A heteroatom-containing spiro compound, a preparation method and application thereof

Abstract

The present application relates to a kind of heteroatom-containing spiro compounds and its preparation method and application, belong to organic luminescent material technical field, the structure general formula of the heteroatom-containing spiro compound is formula 1: The heteroatom-containing spiro organic electroluminescent compound provided in the application has excellent electron transport performance, and can be used as electron transport material, the compound by introducing spiro rigid structure, it has high electron injection and moving rate, and has good film forming property and thermal stability, it is used in the electron transport layer of organic electroluminescent device, can significantly improve the electron transport efficiency from electron transport layer to emitting layer, to improve luminous efficiency, while reducing drive voltage, prolong the service life of device.

Description

Technical Field

[0001] This invention relates to the field of organic light-emitting materials technology, specifically to a heteroatom-containing spirocyclic compound, its preparation method, and its applications. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are gradually coming into view as a new and promising display technology. An OLED is an electroluminescent device formed by a multilayer organic thin-film structure.

[0003] Organic light-emitting diodes (OLEDs) are self-emissive devices that utilize the principle that fluorescent materials emit light by recombination of holes injected from the anode and electrons injected from the cathode when an electric field is applied. They have the following structure: an anode, a cathode, and an organic material layer between them. To improve the efficiency and stability of OLEDs, the organic material layer typically comprises multiple layers of different materials, such as a hole injection layer (HIL), a hole transport layer (HTL), an emissive layer, an electron transport layer (ETL), and an electron injection layer (EIL). In such OLEDs, when a voltage is applied between the anode and cathode, holes from the anode and electrons from the cathode are injected into the organic material layer, and the resulting excitons migrate to the ground state, producing light with a specific wavelength. Currently, the electron transport materials used as electron transport layers typically contain nitrogen-containing heterocycles such as pyridine, pyrimidine, oxadiazole, triazole, and imidazole, as well as electron-withdrawing groups such as phosphoroxy groups, which have electron transport properties. As a key component of OLED structures, the electron transport layer also has a significant impact on device lifespan. For example, the mobility and band structure of the material determine the local electric field, carrier, and Joule heat distribution in and around the electron transport layer, thereby directly affecting the aging rate of organic materials and devices.

[0004] Research on organic electroluminescent materials has been widely carried out in academia and industry, but so far, stable and efficient organic layer materials for organic electrical components have not been fully developed, and the industrialization process of this technology still faces many key problems. Therefore, developing new materials has always been an urgent problem to be solved by those in the field. Summary of the Invention

[0005] The purpose of this invention is to provide a heteroatom-containing spirocyclic compound, its preparation method, and its application, in order to solve the problems mentioned in the background art.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] A heteroatom-containing spirocyclic compound, wherein the general structural formula of the heteroatom-containing spirocyclic compound is Formula 1:

[0008]

[0009] Wherein, n and m cannot both be 0;

[0010] X1-X3 are either C or N, and at least one of them is N;

[0011] L1 and L2 may be the same or different from each other, and are independently linked bonds, substituted or unsubstituted C6-C30 arylene groups, and substituted or unsubstituted C3-C30 heteroarylene groups;

[0012] R1, R2, R3, and R4 may be the same as or different from each other, and each may independently be hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, amino, silyl, or boroalkyl; substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C3-C30 cycloalkyl, or substituted or unsubstituted 3-30 heterocyclic alkyl, wherein the heteroatom is selected from oxygen, nitrogen, or sulfur; substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted 3-20 heteroaryl, wherein the heteroatom is selected from oxygen, nitrogen, or sulfur; substituted or unsubstituted 3-25 heteroarylamine, wherein the heteroatom is selected from oxygen, nitrogen, or sulfur; or substituted or unsubstituted C6-C60 arylamine.

[0013] Ar1 and Ar2 may be the same or different from each other, and each is independently a substituted or unsubstituted C6-C30 aryl or a substituted or unsubstituted 3-30 heteroaryl, the heteroatom of which is selected from oxygen, nitrogen, and sulfur.

[0014] As a further technical solution of the present invention, m and n are both 1.

[0015] As a further technical solution of the present invention, L1 and L2 may be the same or different from each other, and each is independently a linking bond, a substituted or unsubstituted C6-C18 arylene, or a substituted or unsubstituted C3-C10 heteroarylene.

[0016] R1-R4 may be the same or different from each other, and each may be independently hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, or amino; substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted 3-10 heterocyclic alkyl, wherein the heteroatom is selected from oxygen, nitrogen, or sulfur; substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted 3-10 heteroaryl, wherein the heteroatom is selected from oxygen, nitrogen, or sulfur;

[0017] Ar1 and Ar2 may be the same as or different from each other, and each is independently phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, fluorenyl, pyridyl, benzofuranyl, benzothiophene, dibenzofuranyl, dibenzothiophene, phenylnaphthyl or quinolinyl.

[0018] As a further technical solution of the present invention, the heteroatom-containing spirocyclic compound is selected from one of the following formulas 1-1 to 1-6:

[0019]

[0020] As a further technical solution of the present invention, the heteroatom-containing spirocyclic compound is selected from one of the following structural formulas 1-184:

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029] A method for preparing a spirocyclic compound containing heteroatoms includes the following steps:

[0030] Preparation of intermediate 1: raw material B was dissolved in THF, and after venting and cooling, n-BuLi was slowly added to react. Raw material A was added under nitrogen protection, and the temperature was slowly increased and stirred to prepare intermediate 1.

