Organic compound and organic electroluminescent device containing same

Abstract

The invention provides an organic compound and an organic electroluminescent device comprising the same. The organic compound has a structure as shown in a formula I. The organic compound can reduce the driving voltage of the device, improve the luminous efficiency of the device and prolong the service life of the device.

Description

Technical Field

[0001] The invention belongs to the field of organic electroluminescent materials and relates to an organic compound and an organic electroluminescent device containing the organic compound. Background Art

[0002] Organic electroluminescent devices (OLEDs) convert electrical energy into light by applying power to organic electroluminescent materials, and generally include an anode, a cathode, and an organic layer formed between the two electrodes. The organic layer of the organic electroluminescent device may include a hole injection layer, a hole transport layer, a hole auxiliary layer, a luminescent auxiliary layer, an electron blocking layer, a luminescent layer (containing a host material and a dopant material), an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc. Based on the functions achieved by each layer, the various materials used in the organic layer are divided into hole injection materials, hole transport materials, hole auxiliary materials, luminescent auxiliary materials, electron blocking materials, luminescent materials, electron buffer materials, hole blocking materials, electron transport materials, electron injection materials, etc. In an organic electroluminescent device, holes from the anode and electrons from the cathode are injected into the luminescent layer by applying a voltage, and excitons with high energy are generated by the recombination of holes and electrons. The organic light-emitting compound moves to an excited state by energy and emits light by the energy when the organic light-emitting compound returns to the ground state from the excited state.

[0003] As displays become larger in area, driving voltage increases, and problems such as low luminous efficiency and short lifespan emerge, severely limiting the application of organic electroluminescent devices. Therefore, organic materials must solve these efficiency or lifespan problems, and it is necessary to continuously develop new materials for organic light-emitting devices that are highly efficient, have a long lifespan, and are suitable for mass production. Summary of the invention

[0004] In view of the shortcomings of the prior art, an object of the present invention is to provide an organic compound and an organic electroluminescent device comprising the same.

[0005] To achieve this object, the present invention adopts the following technical solutions:

[0006] In one aspect, the present invention provides an organic compound having a structure shown in Formula I:

[0007]

[0008] X is selected from O or S,

[0009] L is selected from naphthylene,

[0010] L 1 , L 2are each independently selected from a connecting bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group, and L 1 , L 2 Not a ring,

[0011] Ar 1 -Ar 3 are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C6-C60 arylamine, substituted or unsubstituted C3-C60 heteroarylamine or substituted or unsubstituted C3-C60 heteroaryl,

[0012] 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 heteroaryl group, C6-C60 aromatic amine group or C3-C60 heteroaromatic amine group.

[0013] Preferably, Ar 1 ,Ar 2 Each independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted phenyl, naphthyl, biphenyl, phenanthrenyl, fluoranthenyl, phenyl, terphenyl, triphenylene, phenylnaphthyl, naphthylphenyl, dimethylfluorenyl, phenylmethylfluorenyl, diphenylfluorenyl, pyridyl, pyridylphenyl, phenylpyridyl, spirobifluorenyl, benzodimethylfluorenyl, benzodiphenylfluorenyl, benzospirobifluorenyl, dibenzofuranyl, benzonaphthofuranyl, benzonaphthothienyl or dibenzothienyl;

[0014] The substituents 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 aromatic amine group or a C3-C60 heteroaromatic amine group.

[0015] Preferably, L 1 , L 2 Each is independently selected from a linker, a phenylene group or a naphthylene group.

[0016] Preferably, 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 or benzonaphthofuranyl.

[0017] Preferably, Ar 3 Selected from phenyl or naphthyl.

[0018] Preferably, Ar 1 ,Ar 2 Each is independently selected from the following groups:

[0019]

[0020] Indicates a connection key.

[0021] Preferably, the organic compound is selected from any one of the following M-1 to M-652:

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048] Where D stands for deuterium.

[0049] In the present invention, the organic compound as described above can be prepared by the following synthetic route:

[0050] 1. Synthesis of intermediate nA:

[0051] The reaction raw materials Mn-Aa and Mn-Ab undergo Suzuki cross-coupling reaction:

[0052]

[0053] 2. Synthesis of Compound M:

[0054] The intermediate Mn-A and Mn-B undergo Buchwald-Hartwig cross-coupling reaction:

[0055]

[0056] In another aspect, the present invention provides an organic electroluminescent material, which comprises the organic compound as described above.

[0057] In another aspect, the present invention provides an organic electroluminescent device, comprising a cathode, an anode and an organic layer between the cathode and the anode, wherein the organic layer comprises the organic compound as described above or the organic electroluminescent material as described above.

[0058] Preferably, the organic layer comprises an electron transport layer, and the electron transport layer comprises the organic compound as described above or the organic electroluminescent material as described above.

[0059] Preferably, the organic layer comprises a light-emitting layer, and the light-emitting layer comprises the organic compound as described above or the organic electroluminescent material as described above.

[0060] Preferably, the organic layer further comprises one or a combination of at least two of a hole injection layer, a first hole transport layer, a second hole transport layer, an electron blocking layer, an electron buffer layer or an electron injection layer.

[0061] Preferably, the light-emitting layer comprises at least one organic compound as described above and at least one compound represented by formula N:

[0062]

[0063] In formula N, R is selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl,

[0064] R 1 Selected from -L 1 Ar 1 , R 2 Selected from -L 2 Ar 2 , R 3 Selected from -L 3 Ar 3 , R 4 Selected from -L 4 Ar 4 ,

[0065] L 1 -L 4 are each independently selected from a connecting bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group,

[0066] Ar 1 -Ar 4 Each is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C6-C60 arylamine, substituted or unsubstituted C3-C60 heteroarylamine, substituted or unsubstituted C6-C60 arylC3-C60 heteroarylamine, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;

[0067] Preferably, Ar 1 -Ar 4Each is independently selected from the following substituted or unsubstituted groups: hydrogen, deuterium, phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, fluoranthenyl, triphenylene, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, benzodimethylfluorenyl, benzodiphenylfluorenyl, benzospirobifluorenyl, dibenzofuranyl or dibenzothiophenyl;

[0068] Preferably, in Formula 1, the R 1 , R 2 , R 3 , R 4 At least one selected from hydrogen;

[0069] Preferably, the R 1 , R 2 , R 3 , R 4 At least two items are selected from hydrogen;

[0070] Preferably, the R 1 , R 2 , R 3 , R 4 Three of them are selected from hydrogen;

[0071] Preferably, the R 2 Selected from L 2 Ar 2 , R 1 , R 3 , R 4 are all selected from hydrogen;

[0072] Preferably, the R 3 Selected from L 3 Ar 3 , R 1 , R 2 , R 4 are all selected from hydrogen;

[0073] Preferably, R is selected from the following substituted or unsubstituted groups: phenyl, biphenyl;

[0074] Preferably, L 1 -L 4 Each is independently selected from a linking bond, a substituted or unsubstituted phenylene group, a naphthylene group or a biphenylene group, a substituted or unsubstituted terphenylene group, and a substituted or unsubstituted naphthylene group.

[0075] On the other hand, the organic electroluminescent device of the present invention as described above is used in optical fiber equipment, lighting equipment, electrophotographic photoreceptor equipment, photoelectric converter, organic solar cell, switching element equipment, organic light-emitting field effect transistor, image sensor or dye laser.

[0076] Definition of Substituent Terms

[0077] As used in the present invention, the term "halogen" may include fluorine, chlorine, bromine or iodine.

[0078] As used in the present invention, the term "C1-C30 alkyl" refers to a monovalent substituent derived from a straight or branched chain 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.

[0079] As used in the present invention, the term "C3-C30 cycloalkyl" refers to a group 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.

