Hydro-naphtho perylene compound, organic electroluminescent device and display device

Abstract

The invention provides a hydrogenated naphtho perylene compound, an organic electroluminescent device and a display device. The hydronaphthalene perylene compound has a structure as shown in a formula BDI, and the intermediate is used for preparing the hydronaphthalene perylene compound. The hydronaphthalene perylene compound provided by the invention can be used as a luminescent layer doping material, and the prepared organic electroluminescent device has relatively low driving voltage, relatively high current efficiency and relatively long service life.

Description

[0001] This application is a divisional application of patent application number 202210729312.0 (the original application was filed on June 24, 2022, and the invention was entitled "A Hydrogenated Naphthobenzyl Compound, an Organic Electroluminescent Device and a Display Device"). Technical Field

[0002] This invention belongs to the field of organic electroluminescent materials technology, specifically relating to a hydrogenated naphthoperylene compound, an organic electroluminescent device, and a display device. Background Technology

[0003] With the rapid development of science and technology, information technology, people have put forward new goals and requirements for the performance of information display systems. High brightness, high resolution, wide viewing angle, and low energy consumption have become research hotspots for displays. Organic light-emitting diode (OLED) display technology can meet these needs, while also possessing other advantages such as a wide operating temperature range and the ability to achieve flexible displays. Therefore, following CRT (cathode ray tube) displays, LCD (liquid crystal display), and PDP (plasma display) flat panel displays, it has become the new favorite of the next generation of flat panel displays. Currently, organic light-emitting diode (OLED) display technology has been applied in smartphones, tablets, and other fields, and is expanding into large-size application areas such as televisions.

[0004] Over the past 30 years, the design of different organic light-emitting diode (OLED) structures, the optimization of their lifetime, efficiency, and other performance characteristics, and the development of various high-performance OLED materials have attracted widespread attention and research. There is an urgent need in this field to develop more diverse and higher-performance materials to meet the increasingly demanding requirements for OLED devices. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a hydrogenated naphthoperylene compound, an organic electroluminescent device, and a display device. The present invention designs the structure of the hydrogenated naphthoperylene compound to make it suitable as a dopant material for the light-emitting layer, thereby producing an organic electroluminescent device with lower driving voltage, higher current efficiency, and longer lifespan.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a hydrogenated naphthoperylene compound having a structure as shown in formula BDI:

[0008] BDI (Body-Induced Difference)

[0009] Among them, Ar 101 Ar 102 Ar201 Ar 202 Each is independently selected from any one of substituted or unsubstituted C6-C40 aryl groups or substituted or unsubstituted C12-C20 heteroaryl groups;

[0010] R 101 and R 102 Each is independently selected from any one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C40 aryl, or substituted or unsubstituted C12-C20 heteroaryl;

[0011] R 101 and R 102 They can be connected in a ring using a single key;

[0012] m and n are each independently selected from 0 or 1, and m and n are not both 0 at the same time;

[0013] Ar 101 Ar 102 Ar 201 Ar 202 R 101 and R 102 The substituents described herein are each independently selected from any one or a combination of at least two of -D, -F, -CN, C1~C12 alkyl, C1~C6 alkoxy, C2~C8 alkenyl, C6~C15 aryl, and C12~C20 heteroaryl.

[0014] In this invention, by designing the structure of hydrogenated naphthoperylene compounds, they can be used as doping materials for the light-emitting layer. The resulting organic electroluminescent devices have lower driving voltage, higher current efficiency, and longer lifespan.

[0015] In this invention, Ar 101 Ar 102 Ar 201 Ar 202 Each is independently selected from any one of substituted or unsubstituted C6~C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.) aryl or substituted or unsubstituted C12~C20 (e.g., C12, C14, C16, C18 or C20, etc.) heteroaryl.

[0016] R 101 and R 102Each is independently selected from any one of the following: substituted or unsubstituted C1-C12 (e.g., C1, C2, C4, C6, C10, or C12); substituted or unsubstituted C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40); or substituted or unsubstituted C12-C20 (e.g., C12, C14, C16, C18, or C20).

[0017] Ar 101 Ar 102 Ar 201 Ar 202 R 101 and R 102 The substituents described herein are each independently selected from any one or a combination of at least two of the following: -D (deuterium atom), -F, -CN, C1~C12 (e.g., C1, C2, C4, C6, C10 or C12), C1~C6 (e.g., C1, C2, C3, C4, C5 or C6), C2~C8 (e.g., C2, C4, C6 or 8), C6~C15 (e.g., C6, C7, C8, C10, C12 or C15), and C12~C20 (e.g., C12, C14, C16, C18 or C20).

[0018] It should be noted that when m is 0, the hydrogenated naphthoperylene compounds represented by the formula BDI do not have... When n is 0, the hydrogenated naphthoperylene compounds represented by formula BDI do not have a group. Group (dashed lines indicate connection sites, the same below).

[0019] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0020] As a preferred embodiment of the present invention, the C6-C40 aryl group is selected from any one of phenyl, diphenyl, terphenyl, naphthyl, anthracene, phenanthrene, fluorenyl, benzo[a]fluorenyl, dibenzo[a]fluorenyl, naphthyl, pyrene, perylene, spirofluorenyl, triphenylene, fluoranyl, hydrogenated benzo[a]anthrayl, ind[a]fluorenyl, benzo[a]ind[a]fluorenyl, dibenzo[a]ind[a]fluorenyl, naphthyl, or benzo[a]naphthylfluorenyl.

