A triamine derivative and an organic electroluminescent device thereof

Abstract

The present invention provides a triamine derivative and an organic electroluminescent device thereof, specifically relating to the field of organic electroluminescence technology. The triamine derivative provided by the present invention has a strong electron-donating ability, good hole mobility, and a suitable HOMO energy level. It can effectively reduce the energy barrier during hole transport in the organic layer, reduce the generation of Joule heat within the device, increase the hole transport capacity, and effectively improve the luminous efficiency of the device. Furthermore, the triamine derivative also has a good refractive index, a high glass transition temperature, good film-forming properties that are not easily crystallized, high thermal stability, and resistance to decomposition, and increases the light extraction efficiency within the device, thereby significantly improving the luminous efficiency of the organic electroluminescent device and extending the device's service life.

Description

Technical Field

[0001] The present invention relates to the technical field of organic electroluminescence, in particular to a triamine derivative and an organic electroluminescent device thereof. Background Art

[0002] Organic Light-Emitting Diode (OLED) has the characteristics of light weight, wide viewing angle, fast response, wide operating temperature range, low energy consumption, high efficiency, good color purity, high clarity, and flexibility. It has been widely used in the fields of lighting and display and is considered by the industry to be one of the most promising display technologies.

[0003] Organic electroluminescent devices typically have a classic sandwich structure consisting of a cathode, an anode, and organic functional layers. The organic functional layers primarily include a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an emissive layer (EML), a hole blocking layer (HBL), an electron transport layer (ETL), and an electron injection layer (EIL). Indium tin oxide (ITO) is typically used as the anode, and a low-work-function metal as the cathode. Driven by an applied voltage, electrons and holes are injected from the cathode and anode, respectively, into the organic layer and migrate within it. Subsequently, the electrons and holes recombine in the emissive layer to produce excitons. When the excitons release energy as light radiation, the electroluminescence of the organic light-emitting device occurs.

[0004] With the demands of the market, the performance requirements for OLED devices are constantly increasing. However, the hole transport materials currently used in organic electroluminescent devices have many drawbacks. On the one hand, the HOMO value and triplet energy level are low, requiring a larger energy barrier for hole transport, increasing the device's driving voltage; low hole mobility leads to an imbalance in hole and electron transport, reducing the device's luminous efficiency; and low glass transition temperature reduces the device's service life. On the other hand, the poor energy level matching between the host material in the light-emitting layer and the adjacent functional layer limits the injection of holes and electrons. The large difference between the singlet and triplet energy levels increases the device's driving voltage. In addition, the plasmon resonance effect between the capping layer material and the electrode material reduces the light extraction efficiency within the device. Therefore, in order to continuously improve the performance of OLED devices, it is particularly important to develop a class of organic electroluminescent materials with good hole transport ability, suitable HOMO energy level, excellent thermal stability, and high glass transition temperature. Summary of the Invention

[0005] In order to solve the above problems, the present invention provides a triamine derivative, which has good hole transport ability, appropriate HOMO energy level, high glass transition temperature, and good light extraction efficiency, and can effectively improve the luminous efficiency and service life of OLED devices.

[0006] The present invention provides a triamine derivative having a structure as shown in Formula I.

[0007]

[0008] In Formula I, the Ar1 to Ar6 are identical or different, at least one of which is selected from the group represented by Formula I-1, and the others are identical or different and are selected from substituted or unsubstituted C6 to C30 aryl groups, or Ar1 and Ar2 can be connected to form a substituted or unsubstituted ring, or Ar3 and Ar4 can be connected to form a substituted or unsubstituted ring, or Ar5 and Ar6 can be connected to form a substituted or unsubstituted ring, and Ar1 and Ar2, Ar3 and Ar4, Ar5 and Ar6 are not connected to form a substituted or unsubstituted ring at the same time;

[0009]

[0010] Said X is selected from any one of O, S, and N(R2);

[0011] R1 and R2 are the same as or different from each other and are selected from any one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted fused ring of a C6-C30 aromatic ring and a C3-C30 aliphatic ring, and a substituted or unsubstituted C2-C30 heteroaryl group, or R2 may be directly connected to any one of L1-L6;

[0012] The b1 is selected from 0, 1, 2 or 3, and the b2 is selected from 0, 1, 2, 3 or 4. When two or more R1s are present, the two or more R1s are the same or different from each other, or two adjacent R1s may be connected to form a substituted or unsubstituted ring;

[0013] R is selected from any one of hydrogen, deuterium, cyano, halogen, or C1-C12 alkyl substituted or unsubstituted by deuterium, or C3-C12 cycloalkyl substituted or unsubstituted;

[0014] Said a is selected from 0, 1, 2, 3, 4 or 5;

[0015] The L a 、L b 、L c, L1, L2, L3, L4, L5, and L6 are the same as or different from each other and are selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C2-C30 heteroarylene group, a substituted or unsubstituted divalent fused ring group of a C6-C30 aromatic ring and a C3-C30 aliphatic ring, and any combination thereof.

[0016] 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 either the anode or the cathode, and the organic layer comprises any one or more of the triamine derivatives.

[0017] Beneficial effects: The triamine derivative represented by formula I provided by the present invention has strong electron donating ability, good hole mobility, and suitable HOMO energy level, which can effectively reduce the energy barrier of holes in the organic layer transmission process, increase the hole transmission capacity, and effectively improve the luminous efficiency of the device. At the same time, the triamine derivative also has a good refractive index, a high glass transition temperature, good film-forming properties that are not easy to crystallize, high thermal stability and not easy to decompose, and increases the light extraction efficiency inside the device, reduces the generation of Joule heat inside the device, greatly improves the luminous efficiency of the organic electroluminescent device and extends the service life of the device. DETAILED DESCRIPTION

[0018] The following is a clear and complete description of the technical solutions of the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without making any creative efforts shall fall within the scope of protection of the present invention.

[0019] In the compounds of the present invention, any atom not designated as a specific isotope is included as any stable isotope of that atom, and includes the atom at both its natural isotopic abundance and unnatural abundance.

[0020] In the present invention, "*" means a portion connecting to another substituent.

[0021] In the present invention, when the position of a substituent on a ring is not fixed, it means that it can be attached to any of the corresponding optional positions of the ring. For example, Can be represented Etc. And so on.

[0022] The halogen mentioned in the present invention refers to fluorine, chlorine, bromine and iodine.

[0023] The alkyl group described in the present invention refers to a hydrocarbon group formed by removing one hydrogen atom from an alkane molecule. It can 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 can be substituted or unsubstituted. The straight-chain alkyl group includes, but is not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, and dodecyl groups; the branched-chain alkyl group includes, but is not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, isomeric groups of n-pentyl, isomeric groups of n-hexyl, isomeric groups of n-heptyl, isomeric groups of n-octyl, isomeric groups of n-nonyl, and isomeric groups of n-decyl groups.

[0024] The cycloalkyl group herein refers to a hydrocarbon group formed by removing one hydrogen atom from a cycloalkane molecule, preferably having 3 to 12 carbon atoms, particularly preferably 3 to 6 carbon atoms. The cycloalkyl group may be substituted or unsubstituted. Examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, cananyl, and norbornyl.

[0025] The aliphatic rings described herein refer to cyclic hydrocarbons with aliphatic properties, containing closed carbon rings within the molecule, preferably having 3 to 60 carbon atoms, more preferably 3 to 30 carbon atoms, further preferably 3 to 18 carbon atoms, even more preferably 3 to 12 carbon atoms, and most preferably 3 to 7 carbon atoms. They can form monocyclic or polycyclic hydrocarbons and can be fully unsaturated or partially unsaturated. Aliphatic rings can be substituted or unsubstituted. Specific examples include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclobutene, cyclopentene, cyclohexene, and cycloheptene. Multiple monocyclic hydrocarbons can also be linked in various ways: two rings within a molecule can share a single carbon atom to form a spirocycle; two carbon atoms on a ring can be connected by a carbon bridge to form a bridged ring; and several rings can be linked to form a cage-like structure.

[0026] The term "aryl" as used herein refers to a monovalent group remaining after removing a hydrogen atom from the aromatic carbon nucleus of an aromatic compound molecule. It can be a monocyclic aryl, a polycyclic aryl, or a fused-ring aryl, preferably having 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 12 carbon atoms. An aryl group can be substituted or unsubstituted. A monocyclic aryl refers to an aryl group with a single aromatic ring, such as, but not limited to, a phenyl group; a polycyclic aryl refers to an aryl group containing two or more independent aromatic rings, such as, but not limited to, a biphenyl group and a terphenyl group; and a fused-ring aryl refers to an aryl group containing two or more aromatic rings fused together by sharing two adjacent carbon atoms, such as, but not limited to, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, perylenyl, fluorenyl, benzofluorenyl, triphenylene, fluoranthenyl, and spirobifluorenyl.

[0027] The heteroaryl group of the present invention is a general term for a group in which one or more aromatic carbon atoms in an aromatic group are replaced by a heteroatom, wherein the heteroatom includes but is not limited to O, S, N, Si or P atoms, and preferably has 2 to 30 carbon atoms, more preferably 2 to 18 carbon atoms, and particularly preferably 2 to 12 carbon atoms. The attachment point of the heteroaryl group may be located on a ring-forming carbon atom or 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, but are not limited to, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, etc.; the polycyclic heteroaryl groups include, but are not limited to, bipyridyl, bipyrimidinyl, phenylpyridinyl, phenylpyrimidinyl, etc.; the fused ring heteroaryl groups include, but are not limited to, 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, etc., but is not limited thereto.

[0028] The fused ring of an aromatic ring and an aliphatic ring described in 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. 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 an aromatic ring and an 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.

[0029] 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 group, as a monocyclic arylene group, it can be a phenylene group, etc., but it is not limited thereto. 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 thereto. 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, fluoren ... etc., but not limited thereto.

[0030] The heteroarylene group of the present invention is a general term for a group in which one or more aromatic carbon atoms in an arylene group are replaced by a heteroatom, including but not limited to oxygen, sulfur, nitrogen, or phosphorus atoms. Preferably, the group has 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 3 to 12 carbon atoms. The attachment point of the heteroarylene group may be located on a ring-forming carbon atom or a ring-forming nitrogen atom. The heteroarylene group may be a monocyclic heteroarylene group, a polycyclic heteroarylene group, or a condensed-ring heteroarylene group. The monocyclic heteroarylene group includes, but is not limited to, pyridylene, pyrimidylene, triazinylene, furylene, thienylene, etc.; the polycyclic heteroarylene group includes, but is not limited to, bipyridylene, bipyrimidylene, phenylpyridylene, etc.; the condensed-ring heteroarylene group includes, but is not limited to, quinolylene, isoquinolylene, indolylene, benzothiophenylene, benzofuranylene, benzoxazolylene, benzimidazolylene, benzothiazolylene, dibenzofuranylene, benzodibenzofuranylene, dibenzothiophenylene, benzodibenzothiophenylene, carbazolylene, benzocarbazolylene, acridinylene, 9,10-dihydroacridinylene, phenoxazinylene, phenothiazinylene, phenoxathiylene, etc., but is not limited to.

