Organic material composition and application thereof

Abstract

The invention relates to the technical field of display, in particular to an organic material composition and application thereof. The organic material composition comprises a first compound and a second compound, and the first compound and the second compound have the following structures: # imgabs0 # is beneficial to matching of HOMO and LUMO energy levels with adjacent energy levels through mutual cooperation of the first compound with the structure as shown in a formula (1) and the second compound with the structure as shown in a formula (2); the organic material composition has relatively high stability and relatively balanced carrier mobility, so that the organic electroluminescent device containing the material has relatively long service life, and also has relatively low driving voltage and relatively high efficiency.

Description

Technical Field

[0001] The present invention relates to the field of display technology, and particularly relates to an organic material composition and its application. Background Art

[0002] An organic electroluminescent device (OLED) converts electrical energy into light by applying electricity to an organic electroluminescent material, and generally includes an anode, a cathode, and an organic layer formed between the two electrodes. The organic layer of the organic EL device may include a hole injection layer, a hole transport layer, a hole auxiliary layer, a light-emitting auxiliary layer, an electron blocking layer, a light-emitting 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. The materials used in the organic layer can be classified into hole injection materials, hole transport materials, hole auxiliary materials, light-emitting auxiliary materials, electron blocking materials, light-emitting materials, electron buffer materials, hole blocking materials, electron transport materials, electron injection materials, etc. depending on their functions. In the organic EL device, holes from the anode and electrons from the cathode are injected into the light-emitting layer by applying a voltage, and excitons with high energy are generated by the recombination of holes and electrons. The organic light-emitting compound emits light by moving energy to the excited state and by the energy when the organic light-emitting compound returns from the excited state to the ground state.

[0003] Currently, due to reasons such as low stability and unbalanced carrier mobility of the functional materials composed of existing organic light-emitting compounds, there are problems of high driving voltage and short lifespan of organic electroluminescent diodes, which severely limit the application of organic electroluminescent diodes. Summary of the Invention

[0004] The purpose of the present invention is to overcome the defects that the functional materials composed of existing organic light-emitting compounds have problems such as low stability and unbalanced carrier mobility, resulting in high driving voltage and short lifespan of organic electroluminescent diodes, which severely limit the application of organic electroluminescent diodes, and thereby provide an organic electroluminescent material and its application.

[0005] Definition of substituent terms in the present invention:

[0006] As used in the present invention, the term "halogen" may include fluorine, chlorine, bromine, or iodine.

[0007] As used in the present invention, the term "C1-C30 alkyl" refers to a monovalent substituent derived from a straight-chain or branched-chain saturated hydrocarbon having 1 to 30 carbon atoms, and examples thereof include but are not limited to methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl.

[0008] As used in the present invention, the term "C3-C30 cycloalkyl" refers to a monocyclic hydrocarbon or polycyclic hydrocarbon derived from a hydrocarbon having 1 to 30 ring backbone carbon atoms, and the cycloalkane may include cyclopropyl, cyclobutyl, adamantyl, etc.

[0009] In the present invention, aryl and arylene include monocyclic, polycyclic or fused-ring aryl, and the rings may be interrupted by short non-aromatic units and may include a spiro structure. Aryl includes, but is not limited to, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthryl, fluorenyl, spirobifluorenyl, etc. Arylene includes, but is not limited to, phenylene, biphenylene, terphenylene, naphthylene, phenanthrylene, anthrylene, fluorenylene, spirobifluorenylene, etc.

[0010] In the present invention, heteroaryl and heteroarylene include monocyclic, polycyclic or fused-ring heteroaryl, 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, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuryl, benzothienyl, isobenzofuryl, dibenzofuryl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, and their derivatives, etc.; heteroarylene includes, but is not limited to, furylene, phenylthioylene, pyrrolylene, imidazolylene, pyrazolylene, thiazolylene, thiadiazolylene, isothiazolylene, isoxazolylene, oxazolylene, oxadiazolylene, triazinylene, tetrazinylene, triazolylene, tetrazolylene, furazanylene, pyridinylene, pyrazinylene, pyrimidinylene, pyridazinylene, benzofurylene, benzothienylene, isobenzofurylene, dibenzofurylene, dibenzothienylene, benzimidazolylene, benzothiazolylene, benzoisothiazolylene, benzoisoxazolylene, benzoxazolylene, isoindolylene, indolylene, indazolylene, benzothiadiazolylene, quinolinylene, isoquinolinylene, cinnolinylene, quinazolinylene, quinoxalinylene, carbazolylene, phenoxazinylene, phenothiazinylene, phenanthridinylene, benzodioxolylene, dihydroacridinylene, and their derivatives, etc.

[0011] As used in the present invention, the term "substituted" means that a hydrogen atom in a compound is replaced by another substituent. This position is not limited to a specific position as long as the hydrogen at this position can be replaced by a substituent. When there are two or more substituents, the two or more substituents may be the same or different.

[0012] As used in the present invention, unless otherwise specified, a hydrogen atom includes protium, deuterium, and tritium.

[0013] In the present invention, in the definition of a group, the range of the number of carbon atoms is defined, and the number of carbon atoms is any integer within the defined range. For example, C6-C30 aryl represents that the number of carbon atoms of the aryl can be any integer within the range included in 6-60, such as 6, 8, 10, 13, 15, 17, 20, 22, 25, or 30, etc.

[0014] The solution adopted in the present invention is as follows:

[0015] The present invention provides an organic material composition, the organic material composition comprising a first compound and a second compound, the first compound having the structure shown in formula (1):

[0016]

[0017] Wherein, X is selected from O, S;

[0018] L’, L 1 、L 2 Each independently is selected from a linking bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group;

[0019] Ar 1 Is selected from a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C6-C60 arylamino group, a substituted or unsubstituted C3-C60 heteroarylamino group, a substituted or unsubstituted C3-C60 heteroaryl group;

[0020] Wherein, Ar 1 Is not any one of the following substituted or unsubstituted benzocarbazole groups:

[0021]

[0022] Ar 2 、Ar are each independently selected from hydrogen, deuterium, halogen, cyano, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C6-C60 arylamino group, a substituted or unsubstituted C3-C60 heteroarylamino group, a substituted or unsubstituted C3-C60 heteroaryl group;

[0023] The second compound has the structure shown in formula (2):

[0024]

[0025] Formula (2)

[0026] Wherein, X 1 -X 14 Each independently is selected from N or CR8 , R 8 is selected from hydrogen, deuterium, and aryl groups having 6 to 30 carbon atoms;

[0027] L is independently selected from a linking bond, substituted or unsubstituted arylene groups having 6 to 30 carbon atoms, and substituted or unsubstituted heteroarylene groups having 3 to 30 carbon atoms;

[0028] Ar3 and Ar4 are each independently selected from substituted or unsubstituted aryl groups having 6 to 30 carbon atoms and substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms;

[0029] The substituents in the substituted arylene groups having 6 to 30 carbon atoms, substituted heteroarylene groups having 3 to 30 carbon atoms, substituted aryl groups having 6 to 60 carbon atoms, substituted arylamino groups having 6 to 60 carbon atoms, substituted heteroarylamino groups having 3 to 60 carbon atoms, and substituted heteroaryl groups having 3 to 60 carbon atoms are selected from one or a combination of two of deuterium, halogen, cyano, alkyl groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, heteroaryl groups having 3 to 30 carbon atoms, arylamino groups having 6 to 60 carbon atoms, and heteroarylamino groups having 3 to 60 carbon atoms.