[0021] Preferably, the C6-C40 aryl group is selected from any one of phenyl, naphthyl, diphenyl, triphenyl, fluoranthyl, fluorenyl, 9,10-diphenylanthryl or benzofluorenyl.

[0022] Preferably, the C12-C20 heteroaryl group is selected from any one of dibenzofuranyl, dibenzothiophenyl, naphthobenzofuranyl, naphthobenzothiophenyl, dinaphthofuranyl, and dinaphthothiophenyl.

[0023] As a preferred embodiment of the present invention, the C1-C12 alkyl group is selected from any one of methyl, ethyl, propyl, butyl, adamantyl, 1-methylcyclohexyl, 1-methylcyclopentyl, cyclopentyl or cyclohexyl.

[0024] Preferably, the C1-C6 alkoxy group is selected from methoxy, ethoxy, propoxy, butoxy, or... Any of the following, with dashed lines representing connection points.

[0025] Preferably, the C6-C15 aryl group is selected from any one of phenyl, naphthyl, or diphenyl.

[0026] As a preferred technical solution of the present invention, the Ar 101 and Ar 102 Each group is independently selected from any one of the following groups, whether substituted or unsubstituted: phenyl, naphthyl, diphenyl, triphenyl, fluoranyl, fluorenyl, 9,10-diphenylanthryl, benzofluorenyl, dibenzofuranyl, dibenzothiophenyl, naphthobenzofuranyl or naphthobenzothiophenyl;

[0027] The substituents are selected from -D, -F, -CN, phenyl, biphenyl, dibenzofuranyl, methyl, deuterated methyl, adamantyl, tert-butyl, 1-methylcyclopentyl, cyclohexyl, cyclopentyl, methoxy, etc. The dashed line represents the connection site, which is any one or a combination of at least two of the following: naphthyl, dibenzothiophene, and naphthobenzothiophene.

[0028] As a preferred technical solution of the present invention, the Ar 201 and Ar 202 Each group is independently selected from any one of the following groups, whether substituted or unsubstituted: phenyl, naphthyl, dibenzofuranyl or diphenyl;

[0029] The substituents are selected from any one or a combination of at least two of methyl, methoxy, phenyl, or dibenzofuranyl.

[0030] Preferably, R 101 and R 102 Each is independently selected from any one of methyl, ethyl, propyl, or phenyl.

[0031] Preferably, R 101 and R 102 same.

[0032] As a preferred embodiment of the present invention, the hydrogenated naphthoperylene compound is selected from any one of the following compounds:

[0033] .

[0034] Preferably, the hydrogenated naphthoperylene compound is selected from any one of the following compounds:

[0035] .

[0036] In this invention, the intermediate for preparing the above-mentioned hydrogenated naphthoperylene compounds is prepared by any one of the following methods:

[0037] ;

[0038] ;

[0039] ;

[0040] ;

[0041]

[0042] R is selected from C1~C6 alkyl (e.g., methyl, ethyl, propyl, cyclopentyl, cyclohexyl, etc.) or C6~C12 aryl (e.g., phenyl, naphthyl, or diphenyl, etc.);

[0043] X and Y are each independently selected from Cl, Br, or I;

[0044] R 101 It has the same scope of protection as the first aspect;

[0045] Ring A represents a carbon ring of C5 to C7 (e.g., C5, C6, or C7), and p is selected from 4, 5, or 6.

[0046] When hydronphthalene compounds Groups and When the functional groups are the same (dashed lines indicate connection sites, the same below), the preparation methods of hydrogenated naphthoperylene compounds are as follows:

[0047] .

[0048] When hydronphthalene compounds Groups and When the functional groups are different (dashed lines indicate connection sites, the same below), the preparation methods of hydrogenated naphthoperylene compounds are as follows:

[0049] ;

[0050] Where X is selected from I, Y is selected from Cl or Br; where X is selected from Br, Y is selected from Cl.

[0051] Or in hydronaphthobenzyl compounds Groups and When the functional groups are different (dashed lines indicate connection sites, the same below), the preparation methods of hydrogenated naphthoperylene compounds are as follows:

[0052] ;

[0053] When Y is selected from I, X is selected from Cl or Br; when Y is selected from Br, X is selected from Cl.

[0054] In a second aspect, the present invention provides an organic electroluminescent device, the organic electroluminescent device comprising an anode, a cathode, and an organic thin film layer disposed between the anode and the cathode;

[0055] The material of the organic thin film layer includes hydrogenated naphthoperylene compounds as described in the first aspect.

[0056] As a preferred embodiment of the present invention, the organic thin film layer includes a light-emitting layer, and the material of the light-emitting layer includes hydrogenated naphthoperylene compounds as described in the first aspect.

[0057] As a preferred embodiment of the present invention, the material of the light-emitting layer includes a doped material, which includes hydrogenated naphthoperylene compounds as described in the first aspect.

[0058] Thirdly, the present invention provides a display device comprising the organic electroluminescent device as described in the second aspect.

