Deuterated compound, light-emitting host material composition and light-emitting device comprising same, and use

Abstract

The present application relates to the technical field of displays, and specifically relates to a deuterated compound, a light-emitting host material composition and a light-emitting device comprising same, and the use. The deuterated compound provided in the present application has a structure as shown below: (1), and a substituent comprises deuterium, such that an organic electroluminescent device comprising the deuterated compound can have a relatively high light-emitting efficiency and a relatively long service life.

Description

A deuterated compound and a luminescent host material composition, a luminescent device and applications thereof

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to the Chinese patent application filed with the China Patent Office on October 31, 2023, with application number 202311444258.6 and invention name “A deuterated compound and a luminescent host material composition, luminescent device and application containing the same”, the entire contents of which are incorporated by reference into this application. Technical Field

[0003] The present application relates to the field of display technology, and in particular to a deuterated compound and a luminescent host material composition, a luminescent device and applications containing the compound. Background Art

[0004] Organic electroluminescent device (OLED) is a device that changes electrical energy into light by applying electricity to an organic electroluminescent material, and generally has a structure comprising an anode, a cathode, and an organic layer between the anode and the cathode. The organic layer of the organic EL device can be composed of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer (which comprises a host material and a doping material), an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc., and the materials used for the organic layer are classified into hole injection materials, hole transport materials, electron blocking materials, light-emitting materials, electron buffer materials, hole blocking materials, electron transport materials, electron injection materials, etc. by their functions. In the organic EL device, due to the application of voltage, holes are injected into the light-emitting layer from the anode, and electrons are injected into the light-emitting layer from the cathode, and high-energy excitons are formed by the recombination of holes and electrons. Through this energy, the organic light-emitting compound reaches an excited state, and luminescence is generated by emitting light due to the energy generated by the excited state of the organic light-emitting compound returning to the ground state.

[0005] The most important factor determining the luminous efficiency of organic EL devices is the luminescent material. The luminescent material must have high quantum efficiency and high electron and hole mobility, and the resulting luminescent material layer must be uniform and stable. Luminescent materials are categorized by the color of their emitted light into blue, green, and red, as well as yellow and orange. Furthermore, luminescent materials can be further divided into host materials and dopant materials based on their function.

[0006] However, existing organic electroluminescent materials have low stability and low molecular quantum yield, resulting in low luminous efficiency and short life of organic electroluminescent devices containing such organic electroluminescent materials, which seriously limits the application of organic electroluminescent devices.

[0007] Summary of the Invention

[0008] The purpose of this application is to overcome the problems of low stability and low molecular quantum yield of existing organic electroluminescent materials, which result in low luminous efficiency and short life of organic electroluminescent devices containing such organic electroluminescent materials, and to provide a deuterated compound and a luminescent host material composition, a luminescent device and applications containing the compound.

[0009] Definitions of substituent terms in this application:

[0010] As used herein, the term "halogen" may include fluorine, chlorine, bromine or iodine.

[0011] As used herein, the term "C1-C30 alkyl" refers to a monovalent substituent derived from a straight-chain or branched saturated hydrocarbon having 1 to 30 carbon atoms, examples of which include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl.

[0012] As used herein, the term "C3-C30 cycloalkyl" refers to a cycloalkane derived from a monocyclic hydrocarbon or a polycyclic hydrocarbon having 1 to 30 ring main chain carbon atoms, and the cycloalkane may include cyclopropyl, cyclobutyl, adamantyl, and the like.

[0013] In the present application, aryl and arylene include monocyclic, polycyclic or condensed ring aromatic groups, the rings may be interrupted by short non-aromatic units, and may contain spiro structures. Aryl includes but is not limited to phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, anthracenyl, fluorenyl, spirobifluorenyl, etc., and arylene includes but is not limited to phenylene, biphenylene, terphenylene, naphthylene, phenanthrenyl, anthracenyl, fluorenyl, spirobifluorenyl, etc.

[0014] In the present application, heteroaryl and heteroarylene include monocyclic, polycyclic or condensed ring heteroaryl groups, and the rings may be interrupted by short non-aromatic units, and the heteroatoms include nitrogen, oxygen, and sulfur. Heteroaryl includes, but is not limited to, furyl, phenylthio, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzo thiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, and derivatives thereof; heteroarylene groups include but are not limited to furylene, phenylenethio, pyrroleene, thiophene ... yl, imidazolylene, pyrazolylene, thiazolylene, thiadiazolylene, isothiazolylene, isoxazolylene, oxazolylene, oxadiazolylene, triazinylene, tetrazinylene, triazolylene, tetrazolylene, furazolylene, pyridylene, pyrazinylene, pyrimidylene, pyridazinylene, benzofuranylene, benzothiophenylene, isobenzofuranylene, dibenzofuranylene, dibenzothiophenylene, benzimidazolylene oxazolyl, benzothiazolylene, benzoisothiazolylene, benzoisoxazolylene, benzoxazolylene, isoindolyl, indolyl, indazolylene, benzothiadiazolylene, quinolinylene, isoquinolinylene, cinnolinylene, quinazolinylene, quinoxalinylene, carbazolylene, phenoxazinylene, phenothiazinylene, phenanthridinylene, benzodioxolylene, dihydroacridinylene, and derivatives thereof.

[0015] As used herein, the term "substituted" refers to a hydrogen atom in a compound being replaced by another substituent. The position is not limited to a specific position, as long as the hydrogen at that position can be replaced by a substituent. When two or more substituents are present, the two or more substituents may be the same or different.

[0016] As used in this application, unless otherwise specified, hydrogen atoms include protium, deuterium, and tritium.

[0017] In the present application, the definition of a group defines the range of the number of carbon atoms, and the number of carbon atoms is any integer within the defined range. For example, a C6-C30 aromatic group represents an aromatic group, and the number of carbon atoms can be any integer within the range of 6-60, such as 6, 8, 10, 13, 15, 17, 20, 22, 25 or 30.

[0018] As used in this application, "organic electroluminescent material" means a material that can be used in an organic electroluminescent device and that can include at least one compound. If necessary, the organic electroluminescent material can be included in any layer constituting the organic electroluminescent device. For example, the organic electroluminescent material can be a hole injection material, a hole transport material, a hole assist material, a luminescence assist material, an electron blocking material, a luminescent material (containing a host material and a dopant material), an electron buffer material, a hole blocking material, an electron transport material, an electron injection material, etc.

[0019] As used in this application, "multiple host materials" means an organic electroluminescent material comprising a combination of at least two host materials. It may mean both a material before being included in an organic electroluminescent device (e.g., before vapor deposition) and a material after being included in an organic electroluminescent device (e.g., after vapor deposition). The multiple host materials of the present application may be included in any light-emitting layer constituting an organic electroluminescent device. Two or more compounds included in the multiple host materials of the present disclosure may be included in one light-emitting layer, or may be included in different light-emitting layers, respectively. For example, when two or more host materials are included in a layer, the layer may be formed by mixed evaporation, or may be formed simultaneously by separate co-evaporation.

[0020] In this application, Indicates a connection key.

[0021] The scheme adopted in this application is as follows:

[0022] The present application provides a deuterated compound having the structure shown in the following formula (1):

[0023] In the formula (1), Ar1 is selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;

[0024] Ar2 is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;

[0025] Ring A is naphthylene, and at least one hydrogen atom on Ring A or Ar2 is replaced by deuterium;

[0026] L is selected from a connecting bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group;

[0027] The substituents in the substituted C6-C30 arylene group, substituted C3-C30 heteroarylene group, substituted C6-C30 aryl group, and substituted C3-C30 heteroaryl group are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C6-C30 aryl, and C3-C30 heteroaryl groups.

[0028] Optionally, Ar1 is selected from hydrogen, deuterium, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl;

[0029] Ar2 is selected from substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl;

[0030] The substituents in the substituted C6-C20 aryl group and the substituted C3-C20 heteroaryl group are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C6-C30 aryl, and C3-C30 heteroaryl;

[0031] Optionally, at least one hydrogen atom on Ring A is replaced by deuterium, and up to five hydrogen atoms are replaced by deuterium.

[0032] Optionally, the formula (1) is selected from one of the following structures:

[0033] Ar1, Ar2, and L are as defined above.

[0034] Optionally, Ar1 is selected from hydrogen, deuterium, substituted or unsubstituted B groups,

[0035] Ar2 is selected from substituted or unsubstituted C groups,

[0036] Wherein, the B group is selected from: phenyl, naphthyl, biphenyl, terphenyl, carbazolyl, dimethylfluorenyl;

[0037] The C group is selected from the group consisting of phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, fluoranthenyl, triphenylene, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, benzodimethylfluorenyl, benzodiphenylfluorenyl, benzospirobifluorenyl, benzofuranyl, dibenzofuranyl, benzothiophenyl, dibenzothiophenyl, carbazolyl, benzocarbazolyl, and dibenzocarbazolyl;

[0038] The substituents of the substituted B group and the substituted C group are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C6-C30 aryl, and C3-C30 heteroaryl.

