Long-lifetime organic electroluminescent compound and organic electroluminescent device comprising same

Abstract

Provided are a long-lifetime organic electroluminescent compound and an organic electroluminescent device comprising same. The general structural formula of the organic electroluminescent compound is as shown in formula I. The organic electroluminescent compound contains a benzonaphthofuran fragment. By replacing dibenzofuran with a benzonaphthofuran structure, the conjugation length of a π electron cloud is extended. When the molecule accepts an electron and transforms into an anionic state, negative charges can be effectively dispersed on the benzonaphthofuran fragment, avoiding excessive local energy caused by uneven distribution of negative charges, thereby enhancing the stability of the material can be increased. It was further discovered that the benzonaphthofuran fragment exhibits good planarity, so that the stability of the material can be significantly improved by means of partial deuteration, and the vibration of carbon-hydrogen bonds can be significantly reduced by deuterating some sites on the benzonaphthofuran structure, thereby enhancing the stability of the benzonaphthofuran and reducing the deuteration cost.

Description

A long-life organic electroluminescent compound and an organic electroluminescent device containing the same Technical Field

[0001] The present invention belongs to the technical field of OLED, and in particular relates to a long-life organic electroluminescent compound and an organic electroluminescent device containing the same. Background Art

[0002] Organic Light-Emitting Diode (OLED) is a display lighting technology that has gradually developed in recent years. Especially in the display industry, OLED displays have attracted widespread attention due to their advantages such as high response, high contrast, and flexibility. The pixel units of full-color OLED display screens currently on the market are composed of three primary colors: red, green, and blue. According to the principle of three primary colors, various colors can be produced by controlling the monochrome grayscale levels of red, green, and blue of the sub-pixel units, thereby displaying a color picture. In three-color light-emitting devices, compared with red and green light materials, blue light materials have higher energy and can be transferred to low-energy green, yellow, and red organic light-emitting materials through energy. And according to the principle of three primary colors, blue light emission is the basis for achieving white and color display. Moreover, the lifespan of blue OLEDs is still insufficient compared to that of red and green OLEDs. Recent studies (Hwang KM, Kim T, Kang SA systematic investigation to unravel the primary determinant of the operational stability of blue fluorescent organic light-emitting diodes[J]. Journal of Materials Chemistry C, 2022, 10(27): 10139-10146.) show that in blue OLED devices, the bond dissociation energy (BDE) of the anionic host molecule in the light-emitting layer has a significant impact on the lifespan compared to other functional layers except the light-emitting layer; although the BDE of the anionic state of other functional layers except the light-emitting layer, such as the hole blocking layer material, is lower than that of the host material, the electrochemical stability of the host material has the greatest impact on the device lifespan.

[0003] Currently, the light-emitting layers in blue organic electroluminescent devices almost all use a host-guest doped luminescence system, that is, electroluminescence is achieved by doping a host material with a guest dopant material. Commonly used blue fluorescent devices mainly use anthracene-based host materials. Studies have found that the efficiency of blue light-emitting devices can be improved by introducing fragments containing highly electronegative oxygen atoms, such as dibenzofuran, into the host material. However, the BDE of the carbon-oxygen bond of anthracene-based host materials containing dibenzofuran fragments in the anionic state is low, approximately 1.727 eV, which is much smaller than the BDE of the carbon-carbon bond in the anionic state (approximately 3.99-4.11 eV). Therefore, the stability of anthracene-based host materials containing dibenzofuran fragments is poor, which will lead to a shortened lifespan of the organic electroluminescent device.

[0004] Introducing special substituents and deuteration are ways to improve material stability. Introducing aromatic substituents can increase device lifespan, but aromatic substituents usually cause changes in the optical properties of the material, leading to a decrease and change in device efficiency. Deuteration usually has a smaller effect on optical properties, but the cost of replacing all hydrogen atoms on the molecule with deuterium is high, and the effect of partial deuteration will have different effects depending on the deuteration site. In particular, when the deuteration site is not the weakest link in the molecule, the market requirement of significantly improving device lifespan cannot be met. Therefore, there is an urgent need to develop a new, long-life light-emitting layer host material that can be used in organic electroluminescent devices.

[0005] Summary of the Invention

[0006] In view of this, the present invention provides a long-life organic electroluminescent compound and an organic electroluminescent device containing the same. The organic electroluminescent compound has high stability. The organic electroluminescent compound provided by the present invention is used as the main material of the light-emitting layer in a blue organic electroluminescent device. The main material of the light-emitting layer can effectively extend the life of the blue organic electroluminescent device, overcoming the defects of the prior art.

[0007] In order to achieve the above-mentioned object of the invention, the present invention adopts the following technical solutions:

[0008] The first aspect of the present invention provides a long-life organic electroluminescent compound, the general structural formula of the organic electroluminescent compound is shown in Formula I:

[0009] D is deuterium, and n is an integer selected from 0 to 8;

[0010] Ar1 is selected from any one of a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted condensed ring aryl group having 10 to 60 carbon atoms, and a substituted or unsubstituted condensed ring heteroaryl group having 8 to 30 carbon atoms;

[0011] The L1 and L2 are selected from single bonds, substituted or unsubstituted arylene groups having 6 to 30 carbon atoms;

[0012] When any one of L1, L2, and Ar1 has a substituent, the substituent of L1, L2, and Ar1 may be one or more, and each is independently selected from any one of deuterium, an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a condensed ring aryl group having 10 to 30 carbon atoms;

[0013] The Ar2 is selected from any one of the structures shown in Formula II-1 to Formula II-3:

[0014] Said X is selected from O or S;

[0015] The R 11 to R 14 、R 21 、R 22 、R 31 to R 34 Any one of them is bonded to L2 of the formula Ⅰ;

[0016] The R 11 to R 14 、R 21 、R 22 、R 31 to R 34 Each is independently selected from any one of hydrogen, deuterium, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms, wherein adjacent groups may be bonded to each other through a linking group or a single bond to form an aromatic ring or a condensed ring;

[0017] When the R 11 to R 14 、R 21 、R 22 When any one of the following is selected from deuterium, the R 31 to R 34 are not selected from deuterium; when the R 11 to R 14 With R 21 、R 22 When neither is selected from deuterium, the R 31 to R 34 At least one of them is selected from deuterium, and when the R 11 to R 14 、R 21 、R 22 、R 31 to R 34When any one of them is selected from deuterium, all hydrogen atoms in the same benzene ring are replaced by deuterium.

[0018] A first aspect of the present invention provides an organic electroluminescent compound containing a benzonaphthofuran fragment (at the Ar2 position). The present invention uses a benzonaphthofuran structure to replace dibenzofuran to extend the conjugated length of the π electron cloud. When the molecule accepts electrons and transforms into an anionic state, the negative charge can be effectively dispersed on the benzonaphthofuran fragment, avoiding excessive local energy caused by uneven negative charge distribution, thereby increasing the stability of the material. It is further found that the benzonaphthofuran fragment has good planarity and the stability of the material can be significantly improved by partial deuteration. By deuterating some sites on the benzonaphthofuran structure, the present invention can significantly reduce the vibration of the carbon-hydrogen bond, enhance the stability of the benzonaphthofuran, and reduce the cost of deuteration.

[0019] In combination with the first aspect, the Ar2 is selected from any one of the structures shown in the following formulas II-11 to II-34, wherein II-11 to II-15 are a group of general structures, II-21 to II-26 are a group of general structures, and II-31 to II-34 are a group of general structures:

[0020] The R 11 to R 14 、R 21 、R 22 、R 311 to R 314 、R 41 to R 44 、R 51 to R 54 、R 61 to R 64 Any one of them is bonded to L2 of the formula Ⅰ;

[0021] The R 11 to R 14 、R 21 、R 22 、R 41 to R 44 、R 51 to R 54 、R 61 to R 64 is selected from hydrogen or deuterium, said R 311 to R 314 is selected from hydrogen, deuterium or an aryl group having 6 to 30 carbon atoms;

[0022] When the R 11 to R 14 、R21 、R 22 、R 61 to R 64 When any one of the following is selected from deuterium, the R 311 to R 314 、R 41 to R 44 、R 51 to R 54 are not selected from deuterium, and when the R 11 to R 14 、R 21 、R 22 、R 311 to R 314 、R 41 to R 44 、R 51 to R 54 、R 61 to R 64 When any one of is selected from deuterium, the hydrogens on the same benzene ring as the hydrogens and the hydrogens on the groups on the same benzene ring as the hydrogens are replaced by deuterium;

[0023] When the R 11 to R 14 、R 21 、R 22 、R 61 to R 64 When neither is selected from deuterium, the R 311 to R 314 、R 41 to R 44 、R 51 to R 54 At least one of them is selected from deuterium, and when the R 11 to R 14 、R 21 、R 22 、R 311 to R 314 、R 41 to R 44 、R 51 to R 54 、R 61 to R 64 When any one of them is selected from deuterium, the hydrogen on the same benzene ring and the hydrogen on the group on the same benzene ring are replaced by deuterium.

[0024] In combination with the first aspect, the II-11 is selected from any one of the structures represented by the following formula II-111 to formula II-114:

[0025] The II-21 is selected from any one of the structures represented by the following formula II-211 to formula II-214:

[0026] The II-31 is selected from any one of the structures shown in the following formula II-311 to formula II-314:

[0027] Any one site in the structures represented by Formula II-111 to Formula II-314 can be bonded to L2 of Formula I.