[0030] It is understandable that

[0031]

[0032] It is understandable that the linking bond L 2 can be connected to the substitutable positions in ring A; Ar 2 can be connected to the substitutable positions in ring A and ring B.

[0033] Preferably, in the formula (1), Ar 1 is selected from substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted arylamino groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroarylamino groups having 3 to 30 carbon atoms, and substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms;

[0034] The substituents in the substituted aryl groups having 6 to 30 carbon atoms, substituted arylamino groups having 6 to 30 carbon atoms, substituted heteroarylamino groups having 3 to 30 carbon atoms, and substituted heteroaryl groups having 3 to 30 carbon atoms are each independently selected from one or a combination of at least two of alkyl groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, aryl groups having 6 to 25 carbon atoms, heteroaryl groups having 3 to 25 carbon atoms, arylamino groups having 6 to 60 carbon atoms, and heteroarylamino groups having 3 to 60 carbon atoms;

[0035] Preferably, Ar 1 is selected from hydrogen, deuterium, halogen, substituted or unsubstituted B groups, where the B groups are selected from the following groups: phenyl, naphthyl, biphenyl, phenanthryl, fluoranthenyl, a radical, terphenyl, triphenylene, phenylnaphthyl, naphthylphenyl, carbazolyl, phenylcarbazolyl, dimethylfluorenyl, phenylmethylfluorenyl, diphenylfluorenyl, pyridyl, pyridylphenyl, phenylpyridyl, spirobifluorenyl, benzodimethylfluorenyl, benzodiphenylfluorenyl, benzospirobifluorenyl, dibenzofuranyl, benzonaphthofuranyl, benzonaphthothiophenyl, spiro[fluorene-9,9'-xanthene]yl, phenylmethylfluorenyl, dinaphthofuranyl, dinaphthothiophenyl, dibenzothiophenyl, diphenylamino, di(benzidine)yl, N-phenyl-benzidineyl or N-phenyl-dibenzofuranaminyl;

[0036] The substituents of the substituted B group are each independently selected from one or a combination of at least two of C1-C6 alkyl, C3-C12 cycloalkyl, C6-C25 aryl, C3-C25 heteroaryl, C6-C60 arylamino, and C3-C60 heteroarylamino;

[0037] Preferably, Ar 1 is selected from phenyl, naphthyl, biphenyl, phenanthryl, a radical, terphenyl, triphenylene, fluoranthenyl, phenylnaphthyl, naphthylphenyl, carbazolyl, dimethylfluorenyl, diphenylfluorenyl, phenylcarbazolyl, phenylphenanthrocarbazolyl, spirobifluorenyl, spiro[fluorene-9,9'-xanthene]yl, phenylmethylfluorenyl, dibenzofuranyl, benzonaphthofuranyl, diphenylamino;

[0038] Preferably, Ar 2 is selected from hydrogen, deuterium, an element, a substituted or unsubstituted C group, where the C group is selected from the following groups: phenyl, naphthyl, biphenyl, phenanthryl, fluoranthenyl, a radical, terphenyl, triphenylene, phenylnaphthyl, naphthylphenyl, carbazolyl, phenylcarbazolyl, dimethylfluorenyl, phenylmethylfluorenyl, diphenylfluorenyl, pyridyl, pyridylphenyl, phenylpyridyl, spirobifluorenyl, benzodimethylfluorenyl, benzodiphenylfluorenyl, benzospirobifluorenyl, dibenzofuranyl, benzonaphthofuranyl, benzonaphthothiophenyl, spiro[fluorene-9,9'-xanthene]yl, phenylmethylfluorenyl, dinaphthofuranyl, dinaphthothiophenyl, dibenzothiophenyl, diphenylamino;

[0039] The substituents of the substituted C group are each independently selected from one or a combination of at least two of C1-C6 alkyl, C3-C12 cycloalkyl, C6-C25 aryl, C3-C25 heteroaryl, C6-C60 arylamino, and C3-C60 heteroarylamino;

[0040] Preferably, Ar 2 is selected from phenyl, naphthyl, biphenyl, phenanthryl, a base, a terphenyl group, a triphenylene group, a fluoranthenyl group, a phenylnaphthyl group, a naphthylphenyl group, a carbazolyl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a phenylcarbazolyl group, a phenylphenanthrocarbazolyl group, a spirobifluorenyl group, a spiro[fluorene-9,9'-xanthene] group, a phenylmethylfluorenyl group, a dibenzofuranyl group, a benzonaphthofuranyl group, a diphenylamino group;

[0041] Preferably, Ar 2 is selected from a naphthyl group;

[0042] Preferably, Ar is selected from a phenyl group or a naphthyl group;

[0043] Preferably, Ar is selected from a naphthyl group;

[0044] Preferably, in the formula (1), L’, L 1 and L 2 each independently is selected from a linking bond, a substituted or unsubstituted C6-C20 arylene group;

[0045] The substituents of the substituted C6-C20 arylene 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 arylamino group, and a C3-C60 heteroarylamino group;

[0046] Preferably, L, L 1 and L 2 each independently is selected from a linking bond, a phenylene group, a biphenylene group, or a naphthylene group;

[0047] Preferably, X is selected from O.

[0048] Preferably, the first compound has a structure shown in any one of N-1 to N-250 as follows:

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060] Preferably, in the formula (2), X 1 -X 14 are all selected from CR 8 , R 8 is defined as above; preferably, any one of X 1 -X 6 is selected from N, and the rest are CR 8 , R 8 is defined as above;

[0061] Preferably, any one of X 1 -X 6 is selected from N, and the rest are CR 8 ; any one of X 7 -X 14 is selected from N, and the rest are CR 8 , R 8 is defined as above;

[0062] Preferably, R 8 is selected from hydrogen, deuterium, phenyl, naphthyl;

[0063] Ar 3 , Ar 4 are each independently selected from substituted or unsubstituted C6-C15 aryl, substituted or unsubstituted C3-C20 heteroaryl;

[0064] The substituents in the substituted C6-C15 aryl and substituted C3-C20 heteroaryl are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C60 arylamine, and C3-C60 heteroarylamine;

[0065] Preferably, Ar3 and Ar4 are each independently selected from substituted or unsubstituted A groups;

[0066] The A groups include: phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, fluoranthenyl, triphenylene, fluorene, dimethylfluorene, diphenylfluorene, spirobifluorene, benzodimethylfluorene, benzodiphenylfluorene, benzospirobifluorene, benzofuran, dibenzofuran, naphthobenzofuran, dinaphthofuran, benzothiophene, dibenzothiophene, naphthobenzothiophene, carbazole, phenylcarbazole, benzophenylcarbazole, dibenzophenylcarbazole, biphenylcarbazole, phenanthrenobenzofuran, dibenzofuranofuran, phenylcarbazolebenzofuran;

[0067] Among them, the substituents of the substituted A group are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C60 arylamino, and C3-C60 heteroarylamino;

[0068] Preferably, Ar3 and Ar4 are each independently selected from phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, fluoranthenyl, triphenylene, fluorenyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, benzo[1,2-b:4,5-b']difluorene, benzo[1,2-b:4,5-b']diphenylfluorene, benzo[1,2-b:4,5-b']spirobifluorene, dibenzofuranyl, naphtho[2,3-b]dibenzofuranyl, dibenzothiophenyl, naphtho[2,3-b]dibenzothiophenyl, carbazolyl, phenylcarbazolyl, benzocarbazolyl, dibenzocarbazolyl, a phenyl substituted with one deuterium, a phenyl substituted with two deuteriums, a naphthyl substituted with one deuterium, and a naphthyl substituted with two deuteriums;

[0069] Preferably, Ls are each independently selected from a linking bond, a substituted or unsubstituted C6-C18 arylene;

[0070] Preferably, L is selected from a linking bond, phenylene.