[0031] Preparation of intermediate 2: Intermediate 1 was dissolved in dichloromethane solution, boron trifluoride diethyl ether was added dropwise, stirred evenly, and the reaction was cooled to obtain intermediate 2;

[0032] Preparation of intermediate 3: Intermediate 2 and raw material C were added to a mixed solution of toluene, ethanol and water. After purging, palladium catalyst and potassium carbonate were added under nitrogen protection. The mixture was stirred evenly and heated to prepare intermediate 3.

[0033] Preparation of intermediate 4: Intermediate 3 was dissolved in carbon tetrachloride solution, BPO was added, NBS was slowly added, the mixture was stirred evenly, and the temperature was slowly increased to prepare intermediate 4.

[0034] Preparation of intermediate 5: Intermediate 4 and raw material D were added to a mixed solution of toluene, ethanol and water. After purging, palladium catalyst, phosphine ligand and cesium carbonate were added under nitrogen protection. The mixture was stirred evenly and heated to prepare intermediate 5.

[0035] Preparation of the finished product: Intermediate 5 and raw material E were added to a mixed solution of toluene, ethanol and water. After purging, palladium catalyst, phosphine ligand and cesium carbonate were added under nitrogen protection. The mixture was stirred evenly and heated to prepare a spirocyclic compound containing heteroatoms.

[0036] The structural formulas of the raw material AE are as follows: The structural formulas of intermediates 1-5 are as follows:

[0037]

[0038] As a further technical solution of the present invention, in the preparation of intermediate 1, raw material B is dissolved in THF, then the gas is purged three times, the temperature is lowered to -78°C, n-BuLi is slowly added, the reaction is carried out for 4 hours, raw material A is added under nitrogen protection, the temperature is slowly raised to 25°C, and the mixture is stirred for 12 hours. Then, distilled water is slowly added to the reaction solution to quench the reaction, and the reaction solution is extracted with DCM. The extracted organic layer is then dried with magnesium sulfate, and the solvent is removed using a rotary evaporator. The remaining substance is purified by column chromatography using a mixed solution of DCM and PE (volume ratio of 1:4) to obtain intermediate 1.

[0039] In the preparation of intermediate 2, intermediate 1 was dissolved in dichloromethane solution, stirred evenly, cooled to 0°C, and boron trifluoride diethyl ether was added dropwise. The reaction was carried out for 10 hours. After the reaction was completed, ethanol was added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM. Then, the extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was purified by column chromatography using a mixed solution of DCM and PE (volume ratio of 1:20) to obtain intermediate 2.

[0040] In the preparation of intermediate 3, intermediate 2 and raw material C toluene, ethanol and water were mixed in a solution, then vented three times, potassium carbonate and palladium catalyst were added under nitrogen protection, stirred until homogeneous, heated to 90°C and refluxed for 6 hours. After the reaction was completed, the temperature was slightly lowered, and the mixture was filtered with diatomaceous earth to remove salt and catalyst. The filtrate was cooled to room temperature and washed three times with water, retaining the organic phase. The aqueous phase was then extracted with ethyl acetate. The combined organic phases were dried with anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic compound. The solid organic compound was completely dissolved with a small amount of dichloromethane and then slowly added dropwise to a petroleum ether solution. After stirring until homogeneous, a precipitate formed. The precipitate was filtered to obtain a solid, which was washed successively with anhydrous ethanol and petroleum ether, and then dried to obtain intermediate 3.

[0041] In the preparation of intermediate 4, intermediate 3 is dissolved in carbon tetrachloride solution, BPO is added, NBS is slowly added, the mixture is stirred evenly, the temperature is slowly raised to 80°C, and the reaction is carried out for 8 hours. After the reaction is completed, the temperature is lowered to room temperature, and the solvent is removed from the reaction solution using a rotary evaporator. The remaining substance is purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (volume ratio of 1:6) to obtain intermediate 4.

[0042] In the preparation of intermediate 5, under nitrogen protection, intermediate 4 and starting material D were dissolved in toluene, ethanol, and aqueous solution. Cesium carbonate, phosphine ligand, and palladium catalyst were added, stirred until homogeneous, heated to 90°C, and refluxed for 6 hours. After the reaction was completed, the temperature was slightly lowered, and the mixture was filtered using diatomaceous earth to remove salts and catalyst. The filtrate was cooled to room temperature, washed three times with water, and the organic phase was retained. The aqueous phase was then extracted with ethyl acetate. The combined organic phases were dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substances were purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (volume ratio 4:1) to obtain intermediate 5. (When n=0, the target compound can be obtained at this step.)

[0043] In the preparation of the finished product, under nitrogen protection, intermediate 5 and raw material D are dissolved in toluene, ethanol, and aqueous solution. Cesium carbonate, palladium catalyst, and phosphine ligand are added, stirred until homogeneous, heated to 90°C, and refluxed for 6 hours. After the reaction is complete, the temperature is slightly lowered, and the mixture is filtered using diatomaceous earth to remove salts and catalyst. The filtrate is cooled to room temperature, washed three times with water, and the organic phase is retained. The aqueous phase is then extracted with ethyl acetate. The combined organic phases are dried using anhydrous magnesium sulfate, and the solvent is removed using a rotary evaporator. The remaining substance is purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (volume ratio 2:1) to obtain a spirocyclic compound containing heteroatoms. (When m and n are both non-zero, the target compound can be obtained at this step.)