[0028] In combination with the first aspect, the Ar1 is selected from any one of a substituted or unsubstituted phenyl group or biphenyl group having 6 to 60 carbon atoms, a substituted or unsubstituted naphthyl group or phenalkenyl group having 10 to 60 carbon atoms, and a substituted or unsubstituted benzonaphthofuranyl group or dinaphthofuranyl group having 8 to 30 carbon atoms;

[0029] When Ar1 has a substituent, the substituent of Ar1 may be one or more, and each is independently selected from any one of deuterium, methyl, ethyl, isopropyl, tert-butyl, halomethyl, adamantyl, phenyl, biphenyl, and naphthyl.

[0030] In combination with the first aspect, L1 and L2 are selected from any one of a single bond, a deuterated or undeuterated phenylene group, and a deuterated or undeuterated biphenylene group.

[0031] In combination with the first aspect, L1 and L2 are selected from a single bond or a phenylene group.

[0032] In combination with the first aspect, X is selected from O.

[0033] In combination with the first aspect, the Ar1 is selected from any one of phenyl, biphenyl, and naphthyl.

[0034] In combination with the first aspect, the organic electroluminescent compound is selected from any one of the following structures:

[0035] The second aspect of the present invention provides an application of the organic electroluminescent compound described in the first aspect in the field of organic electroluminescence.

[0036] A third aspect of the present invention provides an organic electroluminescent device, comprising a first electrode sequentially disposed on a substrate; a second electrode disposed opposite to the first electrode; and one or more organic functional layers disposed between the first electrode and the second electrode;

[0037] Wherein, the organic functional layer includes a light-emitting layer, and the light-emitting layer includes one or more organic electroluminescent compounds as described above.

[0038] In combination with the third aspect, the light-emitting layer includes a host material and a doping material, and the host material includes one or more organic electroluminescent compounds as described above.

[0039] The beneficial effects of the present invention are as follows:

[0040] The present invention provides a long-life organic electroluminescent compound, which contains a benzonaphthofuran fragment. The present invention uses a benzonaphthofuran structure to replace dibenzofuran to extend the conjugated length of the π electron cloud. When the molecule accepts electrons and transforms into an anionic state, the negative charge can be effectively dispersed on the benzonaphthofuran fragment, avoiding excessive local energy caused by uneven negative charge distribution, thereby increasing the stability of the compound. Furthermore, the present invention unexpectedly discovered during the research process that the benzonaphthofuran fragment has good planarity. Deuteration of some sites on the naphthofuran structure can significantly reduce the vibration of carbon-hydrogen bonds and enhance the stability of benzonaphthofuran. The present invention improves the bond dissociation energy at the weakest part by rationally deuterating some sites on the benzonaphthofuran structure, significantly improves the stability of the compound, and reduces the deuteration cost. The organic electroluminescent compound provided by the present invention is used as the main material of the light-emitting layer in a blue organic electroluminescent device. The main material of the light-emitting layer can effectively extend the life of the blue organic electroluminescent device, overcoming the shortcomings of the prior art. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] The specific embodiments of the present invention will be further described in detail below with reference to the accompanying drawings.

[0042] FIG1 is a schematic structural diagram of an organic electroluminescent device containing the organic electroluminescent compound of the present invention;

[0043] Description of the drawings: 1-substrate, 2-anode, 3-hole injection layer, 4-hole transport layer, 5-luminescence auxiliary layer, 6-luminescent layer, 7-electron transport layer, 8-electron injection layer, 9-cathode. DETAILED DESCRIPTION

[0044] In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with preferred embodiments and accompanying drawings. It should be understood by those skilled in the art that the content specifically described below is illustrative and non-restrictive, and should not be used to limit the scope of protection of the present invention. The embodiments and comparative examples of this specification are provided to more completely explain this specification to those skilled in the art. According to the embodiments and comparative examples of this specification, various different forms can be deformed, and the scope of protection of the present invention should not be limited only to the embodiments and comparative examples described in detail below.

[0045] The organic electroluminescent compound of the present invention is suitable for use in light-emitting elements, display panels and electronic devices, and is particularly suitable for use in organic electroluminescent devices. The electronic device of the present invention is a device comprising a layer of at least one organic compound, which may also comprise an inorganic material or a layer formed entirely of an inorganic material. The electronic device is preferably an organic electroluminescent device (OLED), an organic integrated circuit (O-IC), an organic field effect transistor (O-FET), an organic thin film transistor (O-TFT), an organic light-emitting transistor (O-LET), an organic solar cell (O-SC), an organic dye-sensitized solar cell (O-DSSC), an organic optical detector, an organic photoreceptor, an organic field quenching device (O-FQD), a light-emitting electrochemical cell (LEC), an organic laser diode (O-laser) and an organic plasma emission device. The electronic device is preferably an organic electroluminescent device (OLED).

[0046] In order to understand the content of the present invention more clearly, the luminescent characteristics of the organic electroluminescent compound, its preparation method and the device comprising it will be explained in detail in conjunction with the examples. Various chemical reactions can be applied to the synthetic method of the compound of one embodiment of the present invention. However, it should be noted that the synthetic method of the compound of one embodiment of the present invention is not limited to the synthetic method described below. Unless otherwise stated, subsequent synthesis is carried out in anhydrous solvent under a protective gas atmosphere. Solvents and reagents can be purchased from conventional reagent suppliers.

[0047] Intermediate synthesis of host material compounds

[0048] The synthetic route of intermediate A is as follows:

[0049] In a 100 mL reaction flask, add A-5 (0.96 g, 10 mmol), 10 mL D2O and 5 mL isopropanol. Under an argon atmosphere, add catalyst Pt / C (0.12 g, 0.06 mmol). Raise the temperature to 180 ° C. and react for 12 h. Cool to room temperature, remove the catalyst Pt / C, and distill under reduced pressure to obtain A-4 (0.73 g, 72%).

[0050] In a 100 mL reaction bottle, add A-4 (1.01 g, 10 mmol) and 6 mL of acetic acid, cool to -10 ° C, slowly add 3 mL of concentrated nitric acid, react at 0 ° C for 2 h, pour into 30 mL of water, extract twice with 20 mL of dichloromethane, combine the organic phases, dry, concentrate under reduced pressure, and pass through a silica gel column to obtain A-3 (0.65 g, 45%).

[0051] In a 250 mL reaction bottle, add A-3 (1.45 g, 10 mmol), 20 mL of dichloromethane and 1 mL of acetic acid, slowly add N-bromosuccinimide (2.13 g, 12 mmol), react at room temperature for 12 h, add 20 mL of water, stir, separate the liquids, spin dry the organic phase, and recrystallize to obtain A-2 (1.61 g, 72%).

[0052] In a 250 mL reaction bottle, add A-2 (2.23 g, 10 mmol), 20 mL of water, 20 mL of ethanol, ammonium chloride (1.60 g, 30 mmol) and reduced iron powder (1.68 g, 30 mmol), reflux for 8 h, cool to room temperature, filter, add 40 mL of water and 40 mL of dichloromethane, extract twice, combine the organic phases, dry, and concentrate under reduced pressure to obtain A-1 (1.31 g, 68%).

[0053] In a 100 mL reaction flask, A-1 (2.66 g, 10 mmol) and 3 mL of concentrated hydrochloric acid were added at 0°C, and then NaNO2 (1.03 g, 15 mmol) was added to the mixture. The mixture was reacted for 1 h. A saturated solution of KI (2.49 g, 15 mmol) was slowly added under temperature control and stirred for 1 h. The mixture was then warmed to room temperature and reacted for 1 d. The reaction solution was then poured into 50 mL of saturated sodium thiosulfate solution. The aqueous phase was extracted twice with 50 mL of dichloromethane. The organic phases were combined, dried, concentrated, and passed through a silica gel column to obtain intermediate A (1.21 g, 40%).

[0054] The synthetic route of intermediate B is as follows:

[0055] In a 100 mL reaction bottle, compound B-3 (1.58 g, 10 mmol), 10 mL D2O and 5 mL isopropanol were added. In an argon atmosphere, catalyst Pt / C (0.12 g, 0.06 mmol) was added. The temperature was raised to 180 ° C. and the reaction was carried out for 12 h. The temperature was cooled to room temperature. The catalyst Pt / C was filtered out and distilled under reduced pressure to obtain B-2 (1.14 g, 69%).

[0056] In a 250mL reaction bottle, add B-2 (1.65g, 10mmol), 10mL acetonitrile, 10mL water and mandelic acid (3.04g, 2mmol), slowly add N-bromosuccinimide (2.13g, 12mmol), react at room temperature for 36h, add 20mL ethyl acetate, pour into 30mL saturated NaHCO3 solution, stir, stand and separate, take the organic phase, extract the aqueous phase with ethyl acetate (2×20mL), combine the organic phases, dry the organic phases with sodium sulfate, concentrate under reduced pressure, and pass through a silica gel column to obtain B-1 (1.60g, 66%).

[0057] In a 250 mL reaction flask, B-1 (2.43 g, 10 mmol) and 25 mL of dichloromethane were added under nitrogen protection, the temperature was lowered to -78 ° C, BBr3 (10.02 g, 40 mmol) was slowly added, the temperature was slowly raised to room temperature, and the reaction was carried out for 2 h. Saturated NaHCO3 solution was added to terminate the reaction, the pH was adjusted to about 7, 20 mL of water was added, stirred, and allowed to stand for separation. The organic phase was taken, and the aqueous phase was extracted with dichloromethane (2×30 mL). The organic phases were combined, dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure. The organic phase was passed through a silica gel column to obtain B (1.79 g, 78%).

[0058] The synthetic route of intermediate C is as follows:

[0059] Refer to the synthesis method of B-2, except that the intermediate B-3 is replaced by C-3 (1.46 g, 10 mmol), and finally compound C-2 (0.97 g, 65%) is obtained.