[0071] Preferably, the second compound has a structure shown in any one of Formulas 2-1 to 2-28 as follows:

[0072]

[0073]

[0074]

[0075] Preferably, X 1 -X 14 , and the definitions of Ar3 and Ar4 are the same as above;

[0076] Preferably, the second compound has a structure shown in Formula 2-4 or Formula 2-5;

[0077] Preferably, the second compound has any one of the structures of Formula 2-6, Formula 2-22, Formula 2-25, Formula 2-26, Formula 2-27, Formula 2-28, and Formulas 2-8 to 2-20.

[0078] Preferably, the second compound has a structure shown in any one of M-1 to M-723 as follows:

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097] Preferably, in the material composition, the mass ratio of the first compound to the second compound is 1:9 - 9:1;

[0098] Preferably, in the material composition, the mass ratio of the first compound to the second compound is 2:8 - 8:2;

[0099] More preferably, in the material composition, the mass ratio of the first compound to the second compound is 3:7 - 7:3;

[0100] Further preferably, in the material composition, the mass ratio of the first compound to the second compound is 4:6 - 6:4.

[0101] The present invention provides an organic electroluminescent host material composition comprising the above-mentioned organic material composition.

[0102] The present invention provides the use of the above-mentioned organic material composition or the above-mentioned organic electroluminescent host material composition in an optical device;

[0103] Preferably, the optical device includes an organic electroluminescent device.

[0104] The present invention provides an organic electroluminescent device, which includes an anode and a cathode, and an organic layer disposed between the anode and the cathode. The organic layer includes the above-mentioned organic material composition or the above-mentioned organic electroluminescent host material composition;

[0105] Preferably, the organic layer includes a light-emitting layer, and the light-emitting layer includes the above-mentioned organic material composition or the above-mentioned organic electroluminescent host material composition.

[0106] Preferably, the organic layer includes a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer that are sequentially stacked from the anode side to the cathode side;

[0107] Preferably, the material of the light-emitting layer includes a host material and a guest material, and the host material includes the above-mentioned organic material composition or the above-mentioned organic electroluminescent host material composition.

[0108] Preferably, the guest material includes a phosphorescent dopant, and the phosphorescent dopant includes a complex containing a transition metal.

[0109] The present invention provides an organic electroluminescent device, including the above-mentioned organic electroluminescent device.

[0110] The term "organic electroluminescent material" in the present invention means a material that can be used in an organic electroluminescent device and 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 assisting material, a light-emitting assisting material, an electron blocking material, a light-emitting material (including an organic electroluminescent host material and a dopant material), an electron buffering material, a hole blocking material, an electron transport material, an electron injection material, etc.

[0111] An organic electroluminescent material disclosed in the present invention may include one organic electroluminescent material or may include a plurality of organic electroluminescent materials. Among them, the plurality of organic electroluminescent materials means a material containing a combination of at least two organic electroluminescent materials, and the material may be included in any layer constituting the organic electroluminescent device. It may mean both a material before the organic electroluminescent device (e.g., before vapor deposition) and a material after the organic electroluminescent device (e.g., after vapor deposition). For example, the material may be a combination of at least two compositions, and the compositions may be included in at least one of the following: hole injection layer, hole transport layer, hole auxiliary layer, light-emitting auxiliary layer, electron blocking layer, light-emitting layer, electron buffer layer, hole blocking layer, electron transport layer, and electron injection layer. Two compositions in the plurality of organic electroluminescent materials may be included in the same layer or different layers, and may be co-evaporated or co-evaporated by mixing, or may be evaporated individually.

[0112] The term "organic electroluminescent host material composition" disclosed in the present invention means an organic electroluminescent material containing a combination of at least two host materials. It may mean both a material before in the organic electroluminescent device (e.g., before vapor deposition) and a material after in the organic electroluminescent device (e.g., after vapor deposition). The composition disclosed in the present invention may be included in any light-emitting layer constituting the organic electroluminescent device. Two or more compounds among the plurality of host materials included in the composition disclosed in the present invention may be included in one light-emitting layer, or may be separately included in different light-emitting layers. For example: when two or more host materials are included in one layer, the layer may be formed by co-evaporation by mixing, or may be formed simultaneously by separate co-evaporation.

[0113] In the present invention, the first compound can be prepared by the following synthetic route, including the following steps:

[0114] 1. Synthesis of intermediate Nn-A:

[0115] The reaction raw materials Nn-A-a and Nn-A-b undergo a Suzuki cross-coupling reaction to obtain Nn-A:

[0116]

[0117] 2. Synthesis of compound N:

[0118] The intermediate Nn-A and Nn-B undergo a Buchwald-Hartwig cross-coupling reaction to obtain compound N:

[0119]

[0120] Advantages of the present invention:

[0121] The organic material composition of the present invention comprises a first compound and a second compound. The first compound has a structure represented by formula (1), and the second compound has a structure represented by formula (2). The cooperation of the first compound having the structure represented by formula (1) and the second compound having the structure represented by formula (2) is conducive to the matching of the HOMO and LUMO energy levels with adjacent energy levels, enabling the organic material composition to obtain high stability and relatively balanced carrier mobilities. Furthermore, the organic electroluminescent device containing this material has a more excellent lifespan, as well as a lower driving voltage and higher efficiency. Brief Description of the Drawings

[0122] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings required for use in the description of the specific embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0123] Figure 1 It is a structural diagram of the organic electroluminescent device in the device embodiment of the present invention;

[0124] Among them, 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. Specific Embodiments

[0125] The following embodiments are provided to better further understand the present invention. They are not limited to the best embodiments, and do not constitute limitations on the content and protection scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior art features falls within the protection scope of the present invention.

[0126] For those steps or conditions not specified in the embodiments, the operations or conditions of the conventional experimental steps described in the literature in this field can be followed. For the reagents or instruments not specified by the manufacturer, they are all conventional reagent products that can be obtained through commercial purchase.

[0127] Synthesis of intermediates:

[0128] Synthesis of Intermediate 1 - A

[0129] Synthesis of Intermediate M1 - A

[0130]

[0131] After purging the three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser with nitrogen, M1-A-a (10 mmol), M1-A-b (10 mmol), 100 mL of toluene, 20 mL of ethanol, and 20 mL of water were successively added. Potassium carbonate (20 mmol) and Pd(PPh 3 ) 4 (0.05 mmol) were added, and the mixture was heated to 70 - 80 °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, and the mixture was 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 - 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 to 0 - 5 °C, and filtered to obtain Compound 1-A with a yield of 65%.

[0132] The preparation of the following intermediates 2-A to 8-A was the same as that of 1-A, except that M1-A-a was replaced with borate esters at different sites and different-site brominated and chlorinated raw materials were used to replace M1-A-b:

[0133]

[0134] Example 1

[0135] This example provides Compound N-1 in the organic material composition, and its preparation method includes the following steps:

[0136]

[0137] After purging the three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser with nitrogen, intermediate N1-B (10 Nmol), intermediate N1-A (10 mmol), and 100 mL of toluene were successively added. The mixture was heated under reflux to separate water for 0.5 h, the temperature was lowered to 70 - 80 °C, and sodium tert-butoxide (15 mmol), Pd 2 (dba) 3 (0.05 mmol) and s-phos (0.1 mmol) were slowly added. After the system was stable, 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, and the mixture was 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 - 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 64%.