[0039] Optionally, Ar2 is selected from a substituted or unsubstituted C group;

[0040] wherein the C group is selected from the group consisting of phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, fluoranthenyl, triphenylene, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, benzodimethylfluorenyl, benzodiphenylfluorenyl, benzospirobifluorenyl, benzofuranyl, dibenzofuranyl, benzothiophenyl, dibenzothiophenyl, carbazolyl, benzocarbazolyl, and dibenzocarbazolyl;

[0041] wherein the substituent of the substituted C group is selected from deuterium;

[0042] Optionally, the Ar2 is selected from phenyl, at least one deuterium-substituted phenyl, at least one deuterium-substituted naphthyl;

[0043] Optionally, Ar2 is selected from phenyl, at least one deuterium-substituted phenyl, and at least one deuterium-substituted naphthyl, wherein the number of deuteriums in the at least one deuterium-substituted phenyl is 1-2, and the number of deuteriums in the at least one deuterium-substituted naphthyl is 1-6;

[0044] Optionally, Ar1 is selected from hydrogen, deuterium, phenyl, naphthyl, phenanthryl;

[0045] Optionally, Ar1 is selected from hydrogen, deuterium, and phenyl.

[0046] Optionally, L is selected from a linker, a C6-C12 arylene group;

[0047] Optionally, L is selected from a linker, a phenylene group, and a naphthylene group;

[0048] Optionally, Ar2 is selected from 1 or 2 deuterium-substituted phenyl groups, and 1-6 deuterium-substituted naphthyl groups.

[0049] Optionally, the deuterated compound is selected from one of M-1 to M-100:

[0050] The present application also provides a light-emitting host material composition, which comprises a first host material and a second host material, wherein the first host material comprises the deuterated compound according to any one of claims 1 to 7, and the second host material comprises a compound represented by the following formula (2):

[0051] X is selected from O, S;

[0052] L', L 1’ 、L 2’ are independently selected from a connecting bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group, and L', L 1’ , L 2’Each exists independently;

[0053] Among them, Ar 1’ 、Ar 2’ , Ar are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C3-C60 heteroarylamino, and substituted or unsubstituted C3-C60 heteroaryl;

[0054] The substituents in the substituted C6-C30 arylene group, C3-C30 heteroarylene group, substituted C6-C30 aryl group, substituted C3-C30 heteroaryl group, substituted C6-C60 arylamine group, and substituted C3-C60 heteroarylamine group are each independently selected from one or a combination of at least two of deuterium, halogen, cyano, C1-C12 alkyl group, C3-C12 cycloalkyl group, C6-C30 aryl group, C3-C30 heteroaryl group, C6-C60 arylamine group, and C3-C60 heteroarylamine group.

[0055] Optionally, the Ar 1’ 、Ar 2’ , Ar are each independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted E groups: phenyl, naphthyl, biphenyl, phenanthrenyl, fluoranthenyl, phenyl, terphenyl, triphenylene, phenylnaphthyl, naphthylphenyl, dimethylfluorenyl, phenylmethylfluorenyl, diphenylfluorenyl, pyridyl, pyridylphenyl, phenylpyridyl, spirobifluorenyl, benzodimethylfluorenyl, benzodiphenylfluorenyl, benzospirobifluorenyl, dibenzofuranyl, benzonaphthofuranyl, benzonaphthothienyl and dibenzothienyl;

[0056] The substituents of the substituted E group are each independently selected from one or a combination of at least two of a C1-C6 alkyl group, a C3-C12 cycloalkyl group, a C6-C25 aryl group, a C3-C25 heteroaryl group, a C6-C60 arylamine group, and a C3-C60 heteroarylamine group;

[0057] Optional, L', L 1’ , L 2’ Each is independently selected from a connecting bond, a substituted or unsubstituted C6-C12 arylene group, and a substituted or unsubstituted C3-C12 heteroarylene group;

[0058] The substituents of the substituted C6-C12 arylene group and the substituted C3-C12 heteroarylene group are each independently selected from one or a combination of at least two of a C1-C6 alkyl group, a C3-C12 cycloalkyl group, a C6-C25 aryl group, a C3-C25 heteroaryl group, a C6-C60 arylamine group, and a C3-C60 heteroarylamine group;

[0059] Optional, Ar1’ -Ar 2’ Each independently selected from phenyl, naphthyl, biphenyl, phenyl, terphenyl, phenylnaphthyl, naphthylphenyl, dimethylfluorenyl, diphenylfluorenyl, pyridyl, pyridylphenyl, phenylpyridyl, phenylcarbazolyl, phenylbenzocarbazolyl, phenylphenanthrocarbazolyl, spirobifluorenyl, spiro[fluorene-9,9'-xanthenyl]yl, phenylmethylfluorenyl, dibenzofuranyl and benzonaphthofuranyl;

[0060] Optionally, Ar is selected from phenyl or naphthyl;

[0061] Optionally, L' is selected from naphthylene;

[0062] Optional, L 1’ , L 2’ Each is independently selected from a linker, a phenylene group or a naphthylene group.

[0063] Optionally, the second host material comprises a compound selected from N-1 to N-654:

[0064] Optionally, the mass ratio of the first main material to the second main material is 9:1-1:9;

[0065] Optionally, the mass ratio of the first main material to the second main material is 2:8-8:2;

[0066] Optionally, the mass ratio of the first main material to the second main material is 3:7-7:3;

[0067] Further optionally, the mass ratio of the first main material to the second main material is 4:6-6:4.

[0068] The present application also provides an organic electroluminescent material, which includes the above-mentioned deuterated compound or the above-mentioned luminescent host material composition.

[0069] The present application also provides an organic electroluminescent device, which includes a cathode, an anode, and an organic layer located between the cathode and the anode, wherein the organic layer contains the above-mentioned deuterated compound or the above-mentioned light-emitting host material composition.

[0070] The present application also provides applications of the above-mentioned organic electroluminescent device in optical fiber equipment, lighting equipment, electronic photographic photoreceptor equipment, photoelectric converters, organic solar cells, switching element equipment, organic light-emitting field-effect transistors, image sensors or dye lasers.

[0071] Beneficial effects of this application:

[0072] The organic electroluminescent compound provided in the present application has a structure shown in formula (1), wherein some groups in formula (1) are substituted by deuterium, thereby improving the quantum yield of the molecule, which is beneficial to improving the luminous efficiency of the organic light-emitting device containing the compound; in the compound represented by formula (1), deuterium at a specific position and amount can improve the molecular stability of the compound. If the amount of deuteration is too large, the molecular vibration intensity is too large and the molecular stability is poor. In the present application, controlling the position and amount of deuteration can improve the stability of the molecule, which is beneficial to extending the life of the organic light-emitting device containing the compound; in summary, the organic electroluminescent compound provided in the present application can effectively improve the efficiency of the organic light-emitting device and extend its life.

[0073] The present application provides a plurality of host materials, wherein the plurality of host materials include a first host material and a second host material, wherein the first host material includes an organic electroluminescent compound represented by formula (1), and the second host material includes a compound represented by formula (2). The organic electroluminescent compound represented by formula (1) and the compound represented by formula (2) are combined to form a dual host material, which is used in the light-emitting layer of an organic electroluminescent device, and can improve the efficiency of the organic light-emitting device, reduce the driving voltage, and extend the life of the organic light-emitting device. BRIEF DESCRIPTION OF THE DRAWINGS

[0074] In order to more clearly illustrate the specific implementation methods of the present application or the technical solutions in the prior art, the following is a brief introduction to the drawings required for use in the specific implementation methods or the description of the prior art. Obviously, the drawings described below are some implementation methods of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0075] FIG1 is a structural diagram of an organic electroluminescent device in an embodiment of the device of the present application;

[0076] 1-substrate; 2-anode; 3-hole injection layer; 4-hole transport layer; 5-light-emitting layer; 6-electron transport layer; 7-electron injection layer; 8-cathode. DETAILED DESCRIPTION

[0077] The following examples are provided to further better understand the present application, but are not limited to the best implementation mode described herein, and do not limit the content and protection scope of the present application. Any product identical or similar to the present application obtained by anyone under the inspiration of the present application or by combining the features of the present application with other prior arts shall fall within the scope of protection of the present application.

[0078] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in this field can be used. If the manufacturer of the reagents or instruments is not specified, they are all commercially available conventional reagents.