[0031] The divalent fused ring of an aromatic ring and an aliphatic ring described in the present invention is a general term for a divalent group remaining after removing two hydrogen atoms from the fused ring of an aromatic ring and an aliphatic ring. Except that they are each a divalent group, the above description of the fused ring of an aromatic ring and an aliphatic ring is applicable to them.

[0032] In the context of "substituted or unsubstituted" herein, "unsubstituted" means that no hydrogen atom on the group is 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.

[0033] The substituents in the "substituted or unsubstituted" of the present invention can be independently selected from deuterium, cyano, nitro, amino, halogen atoms, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C6 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 any one of the following: Species, preferably deuterium, cyano, halogen atoms, amino, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 heterocycloalkyl, C6-C30 aryl, C2-C30 heteroaryl, specific examples may include deuterium, fluorine, chlorine, bromine, iodine, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, biphenyl, terphenyl, tolyl, pentadeuterated phenyl, biphenyl, 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-1,2-diphenyl-1,2-diphenyl-1 The invention also includes oxazolyl, oxazolyl, thiazolyl, benzothiazolyl, benzotriazolyl, benzoimidazolyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, phenothiazinyl, phenoxazinyl, and the like, but is not limited thereto.

[0034] 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 saturated or unsaturated rings.

[0035] The term "linked to form a ring" as used herein refers to two groups being linked to each other via a chemical bond and optionally aromatized. For example:

[0036]

[0037] In the present invention, the ring formed by connection can be an aromatic ring system, an aliphatic ring system or a ring system formed by the fusion of the two. The ring formed by connection can be a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring or a fused ring, such as benzene, naphthalene, indene, cyclopentene, cyclopentane, cyclopentane acene, cyclohexene, cyclohexane, cyclohexane acene, pyridine, quinoline, isoquinoline, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, phenanthrene or pyrene, but is not limited thereto.

[0038] The present invention provides a triamine derivative having a structure as shown in Formula I.

[0039]

[0040] In Formula I, the Ar1 to Ar6 are identical or different, at least one of which is selected from the group represented by Formula I-1, and the others are identical or different and are selected from substituted or unsubstituted C6 to C30 aryl groups, or Ar1 and Ar2 can be connected to form a substituted or unsubstituted ring, or Ar3 and Ar4 can be connected to form a substituted or unsubstituted ring, or Ar5 and Ar6 can be connected to form a substituted or unsubstituted ring, and Ar1 and Ar2, Ar3 and Ar4, Ar5 and Ar6 are not connected to form a substituted or unsubstituted ring at the same time;

[0041]

[0042]

[0043] R1 and R2 are the same as or different from each other and are selected from any one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted fused ring of a C6-C30 aromatic ring and a C3-C30 aliphatic ring, and a substituted or unsubstituted C2-C30 heteroaryl group, or R2 may be directly connected to any one of L1-L6;

[0044] The b1 is selected from 0, 1, 2 or 3, and the b2 is selected from 0, 1, 2, 3 or 4. When two or more R1s are present, the two or more R1s are the same or different from each other, or two adjacent R1s may be connected to form a substituted or unsubstituted ring;

[0045] R is selected from any one of hydrogen, deuterium, cyano, halogen, or C1-C12 alkyl substituted or unsubstituted by deuterium, or C3-C12 cycloalkyl substituted or unsubstituted;

[0046] Said a is selected from 0, 1, 2, 3, 4 or 5;

[0047] The La 、L b 、L c , L1, L2, L3, L4, L5, and L6 are the same as or different from each other and are selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C2-C30 heteroarylene group, a substituted or unsubstituted divalent fused ring group of a C6-C30 aromatic ring and a C3-C30 aliphatic ring, and any combination thereof.

[0048] Preferably, the triamine derivative has the structure shown below,

[0049]

[0050] Preferably, L a 、L c Connected in a meta position, or in a para position, or in an ortho position.

[0051] Preferably, the Ar1 to Ar6 are the same or different from each other, and at least one of them is selected from the group shown in formula I-1, which means that at least one, at least two, at least three, at least four, at least five or six of Ar1 to Ar6 are selected from the group shown in formula I-1.

[0052] Preferably, Ar1; Ar2; Ar3; Ar4; Ar5; Ar6; Ar1 ​​and Ar2; Ar1 ​​and Ar3; Ar1 ​​and Ar5; Ar2 and Ar3; Ar2 and Ar5; Ar3 and Ar4; Ar3 and Ar5; Ar5 and Ar6; Ar1, Ar2 and Ar3; Ar1, Ar2 and Ar5; Ar1, Ar3 and Ar4; Ar1, Ar3 and Ar5; Ar1, Ar5 and Ar6; Ar3, Ar4 and Ar5; Ar3, Ar5 and Ar6; Ar1, Ar2, Ar3 and Ar4; Ar1, Ar2, Ar3 and Ar5; Ar1, Ar2, Ar5 and Ar6; Ar1, Ar3, Ar4 and Ar5; Ar1, Ar3, Ar5 and Ar6; Ar3, Ar4, Ar5 and Ar6; Ar1, Ar2, Ar3, Ar4 and Ar5; Ar1, Ar2, Ar3, Ar5 and Ar6; Ar1, Ar3, Ar4, Ar5 and Ar6; or, Ar1, Ar2, Ar3, Ar4, Ar5 and Ar6 are selected from the groups shown in formula I-1.

[0053] Preferably, the formula I-1 is selected from any one of the following groups:

[0054]

[0055] The R2 is selected from any one of the following groups which are substituted or unsubstituted by one or more deuteriums: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylene, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, 9-phenylcarbazolyl, dibenzofuranyl, dibenzothiophenyl, dibenzocarbazolyl, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexane, benzocycloheptane, benzocyclopentenyl or benzocyclohexenyl.

[0056] Preferably, the formula I-1 is selected from any one of the following groups:

[0057]

[0058]

[0059] The R3 groups are the same as or different from each other and are selected from hydrogen, deuterium, or any one of the following groups which are substituted or unsubstituted with one or more deuterium groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, benzocyclopropanyl, benzocyclobutanyl, benzocyclopentanyl, benzocyclohexanyl, benzocycloheptyl, benzocyclopentenyl, or benzocyclohexenyl;

[0060] The c1 is selected from 0, 1, 2 or 3, the c2 is selected from 0, 1, 2, 3 or 4, the c3 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, the c4 is selected from 0, 1, 2, 3, 4, 5 or 6, the c5 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, the c6 is selected from 0, 1, 2, 3, 4 or 5, the c7 is selected from 0, 1, 2, 3, 4, 5, 6 or 7, the c8 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, and the c9 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11.

[0061] Preferably, the Ar1 to Ar6 are identical or different from each other, at least one of them is selected from the group shown in formula I-1, and the others are identical or different from each other and are selected from any one of the groups shown below:

[0062]

[0063] The R aare 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-C6 cycloalkyl, a substituted or unsubstituted C6-C30 aromatic ring and a C3-C30 aliphatic ring fused ring, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 heteroaryl group, or R a They may be connected to each other to form a substituted or unsubstituted ring, or R a Can be directly bonded to any one of L1 to L6;

[0064] The R4 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 groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, benzocyclopropanyl, benzocyclobutanyl, benzocyclopentanyl, benzocyclohexanyl, benzocycloheptanyl, benzocyclopentenyl or benzocyclohexenyl;

[0065] The d1 is selected from 0, 1, 2, 3, 4 or 5, the d2 is selected from 0, 1, 2, 3 or 4, the d3 is selected from 0, 1, 2, 3, 4, 5, 6 or 7, the d4 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, and the d5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11. When two or more R4 are present, the two or more R4 are the same or different from each other, or two adjacent R4 can be connected to each other to form a substituted or unsubstituted ring.

[0066] Preferably, the two R a They can be connected to each other to form substituted or unsubstituted ring structures as follows:

[0067]

[0068] The R m Any one of the following groups selected from hydrogen, deuterium, or substituted or unsubstituted with one or more deuterium groups or C1-C12 alkyl groups: methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, tolyl, biphenyl, or terphenyl;

[0069] wherein m1 is selected from 0, 1 or 2; m2 is selected from 0, 1, 2, 3 or 4; m3 is selected from 0, 1, 2, 3, 4, 5 or 6; m4 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; m5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; m6 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12; and m7 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14.

[0070] Preferably, the Ar1 to Ar6 are identical or different from each other, at least one of them is selected from the group shown in formula I-1, and the others are identical or different from each other and are selected from any one of the groups shown below:

[0071]

[0072]

[0073]

[0074] Preferably, in the remaining groups of Ar1 to Ar6, L1 and L2 may be a bond and Ar1 and Ar2 may be connected to form a substituted or unsubstituted carbazole ring, L3 and L4 may be a bond and Ar3 and Ar4 may be connected to form a substituted or unsubstituted carbazole ring, L5 and L6 may be a bond and Ar5 and Ar6 may be connected to form a substituted or unsubstituted carbazole ring, and Ar1 and Ar2, Ar3 and Ar4, Ar5 and Ar6 may not be connected to form a substituted or unsubstituted carbazole ring at the same time. Among them, Ar1 and Ar2, Ar3 and Ar4, Ar5 and Ar6 may form one carbazole ring or two carbazole rings at the same time.

[0075] Preferably, in the remaining groups of Ar1 to Ar6, L1 and L2 may be a bond and Ar1 and Ar2 may be connected to each other to form a substituted or unsubstituted carbazole ring; or L3 and L4 may be a bond and Ar3 and Ar4 may be connected to each other to form a substituted or unsubstituted carbazole ring; or L1, L2, L3, L4 may be a bond and Ar1 and Ar2, Ar3 and Ar4 may be connected to each other at the same time to form a substituted or unsubstituted carbazole ring; or L1, L2, L5, L6 may be a bond and Ar1 and Ar2, Ar5 and Ar6 may be connected to each other at the same time to form a substituted or unsubstituted carbazole ring.

[0076] Preferably, the L a ~L c , L1 to L6 are the same as or different from each other and are selected from a single bond or any one of the following groups and combinations thereof,

[0077]

[0078] The R b 、R c are the same as or different from each other and are selected from any one of hydrogen, deuterium, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C6-C30 fused ring group of an aromatic ring and a C3-C30 aliphatic ring, and a substituted or unsubstituted C6-C30 aryl group;

[0079] The R5 groups are the same as or different from each other and are selected from hydrogen, deuterium, or any one of the following groups which are substituted or unsubstituted with one or more deuterium groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, benzocyclopropanyl, benzocyclobutanyl, benzocyclopentanyl, or benzocyclohexanyl;

[0080] The e1 is selected from 0, 1, 2, 3 or 4, the e2 is selected from 0, 1, 2, 3, 4 or 5, the e3 is selected from 0, 1, 2 or 3, the e4 is selected from 0, 1 or 2, and the e5 is selected from 0, 1, 2, 3, 4, 5 or 6.