[0138] Elemental analysis: C45H30N2O Theoretical values: C, 87.92; H, 4.92; N, 4.56; O, 2.60; Measured values: C, 87.53; H, 5.21; N, 4.66;; HRMS(ESI) m / z [M+H]+: Theoretical value: 614.24; Measured value: 615.25.

[0139] Example 2

[0140] This example provides compound N-4 in the organic material composition, and its preparation method includes the following steps:

[0141]

[0142] After replacing the nitrogen in the three-neck reaction flask equipped with mechanical stirring, thermometer and condenser, add intermediate 4-B (10 mmol), intermediate 1-A (10 mmol), and 100 mL of toluene in sequence, heat to reflux for water separation for 0.5 h, cool to 70 - 80 °C, slowly add sodium tert-butoxide (15 mmol), Pd2(dba)3 (0.05 mmol), s-phos (0.1 mmol), and heat to 100 - 110 °C for reaction for 3 h after the system is stable. Cool to 25 - 30 °C, add 100 mL of water and 100 mL of toluene, stir and separate the liquid. Extract the aqueous phase with 100 mL of toluene once, separate the liquid, 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 N-4, with a yield of 54%.

[0143] Elemental analysis: C57H39N3O Theoretical values: C, 87.55; H, 5.03; N, 5.37; O, 2.05; Measured values: C, 87.82; H, 5.13; N, 5.01; HRMS(ESI) m / z [M+H]+: Theoretical value: 781.31; Measured value: 782.30.

[0144] Example 3

[0145] This example provides compound N-20 in the organic material composition, and its preparation method includes the following steps:

[0146]

[0147] After purging the three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser with nitrogen, intermediate 20-B (10 mmol), intermediate 2-A (10 mmol), and 100 mL of toluene were added successively. The mixture was heated under reflux to separate water for 0.5 h, then 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 reaction mixture was cooled to 25 - 30 °C, 100 mL of water and 100 mL of toluene were added, and the mixture was stirred and separated. The aqueous phase was extracted once with 100 mL of toluene, and then separated. The organic phases were combined, 7 g of anhydrous sodium sulfate was added to the combined organic phase, and the mixture was stirred and dried. After filtration, 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, and the mixture was cooled to 0 - 5 °C and filtered to obtain compound N-20 with a yield of 58%.

[0148] Elemental analysis: C51H32N2O2 Theoretical values: C, 86.91; H, 4.58; N, 3.97; O, 4.54; Measured values: C, 87.32; H, 4.18; N, 3.85; HRMS(ESI) m / z [M+H]+: Theoretical value: 704.25; Measured value: 705.25.

[0149] Example 4

[0150] This example provides compound N-24 in the organic material composition, and its preparation method includes the following steps:

[0151]

[0152] After purging the three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser with nitrogen, intermediate 24-B (10 mmol), intermediate 3-A (10 mmol), and 100 mL of toluene were added successively. The mixture was heated under reflux to separate water for 0.5 h, then 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 reaction mixture was cooled to 25 - 30 °C, 100 mL of water and 100 mL of toluene were added, and the mixture was stirred and separated. The aqueous phase was extracted once with 100 mL of toluene, and then separated. The organic phases were combined, 7 g of anhydrous sodium sulfate was added to the combined organic phase, and the mixture was stirred and dried. After filtration, 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, and the mixture was cooled to 0 - 5 °C and filtered to obtain compound N-24 with a yield of 58%.

[0153] Elemental analysis: C55H34N2O2 Theoretical values: C, 87.51; H, 4.54; N, 3.71; O, 4.24; Measured values: C, 87.89; H, 4.44; N, 3.43; HRMS(ESI) m / z [M+H]+: Theoretical value: 754.26; Measured value: 755.26.

[0154] Example 5

[0155] This example provides compound N-32 in the organic material composition, and its preparation method includes the following steps:

[0156]

[0157] After replacing the nitrogen in the three-necked reaction flask equipped with mechanical stirring, thermometer, and condenser tube, successively add intermediate 32-B (10 mmol), intermediate 4-A (10 mmol), 100 mL of toluene, heat to reflux for water separation for 0.5 h, cool to 70 - 80 °C, slowly add sodium tert-butoxide (15 mmol), Pd2(dba)3 (0.05 mmol), s-phos (0.1 mmol), and heat to 100 - 110 °C for reaction for 3 h after the system is stable. Cool to 25 - 30 °C, add 100 mL of water and 100 mL of toluene, stir and separate the liquid. Extract the aqueous phase once with 100 mL of toluene, separate the liquid, combine the organic phases, add 7 g of anhydrous sodium sulfate to the organic phases, stir and dry, filter, concentrate the organic phases (-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 N-32 with a yield of 58%.

[0158] Elemental analysis: C57H38N2O Theoretical values: C, 89.27; H, 4.99; N, 3.65; O, 2.09; Measured values: C, 89.83; H, 4.65; N, 3.44; HRMS(ESI) m / z [M+H]+: Theoretical value: 766.30; Measured value: 767.28.

[0159] Example 6

[0160] This example provides compound N-51 in the organic material composition, and its preparation method includes the following steps:

[0161]

[0162] After purging the three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser with nitrogen, add intermediate 51-B (10 mmol), intermediate 5-A (10 mmol), and 100 mL of toluene in sequence. Heat under reflux to separate water for 0.5 h, cool down to 70 - 80 °C, slowly add sodium tert-butoxide (15 mmol), Pd2(dba)3 (0.05 mmol), and s-phos (0.1 mmol). After the system stabilizes, heat to 100 - 110 °C and react for 3 h. Cool down to 25 - 30 °C, add 100 mL of water and 100 mL of toluene, stir and separate the layers. Extract the aqueous phase once with 100 mL of toluene, separate the layers, 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 down to 0 - 5 °C, filter to obtain compound N-51, with a yield of 49%.

[0163] Elemental analysis: C68H42N2O Theoretical values: C, 90.44; H, 4.69; N, 3.10; O, 1.77; Measured values: C, 90.47; H, 4.64; N, 3.13; HRMS(ESI) m / z [M + H]+: Theoretical value: 902.33; Measured value: 903.33.

[0164] Example 7

[0165] This example provides compound N-71 in the organic material composition, and its preparation method includes the following steps:

[0166]

[0167] After purging the three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser with nitrogen, add intermediate 71-B (10 mmol), intermediate 6-A (10 mmol), and 100 mL of toluene in sequence. Heat under reflux to separate water for 0.5 h, cool down to 70 - 80 °C, slowly add sodium tert-butoxide (15 mmol), Pd2(dba)3 (0.05 mmol), and s-phos (0.1 mmol). After the system stabilizes, heat to 100 - 110 °C and react for 3 h. Cool down to 25 - 30 °C, add 100 mL of water and 100 mL of toluene, stir and separate the layers. Extract the aqueous phase once with 100 mL of toluene, separate the layers, 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 down to 0 - 5 °C, filter to obtain compound N-71, with a yield of 67%.

[0168] Elemental analysis: C45H28N2O2 Theoretical values: C, 85.97; H, 4.49; N, 4.46; O, 5.09; Measured values: C, 85.99; H, 4.46; N, 4.45; HRMS(ESI) m / z [M+H]+: Theoretical value: 628.22; Measured value: 629.22.