[0060] C-2 (0.75 g, 5 mmol), K2CO3 (0.14 g, 1 mmol), Pd / C (0.25 g, 0.25 mmol Pd), and dichloromethane (10 mL) were added to a two-necked flask equipped with a stir bar. The flask was first degassed and sealed with a balloon gas mixture (0.2 atm of hydrogen and 0.8 atm of nitrogen, with a hydrogen to nitrogen volume ratio of 3:7). The reaction was heated to 150°C in an oil bath and stirred vigorously for 17 h. After completion of the reaction, the Pd / C was filtered, 20 mL of water was added to the filtrate, and the pH was adjusted to neutral with a sufficient amount of dilute hydrochloric acid. The filtrate was extracted with ethyl acetate (3 × 30 mL), and the organic layers were combined and dried over anhydrous Na2SO4. The solvent was evaporated under reduced pressure to obtain the crude product, which was purified by column chromatography to afford C-1 (0.59 g, 80%).

[0061] In a 250 mL reaction flask, C-1 (1.48 g, 10 mmol), diisopropylamine (0.10 g, 1 mmol), and 30 mL of dichloromethane were added, and N-bromosuccinimide (2.13 g, 12 mmol) was slowly added. The temperature was raised to 40°C, and the reaction was carried out for 12 h. The temperature was then lowered to room temperature. The pH of the system was adjusted to 5 with 1 mol / L hydrochloric acid solution. 20 mL of water was added, the mixture was stirred, and the mixture was allowed to stand for separation. The organic phase was taken, and the aqueous phase was extracted with 20 mL of dichloromethane. The organic phases were combined, and the organic phases were dried over anhydrous sodium sulfate, concentrated under reduced pressure, and passed through a silica gel column to obtain C (1.14 g, 50%).

[0062] Synthesis Example

[0063] Example 1

[0064] This example provides a compound H-1, the synthesis route of which is as follows:

[0065] In a 250 ml reaction flask, 35 mL of toluene, potassium acetate (1.96 g, 20 mmol), intermediate B (2.29 g, 10 mmol), 1-j (3.05 g, 12 mmol) and palladium dichloride (0.07 g, 0.1 mmol) were added under nitrogen protection, the temperature was raised to reflux, the reaction was carried out for 8 h, the temperature was lowered to room temperature, 20 mL of water was added, the mixture was stirred, and the stratification was allowed to stand. The organic phase was taken, evaporated to dryness under reduced pressure, and passed through a silica gel column to obtain 1-i (1.96 g, 71%).

[0066] In a 250 mL three-necked flask, 30 mL of toluene, 15 mL of ethanol and 15 mL of water were added under nitrogen protection, followed by the addition of 1-i (2.76 g, 10 mmol), compound 1-h (3.01 g, 10 mmol), potassium carbonate (4.15 g, 30 mmol) and tetrakistriphenylphosphine palladium (0.35 g, 0.3 mmol). The mixture was heated to 80 ° C and reacted for 12 h. The mixture was cooled to room temperature, 15 mL of water was added, stirred, and allowed to stand for stratification. The organic phase was taken, evaporated to dryness under reduced pressure, and passed through a silica gel column to obtain 1-g (2.33 g, 72%).

[0067] In a 250 mL reaction flask, add 35 mL of dimethylformamide and 1-g (3.23 g, 10 mmol), slowly add 60% mass percentage concentration of NaH (1 g, 25 mmol), raise the temperature to 140 ° C, react for 8 h, cool to room temperature, pour into ice water, filter, and pass through a silica gel column to obtain 1-f (1.30 g, 43%).

[0068] Referring to the synthetic method of 1-i, intermediate B was replaced with 1-f (3.03 g, 10 mmol) to obtain 1-e (2.45 g, 70%).

[0069] Referring to the synthesis method of 1-g, 1-i was replaced by 1-e (3.50 g, 10 mmol), and 1-h was replaced by 1-d (2.57 g, 10 mmol) to obtain 1-c (2.92 g, 73%).

[0070] In a 250 mL reaction flask, compound 1-c (4.01 g, 10 mmol), 50 mL of dichloromethane and 1 mL of acetic acid were added, and N-bromosuccinimide (2.13 g, 12 mmol) was slowly added. The reaction was allowed to proceed overnight at room temperature. 50 mL of water was added, stirred, and the liquids were separated. The organic phase was taken, dried, and recrystallized to obtain 1-a (3.69 g, 79%).

[0071] In a 250 mL three-necked flask, 50 mL of toluene, 25 mL of ethanol and 25 mL of water were added under nitrogen protection, followed by the addition of 1-a (4.79 g, 10 mmol), 1-b (1.22 g, 10 mmol), potassium carbonate (4.15 g, 30 mmol) and tetrakistriphenylphosphine palladium (0.35 g, 0.3 mmol). The mixture was heated to 80 °C and reacted for 12 h. The mixture was cooled to room temperature and filtered. The filter cake was dissolved in toluene and then filtered to remove the solid insoluble matter. The mixture was then recrystallized to obtain compound H-1 (3.00 g, 63%), MS: m / z 476.20 [M+].

[0072] Example 2

[0073] This example provides a compound H-2, the synthesis route of which is as follows:

[0074] The same method as that for synthesizing A-4 was used, except that A-5 was replaced with 2-n (0.78 g, 10 mmol), to obtain compound 2-m (0.58 g, 69%).

[0075] In a 100 mL reaction bottle, add 2-m (0.84 g, 10 mmol) and 5 mL of acetic acid, cool to -10 ° C, slowly add 2 mL of concentrated nitric acid, react at 0 ° C for 2 h, pour into 30 mL of water, extract twice with 20 mL of dichloromethane, combine the organic phases, dry, concentrate under reduced pressure, and pass through a silica gel column to obtain 2-l (0.0.65 g, 51%).

[0076] In a 100 mL reaction flask, add 2-l (1.28 g, 10 mmol) and 6 mL of acetic acid, cool to -10 ° C, slowly add 2 mL of concentrated nitric acid, react at 0 ° C for 2 h, pour into 30 mL of water, extract twice with 20 mL of dichloromethane, combine the organic phases, dry, concentrate under reduced pressure, and pass through a silica gel column to obtain the product 2-k (0.95 g, 55%).

[0077] In a 100 mL reaction bottle, add 2-k (1.72 g, 10 mmol), 17 mL of dimethylformamide, potassium carbonate (3.46 g, 25 mmol) and 2-j (2.70 g, 10 mmol), raise the temperature to 90 ° C, react for 12 h, cool to room temperature, pour into 100 mL of ice water, extract the aqueous phase with dichloromethane (2×30 mL), combine the organic phases, dry, concentrate under reduced pressure, and pass through a silica gel column to obtain 2-i (2.73 g, 69%).

[0078] In a 250 mL reaction flask, 32 mL of dimethylformamide, 2-i (3.95 g, 10 mmol), potassium carbonate (2.76 g, 20 mmol) and Pd(PPh3)4 (0.35 g, 0.3 mmol) were added in a nitrogen atmosphere. After stirring at room temperature for 30 min, the mixture was refluxed for 18 h, cooled to room temperature, 100 mL of water was added, stirred for 30 min, and the aqueous phase was extracted with 100 mL of dichloromethane. The organic phase was taken, dried over sodium sulfate, concentrated under reduced pressure, and passed through a silica gel column to obtain 2-h (1.41 g, 53%).

[0079] In a 250 mL reaction bottle, 2-h (2.66 g, 10 mmol), 20 mL of water, 20 mL of ethanol, ammonium chloride (1.60 g, 30 mmol) and reduced iron powder (1.68 g, 30 mmol) were added, refluxed for 12 h, cooled to room temperature, filtered, 40 mL of water and 40 mL of dichloromethane were added, extracted twice, the organic phases were combined, dried over sodium sulfate, and concentrated under reduced pressure to obtain 2-g (1.51 g, 64%).

[0080] In a 100 mL reaction flask, 2-g (2.36 g, 10 mmol) and 6 mL of concentrated nitric acid were added at 0 ° C to obtain a mixed solution. NaNO2 (1.03 g, 15 mmol) was added to the mixed solution and reacted for 1 h. 6 mL of hydrobromic acid and a saturated CuBr solution (2.15 g, 15 mmol) were slowly added under temperature control and stirred for 1 h. The temperature was then raised to 70 ° C and reacted for 2 d. The mixture was poured into 50 mL of saturated sodium thiosulfate solution and adjusted to neutral. The aqueous phase was extracted with dichloromethane (2×50 mL), the organic phases were combined, dried and concentrated, and passed through a silica gel column to obtain 2-f (1.38 g, 46%).

[0081] Referring to the synthetic method of 1-i, intermediate B was replaced with 2-f (3.00 g, 10 mmol) to obtain 2-e (2.40 g, 69%).

[0082] Referring to the synthesis method of 1-g, 1-i was replaced by 2-e (3.47 g, 10 mmol), and 1-h was replaced by 2-d (2.57 g, 10 mmol) to obtain 2-c (2.82 g, 71%).

[0083] Referring to the synthesis method of 1-a, 1-c was replaced with 2-c (3.97 g, 10 mmol) to obtain 2-a (3.67 g, 77%).

[0084] Referring to the synthesis method of compound H-1, 1-a was replaced by 2-a (4.76 g, 10 mmol), and 1-b was replaced by 2-b (1.98 g, 10 mmol) to obtain compound H-2 (3.52 g, 64%), MS: m / z 549.22 [M+].

