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

Abstract

The invention provides a long-life organic electroluminescent compound and an organic electroluminescent device comprising the same. The organic electroluminescent compound contains a benzonaphthofuran fragment, dibenzofuran is replaced with a benzonaphthofuran structure, the conjugation length of pi electron cloud is prolonged, when molecules receive electrons and then are converted into an anion state, negative charges can be effectively dispersed on the benzonaphthofuran fragment, and therefore the organic electroluminescent compound has the advantages that the organic electroluminescent compound can be used for organic electroluminescence. According to the present invention, it is further found that the planarity of the benzonaphthofuran fragment is good, and the stability of the material can be significantly improved through the partial deuteration, such that the partial site on the benzonaphthofuran structure is subjected to the deuteration so as to significantly improve the stability of the material; the vibration of carbon-hydrogen bonds can be obviously reduced, the stability of the benzo-naphthofuran is enhanced, and the deuteration cost is reduced.

Description

[0001] This application is a divisional application of the invention application filed by the present applicant on January 16, 2024, with application number 202410063441.X and invention name “A long-life organic electroluminescent compound and an organic electroluminescent device containing the same”. Technical Field

[0002] The 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

[0003] Organic Light-Emitting Diode (OLED) is a display lighting technology that has gradually developed in recent years. Especially in the display industry, OLED display has attracted widespread attention due to its advantages such as high response, high contrast, and flexibility. The pixel units of full-color OLED display screens on the market are all 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 monochromatic grayscale of red, green, and blue sub-pixel units, thereby displaying a color picture. Compared with red and green light materials in three-color light-emitting devices, blue light materials have higher energy and can be transferred to low-energy green, yellow, and red organic light-emitting materials through energy transfer. 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 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, compared with other functional layers except the light-emitting layer, the bond dissociation energy (BDE) of the anionic host molecule in the light-emitting layer has a significant impact on the lifespan; 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 the BDE of the anionic state of the host material, the electrochemical stability of the host material has the greatest impact on the device lifespan.

[0004] At present, the light-emitting layer in blue organic electroluminescent devices almost all uses a host-guest doped light-emitting system, that is, electroluminescence is achieved by doping the host material with the guest doping material. Commonly used blue fluorescent devices mainly use anthracene-based host materials. Studies have found that the efficiency of blue light devices can be improved by introducing fragments containing oxygen atoms with large electronegativity, such as dibenzofuran, into the host material. However, the BDE of the carbon-oxygen bond of the anthracene-based host material containing dibenzofuran fragments in the anionic state is low, about 1.727eV, which is much smaller than the BDE of the carbon-carbon bond in the anionic state (about 3.99-4.11eV). Therefore, the stability of the anthracene-based host material containing dibenzofuran fragments is poor, which will lead to a decrease in the life of the organic electroluminescent device.

[0005] Introducing special substituents and deuteration are ways to improve material stability. Introducing aromatic substituents can increase device life, but aromatic substituents usually cause changes in the optical properties of the material, resulting in a decrease and change in device efficiency. The effect of deuteration on optical properties is usually small, 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 for significantly improving device life 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. Summary of the invention

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

[0010] D is deuterium, and n is an integer selected from 0 to 8;

[0011] 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;

[0012] The L1 and L2 are selected from single bonds, substituted or unsubstituted arylene groups having 6 to 30 carbon atoms;

[0013] 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;

[0014] The Ar2 is selected from any one of the structures shown in Formula II-1 to Formula II-3:

[0015]

[0016] Said X is selected from O or S;

[0017] The R 11 To R 14 , R 21 , R 22 , R 31 To R 34 Any one of which is bonded to L2 of the formula Ⅰ;

[0018] 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;

[0019] When the R 11 To R 14 , R 21 , R 22 When any one of the above 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 is selected from deuterium, all hydrogen atoms in the same benzene ring are replaced by deuterium.

[0020] The first aspect of the present invention provides an organic electroluminescent compound, which contains 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 anion state, the negative charge can be effectively dispersed on the benzonaphthofuran fragment, avoiding excessive local energy caused by uneven distribution of negative charges, 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. The present invention can significantly reduce the vibration of carbon-hydrogen bonds, enhance the stability of benzonaphthofuran, and reduce the deuteration cost by deuterating some sites on the benzonaphthofuran structure.

[0021] 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:

[0022]

[0023]

[0024] 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 L2 of the formula Ⅰ;

[0025] 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;

[0026] When the R11 To R 14 , R 21 , R 22 , R 61 To R 64 When any one of the above 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 hydrogen on the same benzene ring and the hydrogen on the group on the same benzene ring are replaced by deuterium;

[0027] 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 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.

[0028] In combination with the first aspect, the II-11 is selected from any one of the structures shown in the following formula II-111 to formula II-114:

[0029]

[0030] The II-21 is selected from any one of the structures shown in the following formula II-211 to formula II-214:

[0031]

[0032] The II-31 is selected from any one of the structures shown in the following formula II-311 to formula II-314:

[0033]

[0034] Any one site in the structures represented by Formula II-111 to Formula II-314 can be bonded to L2 of Formula I.

[0035] In combination with the first aspect, 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;

[0036] 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.

[0037] 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.

[0038] In combination with the first aspect, L1 and L2 are selected from a single bond or a phenylene group.

[0039] In combination with the first aspect, X is selected from O.

[0040] In combination with the first aspect, Ar1 is selected from any one of phenyl, biphenyl and naphthyl.

[0041] In combination with the first aspect, the organic electroluminescent compound is selected from any one of the following structures:

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058] 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.