[0044] Compared with the prior art, the beneficial effects of the present invention are: the provided heteroatom-containing spirocyclic organic electroluminescent compound has excellent electron transport performance and can be used as an electron transport material. By introducing a spirocyclic rigid structure, the compound has high electron injection and migration rates, as well as good film-forming properties and thermal stability. When used in the electron transport layer of an organic electroluminescent device, it can significantly improve the electron transport efficiency from the electron transport layer to the light-emitting layer, thereby improving the luminous efficiency, while reducing the driving voltage and extending the device lifespan. Attached Figure Description

[0045] Figure 1 The hydrogen nuclear magnetic resonance spectrum of the heteroatom-containing spirocyclic compound prepared in Example 1;

[0046] Figure 2 The 1H NMR spectrum of the heteroatom-containing spirocyclic compound prepared in Example 2 is shown. Detailed Implementation

[0047] A spirocyclic compound containing heteroatoms has the general structural formula shown in Formula 1 below:

[0048]

[0049] Wherein, n and m cannot both be 0;

[0050] X1-X3 are either C or N, and at least one of them is N;

[0051] L1 and L2 may be the same or different from each other, and are independently linked bonds, substituted or unsubstituted C6-C30 arylene groups, and substituted or unsubstituted C3-C30 heteroarylene groups;

[0052] R1, R2, R3, and R4 may be the same as or different from each other, and each may independently be hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, amino, silyl, or boroalkyl; substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C3-C30 cycloalkyl, or substituted or unsubstituted 3-30 heterocyclic alkyl, wherein the heteroatom is selected from oxygen, nitrogen, or sulfur; substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted 3-20 heteroaryl, wherein the heteroatom is selected from oxygen, nitrogen, or sulfur; substituted or unsubstituted 3-25 heteroarylamine, wherein the heteroatom is selected from oxygen, nitrogen, or sulfur; or substituted or unsubstituted C6-C60 arylamine.

[0053] Ar1 and Ar2 may be the same or different from each other, and each is independently a substituted or unsubstituted C6-C30 aryl or a substituted or unsubstituted 3-30 heteroaryl, the heteroatom of which is selected from oxygen, nitrogen, and sulfur.

[0054] Specifically, spirocyclic compounds containing heteroatoms are selected from one of the following structural formulas 1-184:

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063] A method for preparing a spirocyclic compound containing heteroatoms includes the following steps:

[0064] Preparation of intermediate 1: raw material B was dissolved in THF, and after venting and cooling, n-BuLi was slowly added to react. Raw material A was added under nitrogen protection, and the temperature was slowly increased and stirred to prepare intermediate 1.

[0065] Preparation of intermediate 2: Intermediate 1 was dissolved in dichloromethane solution, boron trifluoride diethyl ether was added dropwise, stirred evenly, and the reaction was cooled to obtain intermediate 2;

[0066] Preparation of intermediate 3: Intermediate 2 and raw material C were added to a mixed solution of toluene, ethanol and water. After purging, palladium catalyst and potassium carbonate were added under nitrogen protection. The mixture was stirred evenly and heated to prepare intermediate 3.

[0067] Preparation of intermediate 4: Intermediate 3 was dissolved in carbon tetrachloride solution, BPO was added, NBS was slowly added, the mixture was stirred evenly, and the temperature was slowly increased to prepare intermediate 4.

[0068] Preparation of intermediate 5: Intermediate 4 and raw material D were added to a mixed solution of toluene, ethanol and water. After purging, palladium catalyst, phosphine ligand and cesium carbonate were added under nitrogen protection. The mixture was stirred evenly and heated to prepare intermediate 5.

[0069] Preparation of the finished product: Intermediate 5 and raw material E were added to a mixed solution of toluene, ethanol and water. After purging, palladium catalyst, phosphine ligand and cesium carbonate were added under nitrogen protection. The mixture was stirred evenly and heated to prepare a spirocyclic compound containing heteroatoms.

[0070] The synthetic route of the above preparation method is as follows:

[0071] When n is 0

[0072]

[0073] When m and n are both not 0

[0074]

[0075] In the above formula, L1, L2, Ar1, Ar2, and R1-R4 are as defined above.

[0076] Example 1

[0077] The synthetic route for a spirocyclic compound containing heteroatoms is as follows:

[0078]

[0079] The specific preparation method is as follows:

[0080] Raw material B (40.00 mmol) was dissolved in THF, then the mixture was ventilated three times, cooled to -78°C, and n-BuLi was slowly added. The reaction was allowed to proceed for 4 h. Raw material A (40.00 mmol) was added under N2 protection, the temperature was slowly raised to 25°C, and the mixture was stirred for 12 h. Distilled water was then slowly added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM. The extracted organic layer was then dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was purified by column chromatography using a mixed solution of DCM and PE (volume ratio 1:4) to obtain intermediate 1 (11.40 g, yield 76.35%).

[0081] Intermediate 1 (30.50 mmol) was dissolved in dichloromethane solution, stirred until homogeneous, cooled to 0 °C, and boron trifluoride diethyl ether (30.50 mmol) was added dropwise. The reaction was allowed to proceed for 10 h. After the reaction was completed, ethanol was added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM. The extracted organic layer was then dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was purified by column chromatography using a mixed solution of DCM and PE (volume ratio 1:20) to obtain intermediate 2 (9.37 g, yield 86.45%).

[0082] Intermediate 2 (26.34 mmol) and starting material C (28.97 mmol) were added to a mixed solution of toluene, ethanol, and water. After purging three times, potassium carbonate (52.68 mmol) and tetraphenylphosphine palladium (0.52 mmol) were added under nitrogen protection. The mixture was stirred until homogeneous, heated to 90 °C, and refluxed for 6 h. After the reaction was completed, the temperature was slightly lowered, and the mixture was filtered with diatomaceous earth to remove salts and catalysts. The filtrate was cooled to room temperature and washed three times with water, retaining the organic phase. The aqueous phase was then extracted with ethyl acetate. The combined organic phases were dried with anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic compound. The solid organic compound was completely dissolved with a small amount of dichloromethane and then slowly added dropwise to a petroleum ether solution. After stirring until homogeneous, a precipitate formed. The precipitate was filtered to obtain a solid, which was washed successively with anhydrous ethanol and petroleum ether, and dried to obtain intermediate 3 (8.23 g, yield 79.84%).

