A hydrogenated naphthaloperylene compound, an intermediate, an organic electroluminescence device, and a display device

Abstract

The application provides a hydrogenated naphthaloperylene compound, an intermediate, an organic electroluminescent device and a display device. The hydrogenated naphthaloperylene compound has a structure as shown in formula BHI, and the intermediate is used for preparing the hydrogenated naphthaloperylene compound. The hydrogenated naphthaloperylene compound provided by the application can be used as a light-emitting layer host material, and the prepared organic electroluminescent device has a lower driving voltage, a higher current efficiency and a longer service life.

Description

Technical Field

[0001] This invention belongs to the field of organic electroluminescent materials technology, specifically relating to a hydrogenated naphthoperylene compound, an intermediate, an organic electroluminescent device, and a display device. Background Technology

[0002] Electroluminescence, also known as electroluminescence or EL for short, is a light-emitting phenomenon in which a solid directly converts electrical energy into light energy by generating an electric field through a voltage applied to two electrodes. Among these, electroluminescence from organic materials is an injection-type composite light emission. Based on their function and structure in organic electroluminescent (OLED) devices, organic electroluminescent materials can be further classified into hole injection layer (HIL), hole transport layer (HTL), emissive layer (EML), electron transport layer (ETL), and electron injection layer (EIL), among others.

[0003] Currently, Organic Light Emitting Diode (OLED) display technology has been applied in smartphones, tablets, and other fields, and is expanding into large-screen applications such as televisions. Over the past 30 years of development, various high-performance OLED materials have been developed. Through different device structure designs and optimizations of device lifespan and efficiency, the commercialization of OLEDs has been accelerated, leading to their widespread application in display and lighting fields. With the continuous development of OLED display technology, various new OLED materials are gradually attracting widespread attention and research in order to improve the performance of OLED devices. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a hydrogenated naphthoperylene compound, an intermediate, an organic electroluminescent device, and a display device. In this invention, the structure of the hydrogenated naphthoperylene compound is designed to serve as the host material for the light-emitting layer, resulting in an organic electroluminescent device with lower driving voltage, higher current efficiency, and longer lifespan.

[0005] To achieve this objective, the present invention adopts the following technical solution:

[0006] In a first aspect, the present invention provides a hydrogenated naphthoperylene compound having a structure as shown in formula BHI:

[0007]

[0008] Among them, Ar 101 and Ar 102 Each is independently selected from any one of substituted or unsubstituted C6-C40 aryl groups or substituted or unsubstituted C12-C30 heteroaryl groups;

[0009] 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;

[0010] R 101 and R 102 They can be connected in a ring using a single key;

[0011] m is selected from 0 or 1;

[0012] Ar 101 Ar 102 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-C30 heteroaryl.

[0013] In this invention, the structure of hydrogenated naphthoperylene compounds is designed to serve as the main material for the light-emitting layer. The resulting organic electroluminescent device has a lower driving voltage, higher current efficiency, and longer lifespan.

[0014] In this invention, Ar 101 and Ar 102 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 groups, or substituted or unsubstituted C12-C30 (e.g., C12, C14, C16, C18, C20, C24, C28, or C30, etc.) heteroaryl groups.

[0015] R 101 and R 102 Each 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).

[0016] Ar 101 Ar 102 R 101 and R 102The 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-C30 (e.g., C12, C14, C16, C18, C20, C24, C28 or C30).

[0017] 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.

[0018] 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]naphthyl.

[0019] Preferably, the C12-C30 heteroaryl group is selected from any one of dibenzofuranyl, dibenzothiophenyl, naphthobenzofuranyl, naphthobenzothiophenyl, dinaphthofuranyl, dinaphthothiophenyl, phenylnaphthobenzothiophenyl, phenyl dibenzothiophenyl, and phenyl dibenzofuranyl.

[0020] Preferably, the C12-C20 heteroaryl group is selected from any one of dibenzofuranyl, dibenzothiophenyl, naphthobenzofuranyl, naphthobenzothiophenyl, dinaphthofuranyl, and dinaphthothiophenyl.

[0021] 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.

[0022] Preferably, the C1-C6 alkoxy group is selected from methoxy, ethoxy, propoxy, butoxy, or... Any of the following, with dashed lines representing connection points;

[0023] Preferably, the C6-C15 aryl group is selected from any one of phenyl, naphthyl, or diphenyl.