[0081] The ring A is selected from substituted or unsubstituted C3-C7 aliphatic rings.

[0082] Preferably, the ring A is selected from any one of the following substituted or unsubstituted groups,

[0083]

[0084] Wherein, “*” represents the connection site of the ring; the dotted line represents a single bond or a double bond.

[0085] Preferably, the triamine derivative is selected from any one of the following structures:

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111] The above lists some specific chemical structures of the triamine derivatives represented by Chemical Formula I of the present invention, but the present invention is not limited to these listed chemical structures. All triamine derivatives based on the structure shown in Chemical Formula I and having substituents as defined above are included.

[0112] 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 either the anode or the cathode, and the organic layer comprises any one or more of the triamine derivatives.

[0113] Preferably, the organic layer of the present invention 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.

[0114] Preferably, the hole transport region of the present invention comprises at least one of a hole injection layer, a hole transport layer, and an electron blocking layer.

[0115] Preferably, at least one of the hole injection layer, hole transport layer, and electron blocking layer described in the present invention comprises any one or more of the triamine derivatives described in the present invention.

[0116] Preferably, the hole transport layer of the present invention comprises a first hole transport layer and / or a second hole transport layer; the first hole transport layer and / or the second hole transport layer comprises any one or more of the triamine derivatives of the present invention.

[0117] Preferably, the light-emitting layer of the present invention comprises a host material and a dopant material, and the host material comprises any one or more of the triamine derivatives of the present invention.

[0118] Preferably, the host material comprises a first host material and / or a second host material.

[0119] Preferably, the electron transport region described in the present invention includes at least one layer of an electron injection layer, an electron transport layer, and a hole blocking layer; preferably, the electron transport region described in the present invention includes at least one layer of an electron transport layer and a hole blocking layer; preferably, the electron transport region described in the present invention includes an electron transport layer.

[0120] Preferably, the organic layer of the present invention is located outside any one of the anode and the cathode, and comprises a covering layer, and the covering layer comprises any one or more of the triamine derivatives of the present invention.

[0121] The organic electroluminescent device of the present invention is usually formed on a substrate. The substrate can be any substrate that does not change during the formation of electrodes and organic layers, and can be made of, for example, glass, plastic, polymer film, silicon, or the like.

[0122] The anode material of the present invention preferably uses a material with a high functional function to improve the 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 multi-layer structure including two or more layers. For example, the anode can have a single-layer structure of Al or a three-layer structure of ITO / Ag / ITO, but is not limited thereto.

[0123] The hole injection layer material of the present invention preferably has good hole-accepting capacity. It can be selected from any one or more of the following structures: metalloporphyrins, oligothiophenes, arylamine derivatives, perylene derivatives, hexanitrile hexaazatriphenylene compounds, phthalocyanine compounds, polycyano conjugated organic materials, quinacridone compounds, anthraquinone compounds, and polyaniline-based and polythiophene-based conductive polymers, but is not limited thereto.

[0124] The hole transport layer material of the present invention preferably has a high hole mobility and can be selected from any one or more of the following structures: carbazole derivatives, triarylamine derivatives, diphenylenediamine derivatives, fluorene derivatives, stilbene derivatives, hexanitrile hexaazatriphenylene compounds, quinacridone compounds, anthraquinone compounds, polyaniline, polythiophene, polyvinylcarbazole, etc. Examples of the hole transport layer material include, but are not limited to, N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), 4-[1-[4-[di(4-methylphenyl)amino]phenyl]cyclohexyl]-N-(3-methylphenyl)-N-(4-methylphenyl)aniline (TAPC), N,N,N',N'-tetrakis(3-methylphenyl)-3,3'-dimethylbenzenediamine (HMTPD), etc. The triamine derivatives of the present invention are preferred.

[0125] The light-emitting layer material of the present invention includes 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"-tris(carbazol-9-yl)triphenylamine (TCTA), 9,10-di(1 ... In addition to the above materials and their combinations, the main material of the light-emitting layer may include other known materials suitable for the light-emitting layer, but is not limited thereto. The triamine derivatives described in the present invention are preferred.

[0126] 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)phenyl]biphenyl (BDAVBi), 4,4'-bis[4-(di-p-tolylamino)phenyl]biphenyl (DPAVBi), bis(2-hydroxyphenylpyridine)beryllium (Bepp2), bis(4,6-difluorophenylpyridine-C2,N)picolinyliridium (FIrpic), tris ... (2-phenylpyridine)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-dimethylaminophenyl)-4H-pyran (DCM), tris[1-phenylisoquinoline-C2,N]iridium (III) (Ir(piq)3), bis(1-phenylisoquinoline)(acetylacetonate)iridium (Ir(piq)2(acac)), etc., but not limited thereto.

[0127] The doping ratio of the host material and the guest material in the light-emitting layer of the present invention is determined by the materials used. The amount of the dopant material used is preferably 0.1 to 70% by mass, more preferably 0.1 to 30% by mass, further preferably 1 to 30% by mass, even more preferably 1 to 20% by mass, and particularly preferably 1 to 10% by mass.

[0128] The hole blocking layer material described in the present invention is preferably a material that can effectively block hole transport 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.

[0129] The electron transport layer material of the present invention preferably has 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-hydroxyquinolinolate)aluminum(III) (Alq3), 8-hydroxyquinolinolate-lithium (Liq), bis(2-methyl-8-hydroxyquinolinolate)(4-phenylphenolate)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 is not limited thereto.

[0130] The electron injection layer material described in the present invention is preferably a material with a smaller potential barrier difference than 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, metallic aluminum, etc., but are not limited thereto.

[0131] 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. The cathode material can be selected from any one or more of the following materials: Ag, Mg, Cu, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF / Ca, LiF / Al, Mo, Ti, compounds thereof, or mixtures thereof (e.g., a mixture of Ag and Mg), but is not limited thereto.

[0132] The cover layer of the present invention is provided on the outside of one or more of the anode and cathode electrodes to reduce total internal reflection losses and improve light extraction efficiency. The cover layer can be selected from any one or more of the following structures: arylamine derivatives, biscarbazole derivatives, benzimidazole derivatives, benzoxazole derivatives, benzothiazole derivatives, triazole derivatives, benzofuran derivatives, diamine derivatives, porphyrin derivatives, phthalocyanine derivatives, Alq3, TPBi, or mixtures thereof, but is not limited thereto. The triamine derivatives of the present invention are preferred.

[0133] The present invention has no special limitation on the thickness of each organic layer of the organic electroluminescent device, and the thickness commonly used in the art can be adopted.

[0134] The organic electroluminescent device of the present invention can be manufactured by sequentially stacking the above-described structures. The manufacturing method can employ known methods such as wet film formation and dry film formation. Specific examples of wet film formation include various coating methods such as spin coating, dipping, casting, and inkjet. Specific examples of dry film formation include vacuum evaporation, sputtering, plasma deposition, and ion plating, but are not limited thereto.

[0135] 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 light, etc.

[0136] The present invention is explained in more detail by the following examples, but it is not intended that the present invention be limited thereby. Based on 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 disclosed entire range without inventive effort.

[0137] The present invention provides a method for preparing the compound represented by Formula I, but the preparation method of the present invention is not limited thereto. The specific synthetic route is as follows:

[0138] Preparation of intermediate A:

[0139]

[0140] Preparation of intermediate B:

[0141]

[0142] Preparation of intermediate C:

[0143]

[0144] Preparation of intermediate D:

[0145]

[0146] Preparation of intermediate E:

[0147]

[0148] Preparation of intermediate F:

[0149]

[0150] Preparation of compounds of formula I:

[0151] 1. When intermediate A / D, intermediate B / E and intermediate C / F are different from each other:

[0152] 2. When intermediate A / D and intermediate B / E are the same:

[0153]

[0154] 3. When intermediates A / D, intermediates B / E, and intermediates C / F are identical:

[0155]

[0156] Among them, X a The same as or different from each other, any one selected from Cl, Br, I; Ar1 ​​to Ar6, L1 to L6, L a ~L c , R, and a are the same as those defined above;

[0157] In the present invention, the above-mentioned substituents can be bonded 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.

[0158] Description of raw materials, reagents and characterization equipment:

[0159] The present invention has no particular limitation on the sources of the raw materials and reagents used in the following examples. They may be commercially available products or prepared using methods well known to those skilled in the art.

[0160] Mass spectrometry was performed using a British Waters G2-Si quadrupole tandem time-of-flight high-resolution mass spectrometer, with chloroform as the solvent;

[0161] 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.

[0162] Synthesis Example 1: Synthesis of Compound 16

[0163]

[0164] Preparation of intermediate A-16:

[0165] Under nitrogen, a-16 (15.79 g, 60.00 mmol), b-16 (11.96 g, 60.00 mmol), and sodium tert-butoxide (10.38 g, 108.00 mmol) were added to 300 ml of toluene. Pd(OAc)2 (0.16 g, 0.72 mmol) and P(t-Bu)3 (2.88 mL of a 0.50 M solution in toluene, 1.44 mmol) were added with stirring. The mixed solution was heated under reflux for 5 h. After completion of the reaction, the reaction solution was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. The mixture was allowed to stand for separation. 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 filtered. The resulting solid was recrystallized from toluene / methanol (volume ratio 8:1) to obtain intermediate A-16 (18.77 g, 82%). The purity of the solid was ≥99.41% as determined by HPLC. Mass spectrum m / z: 381.0631 (theoretical value: 381.0646).

[0166] Preparation of intermediate B-16:

[0167] Under nitrogen, c-16 (18.85 g, 60.00 mmol), d-16 (5.59 g, 60.00 mmol), and sodium tert-butoxide (10.38 g, 108.00 mmol) were added to 300 ml of toluene. Pd(dppf)Cl2 (0.53 g, 0.72 mmol) was added with stirring, and the mixed solution was heated under reflux for 4 h. After completion of the reaction, the reaction solution was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. The mixture was allowed to stand for separation. 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 the resulting solid was filtered with suction. The resulting solid was recrystallized from ethyl acetate to obtain intermediate B-16 (16.65 g, 85%). The purity of the solid was ≥99.34% as determined by HPLC. Mass spectrum: m / z: 326.1846 (theoretical value: 326.1831).

[0168] Preparation of intermediate C-16:

[0169] Under nitrogen, e-16 (7.85 g, 50.00 mmol), d-16 (4.66 g, 50.00 mmol), and sodium tert-butoxide (8.65 g, 90.00 mmol) were dissolved in 250 ml of toluene. Pd(dppf)Cl2 (0.44 g, 0.60 mmol) was added with stirring, and the mixture was heated under reflux for 3.5 h. After completion of the reaction, the mixture was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. The mixture was allowed to stand for separation. 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 the resulting solid was filtered with suction. The resulting solid was recrystallized from ethyl acetate to obtain intermediate C-16 (7.53 g, 89%). The purity of the solid was ≥99.56% as determined by HPLC. Mass spectrum: m / z: 169.0880 (theoretical value: 169.0891).