[0059] Compared with the prior art, the present invention has the following beneficial effects:

[0060] This invention designs the structure of hydrogenated naphthoperylene compounds, which can be used as doping materials for the light-emitting layer. The organic electroluminescent devices prepared in this way have low driving voltage, high current efficiency and long service life. Detailed Implementation

[0061] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0062] Preparation Example 1

[0063] This preparation example provides the intermediate N1-Me and its synthesis method, the synthesis process is as follows:

[0064]

[0065] (1) Synthesis of 1-bromo-8-chloro-2-methylnaphthalene

[0066] In a 500 mL three-necked flask equipped with an acidic gas absorption device, 300 mL of dichloromethane, 17.7 g of 1-chloro-7-methylnaphthalene, and 0.2 g of iron powder were added. The temperature was lowered to 0-5 °C, and a dichloromethane solution (30 mL) containing 18 g of liquid bromine was slowly added dropwise. After the addition was complete, the mixture was reacted at 0-5 °C for 2 hours, then heated to 10-15 °C for 2 hours, and then heated to 20-25 °C for 4 hours. After the reaction was completed, water was added to separate the organic layer, and the organic layer was washed with water and sodium bisulfite aqueous solution. The mixture was then washed with water until neutral, concentrated to dryness, and then distilled under reduced pressure to obtain 20.1 g of 1-bromo-8-chloro-2-methylnaphthalene. The purity of the 1-bromo-8-chloro-2-methylnaphthalene was measured to be 99.68% by gas chromatography.

[0067] Mass spectrometry analysis of the obtained 1-bromo-8-chloro-2-methylnaphthalene revealed a peak with the highest mass-to-charge ratio (m / z) at 255.95 with an intensity of 100%, and another peak at 253.95 with an intensity of approximately 78%. The molecular formula of the product was determined to be: C 11 H8BrCl.

[0068] (2) Synthesis of 1-bromo-8-chloro-2-tribromomethylnaphthalene

[0069] In a 500 mL three-necked flask, add 2.55 g of 1-bromo-8-chloro-2-methylnaphthalene, 100 mL of carbon tetrachloride, and 0.16 g of BPO (benzoyl peroxide). Add NBS (7.0 g of N-bromosuccinimide) in portions. Heat to reflux and react for 8 hours. Cool to room temperature, add water to liquefy the mixture, wash the organic layer with water, dry with magnesium sulfate, filter off the magnesium sulfate, concentrate under reduced pressure to dryness, and proceed directly to the next reaction without purification.

[0070] (3) Synthesis of 1-bromo-8-chloro-2-naphthoic acid

[0071] The 1-bromo-8-chloro-2-tribromomethylnaphthalene obtained in the previous step was added to a three-necked flask, followed by acetic acid (30 mL) and anhydrous potassium acetate (4.0 g). The mixture was refluxed for 6 hours, then cooled slightly, and water (1 mL) was added. The mixture was then refluxed for another 8 hours. After cooling to room temperature, 30 mL of water was added, and a solid precipitated. The solid was filtered and crystallized from ethanol to obtain 1-bromo-8-chloro-2-naphthoic acid (2.0 g).

[0072] Infrared absorption spectroscopy was performed on the product at 3450 cm⁻¹. -1 There is an OH peak at 1750 cm⁻¹. -1 The presence of a C=O peak indicates the formation of a carboxylic acid group.

[0073] (4) Methyl 1-bromo-8-chloro-2-naphthoate (synthesis of N1-Me)

[0074] In a 500 mL three-necked flask equipped with a reflux condenser and a water separator, 5.5 g of 1-bromo-8-chloro-2-naphthoic acid, 10 mL of methanol, 150 mL of toluene, and 1 g of p-toluenesulfonic acid were added. The mixture was heated under reflux for 20 hours to separate the water. After cooling to room temperature, water was added to separate the organic layer. The mixture was then washed with water and concentrated to dryness. Separation was performed by silica gel column chromatography with petroleum ether:dichloromethane = 20:1 (volume ratio) to obtain methyl 1-bromo-8-chloro-2-naphthoic acid (5.3 g).

[0075] Mass spectrometry analysis of the obtained methyl 1-bromo-8-chloro-2-naphthoate revealed a peak with the highest mass-to-charge ratio (m / z) at 299.94 (100% intensity), and another peak at 297.94 (m / z) with an intensity of approximately 78%. The molecular formula of the product was determined to be: C 12 H8BrClO2.

[0076] The obtained methyl 1-bromo-8-chloro-2-naphthoate was analyzed by NMR, and the data are as follows: 1 H-NMR (Bruker, Switzerland, Avance II 400MHz NMR spectrometer, CDCl3), δ8.22 (m, 1H), δ7.68~7.63 (m, 3H), δ7.29 (m, 1H), δ3.88 (s, 3H).

[0077] Preparation Example 2

[0078] This preparation example provides intermediate N2 and its synthesis method. The synthesis process is as follows:

[0079]

[0080] (1) Synthesis of 1-bromo-8-chloro-2-bromomethylnaphthalene

[0081] To a 500 mL three-necked flask, add 2.55 g of 1-bromo-8-chloro-2-methylnaphthalene, 100 mL of carbon tetrachloride, and 0.08 g of BPO (benzoyl peroxide). Add NBS (1.78 g of N-bromosuccinimide) in portions. Heat to reflux and react for 8 hours. Cool to room temperature, add water to liquefy the mixture, wash the organic layer with water, dry with magnesium sulfate, filter off the magnesium sulfate, concentrate under reduced pressure to dryness, and proceed directly to the next reaction without purification.

[0082] (2) Synthesis of 1-bromo-8-chloro-2-naphthyl alcohol

[0083] The 1-bromo-8-chloro-2-bromomethylnaphthalene obtained in the previous step was added to a three-necked flask, followed by acetic acid (30 mL) and anhydrous potassium acetate (1.1 g). The mixture was refluxed for 6 hours, then cooled slightly, and water (1 mL) was added. The mixture was then refluxed for another 8 hours. After cooling to room temperature, 80 mL of water and 30 mL of dichloromethane were added for separation. The organic layer was washed with water, dried over magnesium sulfate, and the desiccant was filtered off. The mixture was then concentrated to dryness under reduced pressure and separated by silica gel column chromatography. Elution was performed using petroleum ether:ethyl acetate = 20:1 (v / v) to obtain 1-bromo-8-chloro-2-naphthalenemethanol (1.0 g).

