-1-55, b-1-5 was replaced by an equal mole of d-1-31, and e-1-5 was replaced by an equal mole of e-1-394 to obtain compound 1-394 (13.16 g), HPLC purity ≧99.97%. Mass spectrum m / z: 832.3834 (theoretical value: 832.3817). Theoretical element content (%) C 63 H 48 N2: C, 90.83; H, 5.81; N, 3.36. Measured element content (%): C, 90.82; H, 5.79; N, 3.37.

[0318] Synthesis Example 22: Preparation of Compound 1-433

[0319]

[0320] According to the same preparation method as compound 1-5 in Synthesis Example 1, a-1-5 was replaced by an equal mole of a-1-31, and b-1-5 was replaced by an equal mole of b-1-433 to obtain compound 1-433 (15.24 g), HPLC purity ≧99.94%. Mass spectrum m / z: 988.5679 (theoretical value: 988.5696). Theoretical element content (%) C 74 H 72 N2: C, 89.83; H, 7.34; N, 2.83. Measured element content (%): C, 89.81; H, 7.32; N, 2.85.

[0321] Synthesis Example 23: Preparation of Compound 1-480

[0322]

[0323] According to the same preparation method as compound 1-31 in Synthesis Example 2, b-1-31 was replaced by an equal mole of b-1-480, and a-1-31 was replaced by an equal mole of c-1-480 to obtain compound 1-480 (16.58 g), HPLC purity ≧99.97%. Mass spectrum m / z: 690.3808 (theoretical value: 690.3819). Theoretical element content (%) C 51 H 30 D 10 N2: C, 88.65; H, 7.29; N, 4.05. Measured element content (%): C, 88.66; H, 7.30; N, 4.03.

[0324] Synthesis Example 24: Preparation of Compound 1-537

[0325]

[0326] According to the same preparation method as compound 1-31 in Synthesis Example 2, a-1-31 was replaced with an equal mole of a-1-537, b-1-31 was replaced with an equal mole of d-1-31, and a-1-31 was replaced with an equal mole of c-1-537 to obtain compound 1-537 (17.37 g), HPLC purity ≧99.93%. Mass spectrum m / z: 826.4274 (theoretical value: 826.4287). Theoretical element content (%) C 62 H 54 N2: C, 90.03; H, 6.58; N, 3.39. Measured element content (%): C, 90.02; H, 6.60; N, 3.40.

[0327] Synthesis Example 25: Preparation of Compound 1-571

[0328]

[0329] According to the same preparation method as compound 1-5 in Synthesis Example 1, a-1-5 was replaced by an equal mole of a-1-31, b-1-5 was replaced by an equal mole of b-1-571, and g-1-5 was replaced by an equal mole of g-1-571 to obtain compound 1-571 (12.23 g), HPLC purity ≧99.90%. Mass spectrum m / z: 848.5082 (theoretical value: 848.5070). Theoretical element content (%) C 63 H 64 N2: C, 89.10; H, 7.60; N, 3.30. Measured element content (%): C, 89.09; H, 7.61; N, 3.28.

[0330] Synthesis Example 26: Preparation of Raw Material A-2-243

[0331]

[0332] Under nitrogen protection, a-2-243 (14.62 g, 85.00 mmol), b-2-243 (26.37 g, 85.00 mmol), Pd(PPh3)4 (1.04 g, 0.90 mmol), K2CO3 (23.50 g, 170 mmol) and 450 mL (toluene: ethanol: water = 2:1:1) mixed solvent were added to the reaction bottle, the mixture was stirred, and the mixed solution of the above reactants 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 the liquid was separated by standing. The organic layer was collected and dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure. The obtained solid was recrystallized with toluene and dried to obtain intermediate A-2-243 (17.55 g, yield 75%); HPLC purity ≧99.72%. Mass spectrum m / z: 275.0781 (theoretical value: 275.0769).

[0333] According to the same preparation method as that of the intermediate A-2-243 in Synthesis Example 26, the raw material a and the raw material b are replaced with equal moles to prepare the raw material A, as shown in the following table:

[0334]

[0335]

[0336] Synthesis Example 27: Preparation of Compound 2-11

[0337]

[0338] Preparation of intermediate M-2-11:

[0339] Under nitrogen protection, A-2-11 (9.01 g, 40.00 mmol), B-2-11 (11.65 g, 40.00 mmol), Pd(OAc)2 (0.11 g, 0.50 mmol), P(t-Bu)3 (2.00 mL of 0.5 M toluene solution, 1.00 mmol), NaOt-Bu (9.61 g, 100.00 mmol) and 300 ml of toluene solvent were added to the reaction bottle, the mixture was stirred, and the mixed solution of the above reactants 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 the liquid was separated by standing. The organic layer was collected and dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure. The temperature was lowered for crystallization, and suction was filtered. The obtained solid was recrystallized from ethyl acetate to obtain intermediate M-2-11 (13.42 g, yield 77%), HPLC purity ≧99.88%. Mass spectrum m / z: 435.2040 (theoretical value: 435.2021).