[0170] Preparation of intermediate I-16:

[0171] Under nitrogen, intermediate A-16 (15.26 g, 40.00 mmol), g-16 (14.70 g, 40.00 mmol), and sodium tert-butoxide (6.73 g, 70.00 mmol) were added to 200 ml of toluene. Pd(OAc)2 (0.10 g, 0.43 mmol) and P(t-Bu)3 (1.72 mL of a 0.5 M toluene solution, 0.86 mmol) were added with stirring. The mixed solution was heated under reflux for 4.5 h. After the reaction was completed, the mixture was cooled to room temperature, extracted with dichloromethane and distilled water, and allowed to stand for separation. The organic phase was collected and dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure. The filtrate was purified by silica gel column chromatography using n-hexane / dichloromethane (volume ratio 10:1) to obtain intermediate I-16 (19.87 g, 80%). The solid purity was ≥99.60% as determined by HPLC. Mass spectrum m / z: 618.9822 (theoretical value: 618.9831).

[0172] Preparation of intermediate II-16:

[0173] Under nitrogen, intermediate I-16 (18.63 g, 30.00 mmol), intermediate B-16 (9.79 g, 30.00 mmol), and sodium tert-butoxide (5.00 g, 52.00 mmol) were added to 150 ml of toluene. Pd2(dba)3 (0.31 g, 0.34 mmol) and P(t-Bu)3 (1.36 mL of a 0.5 M toluene solution, 0.68 mmol) were added with stirring. The mixed solution was heated under reflux for 5 h. After the reaction was completed, the mixture was cooled to room temperature, extracted with dichloromethane and distilled water, and allowed to stand for separation. The organic phase was collected and dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure. The filtrate was purified by silica gel column chromatography using petroleum ether / ethyl acetate (volume ratio 8:1) to obtain intermediate II-16 (20.28 g, 78%). The solid purity was ≥99.83% as determined by HPLC. Mass spectrum m / z: 865.2420 (theoretical value: 865.2401).

[0174] Preparation of compound 16:

[0175] Under nitrogen, intermediate II-16 (17.33 g, 20.00 mmol), intermediate C-16 (3.38 g, 20.00 mmol), and sodium tert-butoxide (2.88 g, 30.00 mmol) were added to 150 ml of toluene. Pd2(dba)3 (0.23 g, 0.25 mmol) and X-Phos (0.24 g, 0.50 mmol) were added with stirring, and the mixed solution was heated under reflux for 6 h. After completion of the reaction, the mixture was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. The mixture was allowed to stand for separation, and the organic layer was collected and dried over anhydrous magnesium sulfate. The mixture was filtered and the filtrate was concentrated by distillation under reduced pressure. The mixture was cooled and crystallized, and the mixture was filtered with suction. The resulting solid was recrystallized from toluene to obtain compound 16 (14.39 g, 72%). The purity of the solid was ≥99.96% as determined by HPLC. Mass spectrum m / z: 998.3537 (theoretical value: 998.3525). Theoretical element content (%) C 70 H 42 D5N3S2: C, 84.13; H, 5.24; N, 4.20. Measured element content (%): C, 84.17; H, 5.21; N, 4.18.

[0176] Synthesis Example 2: Synthesis of Compound 23

[0177]

[0178] Preparation of intermediate A-23:

[0179] Following the same preparation method as that used for Intermediate A-16 in Synthesis Example 1, intermediate A-23 (16.65 g, 83% yield) was obtained by replacing a-16 with an equal molar amount of a-23 and b-16 with an equal molar amount of d-16. The solid purity was ≥99.86% as determined by HPLC. Mass spectrum: m / z: 334.1487 (theoretical value: 334.1470).

[0180] Preparation of intermediate B-23:

[0181] Following the same preparation method as that of Intermediate B-16 in Synthesis Example 1, intermediate B-23 (9.10 g, 87% yield) was obtained by replacing c-16 with an equimolar amount of c-23. The purity of the solid was ≥99.79% as determined by HPLC. Mass spectrum: m / z: 174.1219 (theoretical value: 174.1205).

[0182] Preparation of intermediate II-23:

[0183] Under nitrogen, g-23 (6.41 g, 20.00 mmol), intermediate A-23 (13.38 g, 40.00 mmol), and sodium tert-butoxide (3.36 g, 35.00 mmol) were added to 160 ml of toluene. Pd2(dba)3 (0.20 g, 0.22 mmol) and P(t-Bu)3 (0.88 mL of a 0.5 M toluene solution, 0.44 mmol) were added with stirring. The mixed solution was heated under reflux for 5 h. After the reaction was completed, the mixture was cooled to room temperature, extracted with dichloromethane and distilled water, and allowed to stand for separation. The organic phase was collected and dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure. The filtrate was purified by silica gel column chromatography using petroleum ether / ethyl acetate (volume ratio 10:1) to obtain intermediate II-23 (12.91 g, 78%). The solid purity was ≥99.83% as determined by HPLC. Mass spectrum m / z: 826.2847 (theoretical value: 826.2863).

[0184] Preparation of compound 23:

[0185] Under nitrogen, Intermediate II-23 (10.76 g, 13.00 mmol), Intermediate B-23 (2.27 g, 13.00 mmol), and sodium tert-butoxide (2.50 g, 26.00 mmol) were added to 90 ml of toluene. Pd2(dba)3 (0.15 g, 0.16 mmol) and X-Phos (0.15 g, 0.32 mmol) were added with stirring. The mixed solution was heated under reflux for 5.5 h. After completion of the reaction, the mixture was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. The mixture was allowed to stand for separation. The organic layer was collected and dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure. The mixture was cooled and crystallized, and then filtered with suction. The resulting solid was recrystallized from toluene to obtain Compound 23 (9.41 g, 75%). The purity of the solid was ≥99.91% as determined by HPLC. Mass spectrum: m / z: 964.4319 (theoretical value: 964.4302). Theoretical element content (%) C 70 H 44 D5N5: C, 87.11; H, 5.64; N, 7.26. Measured element content (%): C, 87.09; H, 5.67; N, 7.25.

[0186] Synthesis Example 3: Synthesis of Compound 28

[0187]

[0188] Preparation of intermediate A-28:

[0189] Following the same preparation method as that used for Intermediate A-16 in Synthesis Example 1, an equal amount of a-16 was replaced with an equal amount of a-28, and an equal amount of b-16 was replaced with an equal amount of d-16 to obtain Intermediate A-28 (13.22 g, 85% yield). HPLC analysis of the solid revealed a purity of ≥99.86%. Mass spectrum: m / z: 259.0983 (theoretical value: 259.0997).

[0190] Preparation of compound 28:

[0191] Under nitrogen, g-28 (5.47 g, 15.00 mmol), A-28 (11.67 g, 45.00 mmol), and sodium tert-butoxide (3.56 g, 37.00 mmol) were added to 200 ml of toluene. Pd2(dba)3 (0.16 g, 0.18 mmol) and P(t-Bu)3 (0.72 mL of a 0.5 M toluene solution, 0.36 mmol) were added with stirring. The mixed solution of the above reactants was heated under reflux for 6.5 h. After the reaction was completed, the mixture was cooled to room temperature, and dichloromethane and distilled water were added to the mixture for extraction. The mixture was allowed to stand for separation, and the organic phase 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 filtered. The resulting solid was recrystallized from toluene to obtain compound 28 (9.72 g, 72%). The purity of the solid was determined by HPLC to be ≥99.94%. Mass spectrum m / z: 899.3161 (theoretical value: 899.3148). Theoretical element content (%) C 64 H 41 N3O3: C, 85.41; H, 4.59; N, 4.67. Measured element content (%): C, 85.45; H, 4.55; N, 4.71.

[0192] Synthesis Example 4: Synthesis of Compound 44

[0193]

[0194] Preparation of intermediate A-44:

[0195] Following the same preparation method as that used for Intermediate A-16 in Synthesis Example 1, intermediate A-44 (13.22 g, 85% yield) was obtained by replacing a-16 with an equal molar amount of a-44 and b-16 with an equal molar amount of d-16. The solid purity was ≥99.83% as determined by HPLC. Mass spectrum: m / z: 259.0988 (theoretical value: 259.0997).

[0196] Preparation of intermediate II-44:

[0197] Under nitrogen, g-44 (5.77 g, 18.00 mmol), intermediate A-44 (9.34 g, 36.00 mmol), and sodium tert-butoxide (2.88 g, 30.00 mmol) were added to 150 ml of toluene. Pd2(dba)3 (0.18 g, 0.20 mmol) and P(t-Bu)3 (0.80 mL of a 0.5 M toluene solution, 0.40 mmol) were added with stirring. The mixed solution of the above reactants was heated under reflux for 5.5 h. After the reaction was completed, the mixture was cooled to room temperature, and dichloromethane and distilled water were added to the mixture for extraction. The mixture was allowed to stand for separation, and the organic phase was collected and dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure. It was purified by silica gel column chromatography using petroleum ether / ethyl acetate (volume ratio 9:1) to obtain intermediate II-44 (9.51 g, 78%). The solid purity was ≥99.86% as determined by HPLC. Mass spectrum m / z: 676.1930 (theoretical value: 676.1918).

[0198] Preparation of compound 44:

[0199] Under nitrogen, intermediate II-44 (8.13 g, 12.00 mmol), m-44 (3.45 g, 12.00 mmol), Pd(PPh3)4 (0.17 g, 0.15 mmol), K2CO3 (4.15 g, 30.00 mmol), 30 mL of ethanol, and 30 mL of water were added to 100 mL of toluene. The mixture was stirred and heated under reflux for 4.5 hours. After the reaction, the mixture was cooled to room temperature and filtered to obtain a filter cake, which was rinsed with ethanol and recrystallized from toluene to obtain compound 44 (7.64 g, 72% yield). HPLC analysis of the solid showed a purity of ≥99.91%. Mass spectrum: m / z: 883.3186 (theoretical value: 883.3199). Theoretical element content (%): C 64 H 41 N3O2: C, 86.95; H, 4.67; N, 4.75. Measured element content (%): C, 86.91; H, 4.70; N, 4.72.

[0200] Synthesis Example 5: Synthesis of Compound 104

[0201]

[0202] Preparation of intermediate A-104:

[0203] Following the same preparation method as for Intermediate A-16 in Synthesis Example 1, intermediate A-104 (16.21 g, 83% yield) was obtained by replacing a-16 with an equal molar amount of a-104 and b-16 with an equal molar amount of b-104. The solid purity was ≥99.86% as determined by HPLC. Mass spectrum: m / z: 325.0939 (theoretical value: 325.0925).

[0204] Preparation of intermediate II-104:

[0205] Under nitrogen, g-44 (19.22 g, 60.00 mmol), m-44 (37.33 g, 130.00 mmol), Pd(PPh3)4 (1.39 g, 1.20 mmol), K2CO3 (24.88 g, 180.00 mmol), 120 mL of ethanol, and 120 mL of water were added to 360 mL of toluene. The mixture was stirred and heated under reflux for 4 hours. After the reaction, the mixture was cooled to room temperature and filtered to obtain a filter cake, which was rinsed with ethanol and recrystallized from toluene to obtain intermediate II-104 (29.42 g, 76% yield). The solid purity was ≥99.81% as determined by HPLC. Mass spectrum: m / z: 644.2001 (theoretical value: 644.2019).