[0059] The third aspect of the present invention provides an organic electroluminescent device, comprising a first electrode arranged on a substrate in sequence; a second electrode arranged opposite to the first electrode; and one or more organic functional layers arranged between the first electrode and the second electrode;

[0060] Wherein, the organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises one or more organic electroluminescent compounds as described above.

[0061] 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.

[0062] The beneficial effects of the present invention are as follows:

[0063] The invention provides a long-life organic electroluminescent compound, which contains a benzonaphthofuran fragment. The invention uses a benzonaphthofuran structure to replace dibenzofuran to extend the conjugated length of the π electron cloud. When the molecule accepts electrons and changes into an anion state, the negative charge can be effectively dispersed on the benzonaphthofuran fragment, avoiding excessive local energy caused by uneven distribution of negative charges, thereby increasing the stability of the compound. Furthermore, the invention unexpectedly finds in the process of research that the benzonaphthofuran fragment has good planarity. Deuteration of some sites on the naphthofuran structure can significantly reduce the vibration of the carbon-hydrogen bond and enhance the stability of benzonaphthofuran. The present invention improves the bond dissociation energy at the weakest part by reasonably 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 prolong the life of the blue organic electroluminescent device, overcoming the defects of the prior art. BRIEF DESCRIPTION OF THE DRAWINGS

[0064] The specific implementation modes of the present invention are further described in detail below in conjunction with the accompanying drawings.

[0065] Figure 1 is a schematic structural diagram of an organic electroluminescent device containing the organic electroluminescent compound of the present invention;

[0066] 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

[0067] 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 not restrictive, and the protection scope of the present invention should not be limited to this. The embodiments and comparative examples of this specification are provided to more completely explain this specification to those skilled in the art, and can be deformed into various different forms according to the embodiments and comparative examples of this specification, and the protection scope of the present invention should not be limited only to the embodiments and comparative examples described in detail below.

[0068] 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).

[0069] 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 indicated, the subsequent synthesis is carried out in anhydrous solvent under a protective gas atmosphere. Solvents and reagents can be purchased from conventional reagent suppliers.

[0070] Intermediate synthesis of host material compounds

[0071] The synthetic route of intermediate A is as follows:

[0072]

[0073] In a 100mL reaction bottle, add A-5 (0.96g, 10mmol), 10mL D2O and 5mL isopropanol, under argon atmosphere, add catalyst Pt / C (0.12g, 0.06mmol), raise the temperature to 180°C, react for 12h, cool to room temperature, remove catalyst Pt / C, and distill under reduced pressure to obtain A-4 (0.73g, 72%).

[0074] In a 100mL reaction bottle, add A-4 (1.01g, 10mmol) and 6mL acetic acid, cool to -10℃, slowly add 3mL concentrated nitric acid, react at 0℃ for 2h, pour into 30mL water, extract twice with 20mL dichloromethane, combine the organic phases, dry, concentrate under reduced pressure, and pass through a silica gel column to obtain A-3 (0.65g, 45%).

[0075] In a 250mL reaction bottle, add A-3 (1.45g, 10mmol), 20mL dichloromethane and 1mL acetic acid, slowly add N-bromosuccinimide (2.13g, 12mmol), react at room temperature for 12h, add 20mL water, stir, separate the liquids, spin dry the organic phase, and recrystallize to obtain A-2 (1.61g, 72%).

[0076] In a 250mL reaction bottle, add A-2 (2.23g, 10mmol), 20mL water, 20mL ethanol, ammonium chloride (1.60g, 30mmol) and reduced iron powder (1.68g, 30mmol), reflux for 8h, cool to room temperature, filter, add 40mL water and 40mL dichloromethane to extract twice, combine the organic phases, dry, and concentrate under reduced pressure to obtain A-1 (1.31g, 68%).

[0077] In a 100mL reaction bottle, 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. The mixture was stirred for 1 h, and then the mixture was 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 and concentrated, and passed through a silica gel column to obtain intermediate A (1.21 g, 40%).

[0078] The synthetic route of intermediate B is as follows:

[0079]

[0080] In a 100mL reaction bottle, add compound B-3 (1.58g, 10mmol), 10mL D2O and 5mL isopropanol, add catalyst Pt / C (0.12g, 0.06mmol) in an argon atmosphere, raise the temperature to 180°C, react for 12h, cool to room temperature, filter out the catalyst Pt / C, and distill under reduced pressure to obtain B-2 (1.14g, 69%).

[0081] 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%).

[0082] In a 250mL reaction bottle, add B-1 (2.43g, 10mmol) and 25mL of dichloromethane under nitrogen protection, cool to -78°C, slowly add BBr3 (10.02g, 40mmol), slowly warm to room temperature, react for 2h, add saturated NaHCO3 solution to terminate the reaction, adjust the pH to about 7, add 20mL of water, stir, stand and separate, take the organic phase, extract the aqueous phase with dichloromethane (2×30mL), combine the organic phases, dry the organic phases with sodium sulfate, filter and remove the solvent under reduced pressure, pass through a silica gel column to obtain B (1.79g, 78%).

[0083] The synthetic route of intermediate C is as follows:

[0084]

[0085] 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.

[0086] 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 stirring bar. The flask was first degassed and sealed with a gas mixture balloon (the gas mixture was 0.2 atmospheres of hydrogen and 0.8 atmospheres of nitrogen, and the volume ratio of hydrogen to nitrogen was 3:7). The reaction was heated to 150°C in an oil bath and stirred vigorously for 17 h. After the reaction was completed, Pd / C was filtered, 20 ml of water was added to the filtrate, and a certain amount of dilute hydrochloric acid was added to adjust the pH to neutral. The filtrate was extracted with ethyl acetate (3×30 mL), the organic layers were combined, and the combined organic layers were dried over anhydrous Na2SO4. The solvent was evaporated under reduced pressure to obtain a crude product, and C-1 (0.59 g, 80%) was purified by column chromatography.