[0080] In the present invention, the aryl and arylene groups include monocyclic, polycyclic or condensed ring aromatic groups, the rings may be interrupted by short non-aromatic units, and may contain spiro structures, including but not limited to phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, anthracenyl, fluorenyl, spirobifluorenyl, etc.

[0081] In the present invention, the heteroaryl and heteroarylene group include monocyclic, polycyclic or condensed-ring heteroaryl groups. The rings may be interrupted by short non-aromatic units. The heteroatoms include nitrogen, oxygen and sulfur. Including but not limited to furanyl, 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, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, and derivatives thereof.

[0082] As used in the present invention, 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 the 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.

[0083] As used herein, unless otherwise specified, hydrogen atoms include protium, deuterium and tritium.

[0084] In the present invention, the range of the number of carbon atoms is defined in the definition of the group, and the number of carbon atoms is any integer within the defined range. For example, C6-C30 aromatic group, the number of carbon atoms representing the aromatic group can be any integer within the range of 6-60, such as 6, 8, 10, 13, 15, 17, 20, 22, 25 or 30, etc.

[0085] In another aspect, the present invention provides a hole transport material, wherein the hole transport material comprises any one or a combination of at least two of the benzoxazole compounds described above.

[0086] In another aspect, the present invention provides an organic electroluminescent device, comprising a first electrode, a second electrode and an organic layer between the first electrode and the second electrode, wherein the organic layer comprises any one or a combination of at least two of the benzoxazole compounds described above.

[0087] Preferably, the organic layer comprises a hole transport layer and / or a light emitting layer.

[0088] Preferably, the material of the hole transport layer includes any one or a combination of at least two of the benzoxazole compounds described above.

[0089] Preferably, the light-emitting layer comprises any one or a combination of at least two of the benzoxazole compounds described above.

[0090] In another aspect, the present invention provides an organic electroluminescent product, which comprises the organic electroluminescent device as described above.

[0091] Compared with the prior art, the present invention has the following beneficial effects:

[0092] The introduction of naphthyl groups in the organic compounds of the present invention can adjust the energy level and change the molecular configuration. The structural characteristics of the organic compounds of the present invention are conducive to improving the glass transition temperature of the molecules and at the same time are conducive to reducing the evaporation temperature of the molecules. That is to say, even if the molecular weight of the structure is relatively high, it can ensure a lower evaporation temperature. This excellent performance is not only conducive to the thermal evaporation of materials, but also controls the thermal decomposition rate of materials, thereby improving the stability of the materials in device applications.

[0093] The organic compound of the present invention can reduce the driving voltage of the device, improve the luminous efficiency of the device and extend the service life of the device. BRIEF DESCRIPTION OF THE DRAWINGS

[0094] Figure 1 is a schematic structural diagram of the organic electroluminescent device of the present invention;

[0095] Among them, 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 is a light emitting layer, 6 is an electron transport layer, 7 is an electron injection layer, and 8 is a cathode. DETAILED DESCRIPTION

[0096] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0097] Synthesis of intermediates

[0098] Synthesis of intermediate M1-A

[0099]

[0100] After nitrogen substitution, a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser was added with intermediate M1-Aa (10 mmol), intermediate M1-Ab (10 mmol), 100 mL of toluene, 20 mL of ethanol, 20 mL of water, potassium carbonate (20 mmol), Pd(PPh 3 ) 4 (0.05mmol), heated to 70-80℃, reacted for 3h. Cooled to 25-30℃, added 100mL water, 100mL toluene, stirred and separated, the aqueous phase was extracted once with 100mL toluene, separated, the organic phases were combined, 7g of anhydrous sodium sulfate was added to the organic phase, stirred and dried, filtered, the organic phase was concentrated (-0.08-0.09MPa, 55-60℃) until no liquid flowed out, stirred and added 50mL of a mixed solvent of dichloromethane and petroleum ether, cooled to 0-5℃, filtered, and compound M1-A was obtained with a yield of 67%.

[0101] 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;

[0102] HRMS (ESI) m / z [M+H] + : Theoretical value: 355.08; measured value: 356.32.

[0103] The preparation of the following intermediates M2-A to M12-A is the same as that of M1-A, except that the raw materials M1-Aa substituted with bromine and chlorine at different positions and M1-Ab substituted with boronate at different positions are used:

[0104]

[0105] Synthetic route of intermediate M13-A

[0106]

[0107] After nitrogen substitution, a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser was added with intermediate M13-Aa (10 mmol), intermediate M13-Ab (10 mmol), 100 mL of toluene, 20 mL of ethanol, 20 mL of water, potassium carbonate (20 mmol), Pd(PPh 3 ) 4 (0.05mmol) was heated to 70℃ and reacted for 3h. The temperature was lowered to 25-30℃, 100mL of water and 100mL of toluene were slowly added, and the mixture was stirred and separated. The aqueous phase was extracted once with 100mL of toluene, separated, and the organic phase was combined. The organic phase was washed with water several times until neutral, and then 7g of anhydrous sodium sulfate was added, stirred and dried, filtered, and the organic phase was concentrated (-0.08-0.09MPa, 55-60℃) until no liquid flowed out. 50mL of a mixed solvent of dichloromethane and petroleum ether was added with stirring, and the temperature was lowered to 0-5℃, and filtered to obtain compound M13-A with a yield of 72%.

[0108] 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;

[0109] HRMS (ESI) m / z [M+H] + : Theoretical value: 405.09; measured value: 406.12.

[0110] Example 1

[0111] Synthesis of Compound N-1

[0112]

[0113] After nitrogen substitution, the intermediate M1-B (10 mmol), the intermediate M1-A (10 mmol), and 100 mL of toluene were added to a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser. The mixture was heated to reflux and water was removed for 0.5 h. The temperature was lowered to 70-80 ° C, and sodium tert-butoxide (15 mmol), Pd 2 (dba) 3(0.05mmol), s-phos (0.1mmol), after the system is stable, heat to 100-110℃ and react for 3h. Cool to 25-30℃, add 100mL water, 100mL toluene, stir and separate, extract the aqueous phase with 100mL toluene once, separate, combine the organic phases, add 7g anhydrous sodium sulfate to the organic phase, stir and dry, filter, concentrate the organic phase (-0.08-0.09MPa, 55-60℃) until no liquid flows out, stir and add 20mL petroleum ether, cool to 0-5℃, filter, and obtain compound M-1 with a yield of 68%.

[0114] Elemental analysis: C 41 H 28 N 2 O theoretical value: C, 87.21; H, 5.00; N, 4.96; O, 2.83; measured value: C, 87.15; H, 5.01; N, 4.99;

[0115] HRMS (ESI) m / z [M+H] + : Theoretical value: 564.22; measured value: 565.31.

[0116] Example 2

[0117] Synthesis of Compound M-5

[0118]

[0119] After nitrogen substitution, the intermediate N6-B (10 mmol), the intermediate M1-A (10 mmol), and 100 mL of toluene were added to a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser. The mixture was heated to reflux and water was removed for 0.5 h. The temperature was lowered to 70-80 ° C, and sodium tert-butoxide (15 mmol), Pd 2 (dba) 3 (0.05mmol), s-phos (0.1mmol), after the system is stable, heat to 100-110℃ and react for 3h. Cool to 25-30℃, add 100mL water, 100mL toluene, stir and separate, extract the aqueous phase with 100mL toluene once, separate, combine the organic phases, add 7g anhydrous sodium sulfate to the organic phase, stir and dry, filter, concentrate the organic phase (-0.08-0.09MPa, 55-60℃) until no liquid flows out, stir and add 20mL petroleum ether, cool to 0-5℃, filter, and obtain compound M-5 with a yield of 66%.