[0085] Example 3

[0086] This example provides a compound H-3, the synthesis route of which is as follows:

[0087] In a 100 mL reaction bottle, 3-1 (1.44 g, 10 mmol) and 14 mL of D2O were added, and catalyst Pt / C (0.12 g, 0.06 mmol) was added in an argon atmosphere. The temperature was raised to 180 ° C. and the reaction was carried out for 12 h. The temperature was cooled to room temperature, the catalyst Pt / C was filtered out, and 3-k (1.07 g, 71%) was obtained by distillation under reduced pressure.

[0088] In a 250 mL reaction flask, 3-k (1.51 g, 10 mmol), diisopropylamine (0.10 g, 1 mmol) and 30 mL of dichloromethane were added, and N-bromosuccinimide (2.13 g, 12 mmol) was slowly added. The temperature was raised to 40 ° C. and the reaction was carried out for 12 h. The temperature was cooled to room temperature. The pH of the system was adjusted to 5 with 1 mol / L hydrochloric acid solution, which was weakly acidic. 20 mL of water was added, stirred, and allowed to stand for separation. The organic phase was taken, and the aqueous phase was extracted with 20 mL of dichloromethane. The organic phases were combined, and the organic phases were dried over anhydrous sodium sulfate, concentrated under reduced pressure, and passed through a silica gel column to obtain 3-j (1.19 g, 52%).

[0089] Referring to the synthetic method of 1-i, intermediate B was replaced with 3-j (2.29 g, 10 mmol) to obtain 3-i (1.96 g, 71%).

[0090] Referring to the synthesis method of 1-g, 1-i was replaced by 3-i (2.76 g, 10 mmol), and 1-h was replaced by 3-h (3.01 g, 10 mmol) to obtain 3-g (2.36 g, 73%).

[0091] Referring to the synthesis method of 1-f, 1-g was replaced with 3-g (3.23 g, 10 mmol) to obtain 3-f (1.27 g, 42%).

[0092] Referring to the synthetic method of 1-i, intermediate B was replaced with 3-f (3.03 g, 10 mmol) to obtain 3-e (2.42 g, 69%).

[0093] Referring to the synthesis method of 1-g, 1-i was replaced by 3-e (3.50 g, 10 mmol), and 1-h was replaced by 3-d (2.57 g, 10 mmol) to obtain 3-c (2.88 g, 72%).

[0094] Referring to the synthetic method of 1-a, 1-c was replaced with 3-c (4.01 g, 10 mmol) to obtain 3-a (3.79 g, 79%).

[0095] Referring to the synthesis method of compound H-1, 1-a was replaced by 3-a (4.79 g, 10 mmol), and 1-b was replaced by 3-b (1.79 g, 10 mmol) to obtain compound H-3 (3.26 g, 62%), MS: m / z 533.71 [M+].

[0096] Example 4

[0097] This example provides a compound H-4, the synthesis route of which is as follows:

[0098] Referring to the synthesis method of 1-g, 1-h was replaced with 4-h (3.01 g, 10 mmol) to obtain 4-g (2.29 g, 71%);

[0099] Referring to the synthesis method of 1-f, 1-g was replaced with 4-g (3.23 g, 10 mmol) to obtain 4-f (1.30 g, 43%);

[0100] Referring to the synthetic method of 1-i, intermediate B was replaced with 4-f (3.03 g, 10 mmol) to obtain 4-e (2.52 g, 72%);

[0101] Referring to the synthesis method of 1-g, 1-i was replaced by 4-e (3.50 g, 10 mmol) and 1-h was replaced by 4-d (2.57 g, 10 mmol) to obtain 4-c (2.92 g, 73%);

[0102] Referring to the synthesis method of 1-a, 1-c was replaced with 4-c (4.01 g, 10 mmol) to obtain 4-a (3.64 g, 76%);

[0103] Referring to the synthesis method of compound H-1, 1-a was replaced by 4-a (4.79 g, 10 mmol), and 1-b was replaced by 4-b (1.72 g, 10 mmol) to obtain compound H-4 (3.37 g, 64%), MS: m / z 526.22 [M+].

[0104] Example 5

[0105] This example provides a compound H-5, the synthesis route of which is as follows:

[0106] In a 100 mL reaction bottle, compound 5-k (0.94 g, 10 mmol) and 10 ml of D2O were added, and Pt / C (0.12 g, 0.06 mmol) was added in an argon atmosphere. The temperature was raised to 180°C, reacted for 12 h, cooled to room temperature, the insoluble matter was filtered out, and 5-j (0.70 g, 71%) was obtained by distillation under reduced pressure.

[0107] In a 250 mL reaction flask, 5-j (0.99 g, 10 mmol), diisopropylamine (0.10 g, 1 mmol) and 30 mL of dichloromethane were added, and N-bromosuccinimide (3.92 g, 22 mmol) was slowly added. The temperature was raised to 40 ° C. and the reaction was carried out for 12 h. The temperature was cooled to room temperature. The pH of the system was adjusted to 5 with 1 mol / L hydrochloric acid solution. 20 mL of water was added, stirred, and allowed to stand for separation. The organic phase was taken and the aqueous phase was extracted with 20 mL of dichloromethane. The organic phases were combined, and the organic phases were dried over anhydrous sodium sulfate, concentrated under reduced pressure, and passed through a silica gel column to obtain 5-i (1.66 g, 65%).

[0108] Referring to the synthesis method of 1-g, 1-i was replaced by 5-i (2.55 g, 10 mmol), 1-h was replaced by 5-h (1.72 g, 10 mmol), and 5-g (2.21 g, 73%) was obtained.

[0109] In a 250 mL reaction flask, 5-g (3.02 g, 10 mmol), 30 mL of dimethylformamide, 3-nitropyridine (2.48 g, 20 mmol) and tert-butyl perbenzoate (3.88 g, 20 mmol) were added under nitrogen protection, and palladium acetate (0.11 g, 0.5 mmol) was added. The temperature was raised to reflux and the reaction was carried out for 36 h. The temperature was cooled to room temperature and poured into 100 mL of ice water. The aqueous phase was extracted with dichloromethane (3×50 ml). The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 5-f (0.99 g, 33%).

[0110] Referring to the synthetic method of 1-i, intermediate B was replaced with 5-f (3.00 g, 10 mmol) to obtain 5-e (2.47 g, 71%).

[0111] Referring to the synthesis method of 1-g, 1-i was replaced by 5-e (3.47 g, 10 mmol), 1-h was replaced by 5-d (2.57 g, 10 mmol), and 5-c (2.94 g, 74%) was obtained.

[0112] Referring to the synthetic method of 1-a, 1-c was replaced with 5-c (3.97 g, 10 mmol) to obtain 5-a (3.72 g, 78%).

[0113] Referring to the method for compound H-1, 1-a was replaced with 5-a (4.76 g, 10 mmol) and 1-b was replaced with 5-b (1.72 g, 10 mmol) to obtain compound H-5 (3.19 g, 61%), MS: m / z 523.20 [M+]

[0114] Example 6

[0115] This example provides a compound H-6, the synthesis route of which is as follows:

[0116] Referring to the synthesis method of 1-g, 1-i was replaced by 3-i (2.76 g, 10 mmol), 1-h was replaced by 6-h (3.01 g, 10 mmol), and 6-g (2.42 g, 75%) was obtained.

[0117] Referring to the synthesis method of 1-f, 1-g was replaced with 6-g (3.23 g, 10 mmol) to obtain 6-f (1.30 g, 43%).

[0118] Referring to the synthetic method of 1-i, intermediate B was replaced with 6-f (3.03 g, 10 mmol) to obtain 6-e (2.45 g, 70%).

[0119] Referring to the synthesis method of 1-g, 1-i was replaced by 6-e (3.50 g, 10 mmol), and 1-h was replaced by 6-d (2.66 g, 10 mmol) to obtain 6-c (2.92 g, 73%).

[0120] Referring to the synthetic method of 1-a, 1-c was replaced with 6-c (4.10 g, 10 mmol) to obtain 6-a (3.81, 78%).

[0121] Referring to the method for compound H-1, 1-a was replaced by 6-a (4.88 g, 10 mmol) and 1-b was replaced by 6-b (1.22 g, 10 mmol) to obtain compound H-6 (3.10 g, 64%), MS: m / z 484.66 [M+].

[0122] Example 7

[0123] This example provides a compound H-7, the synthesis route of which is as follows:

[0124] In a 250mL reaction flask, 7-j (1.44g, 10mmol), diisopropylamine (0.10g, 1mmol) and 30mL of dichloromethane were added, and N-bromosuccinimide (2.13g, 12mmol) was slowly added. The temperature was raised to 40°C, the reaction was carried out for 12h, and the temperature was lowered to room temperature. The pH of the system was adjusted to 5 with 1mol / L hydrochloric acid solution, 20mL of water was added, the mixture was stirred, and the mixture was allowed to stand for separation. The organic phase was taken, the aqueous phase was extracted with 20mL of dichloromethane, the organic phases were combined, the organic phases were dried over anhydrous sodium sulfate, concentrated under reduced pressure, and passed through a silica gel column to obtain 7-i (1.20g, 54%).

[0125] Referring to the synthetic method of 1-i, intermediate B was replaced with 7-i (2.23 g, 10 mmol) to obtain 7-h (1.97 g, 73%).

[0126] Referring to the synthesis method of 1-g, 1-i was replaced with 7-h (2.70 g, 10 mmol), and 1-h was replaced with intermediate A (3.04 g, 10 mmol) to obtain 7-g (2.37 g, 74%).

[0127] Referring to the synthesis method of 1-f, 1-g was replaced with 7-g (3.20 g, 10 mmol) to obtain 7-f (1.20 g, 40%).

[0128] Referring to the synthetic method of 1-i, intermediate B was replaced with 7-f (3.00 g, 10 mmol) to obtain 7-e (2.50 g, 72%).