[0024] As a preferred technical solution of the present invention, the Ar 101Selected from any one of the following substituted or unsubstituted groups:

[0025]

[0026]

[0027]

[0028] The substitution refers to the substitution of at least one hydrogen atom in the above-mentioned groups by a deuterium atom;

[0029] The dashed lines represent connection points.

[0030] Preferably, the Ar 102 Selected from any one of the following substituted or unsubstituted groups:

[0031]

[0032] The substitution refers to the substitution of at least one hydrogen atom in the above-mentioned groups by a deuterium atom;

[0033] The dashed lines represent connection points.

[0034] Preferably, the R 101 and R 102 Each is independently selected from any one of methyl, ethyl, propyl, or phenyl.

[0035] Preferably, the R 101 and R 102 same.

[0036] As a preferred embodiment of the present invention, the hydrogenated naphthoperylene compound is selected from any one of the following substituted or unsubstituted compounds:

[0037]

[0038]

[0039]

[0040]

[0041]

[0042] The substitution refers to the replacement of at least one hydrogen atom in the above compound with a deuterium atom.

[0043] It should be noted that the substitution refers to the replacement of at least one hydrogen atom in the above compound by a deuterium atom, and the parent nucleus The hydrogen atoms on it are not replaced by deuterium atoms.

[0044] Preferably, the hydrogenated naphthoperylene compound is selected from any one of the following compounds:

[0045]

[0046] In a second aspect, the present invention provides an intermediate selected from any one of the following compounds:

[0047]

[0048] Wherein, R is selected from C1 to C6 alkyl (e.g., methyl, ethyl, propyl, cyclopentyl, cyclohexyl, etc.) or C6 to C12 aryl (e.g., phenyl, naphthyl, or diphenyl, etc.);

[0049] X and Y are each independently selected from Cl, Br, or I;

[0050] R 101 It has the same scope of protection as the first aspect;

[0051] Ring A represents a carbon ring of C5 to C7 (for example, it can be C5, C6, or C7);

[0052] The intermediate is used to prepare hydrogenated naphthoperylene compounds as described in the first aspect.

[0053] As a preferred embodiment of the present invention, the intermediate is selected from any one of the following compounds:

[0054]

[0055] The intermediate is used to prepare hydrogenated naphthoperylene compounds as described in the first aspect.

[0056] In this invention, the above-mentioned intermediate is prepared by any one of the following methods:

[0057]

[0058] or:

[0059] or:

[0060] or:

[0061] or:

[0062]

[0063] Among them, R, X, Y, R 101 Ring A and the second aspect have the same protection range as the intermediate shown, and p is selected from 4, 5 or 6.

[0064] When m is 1, and Ar 101 and Ar 102 Similarly, the preparation methods for hydrogenated naphthoperylene compounds are as follows:

[0065]

[0066] When m is 0, the preparation method of hydrogenated naphthoperylene compounds is as follows:

[0067]

[0068] When m is 1, and Ar 101 and Ar 102 At the same time, the preparation methods of hydrogenated naphthoperylene compounds are as follows:

[0069]

[0070] Where X is selected from I, Y is selected from Cl or Br; where X is selected from Br, Y is selected from Cl.

[0071] Or:

[0072]

[0073] When Y is selected from I, X is selected from Cl or Br; when Y is selected from Br, X is selected from Cl.

[0074] Thirdly, 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;

[0075] The material of the organic thin film layer includes hydrogenated naphthoperylene compounds as described in the first aspect.

[0076] 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.

[0077] Preferably, the material of the light-emitting layer includes a host material, which includes a hydronphthalene compound as described in the first aspect.

[0078] Fourthly, the present invention provides a display device comprising the organic electroluminescent device as described in the third aspect.

[0079] Compared with the prior art, the present invention has the following beneficial effects:

[0080] In this invention, the structure of hydrogenated naphthoperylene compounds is designed to serve as the main material for the light-emitting layer. The resulting organic electroluminescent device has a lower driving voltage, higher current efficiency, and longer lifespan. Detailed Implementation

[0081] 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.