[0083] Intermediate 3 (21.00 mmol) was dissolved in carbon tetrachloride solution, BPO (2.10 mmol) was added, NBS (42.00 mmol) was slowly added, the mixture was stirred until homogeneous, the temperature was slowly raised to 80 °C, and the reaction was carried out for 8 h. After the reaction was completed, the temperature was lowered to room temperature, and the solvent was removed from the reaction solution using a rotary evaporator. The remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (volume ratio of 1:6) to obtain intermediate 4 (4.79 g, 58.65%).

[0084] Under nitrogen protection, intermediate 4 (12.28 mmol) and starting material D (12.28 mmol) were dissolved in toluene, ethanol, and aqueous solution. Cesium carbonate (24.56 mmol), X-Phos (0.61 mmol), and palladium acetate (0.61 mmol) were added, stirred until homogeneous, heated to 90 °C, and refluxed for 6 h. After the reaction was completed, the temperature was slightly lowered, and the mixture was filtered with diatomaceous earth to remove salts and catalysts. The filtrate was cooled to room temperature, washed three times with water, and the organic phase was retained. The aqueous phase was then extracted with ethyl acetate. The combined organic phases were dried with anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (volume ratio 4:1) to obtain compound 2 (5.95 g, yield 82.65%, MW: 586.70).

[0085] The obtained compound-2 was analyzed, and its proton NMR spectrum is shown below. Figure 1 As shown, the specific results are as follows:

[0086] HPLC purity: >99.5%;

[0087] Mass spectrometry test: theoretical value 586.70; test value 586.43;

[0088] Elemental analysis:

[0089] The calculated values ​​are: C, 85.98; H, 4.47; N, 9.55.

[0090] The test values ​​are: C, 85.76; H, 4.71; N, 9.67.

[0091] Example 2

[0092] The synthetic route for a spirocyclic compound containing heteroatoms is as follows:

[0093]

[0094] The specific preparation method is as follows:

[0095] Raw material B (40.00 mmol) was dissolved in THF, then the mixture was ventilated three times, cooled to -78°C, and n-BuLi was slowly added. The reaction was allowed to proceed for 4 h. Raw material A (40.00 mmol) was added under N2 protection, the temperature was slowly raised to 25°C, and the mixture was stirred for 12 h. Distilled water was then slowly added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM. The extracted organic layer was then dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was purified by column chromatography using a mixed solution of DCM and PE (volume ratio 1:4) to obtain intermediate 1 (11.79 g, yield 78.96%).

[0096] Intermediate 1 (31.55 mmol) was dissolved in dichloromethane solution, stirred until homogeneous, cooled to 0 °C, and boron trifluoride diethyl ether (31.55 mmol) was added dropwise. The reaction was allowed to proceed for 10 h. After the reaction was completed, ethanol was added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM. The extracted organic layer was then dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was purified by column chromatography using a mixed solution of DCM and PE (volume ratio 1:20) to obtain intermediate 2 (9.88 g, yield 88.12%).

[0097] Intermediate 2 (27.77 mmol) and starting material C (30.54 mmol) were added to a mixed solution of toluene, ethanol, and water. After purging three times, potassium carbonate (55.54 mmol) and tetraphenylphosphine palladium (0.55 mmol) were added under nitrogen protection. The mixture was stirred until homogeneous, heated to 90 °C, and refluxed for 6 h. After the reaction was completed, the temperature was slightly lowered, and the mixture was filtered with diatomaceous earth to remove salts and catalysts. The filtrate was cooled to room temperature and washed three times with water, retaining the organic phase. The aqueous phase was then extracted with ethyl acetate. The combined organic phases were dried with anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic compound. The solid organic compound was completely dissolved with a small amount of dichloromethane and then slowly added dropwise to a petroleum ether solution. After stirring until homogeneous, a precipitate formed. The precipitate was filtered to obtain a solid, which was washed successively with anhydrous ethanol and petroleum ether, and dried to obtain intermediate 3 (8.32 g, yield 76.54%).

[0098] Intermediate 3 (21.22 mmol) was dissolved in carbon tetrachloride solution, BPO (2.12 mmol) was added, NBS (42.44 mmol) was slowly added, the mixture was stirred until homogeneous, the temperature was slowly raised to 80 °C, and the reaction was carried out for 8 h. After the reaction was completed, the temperature was lowered to room temperature, and the solvent was removed from the reaction solution using a rotary evaporator. The remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (volume ratio of 1:6) to obtain intermediate 4 (4.61 g, 55.79%).

[0099] Under nitrogen protection, intermediate 4 (11.82 mmol) and starting material D (11.82 mmol) were dissolved in toluene, ethanol, and aqueous solution. Cesium carbonate (23.64 mmol), X-Phos (0.59 mmol), and palladium acetate (0.59 mmol) were added, stirred until homogeneous, heated to 90 °C, and refluxed for 6 h. After the reaction was completed, the temperature was slightly lowered, and the mixture was filtered with diatomaceous earth to remove salts and catalysts. The filtrate was cooled to room temperature and washed three times with water, retaining the organic phase. The aqueous phase was then extracted with ethyl acetate. The combined organic phases were dried with anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (volume ratio 4:1) to obtain compound 22 (6.47 g, yield 82.54%, MW: 663.78).

[0100] The obtained compound -22 was analyzed, and its proton NMR spectrum is shown below. Figure 2 As shown, the specific results are as follows:

[0101] HPLC purity: >99.7%;

[0102] Mass spectrometry test: theoretical value 663.78; test value 664.06;

[0103] Elemental analysis:

[0104] Calculated values ​​are: C, 85.05; H, 4.40; N, 10.55.