[0084] Mass spectrometry analysis of the obtained 1-bromo-8-chloro-2-naphthalenemethanol revealed a peak with the highest mass-to-charge ratio (m / z) at 271.94 (100% intensity), and another peak at 269.94 (m / z) with an intensity of approximately 78%. The molecular formula of the product was determined to be: C 11 H8BrClO.

[0085] The obtained 1-bromo-8-chloro-2-naphthyl alcohol was subjected to NMR analysis, and the data are as follows: 1H-NMR (Bruker, Switzerland, Avance II 400MHz NMR spectrometer, CDCl3), δ7.78 (m, 1H), δ7.66~7.56 (m, 2H), δ7.30 (m, 1H), δ6.92 (d, 1H), δ4.75 (s, 2H), δ1.58 (s, 1H).

[0086] Preparation Example 3

[0087] This preparation example provides another method for synthesizing intermediate N2, and the synthesis process is as follows:

[0088]

[0089] (1) Synthesis of 1-bromo-8-chloro-2-dibromomethylnaphthalene

[0090] To a 500 mL three-necked flask, add 2.55 g of 1-bromo-8-chloro-2-methylnaphthalene (2.55 g), carbon tetrachloride (100 mL), and BPO (benzoyl peroxide, 0.12 g). Add NBS (N-bromosuccinimide, 3.6 g) in portions. Heat to reflux and react for 8 hours. Cool to room temperature, add water to liquefy the mixture, wash the organic layer with water, dry with magnesium sulfate, filter off the magnesium sulfate, concentrate under reduced pressure to dryness, and proceed directly to the next reaction without purification.

[0091] (2) Synthesis of 1-bromo-8-chloro-2-naphthaldehyde

[0092] The 1-bromo-8-chloro-2-tribromomethylnaphthalene obtained in the previous step was added to a three-necked flask, followed by acetic acid (30 mL) and anhydrous potassium acetate (2.4 g). The mixture was refluxed for 6 hours, then cooled slightly, and water (1 mL) was added. The mixture was then refluxed for another 8 hours. After cooling to room temperature, 30 mL of water was added, and a solid precipitated. The solid was filtered and crystallized with isopropanol to obtain 1-bromo-8-chloro-2-naphthaldehyde (2.0 g).

[0093] Mass spectrometry analysis of the obtained 1-bromo-8-chloro-2-naphthaldehyde revealed a peak with the highest mass-to-charge ratio (m / z) at 269.93 (100% intensity), and another peak at 267.93 (m / z) with an intensity of approximately 78%. The molecular formula of the product was determined to be: C 11 H6BrClO.

[0094] (3) Synthesis of 1-bromo-8-chloro-2-naphthyl alcohol

[0095] Add 3.0 g of 1-bromo-8-chloro-2-naphthaldehyde and 100 mL of anhydrous methanol to a 500 mL three-necked flask. Add 0.5 g of KBH4 in portions at room temperature with stirring. After the addition is complete, stir at room temperature for 4 hours. After adding water, a solid precipitates out. Filter, dry, and crystallize from isopropanol to obtain 2.9 g of 1-bromo-8-chloro-2-naphthol.

[0096] Mass spectrometry analysis of the obtained 1-bromo-8-chloro-2-naphthalenemethanol revealed a peak with the highest mass-to-charge ratio (m / z) at 271.94 (100% intensity), and another peak at 269.94 (m / z) with an intensity of approximately 78%. The molecular formula of the product was determined to be: C 11 H8BrClO.

[0097] The obtained 1-bromo-8-chloro-2-naphthyl alcohol was subjected to NMR analysis, and the data are as follows: 1H-NMR (Bruker, Switzerland, Avance II 400MHz NMR spectrometer, CDCl3), δ7.78 (m, 1H), δ7.66~7.56 (m, 2H), δ7.30 (m, 1H), δ6.92 (d, 1H), δ4.75 (s, 2H), δ1.58 (s, 1H).

[0098] Preparation Example 4

[0099] This preparation example provides the intermediate Me-5 and its synthesis method, the synthesis process is as follows:

[0100]

[0101] (1) Synthesis of intermediate Me-1

[0102] Under nitrogen protection, DMF (100 mL), 9-anthraboronic acid (2.22 g), methyl 1-bromo-8-chloro-2-naphthoate (N1-Me) (2.99 g), anhydrous potassium phosphate (3.1 g), and tetra-triphenylphosphine palladium (0.3 g) were added sequentially to a 250 mL three-necked flask. The mixture was slowly heated to 90 °C and reacted for 6 h. After cooling to room temperature, water was added to dissolve the organic layer. The organic layer was washed with water, dried over magnesium sulfate, filtered to remove magnesium sulfate, and the solvent was removed under reduced pressure. The mixture was crystallized from a mixed solvent of toluene and ethanol to obtain intermediate Me-1 (3.1 g).

[0103] Mass spectrometry analysis of intermediate Me-1 showed a mass-to-charge ratio (m / z) of 396.09.