[0120] Elemental analysis: C 41 H 26 N 2 O 2Theoretical value: C, 85.10; H, 4.53; N, 4.84; O, 5.53; Measured value: C, 85.10; H, 4.53; N, 4.84; O, 5.53;

[0121] HRMS (ESI) m / z [M+H] + : Theoretical value: 578.20; measured value: 579.25.

[0122] Example 3

[0123] Synthesis route of M-15

[0124]

[0125] After nitrogen substitution, the intermediate N15-B (10 mmol), the intermediate M1-A (10 mmol), and 100 mL of toluene were added to a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser. The mixture was heated to reflux and water was removed for 0.5 h. The temperature was lowered to 70-80 ° C, and sodium tert-butoxide (15 mmol), Pd 2 (dba) 3 (0.05mmol), s-phos (0.1mmol), after the system is stable, heat to 100-110℃ and react for 3h. Cool to 25-30℃, add 100mL water, 100mL toluene, stir and separate, extract the aqueous phase with 100mL toluene once, separate, combine the organic phases, add 7g anhydrous sodium sulfate to the organic phase, stir and dry, filter, concentrate the organic phase (-0.08-0.09MPa, 55-60℃) until no liquid flows out, stir and add 20mL petroleum ether, cool to 0-5℃, filter, and obtain compound M-15 with a yield of 58%.

[0126] Elemental analysis: C 59 H 39 N 3 O theoretical value: C, 87.92; H, 4.88; N, 5.21; O, 1.99; measured value: C, 87.95; H, 4.89; N, 5.18;

[0127] HRMS (ESI) m / z [M+H] + : Theoretical value: 805.31; measured value: 806.10.

[0128] Example 4

[0129] Synthesis route of N-16

[0130]

[0131] After nitrogen substitution, intermediate M16-B (10 mmol), intermediate M16-A (10 mmol), and 100 mL of toluene were added to a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser. The mixture was heated to reflux for 0.5 h, cooled to 70-80 °C, and sodium tert-butoxide (15 mmol), Pd 2 (dba) 3 (0.05mmol), s-phos (0.1mmol), after the system is stable, heat to 100-110℃ and react for 3h. Cool to 25-30℃, add 100mL water, 100mL toluene, stir and separate, extract the aqueous phase with 100mL toluene once, separate, combine the organic phases, add 7g anhydrous sodium sulfate to the organic phase, stir and dry, filter, concentrate the organic phase (-0.08-0.09MPa, 55-60℃) until no liquid flows out, stir and add 20mL petroleum ether, cool to 0-5℃, filter, and obtain compound M-16 with a yield of 61%.

[0132] Elemental analysis: C51H32N2O2 theoretical value: C, 85.97; H, 4.49; N, 4.46; O, 5.09; measured value: C, 85.94; H, 4.50; N, 4.48;

[0133] HRMS (ESI) m / z [M+H] + : Theoretical value: 628.22; measured value: 629.25.

[0134] Example 5

[0135] Synthesis route of M-18

[0136]

[0137] After nitrogen substitution, the intermediate N18-B (10 mmol), the intermediate M1-A (10 mmol), and 100 mL of toluene were added to a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser. The mixture was heated to reflux and water was removed for 0.5 h. The temperature was lowered to 70-80 ° C, and sodium tert-butoxide (15 mmol), Pd 2 (dba) 3 (0.05mmol), s-phos (0.1mmol), after the system is stable, heat to 100-110℃ and react for 3h. Cool to 25-30℃, add 100mL water, 100mL toluene, stir and separate, extract the aqueous phase with 100mL toluene once, separate, combine the organic phases, add 7g anhydrous sodium sulfate to the organic phase, stir and dry, filter, concentrate the organic phase (-0.08-0.09MPa, 55-60℃) until no liquid flows out, stir and add 20mL petroleum ether, cool to 0-5℃, filter, and obtain compound M-18 with a yield of 61%.

[0138] Elemental analysis: C53H37N3O theoretical value: C, 86.98; H, 5.10; N, 5.74; O, 2.19; measured value: C, 87.00; H, 5.11; N, 5.70;

[0139] HRMS (ESI) m / z [M+H] + : Theoretical value: 731.29; measured value: 732.15.

[0140] Example 6

[0141] Synthesis route of M-23

[0142]

[0143] After nitrogen substitution in a three-necked reaction flask equipped with a mechanical stirrer, a thermometer and a condenser, the intermediate N23-B (10 mmol), the intermediate M1-A (10 mmol) and 100 mL of toluene were added in sequence, heated to reflux to separate water for 0.5 h, 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, and after the system was stabilized, it was heated to 100-110 °C and reacted for 3 h. Cool to 25-30°C, add 100 mL of water and 100 mL of toluene, stir and separate the liquids, extract the aqueous phase once with 100 mL of toluene, separate the liquids, combine the organic phases, add 7 g of anhydrous sodium sulfate to the organic phase, stir and dry, filter, concentrate the organic phase (-0.08-0.09 MPa, 55-60°C) until no liquid flows out, stir and add 20 mL of petroleum ether, cool to 0-5°C, filter, and obtain compound M-23 with a yield of 54%.

[0144] Elemental analysis: C 53 H 37 N 3 O theoretical value: C, 87.03; H, 4.73; N, 5.97; O, 2.27; measured value: C, 87.05; H, 4.74; N, 5.94;

[0145] HRMS (ESI) m / z [M+H] + : Theoretical value: 703.26; measured value: 704.18.

[0146] Example 7

[0147] Synthesis route of M-26

[0148]

[0149] After nitrogen substitution, the intermediate N26-B (10 mmol), the intermediate M1-A (10 mmol), and 100 mL of toluene were added to a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser. The mixture was heated to reflux and water was removed for 0.5 h. The temperature was lowered to 70-80 ° C, and sodium tert-butoxide (15 mmol), Pd 2 (dba) 3 (0.05mmol), s-phos (0.1mmol), after the system is stable, heat to 100-110℃ and react for 3h. Cool to 25-30℃, add 100mL water, 100mL toluene, stir and separate, extract the aqueous phase with 100mL toluene once, separate, combine the organic phases, add 7g anhydrous sodium sulfate to the organic phase, stir and dry, filter, concentrate the organic phase (-0.08-0.09MPa, 55-60℃) until no liquid flows out, stir and add 20mL petroleum ether, cool to 0-5℃, filter, and obtain compound M-26 with a yield of 48%.

[0150] Elemental analysis: C 47 H 31 N 3 O theoretical value: C, 86.35; H, 4.78; N, 6.43; O, 2.45; measured value: C, 86.39; H, 4.80; N, 6.38;

[0151] HRMS (ESI) m / z [M+H] + : Theoretical value: 653.25; measured value: 654.31.

[0152] Example 8

[0153] Synthesis route of M-39

[0154]

[0155] After nitrogen substitution, the intermediate N39-B (10 mmol), the intermediate M2-A (10 mmol), and 100 mL of toluene were added to a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser. The mixture was heated to reflux for 0.5 h and then cooled to 70-80 °C. Sodium tert-butoxide (15 mmol), Pd 2 (dba) 3(0.05mmol), s-phos (0.1mmol), after the system is stable, heat to 100-110℃ and react for 3h. Cool to 25-30℃, add 100mL water, 100mL toluene, stir and separate, extract the aqueous phase with 100mL toluene once, separate, combine the organic phases, add 7g anhydrous sodium sulfate to the organic phase, stir and dry, filter, concentrate the organic phase (-0.08-0.09MPa, 55-60℃) until no liquid flows out, stir and add 20mL petroleum ether, cool to 0-5℃, filter, and obtain compound M-39 with a yield of 62%.