[0129] Referring to the synthesis method of 1-g, 1-i was replaced by 7-e (3.47 g, 10 mmol), 1-h was replaced by 7-d (2.57 g, 10 mmol), and 7-c (2.82 g, 71%) was obtained.

[0130] Referring to the synthesis method of 1-a, 1-c was replaced with 7-c (3.97 g, 10 mmol) to obtain 7-a (3.62 g, 76%).

[0131] Referring to the synthesis method of compound H-1, 1-a was replaced by 7-a (4.76 g, 10 mmol) and 1-b was replaced by 7-b (1.79 g, 10 mmol) to obtain compound H-7 (3.40 g, 64%), MS: m / z 530.69 [M+].

[0132] Example 8

[0133] This example provides a compound H-8, the synthesis route of which is as follows:

[0134] Referring to the synthesis method of intermediate B-1, B-2 was replaced with 8-k (1.58 g, 10 mmol) to obtain compound 8-j (1.52 g, 64%).

[0135] Referring to the synthesis method of intermediate B, B-1 was replaced with 8-j (2.37 g, 10 mmol) to obtain compound 8-i (1.67 g, 75%).

[0136] Referring to the synthetic method of 1-i, intermediate B was replaced with 8-i (2.23 g, 10 mmol) to obtain compound 8-h (1.97 g, 73%).

[0137] Referring to the synthesis method of 1-g, 1-i was replaced by 8-h (2.70 g, 10 mmol), and 1-h was replaced by intermediate A (3.04 g, 10 mmol) to obtain compound 8-g (2.27 g, 71%).

[0138] Referring to the synthesis method of 1-f, 1-g was replaced with 8-g (3.20 g, 10 mmol) to obtain compound 8-f (1.29 g, 43%).

[0139] Referring to the synthetic method of 1-i, intermediate B was replaced with 8-f (3.00 g, 10 mmol) to obtain compound 8-e (2.47 g, 71%).

[0140] Referring to the synthesis method of 1-g, 1-i was replaced by 8-e (3.47 g, 10 mmol), and 1-h was replaced by 8-d (2.57 g, 10 mmol) to obtain compound 8-c (2.94 g, 74%).

[0141] Referring to the synthetic method of 1-a, 1-c was replaced with 8-c (3.97 g, 10 mmol) to obtain compound 8-a (3.72 g, 78%).

[0142] Referring to the synthesis method of compound H-1, 1-a was replaced by 8-a (4.76 g, 10 mmol), and 1-b was replaced by 8-b (1.22 g, 10 mmol) to obtain compound H-8 (2.94 g, 62%), MS: m / z 473.19 [M+].

[0143] Example 9

[0144] This example provides a compound H-9, the synthesis route of which is as follows:

[0145] Referring to the synthesis method of 1-g, 1-h was replaced with 9-h (3.01 g, 10 mmol) to obtain compound 9-g (2.39 g, 74%).

[0146] Referring to the synthesis method of 1-f, 1-g was replaced with 9-g (3.23 g, 10 mmol) to obtain compound 9-f (1.18 g, 39%).

[0147] Referring to the synthetic method of 1-i, intermediate B was replaced with 9-f (3.03 g, 10 mmol) to obtain compound 9-e (2.59 g, 74%).

[0148] Referring to the synthesis method of 1-g, 1-i was replaced by 9-e (3.50 g, 10 mmol), and 1-h was replaced by 9-d (2.57 g, 10 mmol) to obtain compound 9-c (2.84 g, 71%).

[0149] Referring to the synthetic method of 1-a, 1-c was replaced with 9-c (4.01 g, 10 mmol) to obtain compound 9-a (3.69 g, 77%).

[0150] Referring to the synthesis method of compound H-1, 1-a was replaced by 9-a (4.79 g, 10 mmol) and 1-b was replaced by 9-b (1.72 g, 10 mmol) to obtain compound H-9 (3.32 g, 63%), MS: m / z 526.22 [M+].

[0151] Example 10

[0152] This example provides a compound H-10, the synthesis route of which is as follows:

[0153] Referring to the synthesis method of 3-k, 3-1 was replaced with 10-1 (1.44 g, 10 mmol) to obtain compound 10-k (1.03 g, 68%).

[0154] Referring to the synthesis method of 3-j, 3-k was replaced with 10-k (1.51 g, 10 mmol) to obtain compound 10-j (1.26 g, 55%).

[0155] Referring to the synthetic method of 1-i, intermediate B was replaced with 10-j (2.29 g, 10 mmol) to obtain compound 10-i (2.02 g, 73%).

[0156] Referring to the synthesis method of 1-g, 1-i was replaced by 10-i (2.76 g, 10 mmol), 1-h was replaced by 10-h (3.01 g, 10 mmol) to obtain compound 10-g (2.39 g, 74%).

[0157] Referring to the synthesis method of 1-f, 1-g was replaced with 10-g (3.23 g, 10 mmol) to obtain compound 10-f (1.21 g, 40%).

[0158] Referring to the synthetic method of 1-i, intermediate B was replaced with 10-f (3.03 g, 10 mmol) to obtain compound 10-e (2.38 g, 68%).

[0159] Referring to the synthesis method of 1-g, 1-i was replaced by 10-e (3.50 g, 10 mmol), 1-h was replaced by 10-d (2.57 g, 10 mmol) to obtain compound 10-c (2.96 g, 74%).

[0160] Referring to the synthetic method of 1-a, 1-c was replaced with 10-c (4.01 g, 10 mmol) to obtain compound 10-a (3.84 g, 80%).

[0161] Referring to the synthesis method of compound H-1, 1-a was replaced by 10-a (4.79 g, 10 mmol) and 1-b was replaced by 10-b (1.22 g, 10 mmol) to obtain compound H-10 (3.00 g, 63%), MS: m / z 476.20 [M+].

[0162] Example 11

[0163] This example provides a compound H-11, the synthesis route of which is as follows:

[0164] Referring to the synthesis method of 1-g, 1-i was replaced by 3-i (2.76 g, 10 mmol), 1-h was replaced by 11-h (3.01 g, 10 mmol) to obtain compound 6-g (2.39 g, 74%).

[0165] Referring to the synthesis method of 1-f, 1-g was replaced with 11-g (3.23 g, 10 mmol) to obtain compound 11-f (1.33 g, 44%).

[0166] Referring to the synthetic method of 1-i, intermediate B was replaced with 11-f (3.03 g, 10 mmol) to obtain compound 11-e (2.56 g, 73%).

[0167] Referring to the synthesis method of 1-g, 1-i was replaced by 11-e (3.50 g, 10 mmol), and 1-h was replaced by 11-d (2.57 g, 10 mmol) to obtain compound 11-c (2.84 g, 71%).

[0168] Referring to the synthetic method of 1-a, 1-c was replaced with 11-c (4.01 g, 10 mmol) to obtain compound 11-a (3.64 g, 76%).

[0169] Referring to the synthesis method of compound H-1, 1-a was replaced by 11-a (4.79 g, 10 mmol), and 1-b was replaced by 11-b (1.72 g, 10 mmol) to obtain compound H-11 (3.42 g, 65%), MS: m / z 526.22 [M+].

[0170] Example 12

[0171] This example provides a compound H-12, the synthesis route of which is as follows:

[0172] Referring to the synthesis method of 1-g, 1-i was replaced by 10-i (2.76 g, 10 mmol), 1-h was replaced by 12-h (3.01 g, 10 mmol) to obtain compound 12-g (2.42 g, 75%).

[0173] Referring to the synthesis method of 1-f, 1-g was replaced with 12-g (3.23 g, 10 mmol) to obtain compound 12-f (1.39 g, 46%).

[0174] Referring to the synthetic method of 1-i, intermediate B was replaced with 12-f (3.03 g, 10 mmol) to obtain compound 12-e (2.52 g, 72%).

[0175] Referring to the synthesis method of 1-g, 1-i was replaced by 12-e (3.50 g, 10 mmol), and 1-h was replaced by 12-d (3.33 g, 10 mmol) to obtain compound 12-c (3.43 g, 72%).

[0176] Referring to the synthetic method of 1-a, 1-c was replaced with 12-c (4.76 g, 10 mmol) to obtain compound 12-a (4.33 g, 78%).

[0177] Referring to the synthesis method of compound H-1, 1-a was replaced by 12-a (5.56 g, 10 mmol), and 1-b was replaced by 12-b (1.98 g, 10 mmol) to obtain compound H-12 (3.84 g, 61%), MS: m / z 628.27 [M+].

[0178] Example 13

[0179] This example provides a compound H-13, the synthesis route of which is as follows:

[0180] Referring to the synthesis method of 1-g, 1-i was replaced by 10-i (2.76 g, 10 mmol), 1-h was replaced by 13-h (3.01 g, 10 mmol) to obtain compound 13-g (2.36 g, 73%).

[0181] Referring to the synthesis method of 1-f, 1-g was replaced with 13-g (3.23 g, 10 mmol) to obtain compound 13-f (1.27 g, 42%).

[0182] Referring to the synthetic method of 1-i, intermediate B was replaced with 13-f (3.03 g, 10 mmol) to obtain compound 13-e (2.49 g, 71%).

[0183] Referring to the synthesis method of 1-g, 1-i was replaced by 13-e (3.50 g, 10 mmol), and 1-h was replaced by 13-d (2.57 g, 10 mmol) to obtain compound 13-c (2.92 g, 73%).

[0184] Referring to the synthetic method of 1-a, 1-c was replaced with 13-c (4.01 g, 10 mmol) to obtain compound 13-a (3.69 g, 77%).