[0104] (2) Synthesis of intermediate Me-2

[0105] Under nitrogen protection, dry tetrahydrofuran (50 mL) and intermediate Me-1 (4.0 g) were added to a 500 mL three-necked flask. The temperature was lowered to -30 °C, and 130 mL of 3.0 M magnesium methyl bromide solution was slowly added dropwise. After the addition was complete, the mixture was slowly raised to room temperature and reacted for 4 hours. Water and dichloromethane were added to separate the layers. The organic layer was washed with water, dried with magnesium sulfate, and the magnesium sulfate was removed from the organic layer. The mother liquor was placed in a three-necked flask and cooled to 0-5 °C. Methanesulfonic acid (10 g) was added dropwise. The reaction gradually precipitated a solid. After the addition of methanesulfonic acid was complete, the mixture was slowly raised to room temperature and reacted for 2 hours. The mixture was filtered, and the solid was washed with water, then with methanol, then with water again, and dried to obtain intermediate Me-2 (2.9 g).

[0106] Mass spectrometry analysis of intermediate Me-2 revealed a mass-to-charge ratio (m / z) of 378.12.

[0107] (3) Synthesis of intermediate Me-3

[0108] Under nitrogen protection, intermediate Me-2 (8 g), DMF (200 mL), sodium tert-butoxide (2.6 g), Pd(dba)2 (bis(dibenzylacetone palladium, 0.06 g), and PdCl2 (0.01 g) were added to a 500 mL three-necked flask. The mixture was heated to reflux for 12 hours, cooled to room temperature, and separated by adding water and toluene. The organic layer was washed with water until neutral, dried over magnesium sulfate, filtered to remove the desiccant, concentrated to dryness, and separated by silica gel column chromatography. The solution was eluted with petroleum ether to obtain intermediate Me-3 (6.1 g).

[0109] Mass spectrometry analysis of intermediate Me-3 showed a mass-to-charge ratio (m / z) of 342.14.

[0110] (4) Synthesis of intermediate Me-4

[0111] In a 250 mL three-necked flask, DMF (100 mL) and intermediate Me-3 (3.5 g) were added. N-bromosuccinimide solid (1.8 g) was added in portions at 20-25 °C. After the addition was complete, the mixture was reacted at 20-25 °C for 4 hours. Water and chloroform were added to separate the layers. The organic layer was washed with water, dried over magnesium sulfate, filtered to remove magnesium sulfate, concentrated to dryness, separated by silica gel column chromatography, and eluted with petroleum ether to obtain intermediate Me-4 (3.2 g).

[0112] Mass spectrometry analysis of intermediate Me-4 revealed two peaks with the largest mass-to-charge ratio (m / z) at 420.05 and 422.05, confirming the product's molecular formula as C. 27 H 17 Br.

[0113] (5) Synthesis of intermediate Me-5

[0114] In a 250 mL three-necked flask, DMF (100 mL) and intermediate Me-4 (4.2 g) were added. The mixture was heated to 40 °C with stirring. N-iodosuccinimide solid (2.5 g) was added in portions. After the addition was complete, the mixture was reacted at 40 °C for 2 hours, then heated to 80 °C for 16 hours. The mixture was cooled to room temperature, and water and chloroform were added to separate the layers. The organic layer was washed with water, dried over magnesium sulfate, filtered to remove magnesium sulfate, concentrated to dryness, and separated by silica gel column chromatography. The mixture was eluted with petroleum ether to obtain intermediate Me-5 (3.8 g).

[0115] Mass spectrometry analysis of intermediate Me-5 revealed two peaks with the largest mass-to-charge ratio (m / z) at 547.95 and 545.95, confirming the product's molecular formula as C. 27 H 16 BrI.

[0116] The obtained Me-5 was subjected to NMR analysis: 1H-NMR (Bruker, Switzerland, Avance II 400MHz NMR spectrometer, CDCl3), δ8.55 (m, 1H), δ8.26 (m, 1H), δ7.97 (s, 1H), δ7.91 (m, 1H), δ7.80 (m, 1H), δ7.60~7.55 (m, 3H), δ7.48~7.41 (m, 2H), δ1.93 (s, 6H).

[0117] Preparation Example 5

[0118] This preparation example provides the intermediate MC-6 and its synthesis method, as follows:

[0119]

[0120] (1) Synthesis of intermediate MC-1

[0121] The synthesis method of intermediate Me-1 is the same, except that methyl 1-bromo-8-chloro-2-naphthylcarboxylate (N1-Me) is replaced with an equal amount of 1-bromo-8-chloro-2-naphthyl alcohol to obtain intermediate MC-1.

[0122] Mass spectrometry analysis of intermediate MC-1 showed a mass-to-charge ratio (m / z) of 368.10.

[0123] (2) Synthesis of intermediate MC-2

[0124] Add 20 mL of 95% concentrated sulfuric acid to a 500 mL three-necked flask, then add 1 g of polyphosphoric acid and 60 mL of dichloromethane. Stir well, cool to 5 °C, and add dropwise a 20 mL solution of dichloromethane containing 3 g of intermediate MC-1. After the addition is complete, slowly raise the temperature to 20 °C and react for 2 hours. Pour the reaction solution into ice water, separate the layers, wash the organic layer with water until neutral, dry with magnesium sulfate, separate by silica gel column chromatography, and elute with petroleum ether to obtain intermediate MC-2 (1.5 g).

[0125] Mass spectrometry analysis of intermediate MC-2 revealed a mass-to-charge ratio (m / z) of 350.09.