[0156] Elemental analysis: C 41 H 26 N 2 OS theoretical value: C, 82.80; H, 4.41; N, 4.71; O, 2.69; S, 5.39; Measured value: C, 82.77; H, 4.42; N, 4.73; S, 5.40;

[0157] HRMS (ESI) m / z [M+H] + : Theoretical value: 594.17; measured value: 595.33.

[0158] Example 9

[0159] Synthesis route of M-45

[0160]

[0161] After nitrogen substitution, the intermediate N45-B (10 mmol), the intermediate M1-A (10 mmol), and 100 mL of toluene were added to a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser. The mixture was heated to reflux and water was removed for 0.5 h. The temperature was lowered to 70-80 ° C, and sodium tert-butoxide (15 mmol), Pd 2 (dba) 3 (0.05mmol), s-phos (0.1mmol), after the system is stable, heat to 100-110℃ and react for 3h. Cool to 25-30℃, add 100mL water, 100mL toluene, stir and separate, extract the aqueous phase with 100mL toluene once, separate, combine the organic phases, add 7g anhydrous sodium sulfate to the organic phase, stir and dry, filter, concentrate the organic phase (-0.08-0.09MPa, 55-60℃) until no liquid flows out, stir and add 20mL petroleum ether, cool to 0-5℃, filter, and obtain compound M-45 with a yield of 65%.

[0162] Elemental analysis: C 49 H 32 N 2O theoretical value: C, 88.53; H, 4.85; N, 4.21; O, 2.41; measured value: C, 88.49; H, 4.86; N, 4.24;

[0163] HRMS (ESI) m / z [M+H] + : Theoretical value: 664.25; measured value: 665.19.

[0164] Example 10

[0165] Synthesis route of M-60

[0166]

[0167] After nitrogen substitution, the intermediate N60-B (10 mmol), the intermediate M3-A (10 mmol), and 100 mL of toluene were added to a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser. The mixture was heated to reflux and water was removed for 0.5 h. The temperature was lowered to 70-80 ° C, and sodium tert-butoxide (15 mmol), Pd 2 (dba) 3 (0.05mmol), s-phos (0.1mmol), after the system is stable, heat to 100-110℃ and react for 3h. Cool to 25-30℃, add 100mL water, 100mL toluene, stir and separate, extract the aqueous phase with 100mL toluene once, separate, combine the organic phases, add 7g anhydrous sodium sulfate to the organic phase, stir and dry, filter, concentrate the organic phase (-0.08-0.09MPa, 55-60℃) until no liquid flows out, stir and add 20mL petroleum ether, cool to 0-5℃, filter, and obtain compound M-60 with a yield of 60%.

[0168] Elemental analysis: C 47 H 32 N 2 O theoretical value: C, 88.10; H, 5.03; N, 4.37; O, 2.50; measured value: C, 88.05; H, 5.04; N, 4.41;

[0169] HRMS (ESI) m / z [M+H] + : Theoretical value: 640.25; Measured value: 641.30

[0170] Embodiment 11

[0171] Synthesis route of M-73

[0172]

[0173] After nitrogen substitution, the intermediate N73-B (10 mmol), the intermediate M5-A (10 mmol), and 100 mL of toluene were added to a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser. The mixture was heated to reflux and water was removed for 0.5 h. The temperature was lowered to 70-80 °C, and sodium tert-butoxide (15 mmol), Pd 2 (dba) 3 (0.05mmol), s-phos (0.1mmol), after the system is stable, heat to 100-110℃ and react for 3h. Cool to 25-30℃, add 100mL water, 100mL toluene, stir and separate, extract the aqueous phase with 100mL toluene once, separate, combine the organic phases, add 7g anhydrous sodium sulfate to the organic phase, stir and dry, filter, concentrate the organic phase (-0.08-0.09MPa, 55-60℃) until no liquid flows out, stir and add 20mL petroleum ether, cool to 0-5℃, filter, and obtain compound M-73 with a yield of 63%.

[0174] Elemental analysis: C 51 H 33 N 3 O theoretical value: C, 87.03; H, 4.73; N, 5.97; O, 2.27; measured value: C, 87.06; H, 4.75; N, 5.92;

[0175] HRMS (ESI) m / z [M+H] + : Theoretical value: 703.26; Measured value: 704.36

[0176] Example 12

[0177] Synthesis route of M-76

[0178]

[0179] After nitrogen substitution, the intermediate N76-B (10 mmol), the intermediate M5-A (10 mmol), and 100 mL of toluene were added to a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser. The mixture was heated to reflux and water was removed for 0.5 h. The temperature was lowered to 70-80 °C, and sodium tert-butoxide (15 mmol), Pd 2 (dba) 3(0.05mmol), s-phos (0.1mmol), after the system is stable, heat to 100-110℃ and react for 3h. Cool to 25-30℃, add 100mL water, 100mL toluene, stir and separate, extract the aqueous phase with 100mL toluene once, separate, combine the organic phases, add 7g anhydrous sodium sulfate to the organic phase, stir and dry, filter, concentrate the organic phase (-0.08-0.09MPa, 55-60℃) until no liquid flows out, stir and add 20mL petroleum ether, cool to 0-5℃, filter, and obtain compound M-76 with a yield of 64%.

[0180] Elemental analysis: C 53 H 35 N 3 O theoretical value: C, 87.22; H, 4.83; N, 5.76; O, 2.19; measured value: C, 87.25; H, 4.86; N, 5.71;

[0181] HRMS (ESI) m / z [M+H] + : Theoretical value: 729.27; Measured value: 730.08

[0182] Embodiment 13

[0183] Synthesis route of M-80

[0184]

[0185] After nitrogen substitution, the intermediate N80-B (10 mmol), the intermediate M5-A (10 mmol), and 100 mL of toluene were added to a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser. The mixture was heated to reflux and water was removed for 0.5 h. The temperature was lowered to 70-80 ° C, and sodium tert-butoxide (15 mmol), Pd 2 (dba) 3 (0.05mmol), s-phos (0.1mmol), after the system is stable, heat to 100-110℃ and react for 3h. Cool to 25-30℃, add 100mL water, 100mL toluene, stir and separate, extract the aqueous phase with 100mL toluene once, separate, combine the organic phases, add 7g anhydrous sodium sulfate to the organic phase, stir and dry, filter, concentrate the organic phase (-0.08-0.09MPa, 55-60℃) until no liquid flows out, stir and add 20mL petroleum ether, cool to 0-5℃, filter, and obtain compound M-80 with a yield of 68%.

[0186] Elemental analysis: C 41 H 26 N 2 O 2Theoretical value: C, 85.10; H, 4.53; N, 4.84; O, 5.53; Measured value: C, 85.03; H, 4.55; N, 4.88;

[0187] HRMS (ESI) m / z [M+H] + : Theoretical value: 578.20; Measured value: 579.32

[0188] Embodiment 14

[0189] Synthesis route of M-87

[0190]

[0191] After nitrogen substitution in a three-necked reaction flask equipped with a mechanical stirrer, a thermometer and a condenser, the intermediate N87-B (10 mmol), the intermediate M5-A (10 mmol) and 100 mL of toluene were added in sequence, heated to reflux to separate water for 0.5 h, 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, and after the system was stabilized, it was heated to 100-110 °C and reacted for 3 h. Cool to 25-30°C, add 100 mL of water and 100 mL of toluene, stir and separate the liquids, extract the aqueous phase once with 100 mL of toluene, separate the liquids, combine the organic phases, add 7 g of anhydrous sodium sulfate to the organic phase, stir and dry, filter, concentrate the organic phase (-0.08-0.09 MPa, 55-60°C) until no liquid flows out, stir and add 20 mL of petroleum ether, cool to 0-5°C, filter to obtain compound M-87 with a yield of 44%.