[0206] Preparation of compound 104:

[0207] Under nitrogen, II-104 (25.81 g, 40.00 mmol), A-104 (13.02 g, 40.00 mmol), Pd2(dba)3 (0.37 g, 0.40 mmol), P(t-Bu)3 (1.60 mL of a 0.5 M toluene solution, 0.80 mmol), and sodium tert-butoxide (9.61 g, 100.00 mmol) were added to 280 mL of toluene, the mixture was stirred, and heated under reflux for 6 hours. After the reaction was completed, the mixture was cooled to room temperature, and dichloromethane and distilled water were added to the mixture for extraction. The mixture was allowed to stand for separation, and the organic phase 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 resulting solid was recrystallized from toluene to obtain compound 104 (28.03 g, 75%). The solid purity was ≥99.96% as determined by HPLC. Mass spectrum m / z: 933.3191 (theoretical value: 933.3178). Theoretical element content (%) C 68 H 43 N3S: C, 87.43; H, 4.64; N, 4.50. Measured element content (%): C, 87.40; H, 4.68; N, 4.48.

[0208] Synthesis Example 6: Synthesis of Compound 113

[0209]

[0210] Compound 113 (28.83 g) was obtained by the same preparation method as in Example 5, except that a-104 was replaced with an equal molar amount of a-23, b-104 was replaced with an equal molar amount of b-113, g-44 was replaced with an equal molar amount of g-113, and m-44 was replaced with an equal molar amount of m-113. The purity of the solid was ≥99.92% as determined by HPLC. Mass spectrum m / z: 947.4049 (theoretical value: 947.4036). Theoretical element content (%): C 70 H 41 D5N4: C, 88.67; H, 5.42; N, 5.91. Measured element content (%): C, 88.70; H, 5.39; N, 588.

[0211] Synthesis Example 7: Synthesis of Compound 129

[0212]

[0213] Preparation of intermediate D-129:

[0214] Under nitrogen, A-28 (15.56 g, 60.00 mmol), n-129 (12.29 g, 60.00 mmol), and sodium tert-butoxide (8.65 g, 90.00 mmol) were added to 300 ml of toluene. Pd(OAc)2 (0.14 g, 0.63 mmol) and P(t-Bu)3 (2.52 mL of a 0.5 M solution in toluene, 1.26 mmol) were added with stirring. The mixed solution was heated under reflux for 4.5 h. After completion of the reaction, the mixture was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. The mixture was allowed to stand for separation. 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 filtered. The resulting solid was recrystallized from toluene / methanol (volume ratio 7:1) to obtain intermediate D-129 (18.40 g, yield 80%). The purity of the solid was ≥99.82% as determined by HPLC. Mass spectrum m / z: 383.1618 (theoretical value: 383.1631).

[0215] Preparation of intermediate II-129:

[0216] Under nitrogen, g-44 (9.61 g, 30.00 mmol), intermediate C-16 (10.15 g, 60.00 mmol), and sodium tert-butoxide (4.90 g, 51.00 mmol) were added to 400 ml of toluene. Pd2(dba)3 (0.30 g, 0.33 mmol) and P(t-Bu)3 (1.32 mL of a 0.5 M toluene solution, 0.66 mmol) were added with stirring. The mixed solution was heated under reflux for 5 h. After the reaction was completed, the mixture was cooled to room temperature, extracted with dichloromethane and distilled water, and allowed to stand for separation. The organic phase was collected and dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure. The filtrate was purified by silica gel column chromatography using petroleum ether / ethyl acetate (volume ratio 8:1) to obtain intermediate II-129 (12.53 g, 84%). The solid purity was ≥99.85% as determined by HPLC. Mass spectrum m / z: 496.1721 (theoretical value: 496.1706).

[0217] Preparation of compound 129:

[0218] Under nitrogen, intermediate II-129 (9.94 g, 20.00 mmol), D-129 (8.43 g, 22.00 mmol), Pd(PPh3)4 (0.35 g, 0.30 mmol), K2CO3 (5.53 g, 40.00 mmol), 50 mL of ethanol, and 50 mL of water were added to 150 mL of toluene. The mixture was stirred and heated under reflux for 3 h. After the reaction, the mixture was cooled to room temperature and filtered to obtain a filter cake, which was rinsed with ethanol and recrystallized from toluene to obtain compound 129 (12.48 g, 78% yield). HPLC analysis of the solid showed a purity of ≥99.96%. Mass spectrum: m / z: 799.3519 (theoretical value: 799.3501). Theoretical element content (%): C 58 H 37 D4N3O: C, 87.08; H, 5.67; N, 5.25. Measured element content (%): C, 87.12; H, 5.70; N, 5.29.

[0219] Synthesis Example 8: Synthesis of Compound 133

[0220]

[0221] Preparation of intermediate A-133:

[0222] Following the same preparation method as for Intermediate A-16 in Synthesis Example 1, intermediate A-133 (19.51 g, 79% yield) was obtained by replacing a-16 with an equal molar amount of a-133 and b-16 with an equal molar amount of b-133. The solid purity was ≥99.84% as determined by HPLC. Mass spectrum: m / z: 411.1632 (theoretical value: 411.1623).

[0223] Compound 133 (16.29 g) was obtained by the same preparation method as in Example 7, except that A-28 was replaced with an equal molar amount of A-133, n-129 was replaced with an equal molar amount of n-133, g-44 was replaced with an equal molar amount of g-133, and C-16 was replaced with an equal molar amount of B-23. HPLC analysis of the solid showed a purity of ≥99.96%. Mass spectrum m / z: 957.4515 (theoretical value: 957.4503). Theoretical element content (%): C 70 H 39 D 10 N3O: C, 87.74; H, 6.20; N, 4.39. Measured element content (%): C, 87.71; H, 6.17; N, 4.42.

[0224] Synthesis Example 9: Synthesis of Compound 135

[0225]

[0226] Following the same preparation method as in Example 7 for compound 129, n-129 was replaced with an equal molar amount of n-135, and g-44 was replaced with an equal molar amount of g-23 to obtain compound 135 (14.98 g, 83%). HPLC analysis of the solid showed a purity of ≥99.93%. Mass spectrum m / z: 901.3119 (theoretical value: 901.3127). Theoretical element content (%): C 64 H 43 N3OS: C, 85.21; H, 4.80; N, 4.66. Measured element content (%): C, 85.25; H, 4.76; N, 4.62.

[0227] Synthesis Example 10: Synthesis of Compound 167

[0228]

[0229] Preparation of intermediate A-167:

[0230] Following the same preparation method as that used for intermediate A-16 in Synthesis Example 1, intermediate A-16 was replaced with an equal molar amount of a-104, and b-16 was replaced with an equal molar amount of d-16 to obtain intermediate A-167 (14.04 g, 85% yield). HPLC analysis of the solid revealed a purity of ≥99.88%. Mass spectrum: m / z: 275.0752 (theoretical value: 275.0769).

[0231] Compound 167 (13.11 g) was obtained by the same preparation method as in Example 7, except that A-129 was replaced with an equal molar amount of A-167, n-129 was replaced with an equal molar amount of n-167, g-44 was replaced with an equal molar amount of g-113, and C-16 was replaced with an equal molar amount of B-23. HPLC analysis of the solid showed a purity of ≥99.95%. Mass spectrum m / z: 897.3951 (theoretical value: 897.3962). Theoretical element content (%): C 64 H 35 D 10 N3S: C, 85.58; H, 6.17; N, 4.68. Measured element content (%): C, 85.62; H, 6.14; N, 4.71.

[0232] Synthesis Example 11: Synthesis of Compound 182

[0233]

[0234] Preparation of intermediate A-182:

[0235] Following the same preparation method as for Intermediate A-16 in Synthesis Example 1, intermediate A-182 (18.88 g, 81% yield) was obtained by replacing a-16 with an equal molar amount of a-182 and b-16 with an equal molar amount of b-182. The solid purity was ≥99.85% as determined by HPLC. Mass spectrum: m / z: 388.1923 (theoretical value: 388.1939).

[0236] Preparation of intermediate D-182:

[0237] Following the same preparation method as that used in Synthesis Example 7 for Intermediate D-129, intermediate D-182 (23.79 g, 78% yield) was obtained by replacing A-28 with an equal molar amount of A-182 and n-129 with an equal molar amount of n-182. The purity of the solid was ≥99.88% as determined by HPLC. Mass spectrum: m / z: 508.2311 (theoretical value: 508.2322).

[0238] Preparation of intermediate B-182:

[0239] Following the same preparation method as that used for intermediate B-16 in Synthesis Example 1, intermediate B-23 (8.93 g, 83% yield) was obtained by replacing c-16 with an equal molar amount of c-23 and d-16 with an equal molar amount of b-113. HPLC analysis of the solid revealed a purity of ≥99.77%. Mass spectrum: m / z: 179.1531 (theoretical value: 179.1519).

[0240] Preparation of intermediate I-182:

[0241] Following the same preparation method as for Intermediate I-16 in Synthesis Example 1, g-16 was replaced with an equal molar amount of g-182, and A-16 was replaced with an equal molar amount of C-16 to obtain Intermediate I-182 (13.57 g, 83%). HPLC analysis of the solid revealed a purity of ≥99.68%. Mass spectrum: m / z: 407.0089 (theoretical value: 407.0076).

[0242] Preparation of intermediate II-182:

[0243] Following the same preparation method as that used for intermediate II-16 in Synthesis Example 1, I-16 was replaced with an equal molar amount of I-182, and B-16 was replaced with an equal molar amount of B-182 to obtain intermediate II-182 (12.17 g, 80%). HPLC analysis of the solid showed a purity of ≥99.84%. Mass spectrum: m / z: 506.2319 (theoretical value: 506.2334).

[0244] Preparation of compound 182:

[0245] Following the same preparation method as in Example 7 for compound 129, replacing II-129 with an equal molar amount of II-182 and D-129 with an equal molar amount of D-182, compound 182 (14.03 g, 75%) was obtained. HPLC analysis of the solid showed a purity of ≥99.91%. Mass spectrum m / z: 934.4836 (theoretical value: 934.4820). Theoretical element content (%): C 68 H 42 D 10 N4: C, 87.33; H, 6.68; N, 5.99. Measured element content (%): C, 87.29; H, 6.70; N, 5.97.

[0246] Synthesis Example 12: Synthesis of Compound 189

[0247]

[0248] Preparation of intermediate A-189:

[0249] Following the same preparation method as that used for Intermediate A-16 in Synthesis Example 1, intermediate A-189 (15.26 g, 85% yield) was obtained by replacing a-16 with an equal molar amount of a-28 and b-16 with an equal molar amount of b-189. The solid purity was ≥99.83% as determined by HPLC. Mass spectrum: m / z: 299.1323 (theoretical value: 299.1310).