[0340] Preparation of compound 2-11:

[0341] Under nitrogen protection, the intermediate M-2-11 (8.71 g, 20.00 mmol), C-2-11 (5.94 g, 20.00 mmol), Pd2(dba)3 (0.23 g, 0.25 mmol), X-Phos (0.24 g, 0.50 mmol), NaOt-Bu (4.80 g, 50.00 mmol) and 200 ml of toluene solvent were stirred, and the mixed solution of the above reactants was heated to reflux for 6 h. After the reaction was completed, it was cooled to room temperature, distilled water was added, extracted with dichloromethane, and the liquid was separated by standing. The organic layer was collected and dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure. The temperature was lowered for crystallization, and suction was filtered. The obtained solid was recrystallized from toluene to obtain compound 2-11 (9.91 g, yield 76%), HPLC purity ≧99.93%. Mass spectrum m / z: 651.2581 (theoretical value: 651.2596). Theoretical element content (%) C 46 H 37 NOS: C, 84.76; H, 5.72; N, 2.15. Measured element content (%): C, 84.77; H, 5.69; N, 2.16.

[0342] Synthesis Example 28: Preparation of Compound 2-18

[0343]

[0344] According to the same preparation method of compound 2-11 in Synthesis Example 27, A-2-11 was replaced by an equal molar amount of A-2-18, B-2-11 was replaced by an equal molar amount of B-2-18, and C-2-11 was replaced by an equal molar amount of C-2-18 to obtain compound 2-18 (8.32 g), HPLC purity ≧99.90%. Mass spectrum m / z: 577.2059 (theoretical value: 577.2042). Theoretical element content (%) C 42 H 27 NO2: C, 87.33; H, 4.71; N, 2.42. Measured element content (%): C, 87.35; H, 4.69; N, 2.41.

[0345] Synthesis Example 29: Preparation of Compound 2-22

[0346]

[0347] According to the same preparation method of compound 2-11 in Synthesis Example 27, B-2-11 was replaced by an equal mole of B-2-22, and C-2-11 was replaced by an equal mole of C-2-22 to obtain compound 2-22 (8.62 g), HPLC purity ≧ 99.91%. Mass spectrum m / z: 598.2114 (theoretical value: 598.2127). Theoretical element content (%) C 42 H 22 D5NOS: C, 84.25; H, 5.39; N, 2.34. Measured element content (%): C, 84.23; H, 5.42; N, 2.35.

[0348] Synthesis Example 30: Preparation of Compound 2-44

[0349]

[0350] According to the same preparation method of compound 2-11 in Synthesis Example 27, B-2-11 was replaced by an equal mole of B-2-44, and C-2-11 was replaced by an equal mole of C-2-44 to obtain compound 2-44 (9.38 g), HPLC purity ≧ 99.95%. Mass spectrum m / z: 633.2137 (theoretical value: 633.2126). Theoretical element content (%) C 45 H 31 NOS: C, 85.28; H, 4.93; N, 2.21. Measured element content (%): C, 85.30; H, 4.90; N, 2.19.

[0351] Synthesis Example 31: Preparation of Compound 2-75

[0352]

[0353] According to the same preparation method of compound 2-11 in Synthesis Example 27, B-2-11 was replaced by an equal mole of B-2-75, and C-2-11 was replaced by an equal mole of C-2-75 to obtain compound 2-75 (10.04 g), HPLC purity ≧99.98%. Mass spectrum m / z: 643.1951 (theoretical value: 643.1970). Theoretical element content (%) C 46 H 29 NOS: C, 85.82; H, 4.54; N, 2.18. Measured element content (%): C, 85.79; H, 4.55; N, 2.21.

[0354] Synthesis Example 32: Preparation of Compound 2-89

[0355]

[0356] According to the same preparation method of compound 2-11 in Synthesis Example 27, B-2-11 was replaced by an equal mole of B-2-89, and C-2-11 was replaced by an equal mole of C-2-89 to obtain compound 2-89 (9.24 g), HPLC purity ≧ 99.92%. Mass spectrum m / z: 650.2421 (theoretical value: 650.2409). Theoretical element content (%) C 46 H 22 D7NOS: C, 84.89; H, 5.57; N, 2.15. Measured element content (%): C, 84.91; H, 5.60; N, 2.13.

[0357] Synthesis Example 33: Preparation of Compound 2-91

[0358]

[0359] According to the same preparation method of compound 2-11 in Synthesis Example 27, B-2-11 was replaced by an equal mole of B-2-91, and C-2-11 was replaced by an equal mole of C-2-91 to obtain compound 2-91 (9.79 g), HPLC purity ≧ 99.94%. Mass spectrum m / z: 643.1953 (theoretical value: 643.1970). Theoretical element content (%) C 46 H 29 NOS: C, 85.82; H, 4.54; N, 2.18. Measured element content (%): C, 85.80; H, 4.56; N, 2.20.