[0079] Synthesis of intermediates:

[0080] Synthesis of intermediate N1-A

[0081] After nitrogen substitution, a three-necked reaction flask equipped with a mechanical stirrer, thermometer, and condenser was added with intermediate N1-Aa (10 mmol), intermediate N1-Ab (10 mmol), 100 mL of toluene, 20 mL of ethanol, and 20 mL of water. Potassium carbonate (20 mmol) and Pd(PPh3)4 (0.05 mmol) were then added sequentially. The mixture was heated to 70-80°C and allowed to react for 3 h. The reaction mixture was cooled to 25-30°C, and 100 mL of water and 100 mL of toluene were added, followed by stirring and separation. The aqueous phase was extracted once with 100 mL of toluene, separated, and the organic phases were combined. 7 g of anhydrous sodium sulfate was added to the organic phases, stirred, dried, and filtered. The organic phase was concentrated (-0.08-0.09 MPa, 55-60°C) until no liquid flowed out. 50 mL of a mixed solvent of dichloromethane and petroleum ether was added with stirring, the temperature was cooled to 0-5°C, and filtered to obtain compound N1-A in a 67% yield.

[0082] Elemental analysis: C 23 H 14 ClNO theoretical value: C, 77.64; H, 3.97; Cl, ​​9.96; N, 3.94; O, 4.50; Found: C, 77.59; H, 3.98; Cl, ​​9.95; N, 3.98;

[0083] HRMS (ESI) m / z [M+H] + : Theoretical value: 355.08; measured value: 356.32.

[0084] The preparation of intermediates N2-A to N12-A shown below is the same as that of N1-A, except that bromo and chloro starting materials with different substitution sites from N1-Aa and borate starting materials with different substitution sites from N1-Ab are used:

[0085] Synthesis route of intermediate N13-A

[0086] After nitrogen substitution, a three-necked reaction flask equipped with a mechanical stirrer, thermometer, and condenser was added with intermediate N13-Aa (10 mmol), intermediate N13-Ab (10 mmol), 100 mL of toluene, 20 mL of ethanol, 20 mL of water, potassium carbonate (20 mmol), and Pd(PPh3)4 (0.05 mmol). The mixture was heated to 70°C and allowed to react for 3 h. The temperature was lowered to 25-30°C, and 100 mL of water and 100 mL of toluene were slowly added, followed by separation. The aqueous phase was extracted once with 100 mL of toluene, separated, and the organic phases were combined and washed with water several times until neutral. 7 g of anhydrous sodium sulfate was added, stirred, dried, and filtered. The organic phase was concentrated (-0.08-0.09 MPa, 55-60°C) until no liquid was discharged. 50 mL of a mixed solvent of dichloromethane and petroleum ether was added with stirring, the temperature was lowered to 0-5°C, and filtered to obtain compound N13-A in a yield of 72%.

[0087] Elemental analysis: C 27 H 16 ClNO theoretical value: C, 79.90; H, 3.97; Cl, ​​8.73; N, 3.45; O, 3.94; Found: C, 79.90; H, 3.97; Cl, ​​8.73; N, 3.45; O, 3.94;

[0088] HRMS (ESI) m / z [M+H] + : Theoretical value: 405.09; measured value: 406.12.

[0089] Synthesis of intermediate SubM1-B

[0090] After nitrogen substitution, a three-necked reaction flask equipped with a mechanical stirrer, thermometer, and condenser was added with the following: SubM1-Bb (10 mmol), intermediate SubM1-Ba (10 mmol), 100 mL of toluene, 20 mL of ethanol, and 20 mL of water. Potassium carbonate (20 mmol) and Pd(PPh3)4 (0.05 mmol) were then added sequentially. The mixture was heated to 70-80°C and allowed to react for 3 h. The reaction mixture was cooled to 25-30°C, and 100 mL of water and 100 mL of toluene were added, followed by stirring and separation. The aqueous phase was extracted once with 100 mL of toluene, separated, and the organic phases were combined. 7 g of anhydrous sodium sulfate was added, stirred, and dried. The organic phase was filtered and concentrated (-0.08-0.09 MPa, 55-60°C) until no liquid flowed out. A mixed solvent of 50 mL of dichloromethane and petroleum ether was then added with stirring. The reaction mixture was cooled by 0-5°C and filtered to obtain compound SubM1-B-1 in a yield of 59%.

[0091] After nitrogen purge, a three-necked reaction flask equipped with a mechanical stirrer, thermometer, and condenser was added with intermediate SubM1-B-1 (10 mmol), the raw material pinacol diboronate (12 mmol), 100 mL of 1,4-dioxane, potassium acetate (20 mmol), and Pd2(dba)3 (0.05 mmol). The mixture was heated to 100°C and reacted for 3 h. The reaction was then cooled to 25-30°C, and 100 mL of water and 100 mL of toluene were added, followed by separation. The aqueous phase was extracted once with 100 mL of toluene, separated, and the organic phases were combined. 7 g of anhydrous sodium sulfate was added, stirred, and dried. The organic phase was filtered and concentrated (-0.08-0.09 MPa, 55-60°C) until no liquid was released. 50 mL of a mixed solvent of dichloromethane and petroleum ether was added with stirring, the temperature was lowered by 0-5°C, and filtered to obtain intermediate SubM1-B in a yield of 45%.

[0092] Synthesis of intermediate SubM2-B

[0093] The preparation method of SubM2-B is the same as that of SubM1-B, except that SubM2-Ba is used instead of SubM1-Ba, and SubM2-Bb is used instead of SubM1-Bb, to obtain SubM2-B with a yield of 52%.

[0094] Synthesis of intermediate SubM3-B

[0095] The preparation method of SubM3-B is the same as that of SubM1-B, except that SubM3-Ba is used instead of SubM1-Ba, and SubM3-Bb is used instead of SubM1-Bb, to obtain SubM3-B with a yield of 42%.

[0096] Synthesis of intermediate SubM1-A

[0097] After nitrogen substitution, a three-necked reaction flask equipped with a mechanical stirrer, a low-temperature thermometer, and a constant pressure dropping funnel was added with raw material SubM1-Aa (10 mmol) and 100 ml of tetrahydrofuran in sequence. Stirring was started, the temperature was lowered to -70 to -80 ° C, and n-butyl lithium (12 mmol) was added dropwise. The system temperature was maintained during the addition. After completion, the temperature was kept warm for 1 h. D2O (20 mmol) was slowly added, and the temperature was naturally raised to 25 to 30 ° C. 100 ml of water and 100 ml of toluene were added, stirred and separated, the aqueous phase was extracted once with 100 ml of toluene, separated, and the organic phases were combined. 7 g of anhydrous sodium sulfate was added to the organic phase, stirred and dried, filtered, and the organic phase was concentrated (-0.08 to 0.09 MPa, 55 to 60 ° C) until no liquid flowed out to obtain compound SubM1-A-1 with a yield of 76%.

[0098] After nitrogen purge, a three-necked reaction flask equipped with a mechanical stirrer, thermometer, and condenser was charged with the intermediate SubM1-A-1 (10 mmol), the raw material pinacol diboronate (12 mmol), 100 ml of 1,4-dioxane, potassium acetate (20 mmol), and Pd2(dba)3 (0.05 mmol). The mixture was heated to 100°C and reacted for 3 h. The reaction was then cooled to 25-30°C, and 100 ml of water and 100 ml of toluene were added, stirred, and separated. The aqueous phase was extracted once with 100 ml of toluene, separated, and the organic phases were combined. 7 g of anhydrous sodium sulfate was added, stirred, and dried. The organic phase was filtered and concentrated (-0.08-0.09 MPa, 55-60°C) until no liquid was released. 50 ml of a mixed solvent of dichloromethane and petroleum ether was added with stirring, the temperature was lowered by 0-5°C, and filtered to obtain compound SubM1-A in a 62% yield.

[0099] Synthesis of intermediate SubM2-A

[0100] The preparation method of SubM2-A is the same as that of SubM1-A, except that SubM2-Aa is used instead of SubM1-Aa to obtain SubM2-A with a yield of 75%.

[0101] Synthesis of intermediate SubM3-A

[0102] The preparation method of SubM3-A is the same as that of SubM1-A, except that SubM3-Aa is used instead of SubM1-Aa to obtain SubM3-A with a yield of 68%.

[0103] Synthesis of intermediate SubM4-A

[0104] The preparation method of SubM4-A is the same as that of SubM1-A, except that SubM4-Aa is used instead of SubM1-Aa to obtain SubM4-A with a yield of 72%.

[0105] Synthesis of intermediate SubM5-A

[0106] The preparation method of SubM5-A is the same as that of SubM1-A, except that SubM5-Aa is used instead of SubM1-Aa to obtain SubM5-A with a yield of 62%.

[0107] Synthesis of intermediate SubM6-A

[0108] The preparation method of SubM6-A is the same as that of SubM1-A, except that SubM6-Aa is used instead of SubM1-Aa to obtain SubM6-A with a yield of 68%.