[0185] Referring to the synthesis method of compound H-1, 1-a was replaced by 13-a (4.79 g, 10 mmol), and 1-b was replaced by 13-b (1.72 g, 10 mmol) to obtain compound H-13 (3.37 g, 64%), MS: m / z 526.22 [M+].

[0186] Example 14

[0187] This example provides a compound H-14, the synthesis route of which is as follows:

[0188] Referring to the synthesis method of 1-g, 1-i was replaced by 14-h (1.88 g, 10 mmol), and 1-h was replaced by intermediate A (3.04 g, 10 mmol) to obtain compound 14-g (2.31 g, 72%).

[0189] Referring to the synthesis method of 1-f, 1-g was replaced with 14-g (3.20 g, 10 mmol) to obtain compound 14-f (1.23 g, 41%).

[0190] Referring to the synthetic method of 1-i, intermediate B was replaced with 14-f (3.00 g, 10 mmol) to obtain compound 14-e (2.53 g, 73%).

[0191] Referring to the synthesis method of 1-g, 1-i was replaced by 14-e (3.47 g, 10 mmol), and 1-h was replaced by 14-d (2.57 g, 10 mmol) to obtain compound 14-c (2.82 g, 71%).

[0192] Referring to the synthetic method of 1-a, 1-c was replaced with 14-c (3.97 g, 10 mmol) to obtain compound 14-a (3.81 g, 80%).

[0193] Referring to the synthesis method of compound H-1, 1-a was replaced by 14-a (4.76 g, 10 mmol), and 1-b was replaced by 14-b (1.72 g, 10 mmol) to obtain compound H-14 (3.14 g, 60%), MS: m / z 523.20 [M+].

[0194] Example 15

[0195] This example provides a compound H-15, the synthesis route of which is as follows:

[0196] Referring to the synthesis method of 1-g, 1-i was replaced by 3-i (2.76 g, 10 mmol), 1-h was replaced by 15-h (3.01 g, 10 mmol) to obtain compound 15-g (2.29 g, 71%).

[0197] Referring to the synthesis method of 1-f, 1-g was replaced with 15-g (3.23 g, 10 mmol) to obtain compound 15-f (1.27 g, 42%).

[0198] Referring to the synthetic method of 1-i, intermediate B was replaced with 15-f (3.03 g, 10 mmol) to obtain compound 15-e (2.45 g, 70%).

[0199] Referring to the synthesis method of 1-g, 1-i was replaced by 15-e (3.50 g, 10 mmol), 1-h was replaced by 15-d (2.57 g 66 g, 10 mmol) to obtain compound 15-c (2.992 g, 73%).

[0200] Referring to the synthesis method of 1-a, 1-c was replaced with 15-c (4.1001 g, 10 mmol) to obtain compound 15-a (3.78 g 85 g, 79%).

[0201] Referring to the synthesis method of compound H-1, 1-a was replaced by 15-a (4.79 g 87 g, 10 mmol), and 1-b was replaced by 15-b (1.98 g, 10 mmol) to obtain compound H-15 (3.43 g 48 g, 62%), MS: m / z 552.2460.75 [M+].

[0202] Example 16

[0203] This example provides a compound H-16, the synthesis route of which is as follows:

[0204] Referring to the synthetic method of 1-i, intermediate B was replaced with 5-i (2.55 g, 10 mmol) to obtain compound 16-i (2.23 g, 74%).

[0205] Referring to the synthesis method of 1-g, 1-i was replaced by 16-i (3.02 g, 10 mmol), and 1-h was replaced by 16-h (3.33 g, 10 mmol) to obtain compound 16-g (2.74 g, 72%).

[0206] In a 250 mL reaction flask, 16-g (3.81 g, 10 mmol), 40 mL of chloroform, tripotassium phosphate (4.25 g, 20 mmol), and cuprous iodide (2.85 g, 15 mmol) were added, the temperature was raised to reflux, the reaction was carried out for 12 h, the temperature was lowered to room temperature, 40 mL of water was added, the mixture was stirred, and the mixture was allowed to stand for separation. The organic phase was taken, the aqueous phase was extracted with dichloromethane (30 mL*2), the organic phases were combined, dried, concentrated under reduced pressure, and passed through a silica gel column to obtain 16-f (1.41 g, 47%).

[0207] Referring to the synthetic method of 1-i, intermediate B was replaced with 16-f (3.00 g, 10 mmol) to obtain compound 16-e (2.47 g, 71%).

[0208] Referring to the synthesis method of 1-g, 1-i was replaced by 16-e (3.47 g, 10 mmol), and 1-h was replaced by 16-d (2.57 g, 10 mmol) to obtain compound 16-c (2.98 g, 75%).

[0209] Referring to the synthetic method of 1-a, 1-c was replaced with 16-c (3.97 g, 10 mmol) to obtain compound 16-a (3.72 g, 78%).

[0210] Referring to the method for compound H-1, 1-a was replaced with 16-a (4.76 g, 10 mmol) and 1-b was replaced with 16-b (1.22 g, 10 mmol) to obtain compound H-16 (2.98 g, 63%), MS: m / z 473.19 [M+].

[0211] Example 17

[0212] This example provides a compound H-17, the synthesis route of which is as follows:

[0213] Referring to the synthesis method of 1-g, 1-i was replaced by 10-i (2.76 g, 10 mmol), 1-h was replaced by 17-h (3.01 g, 10 mmol) to obtain compound 17-g (2.36 g, 73%).

[0214] Referring to the synthesis method of 1-f, 1-g was replaced with 17-g (3.23 g, 10 mmol) to obtain compound 17-f (1.33 g, 44%).

[0215] Referring to the synthetic method of 1-i, intermediate B was replaced with 17-f (3.03 g, 10 mmol) to obtain compound 17-e (2.49 g, 71%).

[0216] Referring to the synthesis method of 1-g, 1-i was replaced by 17-e (3.50 g, 10 mmol), and 1-h was replaced by 17-d (2.57 g, 10 mmol) to obtain compound 17-c (2.96 g, 74%).

[0217] Referring to the synthesis method of 1-a, 1-c was replaced with 17-c (4.01 g, 10 mmol) to obtain compound 17-a (3.69 g, 77%).

[0218] Referring to the synthesis method of compound H-1, 1-a was replaced by 17-a (4.79 g, 10 mmol), and 1-b was replaced by 17-b (1.72 g, 10 mmol) to obtain compound H-17 (3.21 g, 61%), MS: m / z 526.22 [M+].

[0219] Example 18

[0220] This example provides a compound H-18, the synthesis route of which is as follows:

[0221] Referring to the synthesis method of 1-g, 1-h was replaced with 18-h (3.01 g, 10 mmol) to obtain compound 18-g (2.29 g, 71%).

[0222] Referring to the synthesis method of 1-f, 1-g was replaced with 18-g (3.23 g, 10 mmol) to obtain compound 18-f (1.21 g, 40%).

[0223] Referring to the synthetic method of 1-i, intermediate B was replaced with 18-f (3.03 g, 10 mmol) to obtain compound 18-e (2.56 g, 73%).

[0224] Referring to the synthesis method of 1-g, 1-i was replaced by 18-e (3.50 g, 10 mmol), and 1-h was replaced by 18-d (2.57 g, 10 mmol) to obtain compound 18-c (2.88 g, 72%).

[0225] Referring to the synthesis method of 1-a, 1-c was replaced with 18-c (4.01 g, 10 mmol) to obtain compound 18-a (3.79 g, 78%).

[0226] Referring to the synthesis method of compound H-1, 1-a was replaced by 18-a (4.79 g, 10 mmol), and 1-b was replaced by 18-b (1.27 g, 10 mmol) to obtain compound H-18 (3.13 g, 65%), MS: m / z 481.64 [M+].

[0227] Example 19

[0228] This example provides a compound H-19, the synthesis route of which is as follows:

[0229] The same method as Example 1 was used, except that 1-a was replaced by 19-a (5.56 g, 10 mmol) and 1-b was replaced by 19-b (1.22 g, 10 mmol) to obtain compound H-19 (3.37 g, 61%), MS: m / z 552.24 [M+].

[0230] Example 20

[0231] This example provides a compound H-20, the synthesis route of which is as follows:

[0232] The same method as Example 1 was used, except that 1-a was replaced by 20-a (5.56 g, 10 mmol) and 1-b was replaced by 20-b (1.22 g, 10 mmol) to obtain compound H-20 (3.48 g, 63%), MS: m / z 552.24 [M+].

[0233] Example 21

[0234] This example provides a compound H-21, the synthesis route of which is as follows:

[0235] The same method as Example 1 was used, except that 1-a was replaced by 21-a (5.52 g, 10 mmol) and 1-b was replaced by 21-b (1.72 g 79 g, 10 mmol) to obtain compound H-21 (3.84 g 88 g, 64%), MS: m / z 599.23606.79 [M+].

[0236] Example 22

[0237] This example provides a compound H-22, the synthesis route of which is as follows:

[0238] The same method as Example 1 was used, except that 1-a was replaced by 22-a (4.76 g, 10 mmol) and 1-b was replaced by 22-b (1.22 g, 10 mmol) to obtain compound H-22 (2.94 g, 62%), MS: m / z 473.19 [M+].

[0239] Example 23

[0240] This example provides a compound H-23, the synthesis route of which is as follows:

[0241] The same method as Example 1 was used, except that 1-a was replaced by 23-a (4.79 g, 10 mmol) and 1-b was replaced by 23-b (1.98 g, 10 mmol) to obtain compound H-23 (3.54 g, 64%), MS: m / z 552.24 [M+].