[0087] In a 250mL reaction bottle, add C-1 (1.48g, 10mmol), diisopropylamine (0.10g, 1mmol), 30mL of dichloromethane, slowly add N-bromosuccinimide (2.13g, 12mmol), raise the temperature to 40°C, react for 12h, cool to room temperature, use 1mol / L hydrochloric acid solution to make the system pH 5, add 20mL of water, stir, stand and separate, take the organic phase, extract the aqueous phase with 20mL of dichloromethane, combine the organic phases, dry the organic phases with anhydrous sodium sulfate, concentrate under reduced pressure, and pass through a silica gel column to obtain C (1.14g, 50%).

[0088] Synthesis Example

[0089] Example 1

[0090] This example provides a compound H-1, the synthesis route of which is as follows:

[0091]

[0092]

[0093] In a 250 ml reaction bottle, 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%).

[0094] In a 250mL three-necked flask, 30mL toluene, 15mL ethanol and 15mL water were added under nitrogen protection, and then 1-i (2.76g, 10mmol), compound 1-h (3.01g, 10mmol), potassium carbonate (4.15g, 30mmol) and tetrakistriphenylphosphine palladium (0.35g, 0.3mmol) were added, heated to 80°C for 12h, cooled to room temperature, 15mL of water was added, stirred, allowed to stand for stratification, the organic phase was taken, the organic phase was evaporated to dryness under reduced pressure, and passed through a silica gel column to obtain 1-g (2.33g, 72%).

[0095] In a 250mL reaction bottle, add 35mL of dimethylformamide, 1-g (3.23g, 10mmol), slowly add 60% mass percentage concentration of NaH (1g, 25mmol), heat to 140℃, react for 8h, cool to room temperature, pour into ice water, filter, and pass through a silica gel column to obtain 1-f (1.30g, 43%).

[0096] Referring to the synthesis method of 1-i, intermediate B was replaced with 1-f (3.03 g, 10 mmol) to obtain 1-e (2.45 g, 70%).

[0097] Referring to the synthesis method of 1-g, 1-i was replaced by 1-e (3.50 g, 10 mmol), 1-h was replaced by 1-d (2.57 g, 10 mmol), and 1-c (2.92 g, 73%) was obtained.

[0098] In a 250mL reaction bottle, add compound 1-c (4.01g, 10mmol), 50mL of dichloromethane and 1mL of acetic acid, slowly add N-bromosuccinimide (2.13g, 12mmol), react at room temperature overnight, add 50mL of water, stir, separate the liquids, take the organic phase, spin dry the organic phase, and recrystallize to obtain 1-a (3.69g, 79%).

[0099] In a 250mL three-necked flask, 50mL toluene, 25mL ethanol and 25mL water were added under nitrogen protection, followed by 1-a (4.79g, 10mmol), 1-b (1.22g, 10mmol), potassium carbonate (4.15g, 30mmol) and tetrakistriphenylphosphine palladium (0.35g, 0.3mmol), heated to 80°C for 12h, cooled to room temperature, filtered, the filter cake was dissolved in toluene and filtered to remove solid insolubles, and then recrystallized to obtain compound H-1 (3.00g, 63%), MS: m / z 476.20 [M+].

[0100] Example 2

[0101] This example provides a compound H-2, the synthesis route of which is as follows:

[0102]

[0103]

[0104] 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%).

[0105] In a 100mL reaction bottle, add 2-m (0.84g, 10mmol) and 5mL of acetic acid, cool to -10℃, slowly add 2mL of concentrated nitric acid, react at 0℃ for 2h, pour into 30mL of water, extract twice with 20mL of dichloromethane, combine the organic phases, dry, concentrate under reduced pressure, and pass through a silica gel column to obtain 2-l (0.0.65g, 51%).

[0106] In a 100mL reaction bottle, 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%).

[0107] In a 100mL reaction bottle, add 2-k (1.72g, 10mmol), 17mL dimethylformamide, potassium carbonate (3.46g, 25mmol) and 2-j (2.70g, 10mmol), raise the temperature to 90℃, react for 12h, cool to room temperature, pour into 100mL ice water, extract the aqueous phase with dichloromethane (2×30mL), combine the organic phases, dry, concentrate under reduced pressure, and pass through a silica gel column to obtain 2-i (2.73g, 69%).

[0108] In a 250mL reaction bottle, 32mL of dimethylformamide, 2-i (3.95g, 10mmol), potassium carbonate (2.76g, 20mmol) and Pd(PPh3)4 (0.35g, 0.3mmol) were added in a nitrogen atmosphere. After stirring at room temperature for 30min, the mixture was refluxed for 18h, cooled to room temperature, 100mL of water was added, stirred for 30min, and the aqueous phase was extracted with 100mL 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 (1.41g, 53%).

[0109] In a 250mL reaction bottle, add 2-h (2.66g, 10mmol), 20mL water, 20mL ethanol, ammonium chloride (1.60g, 30mmol) and reduced iron powder (1.68g, 30mmol), reflux for 12h, cool to room temperature, filter, add 40mL water and 40mL dichloromethane to extract twice, combine the organic phases, dry the organic phases with sodium sulfate, and concentrate under reduced pressure to obtain 2-g (1.51g, 64%).