[0105] The test values ​​were: C, 84.76; H, 4.72; N, 10.74.

[0106] Example 3

[0107] The synthetic route for a spirocyclic compound containing heteroatoms is as follows:

[0108]

[0109] The specific preparation method is as follows:

[0110] Raw material B (40.00 mmol) was dissolved in THF, then the mixture was ventilated three times, cooled to -78°C, and n-BuLi was slowly added. The reaction was allowed to proceed for 4 h. Raw material A (40.00 mmol) was added under N2 protection, the temperature was slowly raised to 25°C, and the mixture was stirred for 12 h. Distilled water was then slowly added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM. The extracted organic layer was then dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was purified by column chromatography using a mixed solution of DCM and PE (volume ratio 1:4) to obtain intermediate 1 (11.81 g, yield 79.06%).

[0111] Intermediate 1 (31.60 mmol) was dissolved in dichloromethane solution, stirred until homogeneous, cooled to 0 °C, and boron trifluoride diethyl ether (31.60 mmol) was added dropwise. The reaction was allowed to proceed for 10 h. After the reaction was completed, ethanol was added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM. The extracted organic layer was then dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was purified by column chromatography using a mixed solution of DCM and PE (volume ratio 1:20) to obtain intermediate 2 (9.51 g, yield 84.75%).

[0112] Intermediate 2 (26.73 mmol) and starting material C (29.40 mmol) were added to a mixed solution of toluene, ethanol, and water. After purging three times, potassium carbonate (53.46 mmol) and tetraphenylphosphine palladium (0.53 mmol) were added under nitrogen protection. The mixture was stirred until homogeneous, heated to 90 °C, and refluxed for 6 h. After the reaction was completed, the temperature was slightly lowered, and the mixture was filtered with diatomaceous earth to remove salts and catalysts. The filtrate was cooled to room temperature and washed three times with water, retaining the organic phase. The aqueous phase was then extracted with ethyl acetate. The combined organic phases were dried with anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic compound. The solid organic compound was completely dissolved with a small amount of dichloromethane and then slowly added dropwise to a petroleum ether solution. After stirring until homogeneous, a precipitate formed. The precipitate was filtered to obtain a solid, which was washed successively with anhydrous ethanol and petroleum ether, and dried to obtain intermediate 3 (8.01 g, yield 76.51%).

[0113] Intermediate 3 (20.43 mmol) was dissolved in carbon tetrachloride solution, BPO (2.04 mmol) was added, NBS (40.86 mmol) was slowly added, the mixture was stirred until homogeneous, the temperature was slowly raised to 80 °C, and the reaction was carried out for 8 h. After the reaction was completed, the temperature was lowered to room temperature, and the solvent was removed from the reaction solution using a rotary evaporator. The remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (volume ratio of 1:6) to obtain intermediate 4 (4.48 g, 56.39%).

[0114] Under nitrogen protection, intermediate 4 (11.49 mmol) and starting material D (11.49 mmol) were dissolved in toluene, ethanol, and aqueous solution. Cesium carbonate (22.98 mmol), X-Phos (0.57 mmol), and palladium acetate (0.57 mmol) were added, stirred until homogeneous, heated to 90 °C, and refluxed for 6 h. After the reaction was completed, the temperature was slightly lowered, and the mixture was filtered with diatomaceous earth to remove salts and catalysts. The filtrate was cooled to room temperature and washed three times with water, retaining the organic phase. The aqueous phase was then extracted with ethyl acetate. The combined organic phases were dried with anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (volume ratio 4:1) to obtain compound 83 (6.54 g, yield 86.15%, MW: 661.77).

[0115] The obtained compound -83 was analyzed, and the results are as follows:

[0116] HPLC purity: >99.5%;

[0117] Mass spectrometry test: theoretical value 661.77; test value 661.52;

[0118] Elemental analysis:

[0119] Calculated values ​​are: C, 85.30; H, 4.11; N, 10.58;

[0120] The test values ​​were: C, 85.02; H, 4.36; N, 10.81.

[0121] Example 4

[0122] The synthetic route for a spirocyclic compound containing heteroatoms is as follows:

[0123]

[0124] The specific preparation method is as follows:

[0125] Raw material B (40.00 mmol) was dissolved in THF, then ventilated three times, cooled to -78°C, and n-BuLi was slowly added. The reaction was allowed to proceed for 4 h. Raw material A (40.00 mmol) was added under N2 protection, the temperature was slowly raised to 25°C, and the mixture was stirred for 12 h. Distilled water was then slowly added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM. The extracted organic layer was then dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was purified by column chromatography using a mixed solution of DCM and PE (volume ratio 1:4) to obtain intermediate 1 (11.53 g, yield 77.18%).

[0126] Intermediate 1 (30.85 mmol) was dissolved in dichloromethane solution, stirred until homogeneous, cooled to 0 °C, and boron trifluoride diethyl ether (30.85 mmol) was added dropwise. The reaction was allowed to proceed for 10 h. After the reaction was completed, ethanol was added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM. The extracted organic layer was then dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was purified by column chromatography using a mixed solution of DCM and PE (volume ratio 1:20) to obtain intermediate 2 (9.24 g, yield 84.28%).