[0360] Synthesis Example 34: Preparation of Compound 2-93

[0361]

[0362] According to the same preparation method of compound 2-11 in Synthesis Example 27, B-2-11 was replaced by an equal mole of B-2-93, and C-2-11 was replaced by an equal mole of C-2-93 to obtain compound 2-93 (9.85 g), HPLC purity ≧ 99.93%. Mass spectrum m / z: 693.2140 (theoretical value: 693.2126). Theoretical element content (%) C 50 H 31 NOS: C, 86.55; H, 4.50; N, 2.02. Measured element content (%): C, 86.57; H, 4.48; N, 2.05.

[0363] Synthesis Example 35: Preparation of Compound 2-110

[0364]

[0365] According to the same preparation method of compound 2-11 in Synthesis Example 27, B-2-11 was replaced by an equal mole of B-2-110, and C-2-11 was replaced by an equal mole of C-2-75 to obtain compound 2-110 (10.51 g), HPLC purity ≧99.92%. Mass spectrum m / z: 719.2271 (theoretical value: 719.2283). Theoretical element content (%) C 52 H 33 NOS: C, 86.76; H, 4.62; N, 1.95. Measured element content (%): C, 86.80; H, 4.60; N, 1.93.

[0366] Synthesis Example 36: Preparation of Compound 2-124

[0367]

[0368] According to the same preparation method of compound 2-11 in Synthesis Example 27, A-2-11 was replaced by an equal mole of A-2-124, B-2-11 was replaced by an equal mole of B-2-75, and C-2-11 was replaced by an equal mole of C-2-124 to obtain compound 2-124 (10.09 g), HPLC purity ≧99.94%. Mass spectrum m / z: 720.2250 (theoretical value: 720.2235). Theoretical element content (%) C 51 H 32 N2OS: C, 84.97; H, 4.47; N, 3.89. Measured element content (%): C, 84.94; H, 4.20; N, 3.90.

[0369] Synthesis Example 37: Preparation of Compound 2-132

[0370]

[0371] According to the same preparation method of compound 2-11 in Synthesis Example 27, B-2-11 was replaced by an equal mole of B-2-132, and C-2-11 was replaced by an equal mole of C-2-75 to obtain compound 2-132 (10.83 g), HPLC purity ≧ 99.96%. Mass spectrum m / z: 721.2173 (theoretical value: 721.2188). Theoretical element content (%) C 50 H 31 N3OS: C, 83.19; H, 4.33; N, 5.82. Measured element content (%): C, 83.21; H, 4.35; N, 5.79.

[0372] Synthesis Example 38: Preparation of Compound 2-143

[0373]

[0374] According to the same preparation method of compound 2-11 in Synthesis Example 27, B-2-11 was replaced by an equal mole of B-2-143, and C-2-11 was replaced by an equal mole of C-2-75 to obtain compound 2-143 (15.09 g), HPLC purity ≧ 99.92%. Mass spectrum m / z: 769.2451 (theoretical value: 769.2439). Theoretical element content (%) C 56 H 35 NOS: C, 87.36; H, 4.58; N, 1.82. Measured element content (%): C, 87.40; H, 4.60; N, 1.79.

[0375] Synthesis Example 39: Preparation of Compound 2-146

[0376]

[0377] According to the same preparation method of compound 2-11 in Synthesis Example 27, B-2-11 was replaced by an equal mole of B-2-146, and C-2-11 was replaced by an equal mole of C-2-75 to obtain compound 2-146 (9.99 g), HPLC purity ≧ 99.97%. Mass spectrum m / z: 693.2110 (theoretical value: 693.2126). Theoretical element content (%) C 50 H 31 NOS: C, 86.55; H, 4.50; N, 2.02. Measured element content (%): C, 86.56; H, 4.48; N, 2.05.

[0378] Synthesis Example 40: Preparation of Compound 2-243

[0379]

[0380] According to the same preparation method of compound 2-11 in Synthesis Example 27, A-2-11 was replaced by an equal molar amount of A-2-243, B-2-11 was replaced by an equal molar amount of B-2-243, and C-2-11 was replaced by an equal molar amount of C-2-22 to obtain compound 2-243 (9.21 g), HPLC purity ≧ 99.93%. Mass spectrum m / z: 657.1776 (theoretical value: 657.1762). Theoretical element content (%) C 46 H 27 NO2S: C, 83.99; H, 4.14; N, 2.13. Measured element content (%): C, 83.96; H, 4.15; N, 2.09.

[0381] Synthesis Example 41: Preparation of Compound 2-266

[0382]

[0383] According to the same preparation method of compound 2-11 in Synthesis Example 27, A-2-11 was replaced by an equal mole of A-2-266, B-2-11 was replaced by an equal mole of B-2-266, and C-2-11 was replaced by an equal mole of C-2-266 to obtain compound 2-266 (8.96 g), HPLC purity ≧ 99.91%. Mass spectrum m / z: 658.2092 (theoretical value: 658.2079). Theoretical element content (%) C 46 H 30 N2OS: C, 83.86; H, 4.59; N, 4.25. Measured element content (%): C, 83.90; H, 4.61; N, 4.23.

