High-efficiency narrow-band organic electroluminescent material and application thereof in preparation of organic electroluminescent device

Abstract

The application relates to a high-efficiency narrow-spectrum organic electroluminescent material and application thereof in preparation of an electroluminescent device, and belongs to the technical field of organic electroluminescent materials. The organic electroluminescent material is prepared by a concept design of C=O / N rigid skeleton, is a large steric hindrance protected fluorescent material, is used as a doping material in combination with other host materials, and is used for preparing a light-emitting layer of an organic electroluminescent device. The prepared device has the advantages of narrow working spectrum and high efficiency. When the compound of the application is used as a light-emitting layer guest material, the device has the performances of low working voltage, high efficiency, narrow spectrum and long service life. Since the compound has large rigidity, vibration coupling of a ground state and a first excited singlet state and excitation state structure relaxation are inhibited, spectrum widening and fluorescence quantum yield (PLQY) reduction are caused, large steric hindrance protection is avoided, and aggregation quenching and spectrum widening under high voltage are avoided.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of organic electroluminescent materials, and particularly relates to a high-efficiency narrow-band organic electroluminescent material and application thereof in preparation of an organic electroluminescent device. BACKGROUND

[0002] Since the successful demonstration of organic electroluminescent devices (OLEDs), OLED materials have been widely studied in academia and industry, and they have various advantages, such as light weight, fast response time, wide viewing angle, good chemical tunability of emitting molecules, low energy consumption, compatibility with flexible plastic substrates, and suitability for various types of displays. At present, the technology has been widely applied to lighting, mobile phones, computers and televisions, and is a new type of display technology with rapid development and wide application.

[0003] In order to meet the display requirements of the new generation of ultra-high-definition video, B.T.2020 (Broadcast Television 2020) redefines various parameter indicators of ultra-high-definition video display in the broadcast television and consumer electronics industry, wherein the CIE (Commission Internationale de L'Eclairage, 1931) color coordinates of red, green and blue are (0.708, 0.292), (0.170, 0.797) and (0.131, 0.046), respectively. This requires that the OLED material has a peak position, a narrow spectrum and no shoulder peak, which has posed an unprecedented challenge in the field of OLEDs.

[0004] Generally, due to the great structural flexibility, the vibration relaxation of the light-emitting material is strong, and the full width at half maximum (FWHM) of the spectrum is very wide (usually 70-100 nm), which will result in low spectral color purity. In order to meet the actual application, optical means such as optical filters or optical microcavities are generally used in industry to obtain high color purity, but this inevitably causes energy loss and increases the preparation cost. In order to meet the requirements of B.T.2020, the development of narrow-band light-emitting materials has become a research hotspot in the field of OLEDs.

[0005] The rigid planar light-emitting material has the advantage of narrowing the half-peak width, but the OLED device prepared therefrom requires low doping concentration of the light-emitting material and is difficult to prepare; under high voltage, the aggregation quenching effect is relatively serious, causing the spectrum to be broadened and the efficiency to be seriously rolled down. In order to overcome this shortcoming, the present application converts the original two-dimensional planar material into a three-dimensional material wrapped with a protective group having a large steric effect by adding a protective group having a large steric effect to the periphery of the planar light-emitting material; the OLED device prepared therefrom still maintains a narrow spectrum and high efficiency under high doping concentration, greatly reducing the difficulty of preparation, and even under high voltage, the spectrum broadening and efficiency roll-off caused by the aggregation quenching effect are not obvious. In the present application, the planar rigid material protected by a large steric group is simple to synthesize, stable in structure, narrow in spectrum and high in luminous efficiency, and shows great potential in constructing high-efficiency narrow-spectrum OLEDs. SUMMARY

[0006] The purpose of the present application is to provide a high-efficiency narrow-spectrum organic electroluminescent material and its application in light-emitting devices. The organic electroluminescent material prepared by the concept design of C=O / N rigid skeleton is a fluorescent material protected by a large steric group, which is used as a doping material in combination with other host materials for preparing the light-emitting layer of an organic electroluminescent device, and the prepared device exhibits the advantages of narrow working spectrum and high efficiency.