[0110] In a 100mL reaction bottle, 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 the reaction was continued 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 the mixture was stirred for 1 h. The mixture was then heated to 70°C and reacted for 2 d. The mixture was poured into 50 mL of a saturated sodium thiosulfate solution and adjusted to neutral. The aqueous phase was extracted with dichloromethane (2×50 mL), and the organic phases were combined. The organic phases were dried and concentrated, and passed through a silica gel column to obtain 2-f (1.38 g, 46%).

[0111] Referring to the synthesis method of 1-i, intermediate B was replaced with 2-f (3.00 g, 10 mmol) to obtain 2-e (2.40 g, 69%).

[0112] Referring to the synthesis method of 1-g, 1-i was replaced by 2-e (3.47 g, 10 mmol), 1-h was replaced by 2-d (2.57 g, 10 mmol), and 2-c (2.82 g, 71%) was obtained.

[0113] 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%).

[0114] Referring to the synthesis method of compound H-1, 1-a was replaced by 2-a (4.76 g, 10 mmol), 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+].

[0115] Example 3

[0116] This example provides a compound H-3, the synthesis route of which is as follows:

[0117]

[0118] In a 100mL reaction bottle, add 3-l (1.44g, 10mmol) and 14mL D2O, add catalyst Pt / C (0.12g, 0.06mmol) in argon atmosphere, raise the temperature to 180℃, react for 12h, cool to room temperature, filter out the catalyst Pt / C, and distill under reduced pressure to obtain 3-k (1.07g, 71%).

[0119] In a 250mL reaction bottle, 3-k (1.51g, 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, and the reaction was carried out for 12h. The temperature was then lowered to room temperature. The pH of the system was adjusted to 5 with 1mol / L hydrochloric acid solution to make it weakly acidic. 20mL 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 20mL 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 (1.19g, 52%).

[0120] Referring to the synthesis method of 1-i, intermediate B was replaced with 3-j (2.29 g, 10 mmol) to obtain 3-i (1.96 g, 71%).

[0121] 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 3-h (3.01 g, 10 mmol), and 3-g (2.36 g, 73%) was obtained.

[0122] 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%).

[0123] Referring to the synthesis method of 1-i, intermediate B was replaced with 3-f (3.03 g, 10 mmol) to obtain 3-e (2.42 g, 69%).

[0124] Referring to the synthesis method of 1-g, 1-i was replaced by 3-e (3.50 g, 10 mmol), 1-h was replaced by 3-d (2.57 g, 10 mmol), and 3-c (2.88 g, 72%) was obtained.

[0125] Referring to the synthesis method of 1-a, 1-c was replaced with 3-c (4.01 g, 10 mmol) to obtain 3-a (3.79 g, 79%).

[0126] Referring to the synthesis method of compound H-1, 1-a was replaced by 3-a (4.79 g, 10 mmol), 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+].

[0127] Example 4

[0128] This example provides a compound H-4, the synthesis route of which is as follows:

[0129]

[0130] 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%);

[0131] 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%);

[0132] Referring to the synthesis method of 1-i, intermediate B was replaced with 4-f (3.03 g, 10 mmol) to obtain 4-e (2.52 g, 72%);

[0133] Referring to the synthesis method of 1-g, 1-i was replaced by 4-e (3.50 g, 10 mmol), 1-h was replaced by 4-d (2.57 g, 10 mmol), and 4-c (2.92 g, 73%) was obtained;

[0134] 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%);

[0135] Referring to the synthesis method of compound H-1, 1-a was replaced by 4-a (4.79 g, 10 mmol), 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+].

[0136] Example 5

[0137] This example provides a compound H-5, the synthesis route of which is as follows:

[0138]

[0139] In a 100mL reaction bottle, add compound 5-k (0.94g, 10mmol) and 10ml D2O, add Pt / C (0.12g, 0.06mmol) in an argon atmosphere, raise the temperature to 180°C, react for 12h, cool to room temperature, filter out insoluble matter, and distill under reduced pressure to obtain 5-j (0.70g, 71%).

[0140] In a 250mL reaction bottle, add 5-j (0.99g, 10mmol), diisopropylamine (0.10g, 1mmol) and 30mL of dichloromethane, slowly add N-bromosuccinimide (3.92g, 22mmol), raise the temperature to 40°C, react for 12h, cool to room temperature, use 1mol / L hydrochloric acid solution to make the pH of the system 5, add 20mL of water, stir, stand and separate, take the organic phase, extract the aqueous phase with 20mL of dichloromethane, combine the organic phases, dry the organic phases with anhydrous sodium sulfate, concentrate under reduced pressure, and pass through a silica gel column to obtain 5-i (1.66g, 65%).

[0141] 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.

[0142] In a 250mL reaction bottle, 5-g (3.02g, 10mmol), 30mL of dimethylformamide, 3-nitropyridine (2.48g, 20mmol) and tert-butyl perbenzoate (3.88g, 20mmol) were added under nitrogen protection, palladium acetate (0.11g, 0.5mmol) was added, the temperature was raised to reflux, the reaction was continued for 36h, the temperature was lowered to room temperature, and the mixture was poured into 100mL of ice water. The aqueous phase was extracted with dichloromethane (3×50ml), the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 5-f (0.99g, 33%).

[0143] Referring to the synthesis method of 1-i, intermediate B was replaced with 5-f (3.00 g, 10 mmol) to obtain 5-e (2.47 g, 71%).

[0144] 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.

[0145] Referring to the synthesis method of 1-a, 1-c was replaced with 5-c (3.97 g, 10 mmol) to obtain 5-a (3.72 g, 78%).

[0146] Referring to the method of compound H-1, 1-a was replaced by 5-a (4.76 g, 10 mmol), 1-b was replaced by 5-b (1.72 g, 10 mmol), to obtain compound H-5 (3.19 g, 61%), MS: m / z 523.20 [M+]

[0147] Example 6

[0148] This example provides a compound H-6, the synthesis route of which is as follows:

[0149]

[0150] 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.