[0384] Synthesis Example 42: Preparation of Compound 2-285

[0385]

[0386] According to the same preparation method of compound 2-11 in Synthesis Example 27, A-2-11 was replaced by an equal mole of A-2-18, B-2-11 was replaced by an equal mole of B-2-285, and C-2-11 was replaced by an equal mole of C-2-285 to obtain compound 2-285 (8.96 g), HPLC purity ≧ 99.90%. Mass spectrum m / z: 717.2654 (theoretical value: 717.2668). Theoretical element content (%) C 53 H 35 NO2: C, 88.68; H, 4.91; N, 1.95. Measured element content (%): C, 88.70; H, 4.89; N, 1.96.

[0387] Synthesis Example 43: Preparation of Compound 2-289

[0388]

[0389] According to the same preparation method of compound 2-11 in Synthesis Example 27, A-2-11 was replaced by an equal mole of A-2-18, B-2-11 was replaced by an equal mole of B-2-289, and C-2-11 was replaced by an equal mole of C-2-289 to obtain compound 2-289 (8.55 g), HPLC purity ≧99.94%. Mass spectrum m / z: 657.1771 (theoretical value: 657.1762). Theoretical element content (%) C 46 H 27 NO2S: C, 83.99; H, 4.14; N, 2.13. Measured element content (%): C, 83.97; H, 4.16; N, 2.09.

[0390] Synthesis Example 44: Preparation of Compound 2-300

[0391]

[0392] According to the same preparation method of compound 2-11 in Synthesis Example 27, B-2-11 was replaced by an equal mole of C-2-75, and C-2-11 was replaced by an equal mole of C-2-75 to obtain compound 2-300 (9.47 g), HPLC purity ≧99.96%. Mass spectrum m / z: 657.1775 (theoretical value: 657.1762). Theoretical element content (%) C 46 H 27 NO2S: C, 83.99; H, 4.14; N, 2.13. Measured element content (%): C, 83.95; H, 4.12; N, 2.11.

[0393] Synthesis Example 45: Preparation of Compound 2-322

[0394]

[0395] According to the same preparation method of compound 2-11 in Synthesis Example 27, A-2-11 was replaced by an equal mole of A-2-322, B-2-11 was replaced by an equal mole of C-2-22, and C-2-11 was replaced by an equal mole of C-2-22 to obtain compound 2-322 (9.76 g), HPLC purity ≧ 99.91%. Mass spectrum m / z: 717.2318 (theoretical value: 717.2304). Theoretical element content (%) C 52 H 31NO3: C, 87.01; H, 4.35; N, 1.95. Measured element content (%): C, 87.05; H, 4.33; N, 1.96.

[0396] Synthesis Example 46: Preparation of Compound 2-330

[0397]

[0398] According to the same preparation method of compound 2-11 in Synthesis Example 27, B-2-11 was replaced by an equal mole of B-2-330, and C-2-11 was replaced by an equal mole of C-2-75 to obtain compound 2-330 (10.27 g), HPLC purity ≧ 99.98%. Mass spectrum m / z: 649.1549 (theoretical value: 649.1534). Theoretical element content (%) C 44 H 27 NOS2: C, 81.33; H, 4.19; N, 2.16. Measured element content (%): C, 81.35; H, 4.21; N, 2.13.

[0399] Synthesis Example 47: Preparation of Compound 2-338

[0400]

[0401] According to the same preparation method of compound 2-11 in Synthesis Example 27, A-2-11 was replaced by an equal mole of A-2-338, B-2-11 was replaced by an equal mole of B-2-338, and C-2-11 was replaced by an equal mole of C-2-75 to obtain compound 2-338 (9.78 g), HPLC purity ≧ 99.95%. Mass spectrum m / z: 651.1454 (theoretical value: 651.1439). Theoretical element content (%) C 42 H 25 N3OS2: C, 77.39; H, 3.87; N, 6.45. Measured element content (%): C, 77.41; H, 3.90; N, 6.42.

[0402] Synthesis Example 48: Preparation of Compound 2-353

[0403]

[0404] According to the same preparation method of compound 2-11 in Synthesis Example 27, B-2-11 was replaced by an equal mole of B-2-353, and C-2-11 was replaced by an equal mole of C-2-75 to obtain compound 2-353 (9.55 g), HPLC purity ≧ 99.93%. Mass spectrum m / z: 653.1769 (theoretical value: 653.1785). Theoretical element content (%) C44 H 23 D4NOS2: C, 80.83; H, 4.78; N, 2.14. Measured element content (%): C, 80.79; H, 4.80; N, 2.13.

[0405] Synthesis Example 49: Preparation of Compound 2-356

[0406]

[0407] According to the same preparation method of compound 2-11 in Synthesis Example 27, A-2-11 was replaced by an equal mole of A-2-18, B-2-11 was replaced by an equal mole of B-2-330, and C-2-11 was replaced by an equal mole of C-2-75 to obtain compound 2-356 (9.51 g), HPLC purity ≧99.94%. Mass spectrum m / z: 633.1775 (theoretical value: 633.1762). Theoretical element content (%) C 44 H 27 NO2S: C, 83.39; H, 4.29; N, 2.21. Measured element content (%): C, 83.41; H, 4.30; N, 2.18.