[0126] (3) Synthesis of intermediate MC-3

[0127] Under nitrogen protection, 50 mL of dry tetrahydrofuran was added to a 250 mL three-necked flask, followed by 0.36 g of 60% sodium hydride. The mixture was cooled to 10 °C, and then intermediate MC-2 (3.0 g) was added in portions. After the addition was complete, the mixture was stirred at 10–15 °C for 30 minutes. Then, 1.85 g of 1,4-dibromobutane was added, and the mixture was gradually heated to room temperature with stirring for 2 hours. The reaction mixture was then cooled to 10 °C, and 0.35 g of 60% sodium hydride was added in portions at 10–15 °C. After the addition was complete, the mixture was slowly heated to room temperature with stirring for 2 hours, and then heated to 60 °C for 2 hours. The mixture was then cooled, and 2 mL of methanol was slowly added to decompose the remaining sodium hydride. Water and dichloromethane were then added, and the mixture was separated. The organic layer was washed with water until neutral, dried over magnesium sulfate, and separated by silica gel column chromatography. The solution was eluted with petroleum ether to obtain intermediate MC-3 (1.7 g).

[0128] Mass spectrometry analysis of intermediate MC-3 showed a mass-to-charge ratio (m / z) of 404.13.

[0129] (4) Synthesis of intermediate MC-4

[0130] The synthesis of intermediate Me-3 is similar to that of intermediate Me-2, except that intermediate Me-2 is replaced with an equal amount of intermediate MC-3 to obtain intermediate MC-4.

[0131] Mass spectrometry analysis of intermediate MC-4 revealed a mass-to-charge ratio (m / z) of 368.16.

[0132] (5) Synthesis of intermediate MC-5

[0133] The synthesis of intermediate Me-4 is similar to that of intermediate Me-3, except that intermediate Me-3 is replaced with an equal amount of intermediate MC-4 to obtain intermediate MC-5.

[0134] Mass spectrometry analysis of intermediate MC-5 revealed two peaks with the largest mass-to-charge ratio (m / z) at 446.07 and 448.06, confirming the product's molecular formula as C. 29 H 19 Br.

[0135] (6) Synthesis of intermediate MC-6

[0136] The synthesis of intermediate Me-5 is similar to that of intermediate Me-4, except that intermediate Me-4 is replaced with an equal amount of intermediate MC-5 to obtain intermediate MC-6.

[0137] Mass spectrometry analysis of intermediate MC-6 revealed two peaks with the largest mass-to-charge ratio (m / z) at 571.96 and 573.96, confirming the product's molecular formula as C. 29 H 18 BrI.

[0138] The obtained MC-6 was subjected to NMR analysis: 1H-NMR (Bruker, Switzerland, Avance II 400MHz NMR spectrometer, CDCl3), δ8.54 (m, 1H), δ8.25 (m, 1H), δ7.94 (m, 1H), δ7.76 (m, 1H), δ7.60~7.54 (m, 2H), δ7.49~7.40 (m, 2H), δ7.33 (s, 1H), δ7.00 (m, 1H), δ2.65~2.35 (m, 4H), δ1.83~1.61 (m, 4H).

[0139] Synthesis Example 1

[0140] This synthetic example provides compound 1 and its synthetic method, and the synthetic process is as follows:

[0141]

[0142] Under nitrogen protection, dry toluene (150 mL), intermediate Me-4 (4.21 g), diphenylamine (1.7 g), Pd(dba)2 (bis(dibenzylacetone palladium, 0.0575 g, 0.0001 mol), a 10% (w / w) solution of tri-tert-butylphosphine in toluene (w / w) 0.4 g of tri-tert-butylphosphine solution and 0.0002 mol of tri-tert-butylphosphine, and sodium tert-butoxide (1.44 g, 0.015 mol) were added to a 250 mL three-necked flask. The mixture was heated to reflux and reacted for 12 h. After cooling to room temperature, water was added to dissolve the mixture. The organic layer was then washed with water until neutral, dried with magnesium sulfate, filtered to remove magnesium sulfate, concentrated to dryness, and separated by silica gel column chromatography. The mixture was eluted with a solvent of petroleum ether:ethyl acetate = 20:1 (v / v) to give compound 1 (4.6 g).

[0143] Mass spectrometry analysis of compound 1 showed a mass-to-charge ratio (m / z) of 509.21.

[0144] Elemental analysis of compound 1 showed that the calculated percentages of each element in compound 1 were: C, 91.91%; H, 5.34%; N, 2.75%; while the actual measured percentages were: C, 91.88%; H, 5.33%; N, 2.74%.

[0145] Synthesis Examples 2-19

[0146] Synthesis Examples 2-19 provide compounds 2-19 respectively. The synthesis method of compounds 2-19 is the same as that of compound 1, except that intermediate Me-4 is replaced with other bromides in equal amounts as needed (see Table 1 below), and diphenylamine is replaced with other diarylamine compounds in equal amounts as needed (see Table 1 below).

[0147] Table 1

[0148]

[0149]

[0150]

[0151] Synthesis Example 20

[0152] This synthetic example provides compound D1 and its synthetic method, the synthetic process of which is as follows:

[0153]

[0154] Under nitrogen protection, dry toluene (300 mL), intermediate Me-5 (5.47 g), diphenylamine (3.4 g), Pd(dba)2 (bis(dibenzylacetone)palladium, 0.0575 g, 0.0001 mol), a 10% (w / w) solution of tri-tert-butylphosphine in toluene (w / w = 0.4 g of tri-tert-butylphosphine solution, w / w = 0.0002 mol of tri-tert-butylphosphine), and sodium tert-butoxide (2.88 g, 0.03 mol) were added to a 500 mL three-necked flask. The mixture was first heated to 40 °C for 2 hours, then heated to 60 °C for 2 hours, and then heated to reflux for 18 hours. After cooling to room temperature, water was added to ligate the mixture. The organic layer was then washed with water until neutral, dried with magnesium sulfate, filtered to remove magnesium sulfate, concentrated to dryness, and separated by silica gel column chromatography. The elution was performed with a solvent of petroleum ether:ethyl acetate = 20:1 (v / v) to give compound D1 (4.9 g). g).