[0082] Preparation Example 1

[0083] This preparation example provides the intermediate N1-Me and its synthesis method, the synthesis process is as follows:

[0084]

[0085] (1) Synthesis of 1-bromo-8-chloro-2-methylnaphthalene

[0086] In a 500mL three-necked flask equipped with an acidic gas absorption device, 300mL of dichloromethane, 17.7g of 1-chloro-7-methylnaphthalene, and 0.2g of iron powder were added. The temperature was lowered to 0-5℃, and a 30mL solution of dichloromethane containing 18g of liquid bromine was slowly added dropwise. After the addition was complete, the mixture was reacted at 0-5℃ for 2 hours, then heated to 10-15℃ for 2 hours, and then heated to 20-25℃ 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, then washed with water until neutral. The mixture was concentrated to dryness and then distilled under reduced pressure to obtain 20.1g 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.

[0087] 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.

[0088] (2) Synthesis of 1-bromo-8-chloro-2-tribromomethylnaphthalene

[0089] 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.

[0090] (3) Synthesis of 1-bromo-8-chloro-2-naphthoic acid

[0091] 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).

[0092] 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.

[0093] (4) Synthesis of methyl 1-bromo-8-chloro-2-naphthoate (N1-Me)

[0094] 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).

[0095] Mass spectrometry analysis of the obtained methyl 1-bromo-8-chloro-2-naphthoic acid ester revealed a peak with the highest mass-to-charge ratio (m / z) at 299.94 with an intensity of 100%, and another peak at 297.94 with an intensity of approximately 78%. The molecular formula of the product was determined to be: C 12 H8BrClO2.

[0096] 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 nuclear magnetic resonance spectrometer, CDCl3), δ8.22 (m, 1H), δ7.68–7.63 (m, 3H), δ7.29 (m, 1H), δ3.88 (s, 3H).

[0097] Preparation Example 2

[0098] This preparation example provides intermediate N2 and its synthesis method. The synthesis process is as follows:

[0099]

[0100] (1) Synthesis of 1-bromo-8-chloro-2-bromomethylnaphthalene

[0101] 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.

[0102] (2) Synthesis of 1-bromo-8-chloro-2-naphthyl alcohol

[0103] 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, slightly cooled, 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).

[0104] 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.

[0105] 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).

[0106] Preparation Example 3

[0107] This preparation example provides another method for synthesizing intermediate N2, and the synthesis process is as follows:

[0108]

[0109] (1) Synthesis of 1-bromo-8-chloro-2-dibromomethylnaphthalene

[0110] 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) to a 500 mL three-necked flask. 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.

[0111] (2) Synthesis of 1-bromo-8-chloro-2-naphthaldehyde

[0112] 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).

[0113] 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.

[0114] (3) Synthesis of 1-bromo-8-chloro-2-naphthyl alcohol

[0115] 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.

[0116] 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 with an intensity of 100%, and another peak at 269.94 with an intensity of approximately 78%. The molecular formula of the product was determined to be: C 11 H8BrClO.

[0117] 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).

[0118] Preparation Example 4

[0119] This preparation example provides the intermediate Me-5 and its synthesis method, the synthesis process is as follows:

[0120]

[0121] (1) Synthesis of intermediate Me-1

[0122] Under nitrogen protection, DMF (100 mL), 9-anthraboric 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).

[0123] Mass spectrometry analysis of intermediate Me-1 showed a mass-to-charge ratio (m / z) of 396.09.

[0124] (2) Synthesis of intermediate Me-2

[0125] 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 temperature 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 temperature was slowly raised to room temperature and reacted for 2 hours. The solid was filtered, washed with water, washed with methanol, washed with water again, and dried to obtain intermediate Me-2 (2.9 g).

[0126] Mass spectrometry analysis of intermediate Me-2 revealed a mass-to-charge ratio (m / z) of 378.12.

[0127] (3) Synthesis of intermediate Me-3

[0128] 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 water and toluene were added for separation. The organic layer was washed with water until neutral, dried over magnesium sulfate, filtered to remove the desiccant, concentrated to dryness, separated by silica gel column chromatography, and eluted with petroleum ether to obtain intermediate Me-3 (6.1 g).

[0129] Mass spectrometry analysis of intermediate Me-3 showed a mass-to-charge ratio (m / z) of 342.14.