[0151] 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%).

[0152] Referring to the synthesis method of 1-i, intermediate B was replaced with 6-f (3.03 g, 10 mmol) to obtain 6-e (2.45 g, 70%).

[0153] Referring to the synthesis method of 1-g, 1-i was replaced by 6-e (3.50 g, 10 mmol), 1-h was replaced by 6-d (2.66 g, 10 mmol), and 6-c (2.92 g, 73%) was obtained.

[0154] Referring to the synthesis method of 1-a, 1-c was replaced with 6-c (4.10 g, 10 mmol) to obtain 6-a (3.81, 78%).

[0155] Referring to the method of compound H-1, 1-a was replaced by 6-a (4.88 g, 10 mmol), 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+].

[0156] Example 7

[0157] This example provides a compound H-7, the synthesis route of which is as follows:

[0158]

[0159] In a 250mL reaction bottle, add 7-j (1.44g, 10mmol), diisopropylamine (0.10g, 1mmol) and 30mL of dichloromethane, slowly add N-bromosuccinimide (2.13g, 12mmol), raise the temperature to 40°C, react for 12h, cool to room temperature, use 1mol / L hydrochloric acid solution to make the system pH 5, add 20mL of water, stir, stand and separate, take the organic phase, extract the aqueous phase with 20mL of dichloromethane, combine the organic phases, dry the organic phases with anhydrous sodium sulfate, concentrate under reduced pressure, and pass through a silica gel column to obtain 7-i (1.20g, 54%).

[0160] Referring to the synthesis method of 1-i, intermediate B was replaced with 7-i (2.23 g, 10 mmol) to obtain 7-h (1.97 g, 73%).

[0161] Referring to the synthesis method of 1-g, 1-i was replaced by 7-h (2.70 g, 10 mmol), 1-h was replaced by intermediate A (3.04 g, 10 mmol), and 7-g (2.37 g, 74%) was obtained.

[0162] 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%).

[0163] Referring to the synthesis method of 1-i, intermediate B was replaced with 7-f (3.00 g, 10 mmol) to obtain 7-e (2.50 g, 72%).

[0164] 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.

[0165] 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%).

[0166] Referring to the synthesis method of compound H-1, 1-a was replaced by 7-a (4.76 g, 10 mmol), 1-b was replaced by 7-b (1.79 g, 10 mmol), and compound H-7 (3.40 g, 64%) was obtained, MS: m / z 530.69 [M+].

[0167] Example 8

[0168] This example provides a compound H-8, the synthesis route of which is as follows:

[0169]

[0170] 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%).

[0171] 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%).

[0172] Referring to the synthesis 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%).

[0173] Referring to the synthesis method of 1-g, 1-i was replaced by 8-h (2.70 g, 10 mmol), 1-h was replaced by intermediate A (3.04 g, 10 mmol), and compound 8-g (2.27 g, 71%) was obtained.

[0174] 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%).

[0175] Referring to the synthesis 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%).

[0176] Referring to the synthesis method of 1-g, 1-i was replaced by 8-e (3.47 g, 10 mmol), 1-h was replaced by 8-d (2.57 g, 10 mmol), and compound 8-c (2.94 g, 74%) was obtained.

[0177] Referring to the synthesis 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%).

[0178] Referring to the synthesis method of compound H-1, 1-a was replaced by 8-a (4.76 g, 10 mmol), 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+].

[0179] Example 9

[0180] This example provides a compound H-9, the synthesis route of which is as follows:

[0181]

[0182] 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%).

[0183] 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%).

[0184] Referring to the synthesis 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%).

[0185] Referring to the synthesis method of 1-g, 1-i was replaced by 9-e (3.50 g, 10 mmol), 1-h was replaced by 9-d (2.57 g, 10 mmol), and compound 9-c (2.84 g, 71%) was obtained.

[0186] Referring to the synthesis 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%).

[0187] Referring to the synthesis method of compound H-1, 1-a was replaced by 9-a (4.79 g, 10 mmol), 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+].

[0188] Example 10

[0189] This example provides a compound H-10, the synthesis route of which is as follows:

[0190]

[0191]

[0192] 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%).

[0193] Referring to the synthesis method of 3-j, 3-k was replaced by 10-k (1.51 g, 10 mmol) to obtain compound 10-j (1.26 g, 55%).

[0194] Referring to the synthesis 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%).

[0195] 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), and compound 10-g (2.39 g, 74%) was obtained.

[0196] 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%).

[0197] Referring to the synthesis 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%).

[0198] 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), and compound 10-c (2.96 g, 74%) was obtained.

[0199] Referring to the synthesis 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%).

[0200] Referring to the synthesis method of compound H-1, 1-a was replaced by 10-a (4.79 g, 10 mmol), 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+].

[0201] Embodiment 11

[0202] This example provides a compound H-11, the synthesis route of the compound is as follows:

[0203]

[0204]

[0205] 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), and compound 6-g (2.39 g, 74%) was obtained.

[0206] 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%).

[0207] Referring to the synthesis 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%).

[0208] Referring to the synthesis method of 1-g, 1-i was replaced by 11-e (3.50 g, 10 mmol), 1-h was replaced by 11-d (2.57 g, 10 mmol), and compound 11-c (2.84 g, 71%) was obtained.

[0209] Referring to the synthesis 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%).

[0210] Referring to the synthesis method of compound H-1, 1-a was replaced by 11-a (4.79 g, 10 mmol), 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+].