[0192] Elemental analysis: C 59 H 38 FN 3 O 2 Theoretical value: C, 84.37; H, 4.56; F, 2.26; N, 5.00; O, 3.81; Measured value: C, 84.32; H, 4.57; F, 2.26; N, 5.04;

[0193] HRMS (ESI) m / z [M+H] + : Theoretical value: 839.29; Measured value: 840.33

[0194] Embodiment 15

[0195] Synthesis of Compound M-92

[0196]

[0197] After nitrogen substitution in a three-necked reaction flask equipped with a mechanical stirrer, a thermometer and a condenser, the intermediate N92-B (10 mmol), the intermediate M12-A (10 mmol) and 100 mL of toluene were added in sequence, heated to reflux to separate water for 0.5 h, 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, and after the system was stabilized, it was heated to 100-110 °C and reacted for 3 h. Cool to 25-30°C, add 100 mL of water and 100 mL of toluene, stir and separate the liquids, extract the aqueous phase once with 100 mL of toluene, separate the liquids, combine the organic phases, add 7 g of anhydrous sodium sulfate to the organic phase, stir and dry, filter, concentrate the organic phase (-0.08-0.09 MPa, 55-60°C) until no liquid flows out, stir and add 20 mL of petroleum ether, cool to 0-5°C, filter to obtain compound M-92 with a yield of 55%.

[0198] Elemental analysis: C 51 H 32 N 2 O 2 Theoretical value: C, 86.91; H, 4.58; N, 3.97; O, 4.54; Measured value: C, 86.88; H, 4.59; N, 3.99;

[0199] HRMS (ESI) m / z [M+H] + : Theoretical value: 704.25; Measured value: 705.19

[0200] Example 16

[0201] Synthesis of Compound M-130

[0202]

[0203] After nitrogen substitution, the intermediate N130-B (10 mmol), the intermediate M4-A (10 mmol), and 100 mL of toluene were added to a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser. The mixture was heated to reflux and water was removed for 0.5 h. The temperature was lowered to 70-80 ° C, and sodium tert-butoxide (15 mmol), Pd 2 (dba) 3(0.05mmol), s-phos (0.1mmol), after the system is stable, heat to 100-110℃ and react for 3h. Cool to 25-30℃, add 100mL water, 100mL toluene, stir and separate, extract the aqueous phase with 100mL toluene once, separate, combine the organic phases, add 7g anhydrous sodium sulfate to the organic phase, stir and dry, filter, concentrate the organic phase (-0.08-0.09MPa, 55-60℃) until no liquid flows out, stir and add 20mL petroleum ether, cool to 0-5℃, filter, and obtain compound M-130 with a yield of 65%.

[0204] Elemental analysis: C 47 H 30 N 2 O 2 Theoretical value: C, 86.22; H, 4.62; N, 4.28; O, 4.89; Measured value: C, 86.20; H, 4.61; N, 4.31;

[0205] HRMS (ESI) m / z [M+H] + : Theoretical value: 654.23; Measured value: 655.28

[0206] Embodiment 17

[0207] Synthesis of Compound M-148

[0208]

[0209] After nitrogen substitution, the intermediate N148-B (10 mmol), the intermediate M8-A (10 mmol), and 100 mL of toluene were added to a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser. The mixture was heated to reflux and water was removed for 0.5 h. The temperature was lowered to 70-80 ° C, and sodium tert-butoxide (15 mmol), Pd 2 (dba) 3 (0.05mmol), s-phos (0.1mmol), after the system is stable, heat to 100-110℃ and react for 3h. Cool to 25-30℃, add 100mL water, 100mL toluene, stir and separate, extract the aqueous phase with 100mL toluene once, separate, combine the organic phases, add 7g anhydrous sodium sulfate to the organic phase, stir and dry, filter, concentrate the organic phase (-0.08-0.09MPa, 55-60℃) until no liquid flows out, stir and add 20mL petroleum ether, cool to 0-5℃, filter, and obtain compound M-148 with a yield of 62%.

[0210] Elemental analysis: C 47 H 24 D 6 N 2 O 2Theoretical value: C, 85.43; H, 5.49; N, 4.24; O, 4.84; Measured value: C, 85.36; H, 5.52; N, 4.28;

[0211] HRMS (ESI) m / z [M+H] + : Theoretical value: 660.27; Measured value: 661.17

[0212] Embodiment 17

[0213] Synthesis of Compound M-198

[0214]

[0215] After nitrogen substitution, the intermediate N198-B (10 mmol), the intermediate M4-A (10 mmol), and 100 mL of toluene were added to a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser. The mixture was heated to reflux for 0.5 h and then cooled to 70-80 °C. Sodium tert-butoxide (15 mmol), Pd 2 (dba) 3 (0.05mmol), s-phos (0.1mmol), after the system is stable, heat to 100-110℃ and react for 3h. Cool to 25-30℃, add 100mL water, 100mL toluene, stir and separate, extract the aqueous phase with 100mL toluene once, separate, combine the organic phases, add 7g anhydrous sodium sulfate to the organic phase, stir and dry, filter, concentrate the organic phase (-0.08-0.09MPa, 55-60℃) until no liquid flows out, stir and add 20mL petroleum ether, cool to 0-5℃, filter, and obtain compound M-198 with a yield of 62%.

[0216] Elemental analysis: C 53 H 37 N 3 O theoretical value: C, 87.22; H, 4.83; N, 5.76; O, 2.19; measured value: C, 87.27; H, 4.85; N, 5.70;

[0217] HRMS (ESI) m / z [M+H] + : Theoretical value: 729.27; Measured value: 730.08

[0218] Embodiment 18

[0219] Synthesis of Compound M-214

[0220]

[0221] After nitrogen substitution, the intermediate N214-B (10 mmol), the intermediate M6-A (10 mmol), and 100 mL of toluene were added to a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser. The mixture was heated to reflux for 0.5 h and then cooled to 70-80 °C. Sodium tert-butoxide (15 mmol), Pd 2 (dba) 3 (0.05mmol), s-phos (0.1mmol), after the system is stable, heat to 100-110℃ and react for 3h. Cool to 25-30℃, add 100mL water, 100mL toluene, stir and separate, extract the aqueous phase with 100mL toluene once, separate, combine the organic phases, add 7g anhydrous sodium sulfate to the organic phase, stir and dry, filter, concentrate the organic phase (-0.08-0.09MPa, 55-60℃) until no liquid flows out, stir and add 20mL petroleum ether, cool to 0-5℃, filter, and obtain compound M-214 with a yield of 60%.

[0222] Elemental analysis: C 53 H 37 N 3 O theoretical value: C, 86.98; H, 5.10; N, 5.74; O, 2.19; measured value: C, 87.00; H, 5.11; N, 5.71;

[0223] HRMS (ESI) m / z [M+H] + : Theoretical value: 731.29; Measured value: 732.14

[0224] Embodiment 19

[0225] Synthesis of Compound M-260

[0226]

[0227] After nitrogen substitution, the intermediate N260-B (10 mmol), the intermediate M6-A (10 mmol), and 100 mL of toluene were added to a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser. The mixture was heated to reflux and water was removed for 0.5 h. The temperature was lowered to 70-80 ° C, and sodium tert-butoxide (15 mmol), Pd 2 (dba) 3(0.05mmol), s-phos (0.1mmol), after the system is stable, heat to 100-110℃ and react for 3h. Cool to 25-30℃, add 100mL water, 100mL toluene, stir and separate, extract the aqueous phase with 100mL toluene once, separate, combine the organic phases, add 7g anhydrous sodium sulfate to the organic phase, stir and dry, filter, concentrate the organic phase (-0.08-0.09MPa, 55-60℃) until no liquid flows out, stir and add 20mL petroleum ether, cool to 0-5℃, filter, and obtain compound M-260 with a yield of 50%.