[0169] Example 8

[0170] This example provides compound N-86 in the organic material composition, and its preparation method includes the following steps:

[0171]

[0172] After replacing the nitrogen in the three-necked reaction flask equipped with mechanical stirring, thermometer, and condenser, add intermediate 86-B (10 mmol), intermediate 7-A (10 mmol), and 100 mL of toluene in sequence. Heat under reflux to separate water for 0.5 h, cool down to 70 - 80 °C, slowly add sodium tert-butoxide (15 mmol), Pd2(dba)3 (0.05 mmol), and s-phos (0.1 mmol). After the system is stable, heat to 100 - 110 °C and react for 3 h. Cool down to 25 - 30 °C, add 100 mL of water and 100 mL of toluene, stir and separate the liquid. Extract the aqueous phase once with 100 mL of toluene, separate the liquid, 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 down to 0 - 5 °C, filter to obtain compound N-86, with a yield of 65%.

[0173] Elemental analysis: C57H37N3O Theoretical values: C, 87.78; H, 4.78; N, 5.39; O, 2.05; Measured values: C, 87.74; H, 4.79; N, 5.41; HRMS(ESI) m / z [M+H]+: Theoretical value: 779.29; Measured value: 780.28.

[0174] Example 9

[0175] This example provides compound N-100 in the organic material composition, and its preparation method includes the following steps:

[0176]

[0177] After purging the three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser with nitrogen, 10 mmol of intermediate 100-B, 10 mmol of intermediate 7-A, and 100 mL of toluene were successively added. The mixture was heated under reflux to separate water for 0.5 h, then 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. It was cooled to 25 - 30 °C, 100 mL of water and 100 mL of toluene were added, and the mixture was 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, and the mixture was stirred and dried, 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, and it was cooled to 0 - 5 °C and filtered to obtain compound N-100 with a yield of 57%.

[0178] Elemental analysis: C55H34N2O2 Theoretical values: C, 87.51; H, 4.54; N, 3.71; O, 4.24; Measured values: C, 87.54; H, 4.53; N, 3.70; HRMS(ESI) m / z [M+H]+: Theoretical value: 754.26; Measured value: 755.27.

[0179] Example 10

[0180] This example provides compound N-138 in the organic material composition, and its preparation method includes the following steps:

[0181]

[0182] After purging the three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser with nitrogen, 10 mmol of intermediate 138-B, 10 mmol of intermediate 8-A, and 100 mL of toluene were successively added. The mixture was heated under reflux to separate water for 0.5 h, then 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. It was cooled to 25 - 30 °C, 100 mL of water and 100 mL of toluene were added, and the mixture was 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, and the mixture was stirred and dried, 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, and it was cooled to 0 - 5 °C and filtered to obtain compound N-138 with a yield of 47%.

[0183] Elemental analysis: C57H36N2O2 Theoretical values: C, 87.67; H, 4.65; N, 3.59; O, 4.10; Measured values: C, 87.69; H, 4.64; N, 3.58; HRMS(ESI) m / z [M+H]+: Theoretical value: 780.28; Measured value: 781.28.

[0184] Example 11

[0185] This example provides compound N-202 in the organic material composition, and its preparation method includes the following steps:

[0186]

[0187] The synthesis steps of compound N-202 are the same as those of compound N-32, except that intermediate 202-B is used instead of 32-B, and 6-A is used instead of 4-A, to obtain compound M-202 with a yield of 61%.

[0188] Elemental analysis: C 51 H 34 N 2 O Theoretical values: C, 88.67; H, 4.96; N, 4.06; O, 2.32; Measured values: C, 88.65; H, 4.94; N, 4.10; HRMS(ESI) m / z [M+H]+: Theoretical value: 690.27; Measured value: 691.55.

[0189] Example 12

[0190] This example provides compound M-17 in the organic material composition, and its preparation method includes the following steps:

[0191]

[0192] Take a 50 mL two-necked round-bottom flask, place a stir bar and connect a reflux tube above. After drying, fill it with nitrogen. Add compound M17-A (19.8 mmol, CAS: 1884145-03-2), M17-B (20.75 mmol, CAS: 1883265-32-4), tetrakis(triphenylphosphine)palladium(0) (0.396 mmol), potassium carbonate (39.6 mmol), 35 mL of toluene, 15 mL of ethanol and 15 mL of distilled water, and stir the mixture at 90 °C for 8 hours. After the reaction is completed, add the mixture dropwise to methanol and filter the resulting solid. Purify the resulting solid by column chromatography to obtain compound M-17 (8.5 g, yield: 75%).

[0193] Elemental analysis: C 41 H 25 N 3O; Theoretical values: C, 85.54; H, 4.38; N, 7.30; O, 2.78; Measured values: C, 85.52; H, 4.38; N, 7.32; HRMS(ESI) m / z (M+): Theoretical value: 575.20; Measured value: 576.34.

[0194] Example 13

[0195] This example provides compound M-296 in the organic material composition, and its preparation method includes the following steps:

[0196] (I) Synthesis of intermediate M296-A, and the synthesis route is as follows:

[0197]

[0198] Add intermediate M296-1 (2-bromoquinoline, CAS: 2005-43-8, 20 g) and 200 mL of anhydrous tetrahydrofuran to a 250 mL three-necked flask equipped with a thermometer and magnetic stirring. Under nitrogen protection, cool down to -78 °C, control the temperature and dropwise add n-butyllithium (1.6 M, 45.2 mL). After dropping, stir for 1 h, then control the temperature at -78 °C and dropwise add triisopropyl borate (19.52 g). After dropping, transfer to room temperature and react for 12 h. Dropwise add hydrochloric acid solution (6.5 mL of 36% concentrated hydrochloric acid + 24 mL of water). Add 50 mL of ethyl acetate to the reaction solution, extract and separate with 25 mL of water. Rotate the organic phase to dryness, add 50 mL of n-hexane, reflux and slurry for 1 h, filter at room temperature, and dry to obtain intermediate M296-2, 15 g.

[0199] Add intermediate M296-2 (15 g), intermediate 7-bromo-1-chloronaphthalene (21.9 g), potassium carbonate (16.6 g) and tetrakis(triphenylphosphine)palladium (2.0 g) to a 250 mL three-necked flask equipped with a thermometer and magnetic stirring. Add toluene (80 mL), ethanol (35 mL) and water (35 mL). Under nitrogen protection, heat to 85 °C and react for 6 h. Add 50 mL of ethyl acetate and 25 mL of water to the reaction solution, extract and separate. Stir the organic phase and pass through a column to obtain intermediate M296-3, 15 g.

[0200] Add intermediate M296-3 (15 g), bis(pinacolato)diboron (15.8 g), potassium acetate (10 g) and Pd(dppf)Cl 2 (0.64 g) to a 250 mL three-necked flask equipped with a thermometer and magnetic stirring. Add 1,4-dioxane (150 mL). Under nitrogen protection, heat to 110 °C and react for 4 h. Add 100 mL of toluene and 100 mL of water to the reaction solution, extract and separate. Stir the organic phase and pass through a column to obtain intermediate M296-A, 16 g.

[0201] (2) Synthesis of Compound M-296. The synthetic route is as follows:

[0202]

[0203] Add intermediate M296-A (16 g), intermediate M296-B (2-chloro-4,6-diphenyl-1,3,5-triazine, CAS: 3842-55-5, 11.2 g), potassium carbonate (11.6 g), and tetrakis(triphenylphosphine)palladium(0) (1.3 g) into a 250 mL three-necked flask equipped with a thermometer and a magnetic stirrer. Add toluene (110 mL), ethanol (50 mL), and water (50 mL). Under nitrogen protection, heat to 85 °C and react for 6 h. Add water and ethanol to the reaction solution at room temperature and filter. After drying, 16 g of product M296 is obtained (yield 78%).