[0130] (4) Synthesis of intermediate Me-4

[0131] 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).

[0132] 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.

[0133] (5) Synthesis of intermediate Me-5

[0134] 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. Petroleum ether was used as elution to obtain intermediate Me-5 (3.8 g).

[0135] Mass spectrometry analysis of intermediate Me-5 revealed two peaks with the highest mass-to-charge ratio (m / z) at 547.95 and 545.95, confirming the product's molecular formula as C. 27 H 16 BrI.

[0136] The obtained Me-5 was analyzed by nuclear magnetic resonance: 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).

[0137] Preparation Example 5

[0138] This preparation example provides the intermediate MC-6 and its synthesis method, the synthesis process is as follows:

[0139]

[0140] (1) Synthesis of intermediate MC-1

[0141] 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.

[0142] Mass spectrometry analysis of intermediate MC-1 revealed a mass-to-charge ratio (m / z) of 368.10.

[0143] (2) Synthesis of intermediate MC-2

[0144] 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 and cool to 5 °C. Add 20 mL of dichloromethane solution containing 3 g of intermediate MC-1 dropwise. 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).

[0145] Mass spectrometry analysis of intermediate MC-2 revealed a mass-to-charge ratio (m / z) of 350.09.

[0146] (3) Synthesis of intermediate MC-3

[0147] 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).

[0148] Mass spectrometry analysis of intermediate MC-3 showed a mass-to-charge ratio (m / z) of 404.13.

[0149] (4) Synthesis of intermediate MC-4

[0150] 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.

[0151] Mass spectrometry analysis of intermediate MC-4 revealed a mass-to-charge ratio (m / z) of 368.16.

[0152] (5) Synthesis of intermediate MC-5

[0153] 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.

[0154] 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.

[0155] (6) Synthesis of intermediate MC-6

[0156] 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.

[0157] 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.

[0158] The obtained MC-6 was subjected to NMR analysis: 1H-NMR (Bruker, Switzerland, Avance II 400MHz NMR spectrometer, CDCl3), δ 8.54 (m, 1H), δ 8.25 (m, 1H), δ 7.94 (m, 1H), δ 7.76 (m, 1H), δ 7.60~7.54 (m, 2H), δ 7.49~7.40 (m, 2H), δ 7.33 (s, 1H), δ 7.00 (m, 1H), δ 2.65~2.35 (m, 4H), δ 1.83~1.61 (m, 4H).

[0159] Synthesis Example 1

[0160] This synthetic example provides compound 1 and its synthetic method, and the synthetic process is as follows:

[0161]

[0162] Under nitrogen protection, 60 mL of toluene, 20 mL of ethanol, and 20 mL of water were added sequentially to a 250 mL three-necked flask. Then, intermediate Me-4 (4.21 g), 2-naphthoboric acid (1.72 g), sodium carbonate (2.12 g, 0.02 mol), and tetra-triphenylphosphine palladium (0.115 g, 0.0001 mol) were added. The mixture was slowly heated to 100 °C and reacted for 12 h. After cooling to room temperature, water was added to dissolve the mixture. 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 mixture was eluted with petroleum ether to obtain compound 1 (4.3 g).

[0163] Mass spectrometry analysis of compound 1 showed a mass-to-charge ratio (m / z) of 468.19.

[0164] Synthesis Examples 2-21

[0165] Synthesis Examples 2-21 provide compounds 2-21 respectively. The synthesis method of compounds 2-21 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 2-naphthoboric acid is replaced with other boric acid compounds in equal amounts as needed (see Table 1 below).

[0166] Table 1

[0167]

[0168]

[0169]

[0170]

[0171]

[0172] Synthesis Example 22

[0173] This synthetic example provides compound 22 and its synthetic method, the synthetic process of which is as follows:

[0174]

[0175] Under nitrogen protection, 280 mL of toluene, 30 mL of ethanol, and 30 mL of water were added sequentially to a 500 mL three-necked flask. Then, intermediate Me-5 (5.47 g), 2-naphthoboric acid (3.5 g), sodium carbonate (4.24 g, 0.04 mol), and tetraphenylphosphine palladium (0.23 g, 0.0002 mol) were added. The mixture was slowly heated to 100 °C and reacted for 12 h. After cooling to room temperature, water was added to dissolve the mixture. The organic layer was washed with water until neutral, dried over magnesium sulfate, and the desiccant was filtered off. The mixture was concentrated to dryness and separated by silica gel column chromatography, eluted with petroleum ether, to obtain compound 22 (5.1 g).