[0109] Synthesis of intermediate SubM7-A

[0110] The preparation method of SubM7-A is the same as that of SubM1-A, except that SubM7-Aa is used instead of SubM1-Aa to obtain SubM7-A with a yield of 70%.

[0111] The preparation method of SubM8-A is the same as that of SubM1-A, except that SubM8-Aa is used instead of SubM1-Aa to obtain SubM8-A with a yield of 65%.

[0112] Synthesis of intermediate SubM1-B

[0113] After nitrogen substitution, a three-necked reaction flask equipped with a mechanical stirrer, thermometer, and condenser was added with the following: SubM1-Bb (10 mmol), intermediate SubM1-Ba (10 mmol), 100 mL of toluene, 20 mL of ethanol, and 20 mL of water. Potassium carbonate (20 mmol) and Pd(PPh3)4 (0.05 mmol) were then added sequentially. The mixture was heated to 70-80°C and allowed to react for 3 h. The reaction mixture was cooled to 25-30°C, and 100 mL of water and 100 mL of toluene were added, followed by stirring and separation. The aqueous phase was extracted once with 100 mL of toluene, separated, and the organic phases were combined. 7 g of anhydrous sodium sulfate was added, stirred, and dried. The organic phase was filtered and concentrated (-0.08-0.09 MPa, 55-60°C) until no liquid flowed out. A mixed solvent of 50 mL of dichloromethane and petroleum ether was then added with stirring. The reaction mixture was cooled by 0-5°C and filtered to obtain compound SubM1-B-1 in a yield of 59%.

[0114] After nitrogen purge, a three-necked reaction flask equipped with a mechanical stirrer, thermometer, and condenser was added with intermediate SubM1-B-1 (10 mmol), the raw material pinacol diboronate (12 mmol), 100 mL of 1,4-dioxane, potassium acetate (20 mmol), and Pd2(dba)3 (0.05 mmol). The mixture was heated to 100°C and reacted for 3 h. The reaction was then cooled to 25-30°C, and 100 mL of water and 100 mL of toluene were added, followed by separation. The aqueous phase was extracted once with 100 mL of toluene, separated, and the organic phases were combined. 7 g of anhydrous sodium sulfate was added, stirred, and dried. The organic phase was filtered and concentrated (-0.08-0.09 MPa, 55-60°C) until no liquid was released. 50 mL of a mixed solvent of dichloromethane and petroleum ether was added with stirring, the temperature was lowered by 0-5°C, and filtered to obtain intermediate SubM1-B in a yield of 45%.

[0115] Synthesis of intermediate SubM2-B

[0116] The preparation method of SubM2-B is the same as that of SubM1-B, except that SubM2-Ba is used instead of SubM1-Ba, and SubM2-Bb is used instead of SubM1-Bb, to obtain SubM2-B with a yield of 52%.

[0117] Synthesis of intermediate SubM3-B

[0118] The preparation method of SubM3-B is the same as that of SubM1-B, except that SubM3-Ba is used instead of SubM1-Ba, and SubM3-Bb is used instead of SubM1-Bb, to obtain SubM3-B with a yield of 42%.

[0119] Synthesis of intermediate SubM1-C

[0120] first step:

[0121] After nitrogen replacement, a three-necked reaction flask equipped with a mechanical stirrer, a low-temperature thermometer, and a constant pressure dropping funnel was added in sequence with the raw material SubM1-Ca (14 mmol) and 140 mL of tetrahydrofuran. Stirring was started, the temperature was lowered to -70 to -80 ° C, and n-butyl lithium (16 mmol) was added dropwise. The system temperature was maintained during the addition. After completion, it was kept warm for 1 h, D2O (10 mmol) was slowly added, and the temperature was naturally raised to 25 to 30 ° C. 100 mL of water and 100 mL of toluene were added, stirred and separated, the aqueous phase was extracted once with 100 mL of toluene, separated, and the organic phases were combined. 7 g of anhydrous sodium sulfate was added to the organic phase, stirred and dried, filtered, and the organic phase was concentrated (-0.08 to 0.09 MPa, 55 to 60 ° C) until no liquid flowed out to obtain compound SubM1-C-1 with a yield of 76%.

[0122] Step 2:

[0123] After nitrogen replacement, a three-necked reaction flask equipped with a mechanical stirrer, a low-temperature thermometer, and a constant pressure dropping funnel was added in sequence with the intermediate SubM1-C-1 (10 mmol) and 100 mL of dichloromethane. Stirring was started, the temperature was lowered to -10°C, and triethylamine (12 mmol) was added dropwise. After completion, the temperature was kept warm for 1 h, and trifluoromethanesulfonic anhydride (10 mmol) was slowly added. The temperature was naturally raised to 25-30°C, 100 mL of water and 100 mL of dichloromethane were added, stirred and separated, and the aqueous phase was extracted once with 100 mL of dichloromethane. The liquids were separated, the organic phases were combined, 7 g of anhydrous sodium sulfate was added to the organic phase, stirred and dried, filtered, and the organic phase was concentrated (-0.08-0.09 MPa, 55-60°C) until no liquid flowed out to obtain compound SubM1-C-2 with a yield of 86%.

[0124] Step 3:

[0125] After nitrogen purge, a three-necked reaction flask equipped with a mechanical stirrer, thermometer, and condenser was added with the intermediate SubM1-C-2 (8 mmol), the raw material SubM1-Ca (8 mmol), potassium carbonate (16 mmol), Pd(PPh3)4 (0.04 mmol), 100 mL of 1,4-dioxane, and 30 mL of water. Stirring was initiated and the reaction was heated to 70-75°C for 3 h. The reaction was cooled to 25-30°C, and 100 mL of water and 100 mL of dichloromethane were added, followed by separation. The aqueous phase was extracted once with 100 mL of dichloromethane, separated, and the organic phases were combined. 7 g of anhydrous sodium sulfate was added to the organic phases, stirred, and dried. The organic phases were filtered and concentrated (-0.08-0.09 MPa, 55-60°C) until no liquid flowed out. 20 mL of petroleum ether was added with stirring, the temperature was lowered by 0-5°C, and the crude product was filtered to obtain the product SubM1-C-3. The crude product was recrystallized from toluene to obtain the product SubM1-C-3 in a yield of 77%.

[0126] Step 4:

[0127] After nitrogen purge, a three-necked reaction flask equipped with a mechanical stirrer, thermometer, and condenser was charged with the intermediate SubM1-C-3 (10 mmol), the starting material pinacol diboronate (6 mmol), 100 mL of 1,4-dioxane, potassium acetate (12 mmol), and Pd2(dba)3 (0.05 mmol). The mixture was heated to 100°C and reacted for 3 h. The reaction was then cooled to 25-30°C, and 100 mL of water and 100 mL of toluene were added, followed by separation. The aqueous phase was extracted once with 100 mL of toluene, separated, and the organic phases were combined. 7 g of anhydrous sodium sulfate was added, stirred, and dried. The organic phase was filtered and concentrated (-0.08-0.09 MPa, 55-60°C) until no liquid was released. 50 mL of a mixed solvent of dichloromethane and petroleum ether was added with stirring, the temperature was lowered by 0-5°C, and filtered to obtain compound SubM1-C in a 63% yield.

[0128] Synthesis of intermediate SubM2-C

[0129] After nitrogen substitution, a three-necked reaction flask equipped with a mechanical stirrer, thermometer, and condenser was added with the following ingredients: SubM2-Ca (10 mmol), intermediate SubM8-A (10 mmol), potassium carbonate (20 mmol), Pd(PPh3)4 (0.05 mmol), 100 mL of 1,4-dioxane, and 30 mL of water. The mixture was stirred and heated to 70-75°C for 3 h. The mixture was cooled to 25-30°C, and 100 mL of water and 100 mL of dichloromethane were added and stirred to separate the liquids. The aqueous phase was extracted once with 100 mL of dichloromethane, separated, and the organic phases were combined. 7 g of anhydrous sodium sulfate was added to the organic phases, stirred to dryness, and filtered. The organic phase was concentrated (-0.08-0.09 MPa, 55-60°C) until no liquid flowed out. 20 mL of petroleum ether was added with stirring, the temperature was lowered by 0-5°C, and the crude product was filtered to obtain the intermediate SubM2-C-1. The crude product was recrystallized from toluene to obtain the intermediate SubM2-C-1 in a yield of 72%.