[0228] Elemental analysis: C 59 H 37 N 3 O theoretical value: C, 88.14; H, 4.64; N, 5.23; O, 1.99; measured value: C, 88.16; H, 4.66; N, 5.18;

[0229] HRMS (ESI) m / z [M+H] + : Theoretical value: 803.29; Measured value: 804.22

[0230] Embodiment 20

[0231] Synthesis of Compound M-322

[0232]

[0233] After nitrogen substitution, the intermediate N322-B (10 mmol), the intermediate M11-A (10 mmol), and 100 mL of toluene were added to a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser. The mixture was heated to reflux and water was removed for 0.5 h. The temperature was lowered to 70-80 ° C, and sodium tert-butoxide (15 mmol), Pd 2 (dba) 3 (0.05mmol), s-phos (0.1mmol), after the system is stable, heat to 100-110℃ and react for 3h. Cool to 25-30℃, add 100mL water, 100mL toluene, stir and separate, extract the aqueous phase with 100mL toluene once, separate, combine the organic phases, add 7g anhydrous sodium sulfate to the organic phase, stir and dry, filter, concentrate the organic phase (-0.08-0.09MPa, 55-60℃) until no liquid flows out, stir and add 20mL petroleum ether, cool to 0-5℃, filter, and obtain compound M-322 with a yield of 65%.

[0234] Elemental analysis: C 47 H 30 N 2 O 2Theoretical value: C, 86.22; H, 4.62; N, 4.28; O, 4.89; Measured value: C, 86.18; H, 4.63; N, 4.31;

[0235] HRMS (ESI) m / z [M+H] + : Theoretical value: 654.23; Measured value: 655.26

[0236] Embodiment 21

[0237] Synthesis of Compound M-375

[0238]

[0239] After nitrogen substitution, the intermediate N375-B (10 mmol), the intermediate M9-A (10 mmol), and 100 mL of toluene were added to a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser. The mixture was heated to reflux and water was removed for 0.5 h. The temperature was lowered to 70-80 ° C, and sodium tert-butoxide (15 mmol), Pd 2 (dba) 3 (0.05mmol), s-phos (0.1mmol), after the system is stable, heat to 100-110℃ and react for 3h. Cool to 25-30℃, add 100mL water, 100mL toluene, stir and separate, extract the aqueous phase with 100mL toluene once, separate, combine the organic phases, add 7g anhydrous sodium sulfate to the organic phase, stir and dry, filter, concentrate the organic phase (-0.08-0.09MPa, 55-60℃) until no liquid flows out, stir and add 20mL petroleum ether, cool to 0-5℃, filter, and obtain compound M-375 with a yield of 58%.

[0240] Elemental analysis: C 57 H 35 N 3 O 2 Theoretical value: C, 86.23; H, 4.44; N, 5.29; O, 4.03; Measured value: C, 86.26; H, 4.47; N, 5.23;

[0241] HRMS (ESI) m / z [M+H] + : Theoretical value: 654.23; Measured value: 655.28

[0242] Embodiment 22

[0243] Synthesis of Compound M-502

[0244]

[0245] After nitrogen substitution in a three-necked reaction flask equipped with a mechanical stirrer, a thermometer and a condenser, the intermediate N503-B (10 mmol), the intermediate M10-A (10 mmol) and 100 mL of toluene were added in sequence, heated to reflux to separate water for 0.5 h, 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, and after the system was stabilized, it was heated to 100-110 °C and reacted for 3 h. Cool to 25-30°C, add 100 mL of water and 100 mL of toluene, stir and separate the liquids, extract the aqueous phase once with 100 mL of toluene, separate the liquids, combine the organic phases, add 7 g of anhydrous sodium sulfate to the organic phase, stir and dry, filter, concentrate the organic phase (-0.08-0.09 MPa, 55-60°C) until no liquid flows out, stir and add 20 mL of petroleum ether, cool to 0-5°C, filter, and obtain compound M-502 with a yield of 60%.

[0246] Elemental analysis: C 51 H 32 N 2 O 2 Theoretical value: C, 86.91; H, 4.58; N, 3.97; O, 4.54; Measured value: C, 86.89; H, 4.57; N, 3.99;

[0247] HRMS (ESI) m / z [M+H] + : Theoretical value: 704.25; Measured value: 705.41

[0248] Embodiment 23

[0249] M-527 Synthesis Route

[0250]

[0251] After nitrogen substitution, the intermediate N528-B (10 mmol), the intermediate M10-A (10 mmol), and 100 mL of toluene were added to a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser. The mixture was heated to reflux for 0.5 h, cooled to 70-80 ° C, and sodium tert-butoxide (15 mmol), Pd 2 (dba) 3(0.05mmol), s-phos (0.1mmol), after the system is stable, heat to 100-110℃ and react for 3h. Cool to 25-30℃, add 100mL water, 100mL toluene, stir and separate, extract the aqueous phase with 100mL toluene once, separate, combine the organic phases, add 7g anhydrous sodium sulfate to the organic phase, stir and dry, filter, concentrate the organic phase (-0.08-0.09MPa, 55-60℃) until no liquid flows out, stir and add 20mL petroleum ether, cool to 0-5℃, filter, and obtain compound M-527 with a yield of 43%.

[0252] Elemental analysis: C 53 H 35 N 3 O 2 Theoretical value: C, 85.35; H, 4.73; N, 5.63; O, 4.29; Measured value: C, 85.38; H, 4.74; N, 5.59;

[0253] HRMS (ESI) m / z [M+H] + : Theoretical value: 745.27; Measured value: 746.19

[0254] LUMO and HOMO energy level measurement

[0255] The LUMO and HOMO energy levels of the nitrogen-containing heterocyclic compounds prepared in Examples 1-13 were tested using an electrochemical workstation using cyclic voltammetry (CV Shanghai Chenhua CHI-600E), with platinum wire (Pt) as the counter electrode and silver / silver chloride (Ag / AgCl) as the reference electrode. The test was performed at a scan rate of 100 mV / s in a dichloromethane electrolyte containing 0.1 M tetrabutylammonium hexafluorophosphate under a nitrogen atmosphere, and ferrocene was used for potential calibration, and the absolute energy level of the potential of ferrocene in a vacuum state was set to -4.8 eV:

[0256] HOMO 能阶 =-e(Eox-E 1 / 2 ,ferrocene)+(-4.8)eV

[0257] LUMO 能阶 =-e(Ere-E1 / 2,ferrocene)+(-4.8)eV;

[0258] Where Eox is the oxidation potential, Ere is the reduction potential, and E1 / 2,ferrocene is the ferrocene potential.

[0259] Triplet energy level test conditions: Toluene was used as the solvent to prepare the test compound into a solution (concentration 2*10 - 5mol / L), and the above solution was tested at -78°C using a fluorescence spectrophotometer (Hitachi F-4600). ET1 (eV) represents the triplet energy level of the compound, which is calculated using the following formula:

[0260] ET1 = 1240 / shortest absorption wavelength.

[0261] The test results are shown in Table 1.

[0262] Table 1 Energy level test results of compounds

[0263] Compound HOMO(eV) LUMO(eV) <![CDATA[E T1 (eV)]]> M-1 -5.55 -2.50 2.40 M-16 -5.44 -2.55 2.33 M-528 -5.39 -2.40 2.34 REF-2 -4.68 -2.10 2.44

[0264] It can be seen from Table 1 that the HOMO energy level of the above compounds is between -5.0 and -6.0 (eV), and the triplet energy level E T1 Between -2.2 and -2.40 (eV), there is an energy level with a higher matching degree for the hole transport material in the organic electroluminescent compound or the main material component with hole transport performance in the light-emitting main material.