[0250] Preparation of intermediate D-189:

[0251] Following the same preparation method as that used in Synthesis Example 7 for Intermediate D-129, intermediate D-189 (14.92 g, 86% yield) was obtained by replacing A-28 with an equal molar amount of C-16 and n-129 with an equal molar amount of n-182. The solid purity was ≥99.85% as determined by HPLC. Mass spectrum: m / z: 289.1288 (theoretical value: 289.1274).

[0252] Preparation of compound 189:

[0253] Compound 189 (27.73 g, 76%) was obtained by following the same preparation method as in Example 5, replacing g-44 with an equal molar amount of g-189, m-44 with an equal molar amount of D-189, and A-104 with an equal molar amount of A-189. HPLC analysis of the solid showed a purity of ≥99.95%. Mass spectrum: m / z: 911.3861 (theoretical value: 911.3876). Theoretical element content (%): C 67 H 49 N3O: C, 88.22; H, 5.41; N, 4.61. Measured element content (%): C, 88.17; H, 5.46; N, 4.58.

[0254] Synthesis Example 13: Synthesis of Compound 275

[0255]

[0256] Compound 275 (9.12 g) was obtained by the same preparation method as in Example 2, except that a-23 was replaced with an equal molar amount of a-28, d-16 was replaced with an equal molar amount of b-113, c-23 was replaced with an equal molar amount of c-275, g-23 was replaced with an equal molar amount of g-44, A-23 was replaced with an equal molar amount of B-275, and B-23 was replaced with an equal molar amount of A-275. HPLC analysis of the solid showed a purity of ≥99.97%. Mass spectrum m / z: 876.3889 (theoretical value: 876.3876). Theoretical element content (%): C 64 H 40D5N3O: C, 87.64; H, 5.75; N, 4.79. Measured element content (%): C, 87.61; H, 5.77; N, 4.82.

[0257] Synthesis Example 14: Synthesis of Compound 286

[0258]

[0259] Compound 286 (8.33 g) was obtained by the same preparation method as in Example 2, except that a-23 was replaced with an equal molar amount of a-28, d-16 was replaced with an equal molar amount of b-286, g-23 was replaced with an equal molar amount of g-44, A-23 was replaced with an equal molar amount of B-23, and B-23 was replaced with an equal molar amount of A-286. The purity of the solid was ≥99.98% as determined by HPLC. Mass spectrum m / z: 810.4179 (theoretical value: 810.4191). Theoretical element content (%): C 58 H 26 D 15 N3O: C, 85.89; H, 6.96; N, 5.18. Measured element content (%): C, 85.91; H, 6.92; N, 5.20.

[0260] Synthesis Example 15: Synthesis of Compound 297

[0261]

[0262] Compound 297 (8.93 g) was obtained by the same preparation method as in Example 2, except that a-23 was replaced with an equal molar amount of a-297, d-16 was replaced with an equal molar amount of b-297, g-23 was replaced with an equal molar amount of g-44, A-23 was replaced with an equal molar amount of B-23, and B-23 was replaced with an equal molar amount of A-297. HPLC analysis revealed a solid purity of ≥99.96%. Mass spectrum m / z: 891.4988 (theoretical value: 891.4973). Theoretical element content (%): C 64 H 45 D 10 N3O: C, 86.16; H, 7.34; N, 4.71. Measured element content (%): C, 86.20; H, 7.36; N, 4.68.

[0263] Synthesis Example 16: Synthesis of Compound 301

[0264]

[0265] Compound 301 (8.59 g) was obtained by the same preparation method as in Example 2, except that a-23 was replaced with an equal molar amount of a-28, d-16 was replaced with an equal molar amount of b-301, c-23 was replaced with an equal molar amount of c-301, d-16 was replaced with an equal molar amount of b-113, g-23 was replaced with an equal molar amount of g-189, A-23 was replaced with an equal molar amount of B-301, and B-23 was replaced with an equal molar amount of A-301. HPLC analysis revealed a solid purity of ≥99.98%. Mass spectrum: m / z: 916.5040 (theoretical value: 916.5057). Theoretical element content (%): C 66 H 46 D 10 N3O: C, 86.42; H, 7.25; N, 4.58. Measured element content (%): C, 86.39; H, 7.28; N, 4.62.

[0266] Synthesis Example 17: Synthesis of Compound 309

[0267]

[0268] Compound 309 (8.49 g) was obtained by the same preparation method as in Example 2, except that a-23 was replaced with an equal molar amount of a-309, c-23 was replaced with an equal molar amount of c-309, g-23 was replaced with an equal molar amount of g-44, A-23 was replaced with an equal molar amount of B-309, and B-23 was replaced with an equal molar amount of A-309. HPLC analysis of the solid showed a purity of ≥99.92%. Mass spectrum m / z: 869.3418 (theoretical value: 869.3406). Theoretical element content (%): C 64 H 43 N3O: C, 88.35; H, 4.98; N, 4.83. Measured element content (%): C, 88.38; H, 4.95; N, 4.79.

[0269] Synthesis Example 18: Synthesis of Compound 345

[0270]

[0271] Compound 345 (9.11 g) was obtained by the same preparation method as in Example 2, except that a-23 was replaced with an equal molar amount of a-28, d-16 was replaced with an equal molar amount of b-113, c-23 was replaced with an equal molar amount of c-275, d-16 was replaced with an equal molar amount of b-113, g-23 was replaced with an equal molar amount of g-44, A-23 was replaced with an equal molar amount of B-345, and B-23 was replaced with an equal molar amount of A-345. HPLC analysis revealed a solid purity of ≥99.95%. Mass spectrum: m / z: 886.4521 (theoretical value: 886.4504). Theoretical element content (%): C64 H 30 D 15 N3O: C, 86.65; H, 6.81; N, 4.74. Measured element content (%): C, 86.68; H, 6.79; N, 4.70.

[0272] Synthesis Example 19: Synthesis of Compound 362

[0273]

[0274] Compound 362 (9.56 g) was obtained by the same preparation method as in Example 2, except that a-23 was replaced with an equal molar amount of a-28, d-16 was replaced with an equal molar amount of b-362, g-23 was replaced with an equal molar amount of g-44, A-23 was replaced with an equal molar amount of C-16, and B-23 was replaced with an equal molar amount of A-362. The purity of the solid was ≥99.97% as determined by HPLC. Mass spectrum m / z: 907.4519 (theoretical value: 907.4502). Theoretical element content (%): C 66 H 57 N3O: C, 87.29; H, 6.33; N, 4.63. Measured element content (%): C, 87.32; H, 6.30; N, 4.59.

[0275] Synthesis Example 20: Synthesis of Compound 373

[0276]

[0277] Compound 373 (8.64 g) was obtained by the same preparation method as in Example 2, except that a-23 was replaced with an equal molar amount of a-28, d-16 was replaced with an equal molar amount of b-373, g-23 was replaced with an equal molar amount of g-44, A-23 was replaced with an equal molar amount of B-182, and B-23 was replaced with an equal molar amount of A-373. HPLC analysis showed that the solid purity was ≥99.93%. Mass spectrum m / z: 873.5298 (theoretical value: 873.5287). Theoretical element content (%): C 62 H 31 D 20 N3O: C, 85.18; H, 8.18; N, 4.81. Measured element content (%): C, 85.21; H, 8.15; N, 4.76.

[0278] Synthesis Example 21: Synthesis of Compound 379

[0279]

[0280] Compound 379 (9.64 g) was obtained by the same preparation method as in Example 2, except that g-23 was replaced with an equal molar amount of g-113, A-23 was replaced with an equal molar amount of B-275, and B-23 was replaced with an equal molar amount of A-28. The purity of the solid was ≥99.98% as determined by HPLC. Mass spectrum m / z: 871.3547 (theoretical value: 871.3563). Theoretical element content (%): C 64 H 45 N3O: C, 88.15; H, 5.20; N, 4.82. Measured element content (%): C, 88.20; H, 5.18; N, 4.79.

[0281] Synthesis Example 22: Synthesis of Compound 387

[0282]

[0283] Compound 387 (9.26 g) was obtained by the same preparation method as in Example 2, except that a-23 was replaced with an equal molar amount of a-387, d-16 was replaced with an equal molar amount of b-387, g-23 was replaced with an equal molar amount of g-387, A-23 was replaced with an equal molar amount of B-275, and B-23 was replaced with an equal molar amount of A-387. HPLC analysis showed that the solid purity was ≥99.93%. Mass spectrum m / z: 948.4770 (theoretical value: 948.4785). Theoretical element content (%): C 69 H 48 D7N3O: C, 87.31; H, 6.58; N, 4.43. Measured element content (%): C, 87.28; H, 6.60; N, 4.39.

[0284] Synthesis Example 23: Synthesis of Compound 391

[0285]

[0286] Compound 391 (9.40 g) was obtained by the same preparation method as in Example 2, except that a-23 was replaced with an equal molar amount of a-391, d-16 was replaced with an equal molar amount of b-391, g-23 was replaced with an equal molar amount of g-391, A-23 was replaced with an equal molar amount of B-272, and B-23 was replaced with an equal molar amount of A-391. HPLC analysis of the solid showed a purity of ≥99.95%. Mass spectrum m / z: 989.4331 (theoretical value: 989.4345). Theoretical element content (%): C 73 H 55 N3O: C, 88.54; H, 5.60; N, 4.24. Measured element content (%): C, 88.50; H, 5.58; N, 4.27.

[0287] Synthesis Example 24: Synthesis of Compound 407

[0288]

[0289] Compound 407 (8.87 g) was obtained by the same preparation method as in Example 2, except that a-23 was replaced with an equal molar amount of a-407, g-23 was replaced with an equal molar amount of g-407, A-23 was replaced with an equal molar amount of B-275, and B-23 was replaced with an equal molar amount of A-407. HPLC analysis revealed a solid purity of ≥99.90%. Mass spectrum: m / z: 947.3890 (theoretical value: 947.3876). Theoretical element content (%): C 70 H 49 N3O: C, 88.67; H, 5.21; N, 4.43. Measured element content (%): C, 88.70; H, 5.18; N, 4.39.

[0290] Synthesis Example 25: Synthesis of Compound 429

[0291]

[0292] Compound 429 (9.41 g) was obtained by the same preparation method as in Example 2, except that a-23 was replaced with an equal molar amount of a-28, d-16 was replaced with an equal molar amount of b-429, c-23 was replaced with an equal molar amount of c-429, g-23 was replaced with an equal molar amount of g-44, A-23 was replaced with an equal molar amount of B-429, and B-23 was replaced with an equal molar amount of A-429. The purity of the solid was ≥99.97% as determined by HPLC. Mass spectrum m / z: 939.4851 (theoretical value: 939.4849). Theoretical element content (%): C 68 H 29 D 18 N3O: C, 86.86; H, 6.96; N, 4.47. Measured element content (%): C, 86.90; H, 6.94; N, 4.50.