[0408] Synthesis Example 50: Preparation of Compound 2-388

[0409]

[0410] According to the same preparation method of compound 2-11 in Synthesis Example 27, A-2-11 was replaced by an equal mole of A-2-388, B-2-11 was replaced by an equal mole of B-2-330, and C-2-11 was replaced by an equal mole of C-2-75 to obtain compound 2-388 (10.07 g), HPLC purity ≧99.91%. Mass spectrum m / z: 689.1831 (theoretical value: 689.1847). Theoretical element content (%) C 47 H 31 NOS2: C, 81.83; H, 4.53; N, 2.03. Measured element content (%): C, 81.79; H, 4.55; N, 2.02.

[0411] Synthesis Example 51: Preparation of Compound 2-416

[0412]

[0413] According to the same preparation method of compound 2-11 in Synthesis Example 27, B-2-11 was replaced by an equal mole of B-2-416, and C-2-11 was replaced by an equal mole of C-2-75 to obtain compound 2-416 (9.55 g), HPLC purity ≧ 99.95%. Mass spectrum m / z: 634.1733 (theoretical value: 634.1715). Theoretical element content (%) C 43 H 26 N2O2S: C, 81.37; H, 4.13; N, 4.41. Measured element content (%): C, 81.40; H, 4.09; N, 4.39.

[0414] Synthesis Example 52: Preparation of Compound 2-425

[0415]

[0416] According to the same preparation method of compound 2-11 in Synthesis Example 27, A-2-11 was replaced by an equal mole of A-2-425, B-2-11 was replaced by an equal mole of B-2-425, and C-2-11 was replaced by an equal mole of C-2-22 to obtain compound 2-425 (10.07 g), HPLC purity ≧99.90%. Mass spectrum m / z: 685.1839 (theoretical value: 685.1824). Theoretical element content (%) C 46 H 27 N3O2S: C, 80.56; H, 3.97; N, 6.13. Measured element content (%): C, 80.60; H, 3.92; N, 6.14.

[0417] Synthesis Example 53: Preparation of Compound 2-525

[0418]

[0419] According to the same preparation method of compound 2-11 in Synthesis Example 27, B-2-11 was replaced by an equal mole of B-2-525, and C-2-11 was replaced by an equal mole of C-2-525 to obtain compound 2-525 (9.32 g), HPLC purity ≧ 99.92%. Mass spectrum m / z: 665.2223 (theoretical value: 665.2211). Theoretical element content (%) C 46 H 35 NS2: C, 82.97; H, 5.30; N, 2.10. Measured element content (%): C, 82.95; H, 5.26; N, 2.12.

[0420] Synthesis Example 54: Preparation of Compound 2-532

[0421]

[0422] According to the same preparation method of compound 2-11 in Synthesis Example 27, A-2-11 was replaced by an equal mole of A-2-18, B-2-11 was replaced by an equal mole of B-2-532, and C-2-11 was replaced by an equal mole of C-2-525 to obtain compound 2-532 (8.33 g), HPLC purity ≧ 99.94%. Mass spectrum m / z: 594.1782 (theoretical value: 594.1766). Theoretical element content (%) C 41 H 26 N2OS: C, 82.80; H, 4.41; N, 4.71. Measured element content (%): C, 82.78; H, 4.36; N, 4.72.

[0423] Synthesis Example 55: Preparation of Compound 2-549

[0424]

[0425] According to the same preparation method of compound 2-11 in Synthesis Example 27, B-2-11 was replaced by an equal mole of B-2-549, and C-2-11 was replaced by an equal mole of C-2-549 to obtain compound 2-549 (9.05 g), HPLC purity ≧ 99.96%. Mass spectrum m / z: 659.1751 (theoretical value: 659.1741). Theoretical element content (%) C 46 H 29 NS2: C, 83.73; H, 4.43; N, 2.12. Measured element content (%): C, 83.80; H, 4.39; N, 2.11.

[0426] Synthesis Example 56: Preparation of Compound 2-630

[0427]

[0428] According to the same preparation method of compound 2-11 in Synthesis Example 27, A-2-11 was replaced by an equal mole of A-2-630, B-2-11 was replaced by an equal mole of B-2-630, and C-2-11 was replaced by an equal mole of C-2-630 to obtain compound 2-630 (9.79 g), HPLC purity ≧ 99.92%. Mass spectrum m / z: 719.2382 (theoretical value: 719.2395). Theoretical element content (%) C 51 H 33 N3S: C, 85.09; H, 4.62; N, 5.84. Measured element content (%): C, 85.11; H, 4.58; N, 5.86.

[0429] Synthesis Example 57: Preparation of Compound 2-722

[0430]

[0431] According to the same preparation method of compound 2-11 in Synthesis Example 27, A-2-11 was replaced by an equal mole of A-2-722, B-2-11 was replaced by an equal mole of B-2-722, and C-2-11 was replaced by an equal mole of C-2-525 to obtain compound 2-722 (10.06 g), HPLC purity ≧99.90%. Mass spectrum m / z: 750.1809 (theoretical value: 750.1800). Theoretical element content (%) C 51 H 30 N2OS2: C, 81.57; H, 4.03; N, 3.73. Measured element content (%): C, 81.60; H, 4.06; N, 3.71.