[0211] Example 12

[0212] This example provides a compound H-12, the synthesis route of which is as follows:

[0213]

[0214]

[0215] 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), and compound 12-g (2.42 g, 75%) was obtained.

[0216] 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%).

[0217] Referring to the synthesis 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%).

[0218] Referring to the synthesis method of 1-g, 1-i was replaced by 12-e (3.50 g, 10 mmol), 1-h was replaced by 12-d (3.33 g, 10 mmol), and compound 12-c (3.43 g, 72%) was obtained.

[0219] Referring to the synthesis 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%).

[0220] Referring to the synthesis method of compound H-1, 1-a was replaced by 12-a (5.56 g, 10 mmol), 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+].

[0221] Embodiment 13

[0222] This example provides a compound H-13, the synthesis route of which is as follows:

[0223]

[0224]

[0225] 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), and compound 13-g (2.36 g, 73%) was obtained.

[0226] 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%).

[0227] Referring to the synthesis 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%).

[0228] Referring to the synthesis method of 1-g, 1-i was replaced by 13-e (3.50 g, 10 mmol), 1-h was replaced by 13-d (2.57 g, 10 mmol), and compound 13-c (2.92 g, 73%) was obtained.

[0229] Referring to the synthesis 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%).

[0230] Referring to the synthesis method of compound H-1, 1-a was replaced by 13-a (4.79 g, 10 mmol), 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+].

[0231] Embodiment 14

[0232] This example provides a compound H-14, the synthesis route of which is as follows:

[0233]

[0234]

[0235] Referring to the synthesis method of 1-g, 1-i was replaced by 14-h (1.88 g, 10 mmol), 1-h was replaced by intermediate A (3.04 g, 10 mmol), and compound 14-g (2.31 g, 72%) was obtained.

[0236] 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%).

[0237] Referring to the synthesis 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%).

[0238] Referring to the synthesis method of 1-g, 1-i was replaced by 14-e (3.47 g, 10 mmol), 1-h was replaced by 14-d (2.57 g, 10 mmol), and compound 14-c (2.82 g, 71%) was obtained.

[0239] Referring to the synthesis 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%).

[0240] Referring to the synthesis method of compound H-1, 1-a was replaced by 14-a (4.76 g, 10 mmol), 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+].

[0241] Embodiment 15

[0242] This example provides a compound H-15, the synthesis route of which is as follows:

[0243]

[0244]

[0245] 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), and compound 15-g (2.29 g, 71%) was obtained.

[0246] 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%).

[0247] Referring to the synthesis 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%).

[0248] 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), and compound 15-c (2.992 g, 73%) was obtained.

[0249] 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%).

[0250] Referring to the synthesis method of compound H-1, 1-a was replaced by 15-a (4.79 g 87 g, 10 mmol), 1-b was replaced by 15-b (1.98 g, 10 mmol), and compound H-15 (3.43 g 48 g, 62%) was obtained, MS: m / z 552.2460.75 [M+].

[0251] Example 16

[0252] This example provides a compound H-16, the synthesis route of which is as follows:

[0253]

[0254] Referring to the synthesis 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%).

[0255] Referring to the synthesis method of 1-g, 1-i was replaced by 16-i (3.02 g, 10 mmol), 1-h was replaced by 16-h (3.33 g, 10 mmol), and compound 16-g (2.74 g, 72%) was obtained.

[0256] In a 250mL reaction bottle, add 16-g (3.81g, 10mmol), 40mL chloroform, tripotassium phosphate (4.25g, 20mmol), cuprous iodide (2.85g, 15mmol), raise the temperature to reflux, react for 12h, cool to room temperature, add 40mL water, stir, stand and separate, take the organic phase, extract the aqueous phase with dichloromethane (30mL*2), combine the organic phases, dry, concentrate under reduced pressure, and pass through a silica gel column to obtain 16-f (1.41g, 47%).

[0257] Referring to the synthesis 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%).

[0258] Referring to the synthesis method of 1-g, 1-i was replaced by 16-e (3.47 g, 10 mmol), 1-h was replaced by 16-d (2.57 g, 10 mmol), and compound 16-c (2.98 g, 75%) was obtained.

[0259] Referring to the synthesis 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%).

[0260] Referring to the method for compound H-1, 1-a was replaced by 16-a (4.76 g, 10 mmol), 1-b was replaced by 16-b (1.22 g, 10 mmol), to obtain compound H-16 (2.98 g, 63%), MS: m / z 473.19 [M+].

[0261] Embodiment 17

[0262] This example provides a compound H-17, the synthesis route of which is as follows:

[0263]

[0264] 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), and compound 17-g (2.36 g, 73%) was obtained.

[0265] 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%).

[0266] Referring to the synthesis 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%).

[0267] Referring to the synthesis method of 1-g, 1-i was replaced by 17-e (3.50 g, 10 mmol), 1-h was replaced by 17-d (2.57 g, 10 mmol), and compound 17-c (2.96 g, 74%) was obtained.

[0268] 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%).

[0269] Referring to the synthesis method of compound H-1, 1-a was replaced by 17-a (4.79 g, 10 mmol), 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+].

[0270] Embodiment 18

[0271] This example provides a compound H-18, the synthesis route of the compound is as follows:

[0272]

[0273] 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%).

[0274] 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%).

[0275] Referring to the synthesis 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%).

[0276] Referring to the synthesis method of 1-g, 1-i was replaced by 18-e (3.50 g, 10 mmol), 1-h was replaced by 18-d (2.57 g, 10 mmol), and compound 18-c (2.88 g, 72%) was obtained.

[0277] 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%).

[0278] Referring to the synthesis method of compound H-1, 1-a was replaced by 18-a (4.79 g, 10 mmol), 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+].