[0127] Intermediate 2 (25.97 mmol) and starting material C (28.56 mmol) were added to a mixed solution of toluene, ethanol, and water. After purging three times, potassium carbonate (51.94 mmol) and tetraphenylphosphine palladium (0.51 mmol) were added under nitrogen protection. The mixture was stirred until homogeneous, heated to 90 °C, and refluxed for 6 h. After the reaction was completed, the temperature was slightly lowered, and the mixture was filtered with diatomaceous earth to remove salts and catalysts. The filtrate was cooled to room temperature and washed three times with water, retaining the organic phase. The aqueous phase was then extracted with ethyl acetate. The combined organic phases were dried with anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic compound. The solid organic compound was completely dissolved with a small amount of dichloromethane and then slowly added dropwise to a petroleum ether solution. After stirring until homogeneous, a precipitate formed. The precipitate was filtered to obtain a solid, which was washed successively with anhydrous ethanol and petroleum ether, and dried to obtain intermediate 3 (7.84 g, yield 77.14%).

[0128] Intermediate 3 (20.00 mmol) was dissolved in carbon tetrachloride solution, BPO (2.00 mmol) was added, NBS (40.00 mmol) was slowly added, the mixture was stirred until homogeneous, the temperature was slowly raised to 80 °C, and the reaction was carried out for 8 h. After the reaction was completed, the temperature was lowered to room temperature, and the solvent was removed from the reaction solution using a rotary evaporator. The remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (volume ratio of 1:6) to obtain intermediate 4 (4.64 g, 59.67%).

[0129] Under nitrogen protection, intermediate 4 (11.90 mmol) and starting material D (11.90 mmol) were dissolved in toluene, ethanol, and aqueous solution. Cesium carbonate (23.80 mmol), X-Phos (0.59 mmol), and palladium acetate (0.59 mmol) were added, stirred until homogeneous, heated to 90 °C, and refluxed for 6 h. After the reaction was completed, the temperature was slightly lowered, and the mixture was filtered with diatomaceous earth to remove salts and catalysts. The filtrate was cooled to room temperature and washed three times with water, retaining the organic phase. The aqueous phase was then extracted with ethyl acetate. The combined organic phases were dried with anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (volume ratio 4:1) to obtain compound 159 (6.56 g, yield 79.64%, MW: 692.84).

[0130] The obtained compound -159 was analyzed, and the results are as follows:

[0131] HPLC purity: >99.5%;

[0132] Mass spectrometry test: theoretical value 692.84; test value 693.18;

[0133] Elemental analysis:

[0134] The calculated values ​​are: C, 83.21; H, 4.07; N, 8.09; S, 4.63.

[0135] The test values ​​are: C, 82.96; H, 4.42; N, 8.21; S, 4.49.

[0136] The synthesis methods for other compounds are the same as those in the above examples, and will not be described in detail here. The mass spectra, molecular formulas, and yields of other compounds are shown in Table 1 below:

[0137] Table 1. Mass spectra, molecular formulas, and yields of synthetic examples.

[0138] compound Molecular formula Mass spectrometry calculated values Mass spectrometry test values Yield (%) Example 1 <![CDATA[C 42 H 26 N4]]> 586.70 586.43 82.65 Example 2 <![CDATA[C 47 H 29 N5]]> 663.78 664.06 82.54 Example 3 <![CDATA[C 47 H 27 N5]]> 661.77 661.52 86.15 Example 4 <![CDATA[C 48 H 28 N4S]]> 692.84 693.18 79.64 Compound 3 <![CDATA[C 42 H 26 N4]]> 586.70 586.51 81.25 Compound 5 <![CDATA[C 48 H 30 N4]]> 662.80 662.43 80.59 Compound 8 <![CDATA[C 48 H 30 N4]]> 662.80 662.52 79.34 Compound 19 <![CDATA[C 59 H 37 N5]]> 815.98 816.22 81.49 Compound 21 <![CDATA[C 54 H 34 N4]]> 738.89 738.64 80.27 Compound 30 <![CDATA[C 70 H 44 N4]]> 941.15 941.53 82.64 Compound 42 <![CDATA[C 50 H 30 N4]]> 686.82 686.45 80.25 Compound 48 <![CDATA[C 53 H 31 N5]]> 737.91 737.68 81.27 Compound 65 <![CDATA[C 49 H 29 N5]]> 687.81 688.04 81.67 Compound 72 <![CDATA[C 49 H 29 N5]]> 687.81 687.67 79.89 Compound 77 <![CDATA[C 59 H 35 N5]]> 813.96 814.26 80.88 Compound 81 <![CDATA[C 55 H 33 N5]]> 763.90 763.67 79.39 Compound 91 <![CDATA[C 62 H 38 N2O]]> 827.00 826.84 81.61 Compound 94 <![CDATA[C 55 H 35 N3]]> 737.91 737.58 80.66 Compound 107 <![CDATA[C 59 H 37 N5]]> 815.98 815.65 69.71 Compound 111 <![CDATA[C 52 H 32 N4S]]> 744.92 744.68 81.54 Compound 126 <![CDATA[C 67 H 41 N3]]> 888.09 888.26 70.88 Compound 131 <![CDATA[C 66 H 42 N2]]> 863.08 863.34 78.97 Compound 134 <![CDATA[C 51 H 34 N4]]> 702.86 702.59 81.26 Compound 146 <![CDATA[C 53 H 35 N5]]> 739.88 739.61 80.13 Compound 148 <![CDATA[C 52 H 32 N5]]> 712.86 713.05 81.26 Compound 156 <![CDATA[C 54 H 34 N4]]> 738.89 738.62 81.05 Compound 171 <![CDATA[C 53 H 33 N3]]> 711.87 711.49 79.86

[0139] Application Example 1

[0140] An organic electroluminescent device is fabricated using the following method:

[0141] a. ITO anode: The ITO (indium tin oxide)-Ag-ITO (indium tin oxide) glass substrate with a coating thickness of 150nm is cleaned twice in distilled water and ultrasonically washed for 30 minutes. Then it is cleaned twice more in distilled water and ultrasonically washed for 10 minutes. After washing, it is transferred to a spin dryer for spin drying. Finally, it is baked in a vacuum oven at 220℃ for 2 hours. After baking, it is cooled down and ready for use. Using this substrate as the anode, the device process is carried out by vapor deposition machine, and other functional layers are sequentially vapor deposited on it.