[0432] Synthesis Example 58: Preparation of Compound 2-747

[0433]

[0434] According to the same preparation method of compound 2-11 in Synthesis Example 27, A-2-11 was replaced by an equal mole of A-2-18, B-2-11 was replaced by an equal mole of B-2-747, and C-2-11 was replaced by an equal mole of C-2-747 to obtain compound 2-747 (10.16 g), HPLC purity ≧ 99.93%. Mass spectrum m / z: 757.2451 (theoretical value: 757.2439). Theoretical element content (%) C 55 H 35 NOS: C, 87.16; H, 4.65; N, 1.85. Measured element content (%): C, 87.18; H, 4.70; N, 1.83.

[0435] Synthesis Example 59: Preparation of Compound 2-791

[0436]

[0437] According to the same preparation method of compound 2-11 in Synthesis Example 27, B-2-11 was replaced by an equal mole of B-2-791, and C-2-11 was replaced by an equal mole of C-2-75 to obtain compound 2-791 (10.92 g), HPLC purity ≧ 99.96%. Mass spectrum m / z: 665.2221 (theoretical value: 665.2209). Theoretical element content (%) C 45 H 35NOSSi: C, 81.16; H, 5.30; N, 2.10. Measured element content (%): C, 81.20; H, 5.28; N, 2.09.

[0438] [Device Example 1]

[0439] First, the ITO substrate was cleaned three times in distilled water and ultrasonically washed for 15 minutes. After the distilled water cleaning was completed, ultrasonic washing was performed in sequence with isopropanol, acetone, methanol and other solvents, and then dried at 120°C.

[0440] By using a vacuum evaporation method, HAT-CN is evaporated on a cleaned ITO substrate as a hole injection layer material with an evaporation thickness of 35 nm; compound 1-5 is evaporated on the hole injection layer as a hole transport layer material with an evaporation thickness of 80 nm; RH-1:RD-1=98:2 (mass ratio) is evaporated on the hole transport layer as a light-emitting layer with an evaporation thickness of 40 nm; HB-1 is evaporated on the light-emitting layer as a hole blocking layer with an evaporation thickness of 40 nm; ET-1 and Liq (doping mass ratio of 1:1) are evaporated on the hole blocking layer as electron transport layer materials with an evaporation thickness of 30 nm; LiF is evaporated on the electron transport layer as an electron injection layer with an evaporation thickness of 1.0 nm; then Al is evaporated on the electron injection layer as a cathode with an evaporation thickness of 120 nm; thereby preparing an organic electroluminescent device.

[0441]

[0442] [Device Examples 2 to 25]

[0443] The compound 1-31, compound 1-55, compound 1-63, compound 1-80, compound 1-91, compound 1-105, compound 1-107, compound 1-113, compound 1-135, compound 1-142, compound 1-161, compound 1-165, compound 1-203, compound 1-208, compound 1-231, compound 1-264, compound 1-285, compound 1-319, compound 1-338, compound 1-394, compound 1-433, compound 1-480, compound 1-537, and compound 1-571 of the present invention are used to replace compound 1-5 in device example 1 as a hole transport layer. Except for this, an organic electroluminescent device is prepared by the same preparation method as device example 1.

[0444] [Comparative Device Examples 1 to 4]

[0445] Organic electroluminescent devices were prepared by the same preparation method as in Device Example 1 except that Comparative Compound 1, Comparative Compound 2, Comparative Compound 3 and Comparative Compound 4 were used to replace Compounds 1-5 in Device Example 1 as the hole transport layer.

[0446] The test software, computer, K2400 digital source meter produced by Keithley Company of the United States and PR788 spectrum scanning luminance meter produced by PhotoResearch Company of the United States are combined into a joint IVL test system to test the luminous efficiency of organic electroluminescent devices. The life test adopts the M6000 OLED life test system of McScience Company. The test environment is atmospheric environment and the temperature is room temperature.

[0447] The test results of the luminescent characteristics of the organic electroluminescent devices obtained in device embodiments 1 to 25 of the present invention and comparative embodiments 1 to 4 are shown in Table 1 below.

[0448]

[0449] According to the data results in Table 1, it can be seen that the diamine derivatives of the present invention are applied to organic electroluminescent devices as hole transport layer materials, which can significantly improve the luminous efficiency and service life of the device compared with Comparative Examples 1 to 4. This is because the compounds of the present invention have good hole transport ability, increase the recombination probability of excitons, and reduce the energy consumption in the hole transport process, thereby optimizing the performance of the device.

[0450] [Device Example 26]

[0451] First, the ITO / Ag / ITO substrate was cleaned three times in distilled water and ultrasonically washed for 15 minutes. After the distilled water cleaning, it was ultrasonically washed with isopropanol, acetone, methanol and other solvents in sequence and then dried at 120°C.