[0130] After nitrogen purge, a three-necked reaction flask equipped with a mechanical stirrer, thermometer, and condenser was added with the intermediate SubM4-C-1 (10 mmol), the raw material pinacol diboronate (12 mmol), 100 mL of 1,4-dioxane, potassium acetate (20 mmol), and Pd2(dba)3 (0.05 mmol). The mixture was heated to 100°C and reacted for 3 h. The reaction was then cooled to 25-30°C, and 100 mL of water and 100 mL of toluene were added, followed by separation. The aqueous phase was extracted once with 100 mL of toluene, separated, and the organic phases were combined. 7 g of anhydrous sodium sulfate was added, stirred, and dried. The organic phase was filtered and concentrated (-0.08-0.09 MPa, 55-60°C) until no liquid was discharged. 50 mL of a mixed solvent of dichloromethane and petroleum ether was added with stirring, the temperature was lowered by 0-5°C, and filtered to obtain the intermediate SubM2-C in a 70% yield.

[0131] Synthesis of intermediate SubM3-C

[0132] The preparation method of SubM3-C is the same as that of SubM2-C, except that SubM5-A is used instead of SubM8-A to obtain the intermediate SubM3-C with a yield of 70%.

[0133] Synthesis of intermediate SubM4-C

[0134] The preparation method of SubM4-C is the same as that of SubM2-C, except that SubM4-Ca is used instead of SubM2-Ca, and SubM6-A is used instead of SubM8-A, to obtain the intermediate SubM4-C with a yield of 69%.

[0135] Example 1

[0136] This embodiment provides a deuterated compound N-1. The synthesis of the deuterated compound N-1 specifically includes the following steps:

[0137] After nitrogen substitution in a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser, intermediate N1-B (10 mmol), intermediate N1-A (10 mmol), and 100 mL of toluene were added in sequence. The mixture was heated under reflux to separate water for 0.5 h, cooled to 70-80 ° C, and sodium tert-butoxide (15 mmol), Pd2(dba)3 (0.05 mmol), and s-phos (0.1 mmol) were slowly added. After the system stabilized, it was heated to 100-110 ° C and reacted for 3 h. The temperature was lowered to 25-30°C, 100 mL of water and 100 mL of toluene were added, stirred and separated, the aqueous phase was extracted once with 100 mL of toluene, separated, the organic phases were combined, 7 g of anhydrous sodium sulfate was added to the organic phase, stirred and dried, filtered, and the organic phase was concentrated (-0.08-0.09 MPa, 55-60°C) until no liquid flowed out, 20 mL of petroleum ether was added with stirring, the temperature was lowered to 0-5°C, and filtered to obtain compound N-1 with a yield of 68%.

[0138] Elemental analysis: C 41 H 28 Theoretical value of N2O: C, 87.21; H, 5.00; N, 4.96; O, 2.83; Found: C, 87.15; H, 5.01; N, 4.99;

[0139] HRMS (ESI) m / z [M+H] + : Theoretical value: 564.22; measured value: 565.31.

[0140] Example 2

[0141] This embodiment provides a deuterated compound N-5. The synthesis of the deuterated compound N-5 specifically includes the following steps:

[0142] After nitrogen substitution in a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser, the intermediate N6-B (10 mmol), the intermediate N1-A (10 mmol), and 100 mL of toluene were added in sequence, and the mixture was heated to reflux to separate water for 0.5 h. The temperature was lowered to 70-80 ° C, and sodium tert-butoxide (15 mmol), Pd2(dba)3 (0.05 mmol), and s-phos (0.1 mmol) were slowly added. After the system was stabilized, it was heated to 100-110 ° C and reacted for 3 h. The temperature was lowered to 25-30°C, 100 mL of water and 100 mL of toluene were added, stirred and separated, the aqueous phase was extracted once with 100 mL of toluene, separated, the organic phases were combined, 7 g of anhydrous sodium sulfate was added to the organic phase, stirred and dried, filtered, and the organic phase was concentrated (-0.08-0.09 MPa, 55-60°C) until no liquid flowed out, 20 mL of petroleum ether was added with stirring, the temperature was lowered to 0-5°C, and filtered to obtain compound N-5 with a yield of 66%.

[0143] Elemental analysis: C 41 H 26 Theoretical value of N2O2: C, 85.10; H, 4.53; N, 4.84; O, 5.53; Found: C, 85.10; H, 4.53; N, 4.84; O, 5.53;

[0144] HRMS (ESI) m / z [M+H] + : Theoretical value: 578.20; measured value: 579.25.

[0145] Example 3

[0146] This embodiment provides deuterated compound N-16. The synthesis of deuterated compound N-16 specifically includes the following steps:

[0147] After nitrogen substitution in a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser, intermediate N16-B (10 mmol), intermediate N16-A (10 mmol), and 100 mL of toluene were added in sequence. The mixture was heated to reflux to separate water for 0.5 h, cooled to 70-80 °C, and sodium tert-butoxide (15 mmol), Pd2(dba)3 (0.05 mmol), and s-phos (0.1 mmol) were slowly added. After the system stabilized, it was heated to 100-110 °C and reacted for 3 h. The temperature was lowered to 25-30°C, 100 mL of water and 100 mL of toluene were added, stirred and separated, the aqueous phase was extracted once with 100 mL of toluene, separated, the organic phases were combined, 7 g of anhydrous sodium sulfate was added to the organic phase, stirred and dried, filtered, and the organic phase was concentrated (-0.08-0.09 MPa, 55-60°C) until no liquid flowed out, 20 mL of petroleum ether was added with stirring, the temperature was lowered to 0-5°C, and filtered to obtain compound N-16 with a yield of 61%.

[0148] Elemental analysis: C 51 H 32 N2O2 theoretical value: C, 85.97; H, 4.49; N, 4.46; O, 5.09; found: C, 85.94; H, 4.50; N, 4.48; HRMS (ESI) m / z [M+H] + : Theoretical value: 628.22; measured value: 629.25.

[0149] Example 4

[0150] This embodiment provides deuterated compound N-18. The synthesis of deuterated compound N-18 specifically includes the following steps:

[0151] After nitrogen substitution in a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser, intermediate N18-B (10 mmol), intermediate N1-A (10 mmol), and 100 mL of toluene were added in sequence. The mixture was heated to reflux to separate water for 0.5 h, cooled to 70-80 ° C, and sodium tert-butoxide (15 mmol), Pd2(dba)3 (0.05 mmol), and s-phos (0.1 mmol) were slowly added. After the system was stabilized, it was heated to 100-110 ° C and reacted for 3 h. The temperature was lowered to 25-30°C, 100 mL of water and 100 mL of toluene were added, stirred and separated, the aqueous phase was extracted once with 100 mL of toluene, separated, the organic phases were combined, 7 g of anhydrous sodium sulfate was added to the organic phase, stirred and dried, filtered, and the organic phase was concentrated (-0.08-0.09 MPa, 55-60°C) until no liquid flowed out, 20 mL of petroleum ether was added with stirring, the temperature was lowered to 0-5°C, and filtered to obtain compound N-18 with a yield of 61%.

[0152] Elemental analysis: C 53 H 37N3O theoretical value: C, 86.98; H, 5.10; N, 5.74; O, 2.19; Found: C, 87.00; H, 5.11; N, 5.70;

[0153] HRMS (ESI) m / z [M+H] + : Theoretical value: 731.29; measured value: 732.15.

[0154] Example 5

[0155] This embodiment provides deuterated compound N-45. The synthesis of deuterated compound N-45 specifically includes the following steps:

[0156] After nitrogen substitution in a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser, intermediate N45-B (10 mmol), intermediate N1-A (10 mmol), and 100 mL of toluene were added in sequence. The mixture was heated to reflux to separate water for 0.5 h, and then cooled to 70-80 ° C. Sodium tert-butoxide (15 mmol), Pd2(dba)3 (0.05 mmol), and s-phos (0.1 mmol) were slowly added. After the system was stabilized, it was heated to 100-110 ° C and reacted for 3 h. The temperature was lowered to 25-30°C, 100 mL of water and 100 mL of toluene were added, stirred and separated, the aqueous phase was extracted once with 100 mL of toluene, separated, the organic phases were combined, 7 g of anhydrous sodium sulfate was added to the organic phase, stirred and dried, filtered, and the organic phase was concentrated (-0.08-0.09 MPa, 55-60°C) until no liquid flowed out, 20 mL of petroleum ether was added with stirring, the temperature was lowered to 0-5°C, and filtered to obtain compound N-45 with a yield of 65%.

[0157] Elemental analysis: C 49 H 32 N2O theoretical value: C, 88.53; H, 4.85; N, 4.21; O, 2.41; found: C, 88.49; H, 4.86; N, 4.24; HRMS (ESI) m / z [M+H] + : Theoretical value: 664.25; measured value: 665.19.