[0176] Mass spectrometry analysis of compound 22 revealed a mass-to-charge ratio (m / z) of 594.23.

[0177] Synthesis Examples 23-27

[0178] Synthesis Examples 23-27 provide compounds 23-27 respectively. The synthesis methods of compounds 23-27 are the same as those of compound 22, except that intermediate Me-5 is replaced with an equal amount of other bromides (see Table 2 below) as needed, and 2-naphthoboric acid is replaced with an equal amount of other boric acid compounds (see Table 2 below) as needed.

[0179] Table 2

[0180]

[0181]

[0182] Synthesis Example 28

[0183] This synthetic example provides compound 28 and its synthetic method, the synthetic process of which is as follows:

[0184]

[0185] (1) Synthesis of intermediate 28-1

[0186] Under nitrogen protection, 80 mL of toluene, 20 mL of ethanol, and 5 mL of water were added sequentially to a 250 mL three-necked flask. Then, intermediate Me-5 (5.47 g), 2-naphthoboric acid (1.72 g), sodium carbonate (2.12 g, 0.02 mol), and tetraphenylphosphine palladium (0.115 g, 0.0001 mol) were added. The mixture was slowly heated to 50 °C and reacted for 2 h, then heated to 70 °C and reacted for 6 h. The mixture was cooled to room temperature, and water was added to separate the organic layer. After washing the organic layer with water, the mixture was dried over magnesium sulfate. After filtering to remove the magnesium sulfate, the solvent was removed under reduced pressure. The mixture was separated by silica gel column chromatography and eluted with petroleum ether to obtain intermediate 28-1 (3.3 g).

[0187] Mass spectrometry analysis of intermediate 28-1 revealed two peaks with the largest mass-to-charge ratio (m / z) at 546.10 and 548.10, confirming the product's molecular formula as C. 37 H 23 Br.

[0188] (2) Synthesis of compound 28

[0189] The synthesis of compound 28 was similar to that of compound 1, except that intermediate Me-4 was replaced with an equal amount of intermediate 28-1 and 2-naphthoboric acid was replaced with an equal amount of phenylboronic acid.

[0190] Mass spectrometry analysis of compound 28 showed a mass-to-charge ratio (m / z) of 544.22.

[0191] Synthesis Example 29

[0192] This synthetic example provides compound 29 and its synthetic method, the synthetic process of which is as follows:

[0193]

[0194] The synthesis of compound 29 was similar to that of compound 1, except that intermediate Me-4 was replaced with an equimolar amount of intermediate 28-1 and 2-naphthoboric acid was replaced with deuterated phenylboronic acid.

[0195] Mass spectrometry analysis of compound 29 showed a mass-to-charge ratio (m / z) of 549.25.

[0196] Synthesis Example 30

[0197] This synthetic example provides compound 30 and its synthetic method, the synthetic process of which is as follows:

[0198]

[0199] (1) Synthesis of intermediate 30-1

[0200] The synthesis of intermediate 28-1 was similar to that of intermediate 30-1, except that 2-naphthoboric acid was replaced with an equal amount of deuterated 2-naphthoboric acid.

[0201] Mass spectrometry analysis of intermediate 30-1 revealed two peaks with the largest mass-to-charge ratio (m / z) at 553.14 and 555.14, confirming the product's molecular formula as C. 37 H 16 D7Br.

[0202] (2) Synthesis of compound 30

[0203] The synthesis of compound 30 was performed in accordance with that of compound 1, except that intermediate Me-4 was replaced with an equal amount of intermediate 30-1 and 2-naphthoboric acid was replaced with an equal amount of phenylboronic acid.

[0204] Mass spectrometry analysis of compound 30 showed a mass-to-charge ratio (m / z) of 551.26.

[0205] Synthesis Example 31

[0206] This synthetic example provides compound 31 and its synthetic method, the synthetic process of which is as follows:

[0207]

[0208] The synthesis of compound 31 was similar to that of compound 1, except that intermediate Me-4 was replaced with an equal amount of intermediate 30-1 and 2-naphthoboric acid was replaced with an equal amount of deuterated phenylboronic acid.