[0265] Application Example 1-10 and Comparative Application Example 1-2

[0266] The following application examples 1-10 and comparative application examples 1-2 provide different OLEDs, such as Figure 1 As shown, they all have the following layer structure: substrate 1 (coated glass substrate with indium tin oxide (ITO) as anode 2) / hole injection layer 3 (HIL) / hole transport layer 4 (HTL) / light-emitting layer 5 (EML) / electron transport layer 6 (ETL) / electron injection layer 7 (EIL), and finally cathode 8.

[0267] The materials used are as follows, where REF-1 to REF-4 are comparative compounds:

[0268]

[0269] The preparation of the organic electroluminescent devices of Examples 1-7 and Comparative Examples 1-3 includes the following steps:

[0270] (1) Substrate cleaning: The glass substrate coated with transparent ITO is ultrasonically treated in an aqueous cleaning agent (the composition and concentration of the aqueous cleaning agent: ethylene glycol solvent ≤ 10wt%, triethanolamine ≤ 1wt%), rinsed in deionized water, ultrasonically degreased in an acetone: ethanol mixed solvent (volume ratio 1:1), baked in a clean environment until the water is completely removed, and then cleaned with ultraviolet light and ozone.

[0271] (2) Evaporation of organic light-emitting functional layer:

[0272] The glass substrate with the anode layer is placed in a vacuum chamber and evacuated to 1×10 -6 Up to 2×10 -4 Pa, vacuum evaporating a mixture of HATCN and HT on the above anode layer film, wherein the mass ratio of HATCN to HT is 3:97, as a hole injection layer, and the evaporation thickness is 10 nm;

[0273] A hole transport layer (materials are shown in Table 2) is evaporated on the hole injection layer, and the thickness of the evaporated film is 80 nm;

[0274] The light-emitting layer is deposited on the hole transport layer. The specific preparation method is: vacuum-deposit the light-emitting host material (CBP) and the guest material (piq)2Ir(acac) by co-evaporation, and the total film thickness of the deposition is 30 nm;

[0275] An electron transport layer is evaporated on the light-emitting layer. The specific preparation method is as follows: vacuum evaporation of electron transport material (ET and LiQ mass ratio is 1) in a co-evaporation manner, and the total evaporation film thickness is 30nm;

[0276] An electron injection layer (made of LiQ) is vacuum-deposited on the electron transport layer, with a total film thickness of 1 nm.

[0277] Al was evaporated on the electron injection layer, and the total film thickness of the evaporated layer was 90 nm.

[0278] The parameters of each layer in the device, its material, thickness, etc. are shown in Table 2 below:

[0279] Table 2

[0280]

[0281]

[0282] Test sample: organic electroluminescent device provided in Application Examples 1-8 and Comparative Application Examples 1-3;

[0283] Test 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;

[0284] Test conditions: Photoelectric properties Test conditions: Current density is 10mA / cm 2 ;

[0285] Life test: current density is 50mA / cm 2 , record the time (in hours) when the device brightness drops to 95% of the original brightness;

[0286] The test results are shown in Table 3.

[0287] Table 3

[0288] Serial number Driving voltage(V) Current efficiency (Cd / A) Lifespan T95(hrs) Application Example 1 4.45 15.11 100.8 Application Example 2 4.45 15.26 103.3 Application Example 3 4.43 15.29 101.4 Application Example 4 4.36 16.58 110.5 Application Example 5 4.38 16.28 104.7 Application Example 6 4.38 16.34 105.4 Application Example 7 4.40 15.69 114.8 Application Example 8 4.41 15.46 105.4 Comparative Example 1 5.34 11.09 64.0 Comparative Example 2 5.23 12.42 71.2 Comparative Example 3 4.72 14.03 92.5 Comparative Example 4 4.72 14.58 95.7 Comparative Example 5 4.75 12.64 90.2

[0289] According to the above device performance test, compared with the comparative compounds REF-1 to REF-5, the device in which the compound of the present invention is used as a hole transport material exhibits a reduced driving voltage (as low as below 4.45V) and a higher current efficiency (as high as above 15Cd / A), and a longer life (more than 100h).

[0290] The preparation of the organic electroluminescent devices of Examples 9-13 and Comparative Examples 6-9 comprises the following steps:

[0291] (1) Substrate cleaning: The glass substrate coated with transparent ITO is ultrasonically treated in an aqueous cleaning agent (the composition and concentration of the aqueous cleaning agent: ethylene glycol solvent ≤ 10wt%, triethanolamine ≤ 1wt%), rinsed in deionized water, ultrasonically degreased in an acetone: ethanol mixed solvent (volume ratio 1:1), baked in a clean environment until the water is completely removed, and then cleaned with ultraviolet light and ozone.

[0292] (2) Evaporation of organic light-emitting functional layer:

[0293] The glass substrate with the anode layer is placed in a vacuum chamber and evacuated to 1×10 -6 Up to 2×10 -4 Pa, vacuum evaporating a mixture of HATCN and HT on the above anode layer film, wherein the mass ratio of HATCN to HT is 3:97, as a hole injection layer, and the evaporation thickness is 10 nm;

[0294] A hole transport layer (HT) is evaporated on the hole injection layer, and the thickness of the evaporated film is 80 nm;

[0295] The light-emitting layer is deposited on the hole transport layer. The specific preparation method is: vacuum-deposit the light-emitting host material (the materials are shown in Table 4) and the guest material (piq) by co-evaporation. 2 Ir(acac), total evaporation film thickness is 30nm;

[0296] An electron transport layer is evaporated on the light-emitting layer. The specific preparation method is as follows: vacuum evaporation of electron transport material (ET and LiQ mass ratio is 1) in a co-evaporation manner, and the total evaporation film thickness is 30nm;

[0297] An electron injection layer (made of LiQ) is vacuum-deposited on the electron transport layer, with a total film thickness of 1 nm.

[0298] Al was evaporated on the electron injection layer, and the total film thickness of the evaporated layer was 90 nm.

[0299] The parameters of each layer in the device, its material, thickness, etc. are shown in Table 4 below:

[0300] Table 4

[0301]

[0302]

[0303] Device performance test:

[0304] Test samples: organic electroluminescent devices provided in Application Examples 9-13 and Comparative Application Examples 6-9;

[0305] Test 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;

[0306] Test conditions: Photoelectric properties Test conditions: Current density is 10mA / cm 2 ;

[0307] Life test: current density is 50mA / cm 2 , record the time (in hours) when the device brightness drops to 95% of the original brightness;

[0308] The test results are shown in Table 5 below:

[0309] Table 5

[0310] Serial number Driving voltage(V) Current efficiency (Cd / A) Lifespan T95(hrs) Application Example 9 4.75 9.54 74.5 Application Example 10 4.62 10.25 82.4 Application Example 11 4.64 12.51 92.4 Application Example 12 4.64 10.02 88.3 Application Example 13 4.71 9.68 77.8 Comparative Example 6 5.20 6.28 50.3 Comparative Example 7 5.03 8.69 66.2 Comparative Example 8 4.94 8.92 64.9 Comparative Example 9 4.94 8.73 65.8

[0311] The results shown in Table 5 demonstrate that, compared with the control compounds, the voltage, lifespan and luminous efficiency are all improved, and the driving voltage of the organic device using the organic compound of the present invention as the luminescent material can be as low as below 4.75 V, the current efficiency is as high as above 9.5 Cd / A, and the lifespan is as long as over 74 h.