[0204] Elemental analysis: C 34 H 22 N 4 Theoretical values: C, 83.93; H, 4.56; N, 11.51; Measured values: C, 83.95; H, 4.56; N, 11.49; HRMS(ESI) m / z (M+): Theoretical value: 486.18; Measured value: 487.12.

[0205] Example 14-41

[0206] Provide the preparation methods of compounds M-76, M-108, M-145, M-253, M-394, M-412, M-423, M-442, M-450, M-460, M-461, M-480, M-502, M-520, M-526, M-537, M-548, M-562, M-572, M-579, M-584, M-589, M-599, M-610, M-611, M-308, M-365, or M-371 in Example 12-39. The specific preparation methods are as follows:

[0207] Add raw material Mn-B, raw material Mn-A, potassium carbonate, and tetrakis(triphenylphosphine)palladium(0). Add toluene, ethanol, and water. Under nitrogen protection, heat to react. After the reaction is completed, perform purification treatment to obtain the final product. The dosages of substances and experimental parameters are the same as those in Example 1.

[0208] The structures and yields of raw material Mn-B, raw material Mn-A, and the product are shown in Table 1 below. The elemental analysis results of the prepared compounds are shown in Table 2. The dosages of substances and experimental parameters are the same as those in Example 1.

[0209] Table 1

[0210]

[0211]

[0212]

[0213]

[0214]

[0215] The product characterization data are shown in Table 2 as follows:

[0216] Table 2

[0217]

[0218]

[0219] Example 40

[0220] This example provides compound M-624 in the organic material composition, and its preparation method includes the following steps:

[0221]

[0222] 1) After purging the three-necked reaction flask equipped with mechanical stirring, thermometer, and condenser with nitrogen, successively add SubM3-A (10 mmol), M-1-a (1.05 mmol), 100 mL of 1,4-dioxane, 30 mL of water, add sodium carbonate (20 mmol), Pd(PPh 3 ) 4 (0.05 mmol), heat to 70 - 80 °C, and react for 3 h. Cool to 25 - 30 °C, add 100 mL of water and 100 mL of toluene, stir and separate the liquid. Extract the aqueous phase with 100 mL of toluene once, separate the liquid, combine the organic phases. Add 7 g of anhydrous sodium sulfate to the organic phases, stir and dry, filter. Concentrate the organic phases (-0.08 - 0.09 MPa, 55 - 60 °C) until no liquid flows out. Stir and add a mixed solvent of 50 mL of dichloromethane and petroleum ether, cool to 0 - 5 °C, filter to obtain intermediate IntM-1-a, with a yield of 43%.

[0223] 2) After purging the three-necked reaction flask equipped with mechanical stirring, thermometer, and condenser with nitrogen, successively add intermediate IntM-1-a (10 mmol), intermediate 1-A (10 mmol), potassium carbonate (20 mmol), Pd(PPh 3 ) 4(0.05 mmol), 100 mL of 1,4-dioxane, 30 mL of water. Start stirring and heat to 70 - 75 °C for reaction for 3 h. Cool down to 25 - 30 °C, add 100 mL of water and 100 mL of dichloromethane, stir and separate the layers. Extract the aqueous phase with 100 mL of dichloromethane once, separate the layers, 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 down to 0 - 5 °C, filter to obtain the crude product. Recrystallize the crude product with toluene to obtain product M-624, with a yield of 54%.

[0224] Elemental analysis: C 41 H 24 DN 3 Theoretical values: C, 85.39; H, 4.54; N, 7.29; O, 2.77; Measured values: C, 85.42; H, 4.55; N, 7.24; HRMS(ESI) m / z [M + H]+: Theoretical value: 576.21; Measured value: 577.32.

[0225] Example 41

[0226] This example provides compound M-631 in the organic material composition, and its preparation method includes the following steps:

[0227]

[0228] The preparation method of M-631 is the same as that of M-624, except that in step 1), SubM6-A is used to replace SubM3-A, and the generated intermediate is IntM-8-a; in step 2), IntM-8-a is used to replace IntM-1-a, and SubM1-C is used to replace M-1-b to obtain product M-631, with a yield of 56%.

[0229] Elemental analysis: C 45 H 25 D 2 N 3 Theoretical values: C, 86.10; H, 4.66; N, 6.69; O, 2.55; Measured values: C, 86.15; H, 4.67; N, 6.62; HRMS(ESI) m / z [M + H]+: Theoretical value: 627.23; Measured value: 628.43.

[0230] Example 42

[0231] This example provides compound M-638 in the organic material composition, and its preparation method includes the following steps:

[0232]

[0233] The preparation method of M-638 is the same as that of M-624, except that in step 1), SubM1-A is used to replace SubM3-A to generate the intermediate product IntM-16-a; in step 2), IntM-16-a is used to replace IntM-1-a, and SubM3-B is used to replace M-1-b to obtain the product M-638 with a yield of 56%.

[0234] Elemental analysis: C 51 H 30 DN 3 Theoretical values: C, 87.16; H, 4.59; N, 5.98; O, 2.28; Measured values: C, 87.18; H, 4.61; N, 5.94; HRMS(ESI) m / z [M+H]+: Theoretical value: 702.25; Measured value: 703.25.

[0235] Example 43

[0236] This example provides the compound M-639 in the organic material composition, and its preparation method includes the following steps:

[0237]

[0238] After replacing the nitrogen in the three-necked reaction flask equipped with mechanical stirring, thermometer, and condenser, successively add the intermediate IntM-15-a (10 mmol), the raw material M-16-b (10 mmol), potassium carbonate (20 mmol), Pd(PPh 3 ) 4 (0.05 mmol), 100 mL of 1,4-dioxane, 30 mL of water, start stirring, heat to 70-75 °C and react for 3 h. Cool down to 25-30 °C, add 100 mL of water and 100 mL of dichloromethane, stir and separate the layers. Extract the aqueous phase with 100 mL of dichloromethane once, separate the layers, 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 to 0.09 MPa, 55-60 °C) until no liquid flows out, stir and add 20 mL of petroleum ether, cool down to 0-5 °C, filter to obtain the crude product, and recrystallize the crude product with toluene to obtain the product M-639 with a yield of 62%.

[0239] Elemental analysis: C 41 H 24 DN 3 Theoretical values: C, 85.39; H, 4.54; N, 7.29; O, 2.77; Measured values: C, 85.43; H, 4.55; N, 7.23; HRMS(ESI) m / z [M+H]+: Theoretical value: 576.21; Measured value: 576.46.

[0240] Example 44

[0241] This example provides compound M-650 in the organic material composition, and its preparation method includes the following steps:

[0242]

[0243] The preparation method of M-650 is the same as that of M-624, except that in step 1), SubM7-A is used to replace SubM3-A, and the generated intermediate is IntM-27-a; in step 2), IntM-27-a is used to replace IntM-1-a, and M-27-b is used to replace M-1-b, with a yield of 61%.

[0244] Elemental analysis: C 45 H 26 DN 3 Theoretical values: C, 86.24; H, 4.50; N, 6.70; O, 2.55; Measured values: C, 86.28; H, 4.52; N, 6.64; HRMS(ESI) m / z [M+H]+: Theoretical value: 626.22; Measured value: 627.25.