[0293] Synthesis Example 26: Synthesis of Compound 529

[0294]

[0295] Compound 529 (14.55 g) was obtained by the same preparation method as in Example 1, except that a-16 was replaced with an equal molar amount of a-529, b-16 was replaced with an equal molar amount of d-16, c-16 was replaced with an equal molar amount of c-529, and g-16 was replaced with an equal molar amount of g-529. The purity of the solid was ≥99.95% as determined by HPLC. Mass spectrum: m / z: 1038.4617 (theoretical value: 1038.4600). Theoretical element content (%): C 77 H 50 D4N4: C, 88.98; H, 5.62; N, 5.39. Measured element content (%): C, 88.96; H, 5.59; N, 5.41.

[0296] Synthesis Example 27: Synthesis of Compound 559

[0297]

[0298] Compound 559 (14.26 g) was obtained by the same preparation method as in Example 1, except that e-16 was replaced with an equal molar amount of e-559, A-16 was replaced with an equal molar amount of A-28, and B-16 was replaced with an equal molar amount of B-23. HPLC analysis of the solid showed a purity of ≥99.92%. Mass spectrum m / z: 962.4021 (theoretical value: 962.4033). Theoretical element content (%): C 71 H 42 D5N3O: C, 88.54; H, 5.44; N, 4.36. Measured element content (%): C, 88.58; H, 5.41; N, 4.40.

[0299] Synthesis Example 28: Synthesis of Compound 596

[0300]

[0301] Compound 596 (9.34 g) was obtained by the same preparation method as in Example 2, except that a-23 was replaced with an equal molar amount of a-104, d-16 was replaced with an equal molar amount of b-596, g-23 was replaced with an equal molar amount of g-44, A-23 was replaced with an equal molar amount of B-275, and B-23 was replaced with an equal molar amount of A-596. The purity of the solid was ≥99.96% as determined by HPLC. Mass spectrum m / z: 944.3948 (theoretical value: 944.3930). Theoretical element content (%): C 68 H 40 D7N3S: C, 86.41; H, 5.76; N, 4.45. Measured element content (%): C, 86.39; H, 5.80; N, 4.43.

[0302] Synthesis Example 29: Synthesis of Compound 652

[0303]

[0304] Compound 652 (9.42 g) was obtained by the same preparation method as in Example 2, except that a-23 was replaced with an equal molar amount of a-104, d-16 was replaced with an equal molar amount of b-652, c-23 was replaced with an equal molar amount of c-301, g-23 was replaced with an equal molar amount of g-44, A-23 was replaced with an equal molar amount of B-652, and B-23 was replaced with an equal molar amount of A-652. HPLC analysis of the solid showed a purity of ≥99.91%. Mass spectrum m / z: 928.4579 (theoretical value: 928.4587). Theoretical element content (%): C 66 H 52 D5N3S: C, 85.30; H, 6.72; N, 4.52. Measured element content (%): C, 85.28; H, 6.75; N, 4.49.

[0305] Synthesis Example 30: Synthesis of Compound 665

[0306]

[0307] Compound 665 (9.89 g) was obtained by the same preparation method as in Example 2, except that a-23 was replaced with an equal molar amount of a-104, d-16 was replaced with an equal molar amount of b-665, c-23 was replaced with an equal molar amount of c-665, d-16 was replaced with an equal molar amount of b-113, A-23 was replaced with an equal molar amount of B-665, and B-23 was replaced with an equal molar amount of A-665. HPLC analysis showed that the solid purity was ≥99.97%. Mass spectrum m / z: 1013.4575 (theoretical value: 1013.4588). Theoretical element content (%): C 73 H 43 D 10 N3S: C, 86.44; H, 6.26; N, 4.14. Measured element content (%): C, 86.47; H, 6.30; N, 4.11.

[0308] Synthesis Example 31: Synthesis of Compound 710

[0309]

[0310] Compound 710 (13.46 g) was obtained by the same preparation method as in Example 1, except that a-16 was replaced with an equal molar amount of a-104, b-16 was replaced with an equal molar amount of b-710, c-16 was replaced with an equal molar amount of c-710, and g-16 was replaced with an equal molar amount of g-710. The purity of the solid was ≥99.94% as determined by HPLC. Mass spectrum m / z: 896.3881 (theoretical value: 896.3899). Theoretical element content (%): C 64 H 36 D9N3S: C, 85.68; H, 6.06; N, 4.68. Measured element content (%): C, 85.70; H, 6.01; N, 4.71.

[0311] Synthesis Example 32: Synthesis of Compound 723

[0312]

[0313] Compound 723 (12.64 g) was obtained by the same preparation method as in Example 1, except that C-16 was replaced with an equal molar amount of C-723, E-16 was replaced with an equal molar amount of E-710, G-16 was replaced with an equal molar amount of G-723, and A-16 was replaced with an equal molar amount of A-167. The purity of the solid was ≥99.91% as determined by HPLC. Mass spectrum m / z: 915.3574 (theoretical value: 915.3585). Theoretical element content (%): C 66 H 41 D4N3S: C, 86.52; H, 5.39; N, 4.59. Measured element content (%): C, 86.49; H, 5.42; N, 4.61.

[0314] Synthesis Example 33: Synthesis of Compound 733

[0315]

[0316] Compound 733 (10.03 g) was obtained by the same preparation method as in Example 2, except that a-23 was replaced with an equal molar amount of a-733, d-16 was replaced with an equal molar amount of b-113, g-23 was replaced with an equal molar amount of g-113, A-23 was replaced with an equal molar amount of B-275, and B-23 was replaced with an equal molar amount of A-733. HPLC analysis of the solid showed a purity of ≥99.98%. Mass spectrum m / z: 1001.4521 (theoretical value: 1001.4506). Theoretical element content (%): C 74 H 47 D5N4: C, 88.68; H, 5.73; N, 5.59. Measured element content (%): C, 88.70; H, 5.69; N, 5.61.

[0317] Synthesis Example 34: Synthesis of Compound 759

[0318]

[0319] Compound 759 (8.81 g) was obtained by the same preparation method as in Example 2, except that a-23 was replaced with an equal molar amount of a-759, d-16 was replaced with an equal molar amount of b-759, g-23 was replaced with an equal molar amount of g-391, A-23 was replaced with an equal molar amount of B-23, and B-23 was replaced with an equal molar amount of A-759. HPLC analysis showed that the solid purity was ≥99.92%. Mass spectrum m / z: 868.4367 (theoretical value: 868.4350). Theoretical element content (%): C 63 H 36 D 10 N4: C, 87.06; H, 6.49; N, 6.45. Measured element content (%): C, 87.02; H, 6.51; N, 6.41.

[0320] Synthesis Example 35: Synthesis of Compound 780

[0321]

[0322] Compound 780 (9.58 g) was obtained by the same preparation method as in Example 2, except that d-16 was replaced with an equal molar amount of b-780, g-23 was replaced with an equal molar amount of g-44, A-23 was replaced with an equal molar amount of C-16, and B-23 was replaced with an equal molar amount of A-780. HPLC analysis of the solid showed a purity of ≥99.96%. Mass spectrum m / z: 920.3892 (theoretical value: 920.3879). Theoretical element content (%): C 68 H 48 N4: C, 88.67; H, 5.25; N, 6.08. Measured element content (%): C, 88.70; H, 5.23; N, 6.10.

[0323] Synthesis Example 36: Synthesis of Compound 791

[0324]

[0325] Compound 791 (13.33 g) was obtained by the same preparation method as in Example 1, except that a-16 was replaced with an equal molar amount of a-791, b-16 was replaced with an equal molar amount of d-16, c-16 was replaced with an equal molar amount of c-275, d-16 was replaced with an equal molar amount of b-301, and g-16 was replaced with an equal molar amount of g-791. The purity of the solid was ≥99.94% as determined by HPLC. Mass spectrum m / z: 951.4332 (theoretical value: 951.4349). Theoretical element content (%): C 70 H 45 D5N4: C, 88.29; H, 5.82; N, 5.88. Measured element content (%): C, 88.32; H, 5.78; N, 5.91.

[0326] [Device Example 1]

[0327] First, the ITO substrate was cleaned three times in distilled water and ultrasonically washed for 15 minutes. After the distilled water washing was completed, ultrasonic washing was performed in sequence with isopropyl alcohol, acetone, methanol and other solvents, and then dried at 120°C.

[0328] By vacuum evaporation, NPNPB with a thickness of 30 nm was evaporated on a cleaned ITO substrate as a hole injection layer material; the compound 16 of the present invention was evaporated on the hole injection layer with a thickness of 80 nm as a hole transport layer material; TCP:Ir(piq)3=97:3 (mass ratio) was evaporated on the hole transport layer as a light-emitting layer with a thickness of 40 nm; BAlq was evaporated on the light-emitting layer as a hole blocking layer material with a thickness of 35 nm; Liq was evaporated on the hole blocking layer as an electron transport layer material with a thickness of 35 nm; LiF was evaporated on the electron transport layer as an electron injection layer with a thickness of 1.0 nm; and Al was then evaporated on the electron injection layer as a cathode with a thickness of 120 nm. Thus, an organic electroluminescent device was prepared.

[0329]

[0330] [Device Example 2-36]

[0331] Compound 23, compound 28, compound 44, compound 104, compound 113, compound 129, compound 133, compound 135, compound 167, compound 182, compound 189, compound 275, compound 286, compound 297, compound 301, compound 309, compound 345, compound 362, compound 373, compound 379, compound 387, compound 391, compound 407, compound 429, compound 529, compound 559, compound 596, compound 652, compound 665, compound 710, compound 723, compound 733, compound 759, compound 780, and compound 791 were used to replace compound 16 in device example 1 as hole transport layer materials. Except that, an organic electroluminescent device was prepared by the same preparation method as device example 1.

[0332] [Comparative Device Examples 1-2]

[0333] Organic electroluminescent devices were prepared by the same preparation method as in Device Example 1 except that Comparative Compound 1 and Comparative Compound 2 were used instead of Compound 16 in Device Example 1 as hole transport layer materials.

[0334] A combined IVL test system, comprised of test software, a computer, a Keithley K2400 digital source meter, and a PhotoResearch PR788 spectrum scanning luminance meter, was used to measure the luminous efficiency of organic electroluminescent devices. Lifespan tests were conducted using a McScience M6000 OLED Lifespan Test System. The test environment was atmospheric and room temperature.

[0335] The test results of the luminescence characteristics of the organic electroluminescent devices obtained in device embodiments 1 to 36 of the present invention and comparative device embodiments 1 to 2 are shown in Table 1 below.

[0336]

[0337]

[0338] [Device Example 37]

[0339] First, the ITO substrate was cleaned three times in distilled water and ultrasonically washed for 15 minutes. After the distilled water washing was completed, ultrasonic washing was performed in sequence with isopropyl alcohol, acetone, methanol and other solvents, and then dried at 120°C.