[0142] b. HIL (Hole Injection Layer): The evaporation rate of the vacuum evaporation hole injection layer material HT-1 and P-dopant is as follows; the evaporation rate ratio of HT-1 and P-dopant is 97:3, and the thickness is 10nm.

[0143] c. HTL (Hole Transport Layer): At a certain evaporation rate, HT-1 of 130 nm was vacuum-deposited on the hole injection layer as a hole transport layer, and the structure is shown in the figure.

[0144] d. Light-emitting auxiliary layer: with At a certain evaporation rate, a 10nm EBL-1 layer was vacuum-deposited on the hole transport layer as a light-emitting auxiliary layer.

[0145] e. EML (Emitting Layer): Then, on the above-mentioned emitting auxiliary layer, with... The evaporation rate is such that a host material and a dopant material with a thickness of 20 nm are vacuum-evaporated as the light-emitting layer. The chemical formulas of the host and the dopant are shown below, and the evaporation rate ratio of the host to the dopant is 98:2.

[0146] f. HBL (Hole Blocking Layer): At a certain evaporation rate, a 5nm HB-1 layer was vacuum-deposited on the light-emitting layer as a hole-blocking layer, as shown in the figure:

[0147] g. ETL (Electron Transport Layer): The above-described embodiment provides compound 2 as an electron transport layer by vacuum evaporating 30 nm onto the hole blocking layer at a evaporation rate.

[0148] h, EIL (Electron Injection Layer): with The evaporation rate was such that a Yb film layer of 1.0 nm was deposited to form an electron injection layer.

[0149] i. Cathode: with The evaporation rate ratio of magnesium and silver at 18nm was 1:9, resulting in an OLED device.

[0150] j. Optical extraction layer: with The evaporation rate was used to vacuum evaporate a 70nm thick CPL-1 layer on the cathode as a light extraction layer. The evaporated substrate was then encapsulated. First, the cleaned cover plate was coated with UV adhesive using a coating equipment. Then, the coated cover plate was moved to the pressing section, and the evaporated substrate was placed on the top of the cover plate. Finally, the substrate and cover plate were bonded together using a bonding equipment, while the UV adhesive was cured by light.

[0151] The structural formulas of the materials used in the above method are shown below:

[0152]

[0153] Application Example 2-50

[0154] In Application Examples 2-50, following the method described above, compound 2 used in Application Example 1 was replaced with compounds 3, 5, 8, 10, 16, 19, 21, 22, 26, 29, 30, 32, 38, 42, 46, 48, 52, 56, 59, 61, 65, 69, 72, 75, 77, 81, 83, 88, 91, 94, 107, 111, 115, 119, 124, 126, 129, 131, 134, 136, 146, 148, 156, 159, 161, 164, 167, 171, and 180 as electron transport layers to prepare corresponding organic electroluminescent devices.

[0155] Comparative Examples 1-2

[0156] Comparative Example 1 provides an organic electroluminescent device. The only difference between this organic electroluminescent device and Device Example 1 is that the organic electroluminescent device is prepared by evaporation using existing comparative compounds a and b instead of the electron transport layer (compound 1) in Device Example 1. The chemical structural formulas of comparative compounds a and b are as follows:

[0157]

[0158] The driving voltage, luminous efficiency, BI value, and lifetime of the organic electroluminescent devices obtained in Examples 1-50 and Comparative Examples 1-2 were characterized at a brightness of 1000 nits. The test results are shown in Table 2 below:

[0159] Table 2 Device Test Results

[0160]

[0161]

[0162]

[0163] As shown in Table 2 above, the organic electroluminescent device prepared by using the organic electroluminescent compound provided by the present invention as the electron transport layer has a lower start-up voltage and significantly improved luminous efficiency and lifetime compared with the organic electroluminescent device prepared by using compounds a and b as the electron transport layer.

[0164] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A spirocyclic compound containing heteroatoms, characterized in that, The general structural formula of the heteroatom-containing spirocyclic compounds is Formula 1: Where n is 0 or 1, m is 0 or 1, and n and m cannot be 0 at the same time; X1-X3 are either C or N, and at least one of them is N; The L1 and L2 may be the same or different from each other, and each is independently a linker, an unsubstituted C6-C18 aryl group; R1, R2, R3, and R4 may be the same as or different from each other, and each is independently hydrogen. Ar1 and Ar2 may be the same or different from each other, and each is independently a substituted or unsubstituted C6-C30 aryl or a substituted or unsubstituted 3-30 heteroaryl, wherein the heteroatom is selected from oxygen, nitrogen, or sulfur; the substituted substituent is cyano.

2. The heteroatom-containing spirocyclic compound according to claim 1, characterized in that, Both m and n are 1.

3. The heteroatom-containing spirocyclic compound according to claim 2, characterized in that, Ar1 and Ar2 may be the same as or different from each other, and each is independently phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, fluorenyl, pyridyl, benzofuranyl, benzothiophene, dibenzofuranyl, dibenzothiophene, phenylnaphthyl or quinolinyl.