[0245] Example 45

[0246] This example provides compound M-620 in the organic material composition, and its preparation method includes the following steps:

[0247]

[0248] Add raw material SubM3-B-b (42 mmol), raw material deuterated 1-naphthylboronic acid (42.5 mmol), potassium carbonate (84 mmol) and tetrakis(triphenylphosphine)palladium (2 mmol) to a 250 mL three-necked flask equipped with a thermometer and magnetic stirring. Add toluene (80 mL), ethanol (35 mL) and water (35 mL). Under nitrogen protection, heat to 85 °C and react for 6 h. Add 50 mL of ethyl acetate and 25 mL of water to the reaction solution for extraction and liquid separation. The organic phase is stirred and passed through a column to obtain intermediate M620-A-1, 10 g.

[0249] Add intermediate M620-A-1 (34 mmol), bis(pinacolato)diboron (40 mmol), potassium acetate (68 mmol) and Pd(dppf)Cl 2 (1.7 mmol) to a 250 mL three-necked flask equipped with a thermometer and magnetic stirring. Add 1,4-dioxane (150 mL). Under nitrogen protection, heat to 110 °C and react for 4 h. Add 100 mL of toluene and 100 mL of water to the reaction solution for extraction and liquid separation. The organic phase is stirred and passed through a column to obtain intermediate M620-A-2, 8 g.

[0250]

[0251] After purging the three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser with nitrogen, M620-B-a (10 mmol), M-1-a (1.05 mmol), 100 mL of 1,4-dioxane, and 30 mL of water were successively added. Sodium carbonate (20 mmol) and Pd(PPh 3 ) 4 (0.05 mmol) were added, and the mixture was heated to 70 - 80 °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, and the mixture was 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 phases, stirred and dried, filtered, and the organic phases were 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 to 0 - 5 °C, and filtered to obtain intermediate M620-B-1 with a yield of 46%.

[0252] After purging the three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a condenser with nitrogen, intermediate M620-B-1 (10 mmol), intermediate 1-A (10 mmol), potassium carbonate (20 mmol), and Pd(PPh 3 ) 4 (0.05 mmol), 100 mL of 1,4-dioxane, and 30 mL of water were added. Stirring was started, and the mixture was heated to 70 - 75 °C and reacted 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 stirred and separated. 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, filtered, and the organic phases were 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 the crude product. The crude product was recrystallized from toluene to obtain product M-620 with a yield of 54%.

[0253] Elemental analysis: C 41 H 13 D 12 N 3 Theoretical values: C, 83.79; H, 6.34; N, 7.15; O, 2.72; Measured values: C, 83.77; H, 6.33; N, 7.18; HRMS(ESI) m / z [M + H]+: Theoretical value: 587.28; Measured value: 588.27.

[0254] Device Example

[0255] This example provides an organic electroluminescent device, such as Figure 1As shown, it includes 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 that are sequentially stacked on a substrate 1. Its device structure is: 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).

[0256] The materials for manufacturing the organic electroluminescent device are as follows:

[0257]

[0258] The preparation of the above-mentioned organic electroluminescent device includes the following steps:

[0259] 1) Substrate cleaning:

[0260] 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 ≤ 10 wt%, triethanolamine ≤ 1 wt%), then rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol (the volume ratio of acetone to ethanol is 1:1), baked in a clean environment until all moisture is removed, and then cleaned with ultraviolet light and ozone.

[0261] 2) Organic layer preparation:

[0262] Transfer the ITO transparent substrate to an evaporation equipment and evacuate to 1×10 -6 to 2×10 -4 Pa, and sequentially evaporate a hole injection layer (HIL) / hole transport layer (HTL) / light-emitting layer (EML) / electron transport layer (ETL) / 1 nm electron injection layer (EIL) / thick cathode (Al) on the anode film.

[0263] Among them:

[0264] The material of the hole injection layer (HIL) is a mixture of NDP-9 and HT, and the specific mass ratio is shown in Table 3;

[0265] The material of the hole transport layer (HTL) is shown in Table 3;

[0266] The light-emitting layer (EML) is vacuum-evaporated by co-evaporation. The material of the light-emitting layer includes a host material and a guest material, and the guest material is (piq) 2 Ir(acac), and the specific material of the host material and its ratio to the guest material are shown in Table 3;

[0267] The material of the electron transport layer (ETL) is shown in Table 3;

[0268] The material of the electron injection layer (EIL) is LiQ;

[0269] The cathode is aluminum;

[0270] Some layers of the organic electroluminescent device, their materials and thicknesses are shown in Table 3

[0271] Table 3

[0272]

[0273]

[0274]

[0275]

[0276] The examples in the table represent device examples, and the comparative examples in the table are device comparative examples.

[0277] Test examples

[0278] The organic electroluminescent devices obtained from Device Examples 1-11 and Comparative Examples 1-12 in the device examples were tested.

[0279] Instrument: The characteristics such as current, voltage, brightness, and emission spectrum of the device were synchronously tested using a PR 650 spectral scanning luminance meter and a Keithley K2400 digital source meter system;

[0280] Test conditions: Photoelectric characteristic test conditions: The current density is 10 mA / cm2.

[0281] Lifetime test: The current density is 50 mA / cm2, and the time (in hours) is recorded when the device brightness drops to 95% of the original brightness.

[0282] The test results of the device performance are shown in Table 4:

[0283] Table 4

[0284]

[0285]

[0286] From the comparison of the data corresponding to the examples and comparative examples in Table 4, it can be seen that the organic material composition developed in the present invention has significantly more excellent performance compared to the combinations of the disclosed compounds A, B, C, etc. in the prior art, and can have a lower turn-on voltage after being fabricated into a device.

[0287] Obviously, the above embodiments are merely examples given for clear illustration and are not limitations on the implementation manners. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to enumerate all the implementation manners here. And the obvious changes or modifications derived therefrom still fall within the protection scope of the present invention.

Claims

1. An organic material composition, characterized in that, the organic material composition comprises a first compound and a second compound, and the first compound has a structure represented by formula (1): wherein, X is selected from O, S; L', L 1 , L 2 Each is independently selected from a connecting bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group; Ar 1 selected from 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; 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; the second compound has a structure represented by formula (2): wherein, X 1 -X 14 are each independently selected from N or CR 8 , R 8 is selected from hydrogen, deuterium, aryl having 6 to 30 carbon atoms; L is independently selected from a linking bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group; Ar3 and Ar4 are each independently selected from a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group; The substituents in the substituted C6-C30 arylene group, the substituted C3-C30 heteroarylene group, the substituted C6-C60 aryl group, the substituted C6-C60 arylamino group, the substituted C3-C60 heteroarylamino group, and the substituted C3-C60 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, C3-C30 heteroaryl group, C6-C60 arylamino group, and C3-C60 heteroarylamino group.