[0312] The preparation of the organic electroluminescent devices of Examples 14-33 and Comparative Examples 10-13 comprises the following steps:

[0313] (1) Substrate cleaning: The glass substrate coated with transparent ITO is ultrasonically treated in an aqueous cleaning agent (the composition and concentration of the aqueous cleaning agent: ethylene glycol solvent ≤ 10wt%, triethanolamine ≤ 1wt%), rinsed in deionized water, ultrasonically degreased in an acetone: ethanol mixed solvent (volume ratio 1:1), baked in a clean environment until the water is completely removed, and then cleaned with ultraviolet light and ozone.

[0314] (2) Evaporation of organic light-emitting functional layer:

[0315] The glass substrate with the anode layer is placed in a vacuum chamber and evacuated to 1×10 -6 Up to 2×10 -4 Pa, vacuum evaporating a mixture of HATCN and HT on the above anode layer film, wherein the mass ratio of HATCN to HT is 3:97, as a hole injection layer, and the evaporation thickness is 10 nm;

[0316] A hole transport layer (HT) is evaporated on the hole injection layer, and the thickness of the evaporated film is 80 nm;

[0317] The light-emitting layer is deposited on the hole transport layer. The specific preparation method is: vacuum-deposit the light-emitting host material (the materials are shown in Table 6) and the guest material (piq) by co-evaporation. 2 Ir(acac), total evaporation film thickness is 30nm;

[0318] An electron transport layer is evaporated on the light-emitting layer. The specific preparation method is as follows: vacuum evaporation of electron transport material (ET and LiQ mass ratio is 1) in a co-evaporation manner, and the total evaporation film thickness is 30nm;

[0319] An electron injection layer (made of LiQ) is vacuum-deposited on the electron transport layer, with a total film thickness of 1 nm.

[0320] Al was evaporated on the electron injection layer, and the total film thickness of the evaporated layer was 90 nm.

[0321] The parameters of each layer in the device, its material, thickness, etc. are shown in Table 6 below:

[0322] Table 6

[0323]

[0324]

[0325]

[0326] Device performance test:

[0327] Test sample: organic electroluminescent devices provided in Application Examples 14-33 and Comparative Application Examples 10-13;

[0328] Test 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;

[0329] Test conditions: Photoelectric properties Test conditions: Current density is 10mA / cm 2 ;

[0330] Life test: current density is 50mA / cm 2, record the time (in hours) when the device brightness drops to 95% of the original brightness;

[0331] The test results are shown in Table 7 below:

[0332] Table 7

[0333]

[0334]

[0335] The results shown in Table 5 demonstrate that, compared with the control compounds, the voltage, lifespan and luminous efficiency are all improved, and the driving voltage of the organic device using the organic compound of the present invention as the luminescent material can be as low as below 3.61 V, the current efficiency is as high as above 19 Cd / A, and the lifespan is as long as over 294 h.

[0336] From the above, it can be seen that the introduction of naphthyl groups in the organic compounds of the present invention can adjust the energy level and change the molecular configuration. The structural characteristics of the organic compounds of the present invention are conducive to improving the glass transition temperature of the molecules and at the same time are conducive to reducing the evaporation temperature of the molecules. That is to say, even if the molecular weight of the structure is relatively high, it can ensure a lower evaporation temperature. This excellent performance is not only conducive to the thermal evaporation of materials, but also controls the thermal decomposition rate of materials, thereby improving the stability of materials in device applications.

[0337] The organic material provided in the embodiment of the present invention can match the corresponding light-emitting layer and has a certain hole transport capability. Meanwhile, the evaporation temperature of the material is correspondingly reduced during device preparation, which is beneficial to the device preparation.

[0338] As a luminescent material, this material is combined with compounds with electron transport properties to work synergistically with each other in the luminescent layer, effectively reducing the driving voltage and current working efficiency of the device and extending the device life, achieving significant progress in the application of main materials.

[0339] The organic electroluminescent material of the present invention has 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.

[0340] The applicant declares that the present invention illustrates the organic compounds and applications of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of the raw materials selected by the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. An organic compound, characterized in that The organic compound has a structure shown in Formula I: X is selected from O or S, L is selected from naphthylene, L 1 , L 2 are each independently selected from a connecting bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group, and L 1 , L 2 Not a ring, Ar 1 -Ar 3 are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C6-C60 arylamine, substituted or unsubstituted C3-C60 heteroarylamine or substituted or unsubstituted C3-C60 heteroaryl, 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 heteroaryl group, C6-C60 aromatic amine group or C3-C60 heteroaromatic amine group.

2. The organic compound according to claim 1, characterized in that Ar 1 ,Ar 2 Each independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted phenyl, naphthyl, biphenyl, phenanthrenyl, fluoranthenyl, phenyl, terphenyl, triphenylene, phenylnaphthyl, naphthylphenyl, dimethylfluorenyl, phenylmethylfluorenyl, diphenylfluorenyl, pyridyl, pyridylphenyl, phenylpyridyl, spirobifluorenyl, benzodimethylfluorenyl, benzodiphenylfluorenyl, benzospirobifluorenyl, dibenzofuranyl, benzonaphthofuranyl, benzonaphthothienyl or dibenzothienyl; The substituents 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 aromatic amine group or a C3-C60 heteroaromatic amine group. Preferably, L 1 , L 2 Each is independently selected from a linker, a phenylene group or a naphthylene group.

3. The organic compound according to claim 1 or 2, characterized in that Ar 1 ,Ar 2 Each independently selected from phenyl, naphthyl, phenanthryl, biphenyl, yl, terphenyl, phenylnaphthyl, naphthylphenyl, naphthylnaphthyl, dimethylfluorenyl, diphenylfluorenyl, pyridyl, pyridylphenyl, phenylpyridyl, carbazolyl, phenylcarbazolyl, phenylbenzocarbazolyl, 3,9-diphenyl-9H-carbazole, phenylphenanthrocarbazolyl, spirobifluorenyl, spiro[fluorene-9,9'-xanthenyl]yl, spiro[cyclohexane-1,9'-[9H]fluorene]yl, spiro[fluorene-9,9'-tonyl]yl, 9-phenyl-9H-dibenzo[a,c]carbazolyl, phenylmethylfluorenyl, dibenzofuranyl, dibenzothiophenyl or benzonaphthofuranyl.

4. The organic compound according to any one of claims 1 to 3, characterized in that Ar 3 Selected from phenyl or naphthyl.

5. The organic compound according to any one of claims 1 to 4, characterized in that Ar 1 ,Ar 2 Each is independently selected from the following groups: Indicates a connection key.

6. The organic compound according to any one of claims 1 to 5, characterized in that The organic compound is selected from any one of the following M-1 to M-652: Where D stands for deuterium.

7. An organic electroluminescent material, characterized in that: The organic electroluminescent material comprises the organic compound according to any one of claims 1 to 6.

8. 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 the organic compound according to any one of claims 1 to 6 or the organic electroluminescent material according to claim 7.

9. The organic electroluminescent device according to claim 8, characterized in that: The organic layer comprises an electron transport layer, and the electron transport layer comprises the organic compound according to any one of claims 1 to 6 or the organic electroluminescent material according to claim 7; Preferably, the organic layer comprises a light-emitting layer, and the light-emitting layer comprises the organic compound according to any one of claims 1 to 6 or the organic electroluminescent material according to claim 7; Preferably, the organic layer further comprises one or a combination of at least two of a hole injection layer, a first hole transport layer, a second hole transport layer, an electron blocking layer, an electron buffer layer or an electron injection layer.

10. Use of the organic electroluminescent device according to claim 8 or 9 in optical fiber equipment, lighting equipment, electrophotographic photoreceptor equipment, photoelectric converter, organic solar cell, switching element equipment, organic light-emitting field effect transistor, image sensor or dye laser.

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