4. The heteroatom-containing spirocyclic compound according to claim 1, characterized in that, The heteroatom-containing spirocyclic compounds are selected from one of the following formulas 1-1 to 1-6:

5. The heteroatom-containing spirocyclic compound according to claim 1, characterized in that, The heteroatom-containing spirocyclic compounds are selected from one of the following structural formulas 1-184:

6. A method for preparing a heteroatom-containing spirocyclic compound as described in any one of claims 1-5, comprising the following steps: Preparation of intermediate 1: raw material B was dissolved in THF, and after venting and cooling, n-BuLi was slowly added to react. Raw material A was added under nitrogen protection, and the temperature was slowly increased and stirred to prepare intermediate 1. Preparation of intermediate 2: Intermediate 1 was dissolved in dichloromethane solution, boron trifluoride diethyl ether was added dropwise, stirred evenly, and the reaction was cooled to obtain intermediate 2; Preparation of intermediate 3: Intermediate 2 and raw material C were added to a mixed solution of toluene, ethanol and water. After purging, palladium catalyst and potassium carbonate were added under nitrogen protection. The mixture was stirred evenly and heated to prepare intermediate 3. Preparation of intermediate 4: Intermediate 3 was dissolved in carbon tetrachloride solution, BPO was added, NBS was slowly added, the mixture was stirred evenly, and the temperature was slowly increased to prepare intermediate 4. Preparation of intermediate 5: Intermediate 4 and raw material D were added to a mixed solution of toluene, ethanol and water. After purging, palladium catalyst, phosphine ligand and cesium carbonate were added under nitrogen protection. The mixture was stirred evenly and heated to prepare intermediate 5. Preparation of the finished product: Intermediate 5 and raw material E were added to a mixed solution of toluene, ethanol and water. After purging, palladium catalyst, phosphine ligand and cesium carbonate were added under nitrogen protection. The mixture was stirred evenly and heated to prepare a spirocyclic compound containing heteroatoms. in, The structural formulas of the raw material AE are as follows: The structural formulas of intermediates 1-5 are as follows: In the above formula, L1, L2, Ar1, Ar2, R1-R4, m, and n are defined as described in any one of claims 1-5.

7. The method for preparing the heteroatom-containing spirocyclic compound according to claim 6, characterized in that, In the preparation of intermediate 1, raw material B was dissolved in THF, then the mixture was ventilated three times, cooled to -78°C, and n-BuLi was slowly added. The reaction was carried out for 4 hours. Raw material A was added under nitrogen protection, the temperature was slowly raised to 25°C, and the mixture was stirred for 12 hours. Then, distilled water was slowly added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM. The extracted organic layer was then dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was purified by column chromatography using a mixed solution of DCM and PE at a volume ratio of 1:4 to obtain intermediate 1. In the preparation of intermediate 2, intermediate 1 was dissolved in dichloromethane solution, stirred evenly, cooled to 0°C, and boron trifluoride diethyl ether was added dropwise. The reaction was carried out for 10 hours. After the reaction was completed, ethanol was added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM. Then, the extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was purified by column chromatography using a mixed solution of DCM and PE at a volume ratio of 1:20 to obtain intermediate 2. In the preparation of intermediate 3, intermediate 2 and raw material C toluene, ethanol and water were mixed in a solution, then purged three times, potassium carbonate and palladium catalyst were added under nitrogen protection, stirred evenly, heated to 90°C and refluxed for 6 hours; after the reaction was completed, the temperature was slightly lowered, and the solution was filtered with diatomaceous earth to remove salt and catalyst. After the filtrate was cooled to room temperature, it was washed three times with water, and the organic phase was retained. Then the aqueous phase was extracted with ethyl acetate; after the organic phases were combined, they were dried with anhydrous magnesium sulfate and the solvent was removed using a rotary evaporator to obtain a solid organic compound; the solid organic compound was completely dissolved with a small amount of dichloromethane, and then slowly added dropwise to a petroleum ether solution, stirred evenly, and a precipitate was formed. The precipitate was filtered to obtain a solid, which was washed successively with anhydrous ethanol and petroleum ether, and dried to obtain intermediate 3; In the preparation of intermediate 4, intermediate 3 is dissolved in carbon tetrachloride solution, BPO is added, NBS is slowly added, the mixture is stirred evenly, the temperature is slowly raised to 80°C, and the reaction is carried out for 8 hours. After the reaction is completed, the temperature is lowered to room temperature, and the solvent is removed from the reaction solution using a rotary evaporator. The remaining substance is purified by column chromatography using a mixed solution of dichloromethane and petroleum ether with a volume ratio of 1:6 to obtain intermediate 4. In the preparation of intermediate 5, under nitrogen protection, intermediate 4 and raw material D were dissolved in toluene, ethanol, and aqueous solution. Cesium carbonate, phosphine ligand, and palladium catalyst were added, stirred until homogeneous, heated to 90°C, and refluxed for 6 hours. After the reaction was completed, the temperature was slightly lowered, and the mixture was filtered with diatomaceous earth to remove salts and catalyst. The filtrate was cooled to room temperature, washed three times with water, and the organic phase was retained. The aqueous phase was then extracted with ethyl acetate. The combined organic phases were dried with anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substances were purified by column chromatography using a 4:1 volume ratio of dichloromethane and petroleum ether to obtain intermediate 5. In the preparation of the finished product, under nitrogen protection, intermediate 5 and raw material D were dissolved in toluene, ethanol and aqueous solution, cesium carbonate, palladium catalyst and phosphine ligand were added, stirred evenly, heated to 90°C and refluxed for 6 hours; after the reaction was completed, the temperature was slightly lowered, and the mixture was filtered with diatomaceous earth to remove salt and catalyst. After the filtrate was cooled to room temperature, it was washed three times with water, and the organic phase was retained. Then the aqueous phase was extracted with ethyl acetate; after combining the organic phases, the mixture was dried with anhydrous magnesium sulfate and the solvent was removed using a rotary evaporator; the remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether with a volume ratio of 2:1 to obtain a spirocyclic compound containing heteroatoms.

8. The use of the heteroatom-containing spirocyclic compounds according to any one of claims 1-5 in the preparation of organic electroluminescent devices.

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