[0242] Example 24

[0243] This example provides a compound H-24, the synthesis route of which is as follows:

[0244] The same method as Example 1 was used, except that 1-a was replaced by 24-a (4.79 g 87 g, 10 mmol) and 1-b was replaced by 24-b (1.98 g, 10 mmol) to obtain compound H-24 (3.48 g 53 g, 63%), MS: m / z 552.2460.75 [M+].

[0245] Example 25

[0246] This example provides a compound H-25, the synthesis route of which is as follows:

[0247] The same method as Example 1 was used, except that 1-a was replaced by 25-a (5.52 g, 10 mmol) and 1-b was replaced by 25-b (1.72 g, 10 mmol) to obtain compound H-25 (3.72 g, 62%), MS: m / z 599.23 [M+].

[0248] Example 26

[0249] This example provides a compound H-26, the synthesis route of which is as follows:

[0250] The same method as Example 1 was used, except that 1-a was replaced by 26-a (4.76 g, 10 mmol) and 1-b was replaced by 26-b (1.98 g, 10 mmol) to obtain compound H-26 (3.30 g, 60%), MS: m / z 549.22 [M+].

[0251] Example 27

[0252] This example provides a compound H-27, the synthesis route of which is as follows:

[0253] The same method as Example 1 was used, except that 1-a was replaced by 27-a (5.52 g, 10 mmol) and 1-b was replaced by 27-b (1.72 g, 10 mmol) to obtain compound H-27 (3.78 g, 63%), MS: m / z 599.23 [M+].

[0254] Example 28

[0255] This example provides a compound H-28, the synthesis route of which is as follows:

[0256] The same method as Example 1 was used, except that 1-a was replaced by 28-a (6.29 g, 10 mmol) and 1-b was replaced by 28-b (1.72 g, 10 mmol) to obtain compound H-28 (4.19 g, 62%), MS: m / z 675.26 [M+].

[0257] Example 29

[0258] This example provides a compound H-29, the synthesis route of which is as follows:

[0259] The same method as Example 1 was used, except that 1-a was replaced by 29-a (5.56 g, 10 mmol) and 1-b was replaced by 29-b (1.72 g, 10 mmol) to obtain compound H-29 (3.98 g, 66%), MS: m / z 602.25 [M+].

[0260] Example 30

[0261] This example provides a compound H-30, the synthesis route of which is as follows:

[0262] The same method as Example 1 was used, except that 1-a was replaced by 30-a (5.52 g, 10 mmol) and 1-b was replaced by 30-b (1.98 g, 10 mmol) to obtain compound H-30 (3.94 g, 63%), MS: m / z 625.25 [M+].

[0263] Example 31

[0264] This example provides a compound H-31, the synthesis route of which is as follows:

[0265] The same method as Example 1 was used, except that 1-a was replaced by 31-a (5.56 g, 10 mmol) and 1-b was replaced by 31-b (1.98 g, 10 mmol) to obtain compound H-31 (3.90 g, 62%), MS: m / z 628.27 [M+].

[0266] Example 32

[0267] This example provides a compound H-32, the synthesis route of which is as follows:

[0268] The same method as Example 1 was used, except that 1-a was replaced by 32-a (5.56 g, 10 mmol) and 1-b was replaced by 32-b (1.22 g 27 g, 10 mmol) to obtain compound H-32 (3.54 g 57 g, 64%), MS: m / z 552557.274 [M+].

[0269] Example 33

[0270] This example provides a compound H-33, the synthesis route of which is as follows:

[0271] Referring to the synthetic method of 1-i, intermediate B was replaced by C (2.27 g, 10 mmol) to obtain compound 33-i (1.97 g, 72%).

[0272] Referring to the synthesis method of 1-g, 1-i was replaced by 33-i (2.74 g, 10 mmol), and 1-h was replaced by 33-h (3.01 g, 10 mmol) to obtain compound 33-g (2.38 g, 74%).

[0273] Referring to the synthesis method of 1-f, 1-g was replaced with 33-g (3.21 g, 10 mmol) to obtain compound 33-f (1.29 g, 43%).

[0274] Referring to the synthetic method of 1-i, intermediate B was replaced with 33-f (3.01 g, 10 mmol) to obtain compound 33-e (2.44 g, 70%).

[0275] Referring to the synthesis method of 1-g, 1-i was replaced by 33-e (3.48 g, 10 mmol), and 1-h was replaced by 33-d (2.57 g, 10 mmol) to obtain compound 33-c (2.87 g, 72%).

[0276] Referring to the synthetic method of 1-a, 1-c was replaced with 33-c (3.99 g, 10 mmol) to obtain compound 33-a (3.58 g, 75%).

[0277] Referring to the synthesis method of compound H-1, 1-a was replaced with 33-a (4.77 g, 10 mmol), and 1-b was replaced with 33-b (1.72 g, 10 mmol) to obtain compound H-33 (3.15 g, 60%), MS: m / z 524.66 [M+].

[0278] Example 34

[0279] This example provides a compound H-34, the synthesis route of which is as follows:

[0280] Referring to the synthesis method of 1-g, 1-i was replaced by 33-i (2.76 g, 10 mmol), 1-h was replaced by 34-h (3.01 g, 10 mmol) to obtain compound 34-g (2.25 g, 70%).

[0281] Referring to the synthesis method of 1-f, 1-g was replaced with 34-g (3.21 g, 10 mmol) to obtain compound 34-f (1.20 g, 40%).

[0282] Referring to the synthetic method of 1-i, intermediate B was replaced with 34-f (3.01 g, 10 mmol) to obtain compound 34-e (2.44 g, 70%).

[0283] Referring to the synthesis method of 1-g, 1-i was replaced by 34-e (3.48 g, 10 mmol), and 1-h was replaced by 34-d (2.57 g, 10 mmol) to obtain compound 34-c (2.79 g, 70%).

[0284] Referring to the synthetic method of 1-a, 1-c was replaced with 34-c (3.99 g, 10 mmol) to obtain compound 34-a (3.82 g, 80%).

[0285] Referring to the synthesis method of compound H-1, 1-a was replaced with 34-a (4.77 g, 10 mmol), and 1-b was replaced with 34-b (1.22 g, 10 mmol) to obtain compound H-34 (2.85 g, 60%), MS: m / z 474.60 [M+].

[0286] Comparative Example 1

[0287] This comparative example provides a compound BH-1 that was tested during the research process, and its specific structural formula is:

[0288] Comparative Example 2

[0289] This comparative example provides a compound BH-2 that was tested during the research process, and its specific structural formula is:

[0290] Comparative Example 3

[0291] This comparative example provides a compound BH-3 that was tested during the research process, and its specific structural formula is:

[0292] Comparative Example 4

[0293] This comparative example provides a compound BH-4 that was tested during the research process, and its specific structural formula is:

[0294] Comparative Example 5

[0295] This comparative example provides a compound BH-5 that was tested during the research process, and its specific structural formula is:

[0296] Comparative Example 6

[0297] This comparative example provides a compound BH-6 that was tested during the research process, and its specific structural formula is:

[0298] Comparative Example 7

[0299] This comparative example provides a compound BH-7 that was tested during the research process, and its specific structural formula is:

[0300] Comparative Example 8

[0301] This comparative example provides a compound BH-8 that was tested during the research process, and its specific structural formula is:

[0302] Comparative Example 9

[0303] This comparative example provides a compound BH-9 that was tested during the research process, and its specific structural formula is:

[0304] Compound performance evaluation

[0305] In order to illustrate that the compounds provided by the present invention have higher stability, the molecular structures of the compounds provided in Examples 1 to 34 and Comparative Examples 1 to 4 were subjected to geometry optimization and vibration analysis (Opt+freq) based on the density functional theory (DFT) calculation method (basis set level was set to b3lyp-d3 / 6-31G(d), charge number was 0) using Gaussian 16 A.03 software. The ground state structures of the compounds provided in Examples 1 to 34 and Comparative Examples 1 to 4 were obtained as the basis for subsequent calculations. On the optimized ground state structure, the carbon-oxygen bond of the furan ring in the molecule in the anionic state was subjected to a flexible scan (Relaxed) based on the density functional theory (DFT) calculation method (basis set level was set to b3lyp-d3 / 6-31G(d), charge number was -1). scan), set the carbon-oxygen bond length to increase by 0.1 Å each time, calculate the energy barrier of the carbon-oxygen bond during the breakage process, and use the energy barrier of the carbon-oxygen bond during the breakage process as the BDE of the chemical bond under the anion. The specific calculation results are shown in Table 1.

[0306] Table 1

[0307] As can be seen from the data in Table 1, the BDE of the carbon-oxygen bond of the compound provided by the present invention in the anionic state is ≥1.745 eV, while the BDE of the comparative compound is ≤1.727 eV, indicating that the compound provided by the present invention has high stability. The compound provided by the present invention uses a benzonaphthofuran structure instead of dibenzofuran to extend the conjugated length of the π electron cloud. When the molecule accepts electrons and transforms into an anionic state, the negative charge can be effectively dispersed on the benzonaphthofuran fragment, avoiding instability caused by excessive local energy due to uneven distribution of negative charge.