[0452] By vacuum evaporation, HAT-CN was evaporated on the cleaned ITO / Ag / ITO substrate as a hole injection layer material with a evaporation thickness of 30 nm; compound 1-517 was evaporated on the hole injection layer as a hole transport layer material with a evaporation thickness of 80 nm; GH-1:GD-1=92:8 (mass ratio) was evaporated on the hole transport layer as a light-emitting layer with a evaporation thickness of 40 nm; HB-1 was evaporated on the light-emitting layer as a hole blocking layer material with a evaporation thickness of 35 nm. m; ET-1 and Liq (doping mass ratio of 1:1) are evaporated on the hole blocking layer as electron transport layer materials, and the evaporation thickness is 30nm; LiF is evaporated on the electron transport layer as an electron injection layer, and the evaporation thickness is 0.8nm; then Mg:Ag=1:9 (doping mass ratio) is evaporated on the electron injection layer as a cathode, and the evaporation thickness is 13nm; then compound 2-11 is evaporated on the cathode as a covering layer, and the evaporation thickness is 80nm, thereby preparing an organic electroluminescent device.

[0453] [Device Examples 26 to 58]

[0454] An organic electroluminescent device was prepared by the same preparation method as in Device Example 26, except that the hole transport layer and the covering layer in Device Example 26 were replaced with the following combination.

[0455] Compound 1-285 and Compound 2-18, Compound 1-55 and Compound 2-22, Compound 1-105 and Compound 2-44, Compound 1-105 and Compound 2-75, Compound 1-338 and Compound 2-89, Compound 1-165 and Compound 2-91, Compound 1-319 and Compound 2-93, Compound 1-135 and Compound 2-110, Compound 1-135 and Compound 2-124, Compound 1-165 and Compound 2-132, Compound 1-208 and Compound 2-143, Compound 1-31 and Compound 2-146, Compound 1-394 and Compound 2-243, Compound 1-264 and Compound 2-266, Compound 1-80 and Compound 2-285, Compound 1-63 and Compound 2-289, Compound 1-113 and compound 2-300, compound 1-142 and compound 2-322, compound 1-5 and compound 2-330, compound 1-161 and compound 2-338, compound 1-231 and compound 2-353, compound 1-91 and compound 2-356, compound 1-91 and compound 2-388, compound 1-107 and compound 2-416, compound 1-113 and compound 2-425, compound 1-285 and compound 2-525, compound 1-480 and compound 2-532, compound 1-433 and compound 2-549, compound 1-537 and compound 2-630, compound 1-203 and compound 2-722, compound 1-537 and compound 2-747, compound 1-113 and compound 2-791.

[0456] [Comparative Device Examples 5 to 8]

[0457] The hole transport layer and the covering layer in device example 26 are replaced by comparison compound 1 and compound 2-243, comparison compound 2 and compound 2-525, comparison compound 3 and compound 2-549, and comparison compound 4 and compound 2-289, respectively. In addition, an organic electroluminescent device is prepared by the same preparation method as device example 26.

[0458] The test results of the luminescent characteristics of the organic electroluminescent devices obtained in device embodiments 26 to 58 of the present invention and comparative embodiments 5 to 8 are shown in Table 2 below.

[0459]

[0460] It can be seen from the data results in Table 2 that the luminous efficiency and service life of the organic electroluminescent device of the present invention are significantly improved compared with the comparative device embodiments 5 to 8.

[0461] It should be noted that the present invention is particularly described using individual embodiments. However, without departing from the principles of the present invention, a person skilled in the art may make various improvements in form or detail to the present invention, and these improvements also fall within the scope of protection of the present invention.

Claims

1. A diamine derivative, characterized in that: The diamine derivative has a structure as shown in Formula I; In formula I, the Ar1 to Ar4, L1 to L4, and L contain at least one group represented by formula II-1 or formula II-2, and the Ar1 to Ar4 are the same or different from each other, at least one of which is selected from the group represented by formula III, and the rest are the same or different from each other and are selected from any one of the groups represented by formula V-1 to formula V-4; The R1 is selected from deuterium, substituted or unsubstituted C2-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, Any of the following: The a is selected from 1, 2, 3, 4 or 5; when there are two or more R1, the two or more R1 are the same or different from each other; The R2 is selected from hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, Any of the following: The d1 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, and the d2 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; when there are two or more R2, the two or more R2 are the same or different from each other; Said p1 is selected from 1, 2, 3, 4 or 5, and said p2 is selected from 1, 2, 3 or 4; The L is selected from the following groups: The R is selected from hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, Any of the following: The m1 is selected from 0, 1, 2, 3 or 4, the m2 is selected from 0, 1, 2 or 3, the m3 is selected from 0, 1, 2, 3, 4, 5 or 6, and when two or more R are present, the two or more R are the same as or different from each other. The L1 to L4 are the same or different from each other and are selected from single bonds or groups substituted or unsubstituted by R4 as shown below: phenylene, biphenylene, terphenylene or The R4 is selected from hydrogen, deuterium, cyano, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C12-C30 aryl, Any of the following: The R5 and R6 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 C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl; The f1 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, and the f2 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