[0158] Example 6

[0159] This embodiment provides deuterated compound N-130. The synthesis of deuterated compound N-130 specifically includes the following steps:

[0160] After nitrogen substitution in a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser, intermediate N130-B (10 mmol), intermediate N4-A (10 mmol), and 100 mL of toluene were added in sequence. The mixture was heated to reflux to separate water for 0.5 h, cooled to 70-80 ° C, and sodium tert-butoxide (15 mmol), Pd2(dba)3 (0.05 mmol), and s-phos (0.1 mmol) were slowly added. After the system was stabilized, it was heated to 100-110 ° C and reacted for 3 h. The temperature was lowered to 25-30°C, 100 mL of water and 100 mL of toluene were added, stirred and separated, the aqueous phase was extracted once with 100 mL of toluene, separated, the organic phases were combined, 7 g of anhydrous sodium sulfate was added to the organic phase, stirred and dried, filtered, and the organic phase was concentrated (-0.08-0.09 MPa, 55-60°C) until no liquid flowed out, 20 mL of petroleum ether was added with stirring, the temperature was lowered to 0-5°C, and filtered to obtain compound N-130 with a yield of 65%.

[0161] Elemental analysis: C 47 H 30 N2O2 theoretical value: C, 86.22; H, 4.62; N, 4.28; O, 4.89; found: C, 86.20; H, 4.61; N, 4.31; HRMS (ESI) m / z [M+H] + : Theoretical value: 654.23; Measured value: 655.28

[0162] Example 7

[0163] This embodiment provides a deuterated compound M-1. The synthesis of the deuterated compound M-1 specifically includes the following steps:

[0164] After nitrogen substitution, a three-necked reaction flask equipped with a mechanical stirrer, thermometer, and condenser was added with SubM3-A (10 mmol), M-1-a (1.05 mmol), 1,4-dioxane (100 mL), and water (30 mL). Sodium carbonate (20 mmol) and Pd(PPh3)4 (0.05 mmol) were added in sequence and heated to 70-80°C for 3 h. The reaction was cooled to 25-30°C, 100 mL of water and 100 mL of toluene were added, stirred, and separated. The aqueous phase was extracted once with 100 mL of toluene, separated, and the organic phases were combined. 7 g of anhydrous sodium sulfate was added to the organic phase, stirred, and dried. The organic phase was filtered and concentrated (-0.08-0.09 MPa, 55-60°C) until no liquid flowed out. 50 mL of a mixed solvent of dichloromethane and petroleum ether was added with stirring, the temperature was lowered by 0-5°C, and filtered to obtain the intermediate IntM-1-a in a yield of 43%.

[0165] After nitrogen substitution, a three-necked reaction flask equipped with a mechanical stirrer, thermometer, and condenser was added with intermediate IntM-1-a (10 mmol), intermediate 1-A (10 mmol), potassium carbonate (20 mmol), Pd(PPh3)4 (0.05 mmol), 100 mL of 1,4-dioxane, and 30 mL of water. Stirring was initiated and the reaction was heated to 70-75°C for 3 h. The temperature was lowered to 25-30°C, 100 mL of water and 100 mL of dichloromethane were added, and the mixture was separated by stirring. The aqueous phase was extracted once with 100 mL of dichloromethane, separated, and the organic phases were combined. 7 g of anhydrous sodium sulfate was added to the organic phase, stirred, and dried. The organic phase was filtered and concentrated (-0.08-0.09 MPa, 55-60°C) until no liquid flowed out. 20 mL of petroleum ether was added with stirring, the temperature was lowered by 0-5°C, and the crude product was obtained by filtration. The crude product was recrystallized from toluene to obtain product M-1 in a yield of 54%.

[0166] Elemental analysis: C 41 H 24 DN3O theoretical value: C, 85.39; H, 4.54; N, 7.29; O, 2.77; found: C, 85.42; H, 4.55; N, 7.24; HRMS (ESI) m / z [M+H]+: theoretical value: 576.21; found: 577.32.

[0167] Example 8

[0168] This embodiment provides a deuterated compound M-8. The synthesis of the deuterated compound M-8 specifically includes the following steps:

[0169] The preparation method of M-8 is the same as that of M-1, except that SubM6-A replaces SubM3-A, and SubM1-C replaces M-1-b, to obtain product M-8 with a yield of 56%.

[0170] Elemental analysis: C 45 H 25 D2N3O theoretical value: C, 86.10; H, 4.66; N, 6.69; O, 2.55; found: C, 86.15; H, 4.67; N, 6.62; HRMS (ESI) m / z [M+H]+: theoretical value: 627.23; found: 628.43.

[0171] Example 9

[0172] This embodiment provides a deuterated compound M-15. The synthesis of the deuterated compound M-15 specifically includes the following steps:

[0173] The preparation method of M-15 is the same as that of M-1, except that SubM1-A replaces SubM3-A, and SubM3-B replaces M-1-b, to obtain product M-15 with a yield of 56%.

[0174] Elemental analysis: C 51 H 30 DN3O theoretical value: C, 87.16; H, 4.59; N, 5.98; O, 2.28; found: C, 87.18; H, 4.61; N, 5.94; HRMS (ESI) m / z [M+H]+: theoretical value: 702.25; found: 703.25.

[0175] Example 10

[0176] This embodiment provides a deuterated compound M-16. The synthesis of the deuterated compound M-16 specifically includes the following steps:

[0177] After nitrogen replacement, a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser was added with the intermediate IntM-15-a (10 mmol), the raw material M-16-b (10 mmol), potassium carbonate (20 mmol), Pd(PPh3)4 (0.05 mmol), 100 mL of 1,4-dioxane, and 30 mL of water. Stirring was started and the reaction was heated to 70-75°C for 3 h. The temperature was lowered to 25-30°C, 100 mL of water and 100 mL of dichloromethane were added and stirred to separate the liquids. The aqueous phase was extracted once with 100 mL of dichloromethane, separated, and the organic phases were combined. 7 g of anhydrous sodium sulfate was added to the organic phase and stirred to dryness. The organic phase was filtered and concentrated (-0.08-0.09 MPa, 55-60°C) until no liquid flowed out. 20 mL of petroleum ether was added with stirring, the temperature was lowered by 0-5°C, and the crude product was filtered to obtain the crude product. The crude product was recrystallized from toluene to obtain the product M-16 with a yield of 62%.

[0178] Elemental analysis: C 41 H 24 DN3O theoretical value: C, 85.39; H, 4.54; N, 7.29; O, 2.77; found: C, 85.43; H, 4.55; N, 7.23; HRMS (ESI) m / z [M+H]+: theoretical value: 576.21; found: 576.46.

[0179] Example 11

[0180] This embodiment provides a deuterated compound M-19. The synthesis of the deuterated compound M-19 specifically includes the following steps:

[0181] The preparation method of M-19 is the same as that of M-16, except that SubM1-B is used instead of M-16-b. The product M-19 is obtained with a yield of 57%. Elemental analysis: C 47 H 28 DN3O theoretical value: C, 86.48; H, 4.63; N, 6.44; O, 2.45; found value: C, 86.49; H, 4.62; N, 6.45; HRMS (ESI) m / z [M+H]+: theoretical value: 652.24; found value: 653.23.

[0182] Example 12

[0183] This embodiment provides a deuterated compound M-24. The synthesis of the deuterated compound M-24 specifically includes the following steps:

[0184] The preparation method of M-24 is the same as that of M-16, except that IntM-8-a is used instead of IntM-15-a, and SubM2-B is used instead of M-16-b. The product M-24 is obtained in a yield of 52%.

[0185] Elemental analysis: C 51 H 30 DN3O theoretical value: C, 87.16; H, 4.59; N, 5.98; O, 2.28 found: HRMS (ESI) m / z [M+H] +: C, 87.21; H, 4.60; N, 5.92; theoretical value: 702.25; found: 703.19.

[0186] Example 13

[0187] This embodiment provides a deuterated compound M-27. The synthesis of the deuterated compound M-27 specifically includes the following steps:

[0188] The preparation method of M-27 is the same as that of M-1, except that SubM7-A is used instead of SubM3-A, and M-27-b is used instead of M-1-b. The product M-27 is obtained in a yield of 61%.

[0189] Elemental analysis: C 45 H 26 DN3O theoretical value: C, 86.24; H, 4.50; N, 6.70; O, 2.55; found: C, 86.28; H, 4.52; N, 6.64; HRMS (ESI) m / z [M+H]+: theoretical value: 626.22; found: 627.25.

[0190] Example 14

[0191] This embodiment provides a deuterated compound M-31. The synthesis of the deuterated compound M-31 specifically includes the following steps:

[0192] The preparation method of M-31 is the same as that of M-16, except that M-31-b is used instead of M-16-b to obtain the product M-31 with a yield of 55%. Elemental analysis: C 41 H 24 DN3O theoretical value: C, 85.39; H, 4.54; N, 7.29; O, 2.77; found: C, 85.45; H, 4.56; N, 7.21; HRMS (ESI) m / z [M+H]+: theoretical value: 576.21; found: 577.36.