[0209] Mass spectrometry analysis of compound 31 showed a mass-to-charge ratio (m / z) of 556.29.

[0210] Synthesis Example 32

[0211] This synthetic example provides compound 32 and its synthetic method, the synthetic process of which is as follows:

[0212]

[0213] (1) Synthesis of intermediate 32-1

[0214] The synthesis of intermediate 28-1 was similar to that of intermediate 32-1, except that 2-naphthoboric acid was replaced with an equal amount of phenylboronic acid.

[0215] Mass spectrometry analysis of intermediate 32-1 revealed two peaks with the largest mass-to-charge ratio (m / z) at 496.08 and 498.08, confirming the product's molecular formula as C. 33 H 21 Br.

[0216] (2) Synthesis of compound 32

[0217] The synthesis method of compound 1 is the same, except that intermediate Me-4 is replaced with an equal amount of intermediate 32-1, and 2-naphthoboric acid is replaced with an equal amount of 4-adamantylphenylboronic acid, to obtain compound 32.

[0218] Mass spectrometry analysis of compound 32 showed a mass-to-charge ratio (m / z) of 628.31.

[0219] Synthesis Example 33

[0220] This synthetic example provides compound 33 and its synthetic method, the synthetic process of which is as follows:

[0221]

[0222] The synthesis method of compound 1 is the same, except that intermediate Me-4 is replaced with an equal amount of intermediate 32-1, and 2-naphthoboric acid is replaced with an equal amount of 4-cyclohexylphenylboronic acid, to obtain compound 33.

[0223] Mass spectrometry analysis of compound 33 showed a mass-to-charge ratio (m / z) of 576.28.

[0224] Synthesis Example 34

[0225] This synthetic example provides compound 34 and its synthetic method, the synthetic process of which is as follows:

[0226]

[0227] (1) Synthesis of intermediate 34-1

[0228] The synthesis method is the same as that of intermediate 28-1, except that 2-naphthoboric acid is replaced with an equimolar amount. Intermediate 34-1 was obtained.

[0229] Mass spectrometry analysis of intermediate 34-1 revealed two peaks with the largest mass-to-charge ratio (m / z) at 586.09 and 588.09, confirming the product's molecular formula as C. 39 H 23 BrO.

[0230] (2) Synthesis of compound 34

[0231] The synthesis method of compound 1 is the same, except that intermediate Me-4 is replaced with an equal amount of intermediate 34-1, and 2-naphthoboric acid is replaced with an equal amount of phenylboronic acid, to obtain compound 34.

[0232] Mass spectrometry analysis of compound 34 revealed a mass-to-charge ratio (m / z) of 584.21.

[0233] Synthesis Example 35

[0234] This synthetic example provides compound 35 and its synthetic method, the synthetic process of which is as follows:

[0235]

[0236] (1) Synthesis of intermediate 35-1

[0237] The synthesis method is the same as that of intermediate 28-1, except that 2-naphthoboric acid is replaced with an equimolar amount. Intermediate 35-1 was obtained.

[0238] Mass spectrometry analysis of intermediate 35-1 revealed two peaks with the largest mass-to-charge ratio (m / z) at 636.11 and 638.11, confirming the product's molecular formula as C. 43 H 25 BrO.

[0239] (2) Synthesis of compound 35

[0240] The synthesis method of compound 1 is the same, except that intermediate Me-4 is replaced with an equal amount of intermediate 35-1, and 2-naphthoboric acid is replaced with an equal amount of phenylboronic acid, to obtain compound 35.

[0241] Mass spectrometry analysis of compound 35 showed a mass-to-charge ratio (m / z) of 634.23.

[0242] 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.

[0243] The specific structures of several materials used in the device embodiments of the present invention are as follows:

[0244]

[0245] Device Example 1

[0246] This embodiment of the device provides an organic electroluminescent device, wherein the main material of the light-emitting layer of the organic electroluminescent device is compound 1 provided in synthesis embodiment 1 of the present invention;

[0247] The structure of the organic electroluminescent device is: ITO / HT (100nm) emitting layer (30nm): BH:BD-13% / TPBI (30nm) / LiF (0.5nm) / Al (150nm).