[0155] Mass spectrometry analysis of compound D1 showed a mass-to-charge ratio (m / z) of 676.29.

[0156] Elemental analysis of compound D1 showed that the calculated percentages of each element in compound D1 were: C, 90.50%; H, 5.36%; N, 4.14%; while the actual measured percentages were: C, 90.51%; H, 5.34%; N, 4.15%.

[0157] Synthesis Examples 21-24

[0158] Synthesis Examples 21-24 provide compounds D2-D5 respectively. The synthesis methods of compounds D2-D5 are the same as those of compound D1, except that intermediate Me-5 is replaced with an equal amount of other bromides (see Table 2 below) as needed, and diphenylamine is replaced with an equal amount of other diarylamine compounds (see Table 2 below) as needed.

[0159] Table 2

[0160]

[0161] Synthesis Example 25

[0162] This synthetic example provides compound D6 and its synthetic method, the synthetic process of which is as follows:

[0163]

[0164] (1) Synthesis of intermediate D6-1

[0165] Under nitrogen protection, dry toluene (200 mL), intermediate Me-5 (5.47 g), N-phenyldibenzo[b,d]furan-2-amine (2.6 g), Pd(dba)2 (bis(dibenzylacetone)palladium, 0.0575 g, 0.0001 mol), a 10% (w / w) toluene solution of tri-tert-butylphosphine (0.4 g of tri-tert-butylphosphine solution, 0.0002 mol of tri-tert-butylphosphine), and sodium tert-butoxide (1.44 g) were added to a 500 mL three-necked flask. (g, 0.015mol), first heat to 40℃ for 2 hours, then heat to 60℃ for 8 hours, cool to room temperature, add water to liquefy, then wash the organic layer with water until neutral, dry with magnesium sulfate, filter to remove magnesium sulfate, concentrate to dryness, separate by silica gel column chromatography, and elute with a solvent of petroleum ether:ethyl acetate = 20:1 (volume ratio) to obtain intermediate D6-1 (3.96g).

[0166] Mass spectrometry analysis of intermediate D6-1 revealed two peaks with the largest mass-to-charge ratio (m / z) at 677.14 and 679.13, confirming the product's molecular formula as C. 45 H 28 BrNO.

[0167] Elemental analysis of intermediate D6-1 revealed the following percentages of each element: C, 79.64%; H, 4.16%; Br, 11.77%; N, 2.06%; O, 2.36%; while the actual measured percentages were: C, 79.66%; H, 4.14%; N, 2.08%.

[0168] (2) Synthesis of compound D6

[0169] The synthesis method of compound 1 is the same, except that intermediate Me-4 is replaced with an equal amount of intermediate D6-1, and diphenylamine is replaced with an equal amount of 4,4′-dimethyldiphenylamine, to obtain compound D6.

[0170] Mass spectrometry analysis of compound D6 revealed a mass-to-charge ratio (m / z) of 794.33.

[0171] Synthesis Example 26

[0172] This synthetic example provides compound D7 and its synthetic method, the synthetic process of which is as follows:

[0173]

[0174] The synthesis method of compound 1 is the same, except that intermediate Me-4 is replaced with an equal amount of intermediate D6-1 to obtain compound D7.

[0175] Mass spectrometry analysis of compound D7 showed a mass-to-charge ratio (m / z) of 766.30.

[0176] Synthesis Example 27

[0177] This synthetic example provides compound D8 and its synthetic method, the synthetic process of which is as follows:

[0178]

[0179] (1) Synthesis of intermediate D8-1

[0180] The synthesis method of intermediate D6-1 is the same as that of intermediate D8-1, except that intermediate Me-5 is replaced with an equal amount of intermediate MC-6.

[0181] Mass spectrometry analysis of intermediate D8-1 revealed two peaks with the largest mass-to-charge ratio (m / z) at 703.15 and 705.15, confirming the product's molecular formula as: C 47 H 30 BrNO.

[0182] (2) Synthesis of compound D8

[0183] The synthesis method of compound D6 is the same, except that intermediate D6-1 is replaced with an equal amount of intermediate D8-1 to obtain compound D8.

[0184] Mass spectrometry analysis of compound D8 revealed a mass-to-charge ratio (m / z) of 820.35.

[0185] Other compounds for which specific synthesis steps are not listed can be prepared using common knowledge in the art, in conjunction with the above examples.

[0186] The specific structures of several materials used in the device embodiments of the present invention are as follows:

[0187]

[0188] Device Example 1

[0189] This embodiment of the device provides an organic electroluminescent device, wherein the doping material of the light-emitting layer of the organic electroluminescent device is compound 1 provided in synthesis embodiment 1 of the present invention;

[0190] The structure of the organic electroluminescent device is: ITO / HT (100nm) / light-emitting layer (30nm): BH:BD 3% / TPBI (30nm) / LiF (0.5nm) / Al (150nm).

[0191] The fabrication process of organic electroluminescent devices is as follows:

[0192] The glass substrate coated with an ITO transparent conductive layer (as the anode) was ultrasonically treated in a cleaning agent, then rinsed in deionized water, then ultrasonically degreased in a mixed solvent of acetone and ethanol, then baked in a clean environment until completely dehydrated, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam to improve the surface properties and enhance the bonding ability with the hole layer.