[0279] Embodiment 19

[0280] This example provides a compound H-19, the synthesis route of which is as follows:

[0281]

[0282] 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+].

[0283] Embodiment 20

[0284] This example provides a compound H-20, the synthesis route of which is as follows:

[0285]

[0286] 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+].

[0287] Embodiment 21

[0288] This example provides a compound H-21, the synthesis route of which is as follows:

[0289]

[0290] 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+].

[0291] Embodiment 22

[0292] This example provides a compound H-22, the synthesis route of which is as follows:

[0293]

[0294] 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+].

[0295] Embodiment 23

[0296] This example provides a compound H-23, the synthesis route of which is as follows:

[0297]

[0298] 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+].

[0299] Embodiment 24

[0300] This example provides a compound H-24, the synthesis route of which is as follows:

[0301]

[0302] 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+].

[0303] Embodiment 25

[0304] This example provides a compound H-25, the synthesis route of which is as follows:

[0305]

[0306] 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+].

[0307] Embodiment 26

[0308] This example provides a compound H-26, the synthesis route of which is as follows:

[0309]

[0310] 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+].

[0311] Embodiment 27

[0312] This example provides a compound H-27, the synthesis route of which is as follows:

[0313]

[0314] 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+].

[0315] Embodiment 28

[0316] This example provides a compound H-28, the synthesis route of the compound is as follows:

[0317]

[0318] 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+].

[0319] Embodiment 29

[0320] This example provides a compound H-29, the synthesis route of which is as follows:

[0321]

[0322] 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+].

[0323] Embodiment 30

[0324] This embodiment provides a compound H-30, the synthesis route of the compound is as follows:

[0325]

[0326] 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+].

[0327] Embodiment 31

[0328] This example provides a compound H-31, the synthesis route of which is as follows:

[0329]

[0330] 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+].

[0331] Embodiment 32

[0332] This example provides a compound H-32, the synthesis route of which is as follows:

[0333]

[0334] 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+].

[0335] Embodiment 33

[0336] This example provides a compound H-33, the synthesis route of which is as follows:

[0337]

[0338]

[0339] Referring to the synthesis method of 1-i, intermediate B was replaced by C (2.27 g, 10 mmol) to obtain compound 33-i (1.97 g, 72%).

[0340] Referring to the synthesis method of 1-g, 1-i was replaced by 33-i (2.74 g, 10 mmol), 1-h was replaced by 33-h (3.01 g, 10 mmol), and compound 33-g (2.38 g, 74%) was obtained.

[0341] 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%).

[0342] Referring to the synthesis 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%).

[0343] Referring to the synthesis method of 1-g, 1-i was replaced by 33-e (3.48 g, 10 mmol), 1-h was replaced by 33-d (2.57 g, 10 mmol), and compound 33-c (2.87 g, 72%) was obtained.

[0344] Referring to the synthesis 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%).

[0345] Referring to the synthesis method of compound H-1, 1-a was replaced by 33-a (4.77 g, 10 mmol), 1-b was replaced by 33-b (1.72 g, 10 mmol), to obtain compound H-33 (3.15 g, 60%), MS: m / z 524.66 [M+].

[0346] Embodiment 34

[0347] This example provides a compound H-34, the synthesis route of which is as follows:

[0348]

[0349]

[0350] 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), and compound 34-g (2.25 g, 70%) was obtained.

[0351] 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%).

[0352] Referring to the synthesis 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%).

[0353] Referring to the synthesis method of 1-g, 1-i was replaced by 34-e (3.48 g, 10 mmol), 1-h was replaced by 34-d (2.57 g, 10 mmol), and compound 34-c (2.79 g, 70%) was obtained.

[0354] Referring to the synthesis 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%).

[0355] Referring to the synthesis method of compound H-1, 1-a was replaced by 34-a (4.77 g, 10 mmol), 1-b was replaced by 34-b (1.22 g, 10 mmol), to obtain compound H-34 (2.85 g, 60%), MS: m / z 474.60 [M+].

[0356] Comparative Example 1

[0357] This comparative example provides a compound BH-1 that has been tested during the research process, and its specific structural formula is:

[0358]

[0359] Comparative Example 2

[0360] This comparative example provides a compound BH-2 that has been tested during the research process, and its specific structural formula is:

[0361]

[0362] Comparative Example 3

[0363] This comparative example provides a compound BH-3 that has been tested during the research process, and its specific structural formula is:

[0364]

[0365] Comparative Example 4

[0366] This comparative example provides a compound BH-4 that has been tested during the research process, and its specific structural formula is:

[0367]

[0368] Comparative Example 5

[0369] This comparative example provides a compound BH-5 that has been tested during the research process, and its specific structural formula is:

[0370]

[0371] Comparative Example 6

[0372] This comparative example provides a compound BH-6 that has been tested during the research process, and its specific structural formula is:

[0373]

[0374] Comparative Example 7

[0375] This comparative example provides a compound BH-7 that has been tested during the research process, and its specific structural formula is:

[0376]

[0377] Comparative Example 8

[0378] This comparative example provides a compound BH-8 that has been tested during the research process, and its specific structural formula is:

[0379]

[0380] Comparative Example 9

[0381] This comparative example provides a compound BH-9 that has been tested during the research process, and its specific structural formula is:

[0382]

[0383] Compound performance evaluation

[0384] 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 respectively subjected to geometric optimization and vibration analysis (Opt+freq) based on the density functional theory (DFT) calculation method (the basis set level was set to b3lyp-d3 / 6-31G(d), and the charge number was 0) by using Gaussian 16A.03 software, and the ground state structures of the compounds provided in Examples 1 to 34 and Comparative Examples 1 to 4 were respectively obtained as the basis for subsequent calculations. On the optimized ground state structure, based on the density functional theory (DFT) calculation method (the basis set level was set to b3lyp-d3 / 6-31G(d), and the charge number was -1), the carbon-oxygen bonds of the furan rings in the molecules in the anionic state were flexibly scanned (Relaxed scan), set the carbon-oxygen bond length to increase by 0.1A each time, calculate the energy barrier of the carbon-oxygen bond in the breaking process, and take the energy barrier of the carbon-oxygen bond in the breaking process as the BDE of the chemical bond under the anion. The specific calculation results are shown in Table 1.