[0248] The fabrication process of organic electroluminescent devices is as follows:

[0249] 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.

[0250] The material was placed in a vacuum chamber and evacuated to a vacuum level of 1×10⁻⁵ to 1×10⁻⁶ Pa, and then vacuum-deposited onto a cleaned ITO substrate. The light-emitting layer (30 nm): BH:BD-1 3% refers to the fact that BH and BD-1 are co-evaporated in a volume ratio of 97:3 to form the light-emitting layer, with a thickness of 30 nm. TPBI is the electron transport layer, LiF is the electron injection layer, and BH is the host material of the light-emitting layer. In this embodiment, the host material of the light-emitting layer (i.e., BH) is compound 1 provided in synthesis example 1 of this invention.

[0251] Device Examples 2-21

[0252] Device Examples 2-21 each provide an organic electroluminescent device, which differs from Device Example 1 only in that the main material of the light-emitting layer is different (see Table 3 below), while other conditions are the same as those in Device Example 1.

[0253] Device Comparison Example 1-2

[0254] Comparative Examples 1 and 2 each provide an organic electroluminescent device, which differs from Device Example 1 only in that the main material of the light-emitting layer is different (see Table 3 below), while other conditions are the same as Device Example 1.

[0255] Performance testing

[0256] 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 its original brightness while maintaining an initial brightness of 2000 nits with a constant current density. Driving voltage, current efficiency, and LT90 are all relative values.

[0257] The test results of the above organic electroluminescent devices are shown in Table 3 below:

[0258] Table 3

[0259]

[0260] As shown in Table 3, this invention, through the design of the structure of hydrogenated naphthoperylene compounds, further improves the structure of the parent core. The design yields hydrogenated naphthoperylene compounds that can be used as the main material for the light-emitting layer. The organic electroluminescent devices prepared in this way have lower driving voltage, higher current efficiency, and longer lifespan.

[0261] 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 the structure shown in formula BHI: BHI; Among them, Ar 101 The substituent is selected from any one of the following substituted or unsubstituted groups: phenyl, naphthyl, triphenylene, fluoranthyl, anthracene, phenanthryl, fluorenyl, indoxfluorenyl, dibenzofuranyl, dibenzothiophene, naphthobenzofuranyl, naphthobenzothiophene, wherein the substituent is selected from any one of -D, methyl, ethyl, propyl, butyl, adamantyl, 1-methylcyclohexyl, 1-methylcyclopentyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, diphenyl, dibenzofuranyl, or dibenzothiophene; Ar 102 Selected from any one of the following groups, substituted or unsubstituted: phenyl, diphenyl, triphenyl or naphthyl, wherein the substituted substituent is selected from -D; R 101 and R 102 Each is independently selected from any one of methyl, ethyl, or propyl; R 101 and R 102 Connecting them into a ring via a single bond, or R 101 and R 102 No connection; m is selected from 0 or 1.

2. The hydrogenated naphthoperylene compound according to claim 1, characterized in that, The Ar 101 Selected from any one of the following unsubstituted groups: ； The dashed lines represent connection points.

3. A hydrogenated naphthoperylene compound, characterized in that, The hydrogenated naphthoperylene compounds are selected from any one of the following substituted or unsubstituted compounds: ； The substitution refers to the replacement of at least one hydrogen atom in the above compound with a deuterium atom.

4. An intermediate, characterized in that, The intermediate is selected from any one of the following compounds: 、 、 、 ； Among them, X and Y are each independently selected from Cl, Br or I; R 101 It has the same scope of protection as claim 1; The intermediate is used to prepare the hydrogenated naphthoperylene compounds as described in any one of claims 1-3.

5. The intermediate according to claim 4, characterized in that, The intermediate is selected from any one of the following compounds: 、 、 、 ； The intermediate is used to prepare the hydrogenated naphthoperylene compounds as described in any one of claims 1-3.

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 organic thin film layer includes a light-emitting layer, and the material of the light-emitting layer includes a host material, which includes a hydrogenated naphthoperylene compound as described in any one of claims 1-3.

7. A display device, characterized in that, The display device includes the organic electroluminescent device as described in claim 6.

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