[0193] The material was placed inside a vacuum chamber, and the vacuum was evacuated to 1×10⁻⁶. -5 ~1×10 -6 Pa is sequentially vacuum-deposited onto the cleaned ITO substrate. The light-emitting layer (30 nm): BH:BD 3% refers to the fact that BH and BD are co-evaporated in a volume ratio of 97:3 to form the light-emitting layer, with a thickness of 30 nm; BD is the doping material for the light-emitting layer, and in this embodiment, BD is compound 1. TPBI is the electron transport layer; LiF is the electron injection layer.

[0194] Device Examples 2-21

[0195] Device Examples 2-21 each provide an organic electroluminescent device, which differs from Device Example 1 only in that the doping material of the light-emitting layer is different (see Table 3 below), while other conditions are the same as those in Device Example 1.

[0196] Device Comparison Example 1-2

[0197] Comparative Examples 1 and 2 each provide an organic electroluminescent device, which differs from Device Example 1 only in that the doping material of the light-emitting layer is different (see Table 3 below), while other conditions are the same as those in Device Example 1.

[0198] Performance testing

[0199] Test method: The driving voltage, current efficiency, and lifetime LT90 of the OLED devices provided above were tested using the OLED-1000 multi-channel accelerated aging lifetime and color performance analysis system manufactured by Hangzhou Yuanfang. LT90 refers to the time required for the brightness to drop to 90% of the original brightness while maintaining the current density at an initial brightness of 2000 nits. The driving voltage, current efficiency, and LT90 are all relative values.

[0200] The test results of the above organic electroluminescent devices are shown in Table 3 below:

[0201] Table 3

[0202]

[0203] As can be seen from Table 1, this invention, through the design of the structure of hydrogenated naphthoperylene compounds, further improves the core structure ( ) and substituents (-R) on the parent nucleus structure 101 and -R 102 The design of the hydrogenated naphthoperylene compound can be used as a dopant material for the light-emitting layer. The organic electroluminescent device prepared by this method has a low driving voltage, high current efficiency and long service life.

[0204] The applicant declares that the detailed process flow of this invention is illustrated by the above embodiments, but this invention is not limited to the above detailed process flow, that is, it does not mean that this invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the product of this invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of this invention.

Claims

1. A hydrogenated naphthoperylene compound, characterized in that, The hydrogenated naphthoperylene compounds have a structure as shown in formula BDI: BDI (Body-Induced Difference); Among them, Ar 101 and Ar 102 Each group is independently selected from any one of the following groups, whether substituted or unsubstituted: phenyl, naphthyl, diphenyl, triphenyl, fluoranyl, fluorenyl, benzofluorenyl, dibenzofuranyl, dibenzothiophenyl, naphthobenzofuranyl or naphthobenzothiophenyl; The substituents are selected from -D, -F, -CN, phenyl, biphenyl, dibenzofuranyl, methyl, deuterated methyl, adamantyl, tert-butyl, 1-methylcyclopentyl, cyclohexyl, cyclopentyl, methoxy, etc. The combination of any one or at least two of naphthyl, dibenzothiophene, and naphthobenzothiophene, with dashed lines indicating connection sites; Ar 201 Ar 202 Each is independently selected from any one of substituted or unsubstituted C6-C40 aryl groups or substituted or unsubstituted C12-C20 heteroaryl groups; R 101 and R 102 Each is independently selected from any one of methyl, ethyl, or propyl; R 101 and R 102 Connect them in a loop using a single key or leave them unconnected; m and n are each independently selected from 0 or 1, and m and n are not both 0 at the same time; Ar 201 Ar 202 The substituents described herein are each independently selected from any one or a combination of at least two of -D, -F, -CN, C1~C12 alkyl, C1~C6 alkoxy, C2~C8 alkenyl, C6~C15 aryl, and C12~C20 heteroaryl.

2. The hydrogenated naphthoperylene compound according to claim 1, characterized in that, Both m and n are selected from 1.

3. The hydrogenated naphthoperylene compound according to claim 2, characterized in that, The hydrogenated naphthoperylene compounds are selected from any one of the following compounds: 。 4. An intermediate, characterized in that, The intermediate includes the following compounds: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 ； Where R is selected from C1~C6 alkyl or C6~C12 aryl; X and Y are each independently selected from Cl, Br, or I; R 101 It has the same definition as claim 1; Ring A represents a carbon ring with capacities of C5 to C7. Ar 101 and Ar 102 Ar 201 Ar 202 It has the same definition as claim 1.

5. The intermediate according to claim 4, characterized in that, The intermediate includes the following compounds: 、 、 、 、 、 、 、 、 、 、 。 6. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes an anode, a cathode, and an organic thin film layer disposed between the anode and the cathode; The material of the organic thin film layer includes the hydrogenated naphthoperylene compounds as described in any one of claims 1-3.

7. The organic electroluminescent device according to claim 6, characterized in that, The organic thin film layer includes a light-emitting layer, and the material of the light-emitting layer includes the hydrogenated naphthoperylene compounds as described in any one of claims 1-3.

8. The organic electroluminescent device according to claim 7, characterized in that, The material of the light-emitting layer includes a doped material, which includes a hydronphthalene compound as described in any one of claims 1-3.

9. A display device, characterized in that, The display device includes an organic electroluminescent device as described in any one of claims 6-8.

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