[0308] Device Example 1

[0309] This embodiment provides a blue organic electroluminescent device, and its preparation method is as follows: first, on the ITO layer (anode) formed on the substrate, HT-1 and p-dopant-1 (the mass ratio of HT-1 to p-dopant-1 is 97:3) are vacuum deposited to a thickness of 10 nm to form a hole injection layer; secondly, on the hole injection layer, HT-1 is vacuum deposited to a thickness of 120 nm to form a hole transport layer; thirdly, on the hole transport layer, B is vacuum deposited to a thickness of 5 nm. prime-1 forms a light-emitting auxiliary layer; again, on the above-mentioned light-emitting auxiliary layer, a composition of a main material and a dopant material is vacuum deposited with a thickness of 20 nm to form a light-emitting layer, wherein H-1 provided in Example 1 is used as a main material compound, BD-1 is used as a dopant material compound, and the mass ratio of the main material compound to the dopant material compound is 98:2; then, on the above-mentioned light-emitting layer, HBL-1 is vacuum deposited with a thickness of 5 nm to form a hole blocking layer; a mixture of ET-1 and Liq (the mass ratio of ET-1 to Liq is 1:1) is vacuum deposited with a thickness of 30 nm to form an electron transport layer; then, on the above-mentioned electron transport layer, LiF is deposited with a thickness of 0.2 nm to form an electron injection layer, and finally, on the above-mentioned electron injection layer, aluminum (Al) is deposited with a thickness of 150 nm to form a cathode, thereby preparing a blue light-emitting organic electroluminescent device.

[0310] Except for the main material compound of the light-emitting layer, the molecular structures of the materials in the remaining layers are as follows:

[0311] The doping material may be selected from but not limited to the following structures:

[0312] The electrode preparation method and the deposition method of each functional layer in this embodiment are conventional methods in the art, such as vacuum thermal evaporation or inkjet printing, etc., and will not be described in detail here.

[0313] Device Examples 2-35

[0314] The method is the same as that of device embodiment 1, except that the host material compound and the dopant material compound in the light-emitting layer are replaced with the combinations in Table 2, respectively.

[0315] Table 2 Comparison of main material compounds and dopant material compounds in device examples

[0316] Device Comparative Examples 1-10

[0317] The method is the same as that of device embodiment 1, except that the host material compound and the dopant material compound in the light-emitting layer material are replaced with the combinations in Table 3, respectively.

[0318] Table 3 Comparison table of main material compounds and dopant material compounds in device comparative examples

[0319] Device performance effect example 1

[0320] The organic electroluminescent devices provided in device examples 1-35 and device comparative examples 1-10 were tested using a standard method. 2 The driving voltage, brightness, electroluminescent current efficiency (measured in cd / A) and external quantum efficiency (EQE, measured in percentage) of the organic electroluminescent device are determined at a current density of 50 mA / cm2. The luminescence spectrum is calculated from the current / voltage / luminous density characteristic line (IVL characteristic line) exhibiting Lambertian emission characteristics. The lifetime LT is defined as the time after which the brightness decreases from the initial luminous brightness L0 to a specific proportion L1 when operating at a constant current J; J = 50 mA / cm2. 2 The expression of L1=90% means that at 50mA / cm 2 When working under 100mA / cm2, the luminance drops to 90% of its initial value L0 after time LT. Similarly, J = 20mA / cm2 2 , L1 = 80% means that at 20mA / cm 2 When working under , the luminous brightness drops to 80% of its initial value L0 after time LT.

[0321] The test instruments and methods for the performance test of the above-mentioned OLED devices are as follows:

[0322] Brightness was tested using a spectral scanner, PhotoResearch PR-635;

[0323] Current density and turn-on voltage: tested using a Keithley 2400 digital source meter;

[0324] Life test: Use LT-96ch life test device.

[0325] The performance test results of the above devices are listed in Table 4.

[0326] Table 4. Performance test results of blue light devices

[0327] As can be seen from the device performance test results in Table 4 above, the lifespan of the organic electroluminescent device provided by the present invention is significantly increased compared with the device comparative example. During the research process, the present invention unexpectedly discovered that the planarity of the benzonaphthofuran fragment is good. By deuterating only some sites on the benzonaphthofuran structure, the vibration of the carbon-hydrogen bond can be significantly reduced, and the stability of the benzonaphthofuran can be enhanced. The present invention improves the bond dissociation energy at the weakest part by rationally deuterating some sites on the benzonaphthofuran structure, significantly improves the stability of the compound, and reduces the deuteration cost. The organic compound provided by the present invention is applied as the main material of the light-emitting layer to a blue organic electroluminescent device. The main material of the light-emitting layer can extend the lifespan of the blue organic electroluminescent device, overcoming the defects of the prior art.

[0328] The above description is merely a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present invention are intended to be covered by the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims.

Claims

1. A long-life organic electroluminescent compound, characterized in that, The general structural formula of the organic electroluminescent compound is shown in Formula I as follows: Wherein, D is deuterium, and n is an integer selected from 0 to 8; Ar1 is selected from any one of a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted condensed polycyclic aryl group having 10 to 60 carbon atoms, and a substituted or unsubstituted condensed polycyclic heteroaryl group having 8 to 30 carbon atoms; L1 and L2 are selected from a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; When any one of L1, L2, and Ar1 has a substituent, the substituents of L1, L2, and Ar1 can be one or more, and are each independently selected from deuterium, an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a condensed polycyclic aryl group having 10 to 30 carbon atoms; The Ar2 is selected from any one of the structures represented by Formula II-1 to Formula II-3: X is selected from O or S; The R 11 to R 14 , R 21 , R 22 , R 31 to R 34 any one of which is bonded to the L2 of the formula I; The R 11 to R 14 , R 21 , R 22 , R 31 to R 34 are each independently selected from any one of hydrogen, deuterium, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms, wherein adjacent groups may be bonded to each other through a linking group or a single bond to form an aromatic ring or a condensed ring; When any one of R 11 to R 14 , R 21 , R 22 is selected from deuterium, none of R 31 to R 34 is selected from deuterium; when none of R 11 to R 14 and R 21 , R 22 is selected from deuterium, at least one of R 31 to R 34 is selected from deuterium, and when any one of R 11 to R 14 , R 21 , R 22 , R 31 to R 34 is selected from deuterium, the hydrogens belonging to the same benzene ring as it are all replaced by deuterium.

2. The organic electroluminescent compound according to claim 1, wherein Ar2 is selected from any one of the structures represented by the following Formula II-11 to Formula II-34: The R 11 to R 14 , R 21 , R 22 , R 311 to R 314 , R 41 to R 44 , R 51 to R 54 , R 61 to R 64 any one of which is bonded to the L2 of the formula Ⅰ; The R 11 to R 14 , R 21 , R 22 , R 41 to R 44 , R 51 to R 54 , R 61 to R 64 is selected from hydrogen or deuterium, and the R 311 to R 314 is selected from hydrogen, deuterium or an aryl group having 6 to 30 carbon atoms; When any one of R 11 to R 14 、R 21 、R 22 、R 61 to R 64 is selected from deuterium, R 311 to R 314 、R 41 to R 44 、R 51 to R 54 are not selected from deuterium, and when any one of R 11 to R 14 、R 21 、R 22 、R 311 to R 314 、R 41 to R 44 、R 51 to R 54 、R 61 to R 64 is selected from deuterium, the hydrogen on the same benzene ring and the hydrogen on the group on the same benzene ring as it are all substituted by deuterium; When the R 11 to R 14 、R 21 、R 22 、R 61 to R 64 are not selected from deuterium, at least one of the R 311 to R 314 、R 41 to R 44 、R 51 to R 54 is selected from deuterium, and when any one of the R 11 to R 14 、R 21 、R 22 、R 311 to R 314 、R 41 to R 44 、R 51 to R 54 、R 61 to R 64 is selected from deuterium, the hydrogens on the same benzene ring as it and the hydrogens on the groups on the same benzene ring as it are all replaced by deuterium.

3. The organic electroluminescent compound according to claim 2, wherein The II-11 is selected from any one of the structures represented by the following Formula II-111 to Formula II-114: The II-21 is selected from any one of the structures represented by the following Formula II-211 to Formula II-214: The II-31 is selected from any one of the structures represented by the following Formula II-311 to Formula II-314: Any one site in the structures represented by Formula II-111 to Formula II-314 can be bonded to L2 of Formula I.

4. The organic electroluminescent compound according to claim 1, wherein Ar1 is selected from any one of a substituted or unsubstituted phenyl or biphenyl group having 6 to 60 carbon atoms, a substituted or unsubstituted naphthyl or phenalenyl group having 10 to 60 carbon atoms, and a substituted or unsubstituted benzonaphthofuranyl or dinaphthofuranyl group having 8 to 30 carbon atoms; When Ar1 has a substituent, the substituents of Ar1 can be one or more, and are each independently selected from deuterium, methyl, ethyl, isopropyl, tert-butyl, halomethyl, adamantyl, phenyl, biphenyl, and naphthyl; 5. The organic electroluminescent compound according to claim 1, wherein L1 and L2 are selected from a single bond, a deuterated or undeuterated phenylene group, and a deuterated or undeuterated biphenylene group; 6. The organic electroluminescent compound according to claim 1, characterized in that, Ar1 is selected from any one of phenyl, biphenyl, naphthyl, phenalenyl, benzonaphthofuranyl, dinaphthofuranyl, methylnaphthyl, ethylbenzene, deuterated phenyl, and deuterated naphthyl; 7. The organic electroluminescent compound according to claim 1, wherein The organic electroluminescent compound is selected from any one of the following structures:

8. The organic electroluminescent compound according to any one of claims 1-7, characterized in that, The organic electroluminescent compound is applied to the field of organic electroluminescence.

9. An organic electroluminescent device, characterized in that, It includes a first electrode sequentially disposed on a substrate; a second electrode disposed opposite to the first electrode; and one or more organic functional layers disposed between the first electrode and the second electrode; Wherein, the organic functional layer includes a light-emitting layer, and the light-emitting layer includes one or more organic electroluminescent compounds according to any one of claims 1-7.

10. The organic electroluminescent device according to claim 9, wherein The light-emitting layer includes a host material and a doping material, and the host material includes one or more organic electroluminescent compounds according to any one of claims 1-7.

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