[0385] Table 1

[0386]

[0387]

[0388] It can be seen from the data in Table 1 that 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 stability of the compound provided by the present invention is relatively high. The compound provided by 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, thereby avoiding instability caused by excessive local energy due to uneven distribution of negative charge.

[0389] Device Example 1

[0390] The present embodiment provides a blue light organic electroluminescent device, and the preparation method thereof is as follows: first, on the ITO layer (anode) formed on the substrate, HT-1 and p-dopant-1 are vacuum deposited with a thickness of 10 nm (the mass ratio of HT-1 to p-dopant-1 is 97:3) to form a hole injection layer; secondly, on the hole injection layer, HT-1 is vacuum deposited with a thickness of 120 nm to form a hole transport layer; and secondly, on the hole transport layer, B is vacuum deposited with 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 doping material is vacuum deposited with a thickness of 20nm 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 doping material compound, and the mass ratio of the main material compound to the doping material compound is 98:2; then, on the above-mentioned light-emitting layer, HBL-1 is vacuum deposited with a thickness of 5nm 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 30nm to form an electron transport layer; then, on the above-mentioned electron transport layer, LiF is deposited with a thickness of 0.2nm to form an electron injection layer, and finally, on the above-mentioned electron injection layer, aluminum (Al) is deposited with a thickness of 150nm to form a cathode, and a blue light organic electroluminescent device is prepared.

[0391] Except for the main material compound of the light-emitting layer, the molecular structures of the materials in the remaining layers are as follows:

[0392]

[0393] The doping material can be selected from but not limited to the following structures:

[0394]

[0395] 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., which will not be described in detail here.

[0396] Device Example 2-35

[0397] The method is the same as that of device embodiment 1, except that the main material compound and the doping material compound in the light-emitting layer are replaced with the combinations in Table 2, respectively.

[0398] Table 2 Comparison table of main material compounds and dopant material compounds in device examples

[0399]

[0400] Device Comparison Examples 1-10

[0401] The method is the same as that of device embodiment 1, except that the main material compound and the doping material compound in the light-emitting layer material are replaced with the combinations in Table 3 respectively.

[0402] Table 3 Comparison table of main material compounds and doping material compounds in device comparative examples

[0403] Device Comparison Host material compound Dopant Compounds Device Comparative Example 1 BH-1 BD-1 Device Comparison Example 2 BH-2 BD-1 Device Comparison Example 3 BH-3 BD-1 Device Comparison Example 4 BH-4 BD-1 Device Comparison Example 5 BH-5 BD-1 Device Comparative Example 6 BH-6 BD-1 Device Comparison Example 7 BH-7 BD-1 Device Comparison Example 8 BH-8 BD-1 Device Comparative Example 9 BH-9 BD-1 Device Comparative Example 10 BH-1 BD-2

[0404] Device performance effect example 1

[0405] The organic electroluminescent devices provided in device examples 1-35 and device comparative examples 1-10 were tested by standard methods. 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 500 mA / cm2, which are calculated from the current / voltage / luminescent density characteristic line (IVL characteristic line) showing Lambertian emission characteristics as a function of luminous density, and the luminescent spectrum. The lifetime LT is defined as the time after which the brightness drops 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 L1 = 90% means that at 50 mA / cm 2 When working under LT, the luminance drops to 90% of its initial value L0 after time LT. Similarly, J = 20 mA / cm 2 , L1 = 80% means, at 20mA / cm 2 When working under LT, the luminous brightness drops to 80% of its initial value L0 after time LT.

[0406] The test instrument and method for performing performance test on the above OLED device are as follows:

[0407] Brightness was tested using a spectral scanner PhotoResearch PR-635;

[0408] Current density and lighting voltage: tested using a digital source meter Keithley 2400;

[0409] Life test: Use LT-96ch life test device.

[0410] The performance test results of the above devices are listed in Table 4.

[0411] Table 4 Blue light device performance test results

[0412]

[0413] It can be seen from the device performance test results in Table 4 above that the life of the organic electroluminescent device provided by the present invention is significantly increased compared with the device control example. The present invention unexpectedly found in the process of research that the planarity of the benzonaphthofuran fragment is good, and only by deuterating 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 reasonably 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 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 prolong the life of the blue organic electroluminescent device, overcoming the defects of the prior art.

[0414] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A long-life organic electroluminescent compound, characterized in that: The organic electroluminescent compound is selected from one of the structures shown below:

2. The organic electroluminescent compound according to claim 1, characterized in that The organic electroluminescent compound is applied to the field of organic electroluminescence.

3. An organic electroluminescent device, characterized in that: The method comprises a first electrode sequentially arranged on a substrate; a second electrode arranged opposite to the first electrode; and one or more organic functional layers arranged between the first electrode and the second electrode; Wherein, the organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises one or more organic electroluminescent compounds according to claim 1.

4. The organic electroluminescent device according to claim 3, characterized in that: The light-emitting layer comprises a host material and a doping material, wherein the host material comprises one or more organic electroluminescent compounds according to claim 1 .

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