2. The organic material composition according to claim 1, characterized in that, In the formula (1), Ar 1 is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, and substituted or unsubstituted C3-C30 heteroaryl; the substituents in the substituted C6-C30 aryl group, the substituted C6-C30 arylamino group, the substituted C3-C30 heteroarylamino group, and the substituted C3-C30 heteroaryl 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 arylamino group, and a C3-C60 heteroarylamino group; Preferably, Ar 1 is selected from hydrogen, deuterium, an element, a substituted or unsubstituted B group, where the B group is selected from the following groups: phenyl, naphthyl, biphenyl, phenanthryl, fluoranthenyl, anthryl, terphenyl, triphenylene, phenylnaphthyl, naphthylphenyl, carbazolyl, phenylcarbazolyl, dimethylfluorenyl, phenylmethylfluorenyl, diphenylfluorenyl, pyridyl, pyridylphenyl, phenylpyridyl, spirobifluorenyl, benzodimethylfluorenyl, benzodiphenylfluorenyl, benzospirobifluorenyl, dibenzofuranyl, benzonaphthofuranyl, benzonaphthothiophenyl, spiro[fluorene-9,9'-xanthene]yl, phenylmethylfluorenyl, dinaphthofuranyl, dinaphthothiophenyl, dibenzothiophenyl, diphenylamino, diarylamino, N-phenyl-diarylamino or N-phenyl-dibenzofuranamino; the substituents of the substituted B 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 arylamino group, and a C3-C60 heteroarylamino group; Preferably, Ar 1 is selected from phenyl, naphthyl, biphenyl, phenanthryl, anthryl, terphenyl, triphenylene, fluoranthenyl, phenylnaphthyl, naphthylphenyl, carbazolyl, dimethylfluorenyl, diphenylfluorenyl, phenylcarbazolyl, phenylphenanthrocarbazolyl, spirobifluorenyl, spiro[fluorene-9,9'-xanthene]yl, phenylmethylfluorenyl, dibenzofuranyl, benzonaphthofuranyl, diphenylamino; Preferably, Ar 2 is selected from hydrogen, deuterium, elements, substituted or unsubstituted C groups, where the C groups are selected from the following groups: phenyl, naphthyl, biphenyl, phenanthryl, fluoranthenyl, group, terphenyl, triphenylene, phenylnaphthyl, naphthylphenyl, carbazolyl, phenylcarbazolyl, dimethylfluorenyl, phenylmethylfluorenyl, diphenylfluorenyl, pyridyl, pyridylphenyl, phenylpyridyl, spirobifluorenyl, benzodimethylfluorenyl, benzodiphenylfluorenyl, benzospirobifluorenyl, dibenzofuranyl, benzonaphthofuranyl, benzonaphthothiophenyl, spiro[fluorene-9,9'-xanthene]yl, phenylmethylfluorenyl, dinaphthofuranyl, dinaphthothiophenyl, dibenzothiophenyl, diphenylamino; the substituents of the substituted C 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 arylamino group, and a C3-C60 heteroarylamino group; Preferably, Ar 2 is selected from phenyl, naphthyl, biphenyl, phenanthryl, anthryl, terphenyl, triphenylene, fluoranthenyl, phenylnaphthyl, naphthylphenyl, carbazolyl, dimethylfluorenyl, diphenylfluorenyl, phenylcarbazolyl, phenylphenanthrocarbazolyl, spirobifluorenyl, spiro[fluorene-9,9'-xanthene]yl, phenylmethylfluorenyl, dibenzofuranyl, benzonaphthofuranyl, diphenylamino; Preferably, Ar 2 is selected from naphthyl; Preferably, Ar is selected from a phenyl group or a naphthyl group; Preferably, Ar is selected from a naphthyl group; Preferably, in the formula (1), L’, L 1 and L 2 each independently selected from a linking bond, a substituted or unsubstituted C6-C20 arylene group; the substituents of the substituted C6-C20 arylene 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 arylamino group, and a C3-C60 heteroarylamino group; Preferably, L, L 1 and L 2 are each independently selected from a linking bond, a phenylene group, a biphenylene group or a naphthylene group; Preferably, X is selected from O.

3. The organic material composition according to claim 1 or 2, characterized in that, the first compound has any one of the structures represented by N-1 to N-250 as follows:

4. The organic material composition according to any one of claims 1-3, characterized in that, In the formula (2), X 1 -X 14 are all selected from CR 8 , R 8 is defined as in claim 1; Preferably, X 1 -X 6 any one of them is selected from N, and the rest are CR 8 , R 8 is defined as in claim 1; Preferably, X 1 -X 6 Any one of them is selected from N, and the rest are CR 8 ; X 7 -X 14 Any one of them is selected from N, and the rest are CR 8 , R 8 is defined as in claim 1; Preferably, R 8 is selected from hydrogen, deuterium, phenyl, naphthyl; Ar 3 、Ar 4 each independently selected from substituted or unsubstituted C6-C15 aryl, substituted or unsubstituted C3-C20 heteroaryl; The substituents in the substituted C6-C15 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 group, C3-C30 cycloalkyl group, C6-C30 aryl group, C3-C30 heteroaryl group, C6-C60 arylamino group, and C3-C60 heteroarylamino group; Preferably, Ar3 and Ar4 are each independently selected from substituted or unsubstituted A groups; The A groups include: phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, fluoranthenyl, triphenylene, fluorenyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, benzo-dimethylfluorenyl, benzo-diphenylfluorenyl, benzo-spirobifluorenyl, benzofuranyl, dibenzofuranyl, naphtho-benzofuranyl, dinaphthofuranyl, benzothiophenyl, dibenzothiophenyl, naphtho-benzothiophenyl, carbazolyl, phenylcarbazolyl, benzo-phenylcarbazolyl, dibenzo-phenylcarbazolyl, biphenylcarbazolyl, phenanthro-benzofuranyl, dibenzofurano-furanyl, phenylcarbazolo-benzofuranyl; Among them, the substituents of the substituted A 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, C3-C30 heteroaryl group, C6-C60 arylamino group, and C3-C60 heteroarylamino group; Preferably, Ar3 and Ar4 are each independently selected from phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, fluoranthenyl, triphenylene, fluorenyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, benzo-dimethylfluorenyl, benzo-diphenylfluorenyl, benzo-spirobifluorenyl, dibenzofuranyl, naphtho-benzofuranyl, dibenzothiophenyl, naphtho-benzothiophenyl, carbazolyl, phenylcarbazolyl, benzo-carbazolyl, dibenzo-carbazolyl; Preferably, Ls are each independently selected from a linking bond, a substituted or unsubstituted C6-C18 arylene group; Preferably, L is selected from a linking bond, a phenylene group.

5. The organic material composition according to any one of claims 1-4, characterized in that, the second compound has a structure shown in any one of formulas 2-1 to 2-28 below: Preferably, X 1 -X 14 The definitions of Ar3 and Ar4 are the same as those in claim 1 or 2; Preferably, the second compound has a structure shown in formula 2-4 or formula 2-5; Preferably, the second compound has any one of the structures of formula 2-6, formula 2-22, formula 2-25, formula 2-26, formula 2-27, formula 2-28, formula 2-8 to formula 2-20.

6. The organic material composition according to any one of claims 1-5, characterized in that, the second compound has a structure shown in any one of M-1 to M-723 below:

7. The organic material composition according to any one of claims 1-6, characterized in that, in the material composition, the mass ratio of the first compound to the second compound is 1:9 - 9:1; Preferably, in the material composition, the mass ratio of the first compound to the second compound is 2:8 - 8:2; More preferably, in the material composition, the mass ratio of the first compound to the second compound is 3:7 - 7:3; Further preferably, in the material composition, the mass ratio of the first compound to the second compound is 4:6 - 6:

4.

8. An organic electroluminescent host material composition, characterized in that it comprises the organic material composition according to any one of claims 1 - 7.

9. Use of the organic material composition according to any one of claims 1 - 7 or the organic electroluminescent host material composition according to claim 8 in an optical device; Preferably, the optical device comprises an organic electroluminescent device.

10. An organic electroluminescent device, characterized in that the organic electroluminescent device comprises an anode and a cathode, and an organic layer disposed between the anode and the cathode, and the organic layer comprises the organic material composition according to any one of claims 1 - 7 or the organic electroluminescent host material composition according to claim 8; Preferably, the organic layer comprises a light-emitting layer, and the light-emitting layer comprises the organic material composition according to any one of claims 1 - 7 or the organic electroluminescent host material composition according to claim 8.

11. An organic electroluminescent device, characterized in that it comprises the organic electroluminescent device according to claim 10.

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