[0193] Example 15

[0194] This embodiment provides a deuterated compound M-53. The synthesis of the deuterated compound M-53 specifically includes the following steps:

[0195] The preparation method of M-53 is the same as that of M-1, except that SubM4-A replaces SubM3-A, and SubM2-C replaces M-1-b, to obtain product M-53 with a yield of 58%.

[0196] Elemental analysis: C 41 H 23 Theoretical value for D2N3O: C, 85.25; H, 4.71; N, 7.27; O, 2.77. Found: C, 85.28; H, 4.72; N, 7.22; HRMS (ESI) m / z [M+H]+: Theoretical value: 577.21; Found: 578.40.

[0197] Example 16

[0198] This embodiment provides a deuterated compound M-57. The synthesis of the deuterated compound M-57 specifically includes the following steps:

[0199] The preparation method of M-57 is the same as that of M-1, except that SubM2-A replaces SubM3-A, and SubM3-C replaces M-1-b, to obtain product M-57 with a yield of 54%.

[0200] Elemental analysis: C 41 H 22 D3N3O theoretical value: C, 85.10; H, 4.88; N, 7.26; O, 2.76 found: C, 85.14; H, 4.90; N, 7.22; HRMS (ESI) m / z [M+H] +: theoretical value: 578.22; found: 579.40.

[0201] Example 17

[0202] This embodiment provides a deuterated compound M-68. The synthesis of the deuterated compound M-68 specifically includes the following steps:

[0203] The preparation method of M-68 is the same as that of M-16, except that IntM-57-a is used instead of IntM-15-a, and M-68-b is used instead of M-16-b. The product M-68 is obtained in a yield of 60%.

[0204] Elemental analysis: C 41 H 23 Theoretical value of D2N3O: C, 85.25; H, 4.71; N, 7.27; O, 2.77. Found: C, 85.28; H, 4.72; N, 7.22; HRMS (ESI) m / z [M+H]+: theoretical value: 577.21; found: 578.56.

[0205] Example 18

[0206] This embodiment provides a deuterated compound M-72. The synthesis of the deuterated compound M-72 specifically includes the following steps:

[0207] The preparation method of M-72 is the same as that of M-16, except that SubM4-C is used instead of M-16-b to obtain the product M-72 with a yield of 57%. Elemental analysis: C 41 H 23 Theoretical value for D2N3O: C, 85.25; H, 4.71; N, 7.27; O, 2.77. Found: C, 85.30; H, 4.72; N, 7.21; HRMS (ESI) m / z [M+H]+: Theoretical value: 577.21; Found: 578.54.

[0208] Example 19

[0209] This embodiment provides a deuterated compound M-81. The synthesis of the deuterated compound M-81 specifically includes the following steps:

[0210] The preparation method of M-81 is the same as that of M-16, except that IntM-57-a is used instead of IntM-15-a, and M-81-b is used instead of M-16-b. The product M-81 is obtained in a yield of 61%.

[0211] Elemental analysis: C 41 H 23D2N3O theoretical value: C, 85.25; H, 4.71; N, 7.27; O, 2.77; found: C, 85.28; H, 4.72; N, 7.21; HRMS (ESI) m / z [M+H] +: theoretical value: 577.21; found: 578.18.

[0212] Example 20

[0213] This embodiment provides a deuterated compound M-86. The synthesis of the deuterated compound M-86 specifically includes the following steps:

[0214] The preparation method of M-86 is the same as that of M-16, except that M-86-b is used instead of M-16-b to obtain the product M-86 with a yield of 58%. Elemental analysis: C 41 H 24 DN3O theoretical value: C, 85.39; H, 4.54; N, 7.29; O, 2.77 found: C, 85.45; H, 4.55; N, 7.21; HRMS (ESI) m / z [M+H] +: theoretical value: 576.21; found: 577.32.

[0215] Example 21

[0216] This embodiment provides a deuterated compound M-98. The synthesis of the deuterated compound M-98 specifically includes the following steps:

[0217] The preparation method of M-98 is the same as that of M-1, except that SubM7-A is used instead of SubM3-A, and M-98-b is used instead of M-1-b. The product M-98 is obtained in a yield of 64%.

[0218] Elemental analysis: C 45 H 26 DN3O theoretical value: C, 86.24; H, 4.50; N, 6.70; O, 2.55; found: C, 86.27; H, 4.52; N, 6.64; HRMS (ESI) m / z [M+H]+: theoretical value: 626.22; found: 627.35.

[0219] Example 22

[0220] This embodiment provides a deuterated compound M-99. The synthesis of the deuterated compound M-99 specifically includes the following steps:

[0221] The preparation method of M-99 is the same as that of M-16, except that M-99-b is used instead of M-16-b to obtain the product M-99 with a yield of 52%. Elemental analysis: C 41 H24 DN3O theoretical value: C, 85.39; H, 4.54; N, 7.29; O, 2.77; found: C, 85.43; H, 4.55; N, 7.24; HRMS (ESI) m / z [M+H]+: theoretical value: 576.21; found: 577.64.

[0222] Device Examples and Comparative Examples

[0223] Some of the materials used to make the organic electroluminescent devices in the device examples and comparative examples are as follows:

[0224] The organic electroluminescent device structures in the device embodiment and the comparative example are similar (as shown in Figure 1), including an anode 2, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7 and a cathode 8 stacked in sequence on a substrate 1, and the device structure is: substrate + anode (indium tin oxide (ITO) coated glass substrate) / hole injection layer (HIL) / hole transport layer (HTL) / light-emitting layer (EML) / electron transport layer (ETL) / electron injection layer (EIL) / cathode (Al).

[0225] The preparation of the organic electroluminescent device in the device embodiment and the comparative example includes the following steps:

[0226] 1) Substrate cleaning:

[0227] A glass substrate coated with transparent ITO was ultrasonically treated in an aqueous detergent (the composition and concentration of the aqueous detergent: ethylene glycol solvent ≤ 10wt%, triethanolamine ≤ 1wt%), then rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol (acetone and ethanol volume ratio of 1:1), baked in a clean environment to completely remove moisture, and then cleaned with ultraviolet light and ozone.

[0228] 2) Preparation of organic layer:

[0229] The ITO transparent substrate was transferred to the evaporation equipment and vacuumed to 1×10 -6 to 2×10 -4 Pa, the hole injection layer (HIL) / hole transport layer (HTL) / emitting layer (EML) / electron transport layer (ETL) / electron injection layer (EIL) / cathode (Al) are sequentially deposited on the anode.

[0230] in:

[0231] The hole injection layer (HIL) material is a mixture of NDP-9 and HT, where the mass ratio of NDP-9 to HT is 3:97. The evaporation is carried out by co-evaporation. The materials and thickness are shown in Table 1.

[0232] The materials and thickness of the hole transport layer (HTL) are shown in Table 1;

[0233] The preparation of the light-emitting layer (EML) was carried out by co-evaporation. The specific materials and thickness are shown in Table 1.

[0234] The specific materials and thickness of the electron transport layer (ETL) are shown in Table 1. The evaporation is carried out by co-evaporation.

[0235] The material of the electron injection layer (EIL) is LiQ, and the material and thickness are shown in Table 1;

[0236] The thickness and materials of each layer are shown in Table 1.

[0237] The specific materials and thicknesses of the device examples and comparative examples are shown in Table 1 below:

[0238] Table 1

[0239] The examples in Table 1 refer to device examples, and the comparative examples refer to device comparative examples.

[0240] Test Case

[0241] The organic electroluminescent devices obtained from device examples 1-26 and comparative examples 1-9 in the device examples were tested.

[0242] Instruments: The device's current, voltage, brightness, luminous spectrum and other characteristics are tested synchronously using a PR 650 spectrum scanning luminance meter and a Keithley K 2400 digital source meter system;

[0243] Test conditions: Photoelectric characteristics test conditions: Current density is 10mA / cm 2 .

[0244] Life test: current density is 50mA / cm 2 , record the time (in hours) when the device brightness drops to 95% of the original brightness.

[0245] The device performance test results are shown in Table 2:

[0246] Table 2

[0247] The examples in Table 2 refer to device examples, and the comparative examples refer to device comparative examples.

[0248] From Table 2 we can see that:

[0249] By comparing the data corresponding to the examples and comparative examples in Table 2, it can be seen that the deuterated compounds provided in this application have significantly better performance than CBP, REF-1 to REF-4 disclosed in the prior art, and can have a lower driving voltage after being prepared into devices.