2. A diamine derivative according to claim 1, characterized in that: The formula III is selected from any one of the groups shown below; The R a selected from deuterium, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted cyclopropanyl, substituted or unsubstituted cyclobutanyl, substituted or unsubstituted cyclopentanyl, substituted or unsubstituted cyclohexanyl, substituted or unsubstituted cycloheptyl, substituted or unsubstituted cyclooctyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornyl, substituted or unsubstituted camphenyl, Any of the following: a1 is selected from 1, 2, 3, 4 or 5, a2 is selected from 0, 1, 2, 3 or 4, and a3 is selected from 0, 1, 2 or 3; when there are two or more R a When two or more R a the same as or different from one another; The R b are the same as or different from each other and are selected from any one of hydrogen, deuterium, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted cyclopropanyl, substituted or unsubstituted cyclobutanyl, substituted or unsubstituted cyclopentanyl, substituted or unsubstituted cyclohexanyl, substituted or unsubstituted cycloheptyl, substituted or unsubstituted cyclooctyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornyl, substituted or unsubstituted camphenyl, substituted or unsubstituted phenyl, and substituted or unsubstituted biphenyl; The b1 is selected from 0, 1, 2, 3, 4 or 5, and the b2 is selected from 0, 1, 2, 3 or 4; when there are two or more R b When two or more R b The same as or different from each other.

3. A diamine derivative according to claim 1, characterized in that: The formula III is selected from any one of the groups shown below; s1 is selected from 1, 2, 3, 4, or 5, s2 is selected from 0, 1, 2, 3, or 4, s3 is selected from 0, 1, 2, 3, 4, or 5, s4 is selected from 0, 1, 2, 3, 4, 5, 6, or 7, s5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, s7 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13, s8 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15, s9 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, s 10 Selected from 0, 1, 2 or 3.

4. A diamine derivative according to claim 1, characterized in that: The formula II-1 is selected from any one of the groups shown below; The e1 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, the e2 is selected from 0, 1, 2, 3, 4, or 5, the e3 is selected from 0, 1, 2, 3, 4, 5, 6, or 7, the e4 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, and the e5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15.

5. A diamine derivative according to claim 1, characterized in that: The formula II-2 is selected from any one of the groups shown below; 6. A diamine derivative according to claim 1, characterized in that: The L is selected from any one of the following groups; The R's are the same as or different from each other and are selected from any one of hydrogen, deuterium, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted cyclopropane, substituted or unsubstituted cyclobutane, substituted or unsubstituted cyclopentane, substituted or unsubstituted cyclohexane, substituted or unsubstituted cycloheptane, substituted or unsubstituted cyclooctane, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornyl, substituted or unsubstituted camphenyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, and substituted or unsubstituted naphthyl; The n1 is selected from 0, 1, 2, 3 or 4, the n2 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, the n3 is selected from 0, 1, 2, 3, 4, 5 or 6, and when two or more R are present, the two or more R are the same as or different from each other.

7. A diamine derivative according to claim 1, characterized in that: The L1 to L4 are the same or different from each other and are selected from a single bond or any one of the groups shown below; R4 is selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, methyl, deuterated methyl, ethyl, isopropyl, deuterated isopropyl, tert-butyl, deuterated tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, and norbornyl; The q1 is selected from 0, 1, 2, 3 or 4, and the q2 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

8. A diamine derivative according to claim 1, characterized in that: The diamine derivative is selected from any one of the structures shown below; 9. An organic electroluminescent device, comprising an anode, an organic layer, and a cathode, wherein the organic layer is located between the anode and the cathode or outside any one of the anode and the cathode, characterized in that: The organic layer comprises any one or more of the diamine derivatives according to any one of claims 1 to 8.

10. The organic electroluminescent device according to claim 9, wherein the organic layer is located outside any one of the anode and the cathode, and the organic layer comprises a covering layer, wherein: The covering layer comprises any one or more of the structures shown in Formula IV; In formula IV, X is selected from O or S; The ring M and the ring N are the same as or different from each other, and are selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted phenanthrene ring, or a substituted or unsubstituted triphenylene ring, and the ring M and the ring N are not simultaneously selected from a substituted or unsubstituted benzene ring; The x1 is selected from any one of O, S, and N(R3); The R3 is selected from any one of 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 R3 can be directly combined with L b Bonding; The z are the same as or different from each other and are selected from CH or N atoms. When z is bonded to other groups, the z is selected from C atoms; Ar5 is selected from any one of a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 heteroaryl group, and a substituted or unsubstituted C6-C30 aromatic ring and a C3-C30 aliphatic ring fused ring. The L a , L b , L c are the same as or different from each other and are 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 divalent substituted or unsubstituted C6-C30 aromatic ring and a C3-C30 aliphatic ring fused ring, and combinations thereof; The R 11 , R 12 , R 13 , R 14 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, and substituted or unsubstituted C2-C30 heteroaryl; The c1 is selected from 0, 1, 2, 3 or 4, the c2 is selected from 0, 1, 2 or 3, and the c3 is selected from 0, 1 or 2. When there are two or more R 11 , R 12 , R 13 , R 14 When two or more R 11 , R 12 , R 13 , R 14 Same or different from each other, or two adjacent R 14 They may be linked to each other to form a substituted or unsubstituted ring.

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