[0340] By vacuum evaporation, NPNPB with a thickness of 28 nm was evaporated on a cleaned ITO substrate as a hole injection layer material; NDDP with a thickness of 60 nm was evaporated on the hole injection layer as a first hole transport layer material; compound 16 of the present invention was evaporated on the first hole transport material with a thickness of 20 nm as a second hole transport material; CDBP:Ir(ppy)2(acac)=94:6 (mass ratio) was evaporated on the second hole transport layer as a light-emitting layer with a thickness of 40 nm; TPBi was evaporated on the light-emitting layer as an electron transport layer material with a thickness of 30 nm; LiF was evaporated on the electron transport layer as an electron injection layer with a thickness of 1.0 nm; and Al was then evaporated on the electron injection layer as a cathode with a thickness of 130 nm, thereby preparing an organic electroluminescent device.

[0341]

[0342] [Device Examples 38-72]

[0343] Compound 23, compound 28, compound 44, compound 104, compound 113, compound 129, compound 133, compound 135, compound 167, compound 182, compound 189, compound 275, compound 286, compound 297, compound 301, compound 309, compound 345, compound 362, compound 373, compound 379, compound 387, compound 391, compound 407, compound 429, compound 529, compound 559, compound 596, compound 652, compound 665, compound 710, compound 723, compound 733, compound 759, compound 780, and compound 791 were used to replace compound 16 in device example 37 as the second hole transport layer material. Except that, an organic electroluminescent device was prepared by the same preparation method as device example 37.

[0344] [Comparative Device Examples 3-4]

[0345] An organic electroluminescent device was prepared by the same preparation method as in Device Example 37 except that Comparative Compound 1 and Comparative Compound 2 were used to replace Compound 16 in Device Example 37 as the second hole transport layer material.

[0346] The test results of the luminescence characteristics of the organic electroluminescent devices obtained in device embodiments 37 to 72 of the present invention and comparative device embodiments 3 to 4 are shown in Table 2 below.

[0347]

[0348]

[0349] According to the data in Tables 1 and 2, it can be seen that compared with comparative device Examples 1 to 4, in organic electroluminescent devices, the triamine derivatives provided by the present invention as a single hole transport layer or a second hole transport layer material can effectively improve the luminous efficiency and service life of the device.

[0350] [Device Example 73]

[0351] First, the ITO / Ag / ITO substrate was cleaned three times in distilled water and ultrasonically washed for 15 minutes. After the distilled water washing was completed, it was ultrasonically washed with isopropyl alcohol, acetone, methanol and other solvents in sequence and then dried at 120°C.

[0352] By vacuum evaporation, NPNPB with a thickness of 32 nm was evaporated on a cleaned ITO / Ag / ITO substrate as a hole injection layer material; NDDP with a thickness of 70 nm was evaporated on the hole injection layer as a hole transport layer material; MCP:Ir(piq)2(acac)=98:2 (mass ratio) was evaporated on the hole transport layer as a light-emitting layer with a thickness of 40 nm; Alq3 and Liq (doping ratio of 1:1) were evaporated on the light-emitting layer as electron transport layer materials with a thickness of 28 nm; LiF was evaporated on the electron transport layer as an electron injection layer with a thickness of 1.0 nm; then Mg:Ag=1:9 was evaporated on the electron injection layer as a cathode with a thickness of 12 nm; then the compound 28 of the present invention was evaporated on the cathode as a covering layer with a thickness of 70 nm, thereby preparing an organic electroluminescent device.

[0353]

[0354] [Device Examples 74-90]

[0355] Compound 44, compound 129, compound 167, compound 275, compound 286, compound 297, compound 309, compound 345, compound 362, compound 379, compound 407, compound 429, compound 596, compound 652, compound 665, compound 733, and compound 780 of the present invention were used to replace compound 28 in device example 73 as covering layer materials, except that an organic electroluminescent device was prepared by the same preparation method as device example 73.

[0356] [Comparative Device Example 5]

[0357] An organic electroluminescent device was prepared by the same preparation method as in Device Example 73, except that Comparative Compound 3 was used instead of Compound 28 in Device Example 73 as the covering layer material.

[0358] The test results of the luminescence characteristics of the organic electroluminescent devices obtained in device embodiments 73 to 90 of the present invention and comparative device embodiment 5 are shown in Table 3 below.

[0359]

[0360] According to the data in Table 3, it can be seen that, compared with the comparative device Example 5, the application of the triamine derivative provided by the present invention in the organic electroluminescent device as a covering layer material can improve the light extraction efficiency inside the device, thereby effectively increasing the luminous efficiency and service life of the device.

[0361] [Device Example 91]

[0362] First, the ITO substrate was cleaned three times in distilled water and ultrasonically washed for 15 minutes. After the distilled water washing was completed, ultrasonic washing was performed in sequence with isopropyl alcohol, acetone, methanol and other solvents, and then dried at 120°C.

[0363] By using a vacuum evaporation method, NPNPB with a thickness of 30 nm was evaporated on a cleaned ITO substrate as a hole injection layer material; NPB with a thickness of 75 nm was evaporated on the hole injection layer as a hole transport layer material; the compound of the present invention 23:Ir(ppy)3=93:7 (mass ratio) was evaporated on the hole transport layer as a light-emitting layer with a thickness of 40 nm; TmPyPB and Liq (doping ratio of 1:1) were evaporated on the light-emitting layer as electron transport layer materials with a thickness of 30 nm; LiF was evaporated on the electron transport layer as an electron injection layer with a thickness of 1.0 nm; and Al was then evaporated on the electron injection layer as a cathode with a thickness of 130 nm. Thus, an organic electroluminescent device was prepared.

[0364]

[0365] [Device Examples 92-108]

[0366] Compound 44, compound 104, compound 113, compound 182, compound 275, compound 286, compound 345, compound 373, compound 379, compound 529, compound 596, compound 652, compound 665, compound 733, compound 759, compound 780, and compound 791 of the present invention were used to replace compound 23 in device example 91 as the main material of the light-emitting layer. Except for this, an organic electroluminescent device was prepared by the same preparation method as device example 73.

[0367] [Comparative Device Example 6]

[0368] An organic electroluminescent device was prepared by the same preparation method as that of Device Example 91, except that Comparative Compound 2 was used instead of Compound 23 in Device Example 91 as the main material of the light-emitting layer.

[0369] The test results of the luminescence characteristics of the organic electroluminescent devices obtained in device embodiments 91 to 108 of the present invention and comparative device embodiment 6 are shown in Table 4 below.

[0370]

[0371]

[0372] According to the data in Table 4, compared with the comparative device Example 6, the application of the triamine derivative provided by the present invention in the organic electroluminescent device as a host material can significantly improve the luminous efficiency and service life of the device.

Claims

1. A triamine derivative, characterized in that The triamine derivative has a structure as shown in Formula I, In formula I, the Ar1 to Ar6 are the same or different from each other, and at least one of them is selected from the group represented by formula I-1: The formula I-1 is selected from any one of the groups shown below, The R3 are the same as or different from each other and are selected from any one of the following groups which are substituted or unsubstituted with one or more deuterium groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and phenyl; The R 3a are the same as or different from each other and are selected from hydrogen and deuterium; Said c1 is selected from 0, 1, 2 or 3, said c2 is selected from 0, 1, 2, 3 or 4, said c4 is selected from 0, 1, 2, 3, 4, 5 or 6, said c6 is selected from 0, 1, 2, 3, 4 or 5, said c7 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; The rest of Ar1 to Ar6 are the same as or different from each other and are selected from any one of the following groups: The R4 are the same as or different from each other and are selected from any one of hydrogen, deuterium, or any one of the following groups which are substituted or unsubstituted with one or more deuterium groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and phenyl; The R 4a are the same as or different from each other and are selected from hydrogen, deuterium, or any one of the following groups which are substituted or unsubstituted with one or more deuterium groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, and phenyl; The d1 is selected from 0, 1, 2, 3, 4 or 5, the d2 is selected from 0, 1, 2, 3 or 4, the d3 is selected from 0, 1, 2, 3, 4, 5, 6 or 7, when there are two or more R4, the two or more R4 are the same or different from each other; when there are two or more R 4a When two or more R 4a Same or different from each other, or two adjacent R 4a They are connected to each other to form a substituted or unsubstituted cyclopentane ring, or a substituted or unsubstituted cyclohexane ring; Alternatively, in the remaining groups of Ar1 to Ar6, L1 and L2 are a bond and Ar1 and Ar2 are connected to each other to form a substituted or unsubstituted carbazole ring, L3 and L4 are a bond and Ar3 and Ar4 are connected to each other to form a substituted or unsubstituted carbazole ring, L5 and L6 are a bond and Ar5 and Ar6 are connected to each other to form a substituted or unsubstituted carbazole ring, and Ar1 and Ar2, Ar3 and Ar4, Ar5 and Ar6 are not connected to each other to form a substituted or unsubstituted carbazole ring at the same time; wherein, Ar1 and Ar2, Ar3 and Ar4, Ar5 and Ar6 simultaneously form two carbazole rings; The R is selected from any one of hydrogen and deuterium; Said a is selected from 0, 1, 2, 3, 4 or 5; The L a ~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, The L1 to L6 are the same or different from each other and are selected from a single bond or any one of the following groups: The R5 are the same as or different from each other and are selected from hydrogen and deuterium; The e1 is selected from 0, 1, 2, 3 or 4; The substituent in the "substituted or unsubstituted" is selected from deuterium.

2. A triamine derivative according to claim 1, characterized in that: Ar1, Ar3, Ar5, Ar1 and Ar2, Ar1 and Ar3, Ar1 and Ar5, Ar3 and Ar4, Ar3 and Ar5, Ar5 and Ar6, Ar1, Ar2 and Ar3, Ar1, Ar2 and Ar5, Ar1, Ar3 and Ar4, Ar1, Ar3 and Ar5, Ar1, Ar5 and Ar6, Ar3, Ar4 and Ar5 or Ar3, Ar5 and Ar6 are selected from the groups shown in formula I-1.

3. A triamine derivative according to claim 1, characterized in that: The formula I-1 is selected from any one of the following groups:

4. A triamine derivative according to claim 1, characterized in that: In the remaining groups of Ar1 to Ar6, Ar1 and Ar2, Ar3 and Ar4, Ar5 and Ar6 are not connected to each other to form a substituted or unsubstituted carbazole ring.

5. A triamine derivative according to claim 1, characterized in that: The Ar1 to Ar6 are identical or different from each other, at least one of which is selected from the group shown in formula I-1, and the others are identical or different from each other and are selected from any one of the groups shown below:

6. A triamine derivative, characterized in that The triamine derivative is selected from any one of the structures shown below, 7. 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 of either the anode or the cathode, characterized in that: The organic layer comprises one or more of the triamine derivatives according to any one of claims 1 to 6.

8. The organic electroluminescent device according to claim 7, wherein the organic layer is located between the anode and the cathode, and the organic layer comprises a hole transport region, a light emitting layer, and an electron transport region, wherein: The hole transport region and / or the light emitting layer comprises any one or more of the triamine derivatives according to any one of claims 1 to 6.

9. The organic electroluminescent device according to claim 7, characterized in that: The organic layer is located outside of any one of the anode and the cathode. The organic layer includes a covering layer. The covering layer includes any one or more of the triamine derivatives according to any one of claims 1 to 6.

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