[0250] As can be seen from the above, the deuterated compound with the structure of formula (1) provided by the present application and the compound with the structure of formula (2) can cooperate with each other to significantly improve the carrier injection efficiency, reduce the interlayer energy level difference, balance the electron and hole transmission rate, and effectively improve the efficiency of the organic electroluminescent diode and extend the life of the organic electroluminescent diode. Such materials are suitable as luminescent host materials, especially for red light host materials, hole transport materials, electron blocking materials, and are also suitable as electron transport materials and hole blocking materials, so that the device luminous efficiency is greatly improved and the device life is longer. The combination of such compounds can also be used in the field of organic electroluminescent display. Specifically, the combination of such compounds can be used as a hole injection material or as a hole transport material in an organic electroluminescent display, and can also be used as a luminescent host material or a luminescent material in a fluorescent device. In summary, the present application provides a new organic electroluminescent material with HOMO, LUMO and ET1 values ​​close to each other, which can reduce the driving voltage of the device, improve the luminous efficiency of the device and extend the service life of the device.

[0251] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will readily appreciate that other variations or modifications based on the above descriptions are possible. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. A deuterated compound, characterized in that: It has the structure shown in the following formula (1): In the formula (1), Ar1 is selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; Ar2 is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; Ring A is naphthylene, and at least one hydrogen atom on Ring A or Ar2 is replaced by deuterium; L is selected from a connecting bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group; The substituents in the substituted C6-C30 arylene group, substituted C3-C30 heteroarylene group, substituted C6-C30 aryl group and substituted C3-C30 heteroaryl group are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl group, C3-C30 cycloalkyl group, C6-C30 aryl group and C3-C30 heteroaryl group.

2. The deuterated compound according to claim 1, characterized in that Ar1 is selected from hydrogen, deuterium, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl; Ar2 is selected from substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl; The substituents in the substituted C6-C20 aryl group and the substituted C3-C20 heteroaryl group are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C6-C30 aryl, and C3-C30 heteroaryl; Optionally, at least one hydrogen atom on ring A is replaced by deuterium, and at most five hydrogen atom(s) are replaced by deuterium.

3. The deuterated compound according to claim 1 or 2, characterized in that The formula (1) is selected from one of the following structures: Ar1, Ar2, and L are as defined in claim 1.

4. The deuterated compound according to any one of claims 1 to 3, characterized in that: Ar1 is selected from hydrogen, deuterium, substituted or unsubstituted B groups, Ar2 is selected from substituted or unsubstituted C groups, Wherein, the B group is selected from: phenyl, naphthyl, biphenyl, terphenyl, carbazolyl, dimethylfluorenyl; The C group is selected from the group consisting of phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, fluoranthenyl, triphenylene, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, benzodimethylfluorenyl, benzodiphenylfluorenyl, benzospirobifluorenyl, benzofuranyl, dibenzofuranyl, benzothiophenyl, dibenzothiophenyl, carbazolyl, benzocarbazolyl, dibenzocarbazolyl; The substituents of the substituted B group and the substituted C group are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C6-C30 aryl, and C3-C30 heteroaryl.

5. The deuterated compound according to any one of claims 1 to 4, characterized in that: Ar2 is selected from substituted or unsubstituted C groups; Wherein the C group is selected from the group consisting of phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, fluoranthene, triphenylene, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, benzodimethylfluorenyl, benzodiphenylfluorenyl, benzospirobifluorenyl, benzofuranyl, dibenzofuranyl, benzothiophenyl, dibenzothiophenyl, carbazolyl, benzocarbazolyl, dibenzocarbazolyl; wherein the substituent of the substituted C group is selected from deuterium; Optionally, Ar2 is selected from phenyl, at least one deuterium-substituted phenyl, at least one deuterium-substituted naphthyl; Optionally, Ar2 is selected from phenyl, at least one deuterium-substituted phenyl, and at least one deuterium-substituted naphthyl, wherein the number of deuteriums in the at least one deuterium-substituted phenyl is 1-2, and the number of deuteriums in the at least one deuterium-substituted naphthyl is 1-6; Optionally, Ar1 is selected from hydrogen, deuterium, phenyl, naphthyl, phenanthryl; Optionally, Ar1 is selected from hydrogen, deuterium, and phenyl.

6. The deuterated compound according to any one of claims 1 to 5, characterized in that: L is selected from a connecting bond, a C6-C12 arylene group; Optionally, L is selected from a linker, a phenylene group, and a naphthylene group; Optionally, Ar2 is selected from 1 or 2 deuterium-substituted phenyl groups, 1-6 deuterium-substituted naphthyl groups.

7. The deuterated compound according to any one of claims 1 to 6, characterized in that: The deuterated compound is selected from one of M-1 to M-100:

8. A light-emitting host material composition, characterized in that: The light-emitting host material composition comprises a first host material and a second host material, wherein the first host material comprises the deuterated compound according to any one of claims 1 to 7, and the second host material comprises a compound represented by the following formula (2): X is selected from O, S; L', L 1’ , L 2’ are independently selected from a connecting bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group, and L', L 1’ , L 2’ Each exists independently; Among them, Ar 1’ ,Ar 2’ , Ar are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C6-C60 aryl, substituted or Unsubstituted C6-C60 aromatic amino groups, substituted or unsubstituted C3-C60 heteroaromatic amino groups, and substituted or unsubstituted C3-C60 heteroaryl groups; The substituents in the substituted C6-C30 arylene group, C3-C30 heteroarylene group, substituted C6-C30 aryl group, substituted C3-C30 heteroaryl group, substituted C6-C60 aromatic amine group and substituted C3-C60 heteroaromatic amine group are each independently selected from one or a combination of at least two of deuterium, halogen, cyano, C1-C12 alkyl group, C3-C12 cycloalkyl group, C6-C30 aryl group, C3-C30 heteroaromatic group, C6-C60 aromatic amine group and C3-C60 heteroaromatic amine group.

9. The light-emitting host material composition according to claim 8, characterized in that: The Ar 1’ ,Ar 2’ , Ar are each independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted E groups: phenyl, naphthyl, biphenyl, phenanthrenyl, fluoranthenyl, 1-diphenyl, ... The substituents of the substituted E group are each independently selected from one or a combination of at least two of a C1-C6 alkyl group, a C3-C12 cycloalkyl group, a C6-C25 aryl group, a C3-C25 heteroaryl group, a C6-C60 arylamine group, and a C3-C60 heteroarylamine group; Optional, L', L 1’ , L 2’ Each is independently selected from a connecting bond, a substituted or unsubstituted C6-C12 arylene group, and a substituted or unsubstituted C3-C12 heteroarylene group; The substituents of the substituted C6-C12 arylene group and the substituted C3-C12 heteroarylene group are each independently selected from one or a combination of at least two of a C1-C6 alkyl group, a C3-C12 cycloalkyl group, a C6-C25 aryl group, a C3-C25 heteroaryl group, a C6-C60 arylamine group, and a C3-C60 heteroarylamine group; Optional, Ar 1’ -Ar 2’ Each independently selected from phenyl, naphthyl, biphenyl, phenyl, terphenyl, phenylnaphthyl, naphthylphenyl, dimethylfluorenyl, diphenylfluorenyl, pyridyl, pyridylphenyl, phenylpyridyl, phenylcarbazolyl, phenylbenzocarbazolyl, phenylphenanthrocarbazolyl, spirobifluorenyl, spiro[fluorene-9,9'-xanthene]yl, phenylmethylfluorenyl, dibenzofuranyl and benzonaphthofuranyl; Optionally, Ar is selected from phenyl or naphthyl; Optionally, L' is selected from naphthylene; Optional, L 1’ , L 2’ Each is independently selected from a linker, a phenylene group or a naphthylene group.

10. The light-emitting host material composition according to claim 8 or 9, characterized in that: The second host material comprises a compound selected from N-1 to N-654:

11. The light-emitting host material composition according to any one of claims 8 to 10, characterized in that: The mass ratio of the first main material to the second main material is 9:1-1:9; Optionally, the mass ratio of the first main material to the second main material is 2:8-8:2; Optionally, the mass ratio of the first main material to the second main material is 3:7-7:3; Further optionally, the mass ratio of the first main material to the second main material is 4:6-6:

4.

12. An organic electroluminescent material, characterized in that: The organic electroluminescent material comprises a deuterated compound according to any one of claims 1 to 7 or a light-emitting host material composition according to any one of claims 8 to 11.

13. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises a cathode, an anode and an organic layer located between the cathode and the anode, wherein the organic layer comprises a deuterated compound according to any one of claims 1 to 7 or a light-emitting host material composition according to any one of claims 8 to 11.

14. Use of the organic electroluminescent device according to claim 13 in optical fiber equipment, lighting equipment, electrophotographic photosensitive body equipment, photoelectric converter, organic solar cell, switching element equipment, organic light emitting field effect transistor, image sensor or dye laser.

Images