[0007] The high-efficiency narrow-spectrum organic electroluminescent material according to the present application has a general structure represented by one of formulas I, II, III, IV and V:

[0008]

[0009] X is independently selected from:

[0010]

[0011] Y 1 , Y 2 are the same or different and are independently selected from:

[0012]

[0013] Z 1 , Z 2 are the same or different and are independently selected from

[0014] represents the bonding position;

[0015] X and Y 1 , Y 2 and Z 1 , Z 2 at least one of which is a group with electron-withdrawing properties R is selected from hydrogen, C1-C10 alkyl, C1-C10 alkoxy, C6-C10 aryl;

[0016] R is selected from hydrogen, C1-C10 alkyl, C1-C10 alkoxy, C6-C10 aryl;

[0017] Further, R is preferably hydrogen, C1-C4 alkyl, phenyl.

[0018] In the specific embodiments of the present application, the high-efficiency narrow-band organic electroluminescent material as the guest material has one of the following structural formulas:

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041] In the specific embodiments of the present application, the preparation method and conditions of the high-efficiency narrow-band organic electroluminescent material can refer to the steps and conditions of similar reactions in the art.

[0042] The preparation method of the high-efficiency narrow-band organic electroluminescent material described in the present application is as follows:

[0043] Alkylation or arylation:

[0044]

[0045] R' is independently selected from X1is independently selected from When R is hydrogen, no alkylation or arylation is performed, and the subsequent reaction is directly performed, which is not described separately below.

[0046] Under N2atmosphere, raw material 1-1 and AlCl3(raw material 1-1:AlCl3=1:2.2 (molar ratio), except for special instructions, the use ratio of raw materials in the present application is molar ratio) were dispersed in dry DCM, and alkyl chloride (R-Cl, raw material 1-1:alkyl chloride = 1:4) was slowly added dropwise. Stirring was performed at -45°C for 4h. The reaction was quenched with ice water, and the liquid phase was removed by filtration under reduced pressure. The crude product was purified by silica gel column chromatography (DCM as eluent), concentrated to 20mL with DCM, and the alkylated product 1-2 was obtained by precipitation and filtration.

[0047] Raw material 1-1 and silica gel were dispersed in DCM, kept at 0°C for 15min, and a DCM solution of NBS (raw material 1-1:NBS = 1:2.2) was slowly added dropwise under light shielding conditions. The temperature was naturally increased to room temperature, and stirring was performed overnight. After rotary evaporation, the crude product was purified by silica gel column chromatography (DCM as eluent), and recrystallized with DCM and MeOH to obtain the phenylated intermediate 1-3.

[0048] Under N2atmosphere, the phenylated intermediate 1-3, phenylboronic acid (phenylated intermediate 1-3:phenylboronic acid = 1:1.1), Pd(PPh3)4 (phenylated intermediate 1-3:Pd(PPh3)4 = 33:1), K2CO3 (phenylated intermediate 1-3:K2CO3 = 1:2) were dispersed in a mixed solution of toluene, ethanol, H2O (toluene:ethanol:H2O = 10:1:5 (volume ratio)), and refluxing was performed for 8h. The liquid was separated, the aqueous phase was extracted with DCM three times, the organic phases were combined and rotary evaporated. The crude product was purified by silica gel column chromatography (DCM as eluent), and recrystallized with DCM and MeOH to obtain the phenylated product 1-4.

[0049] Preparation of important intermediates:

[0050] (X 1-1 indicates )

[0051] Compound 2-1, 1,4-diiodobenzene (compound 1:1,4-diiodobenzene = 2.2:1), CuI (compound 1:CuI = 5:1), 2,2,6,6-tetramethylheptane-3,5-dione (TMHD) compound 1:2,2,6,6-tetramethylheptane-3,5-dione = 2.5:1), and Cs2CO3 (compound 1:Cs2CO3 = 1:2) were dispersed in DMF under N2 atmosphere, and refluxed at 150°C for 8h. After cooling to room temperature, the filter cake was obtained by filtration under reduced pressure. The crude product was purified by silica gel column chromatography (DCM as eluent), and recrystallized with DCM and methanol to obtain compound 2-2.

[0052] Br2 (compound 2-2:Br2 = 1:10) was added to a DCM solution of compound 2-2 at room temperature, and K2CO3 (compound 2-2:K2CO3 = 1:2) was added after 2h, and stirred for another 22h. The reaction was quenched with saturated sodium sulfite solution, and the water layer was washed with DCM 3 times. The organic layer was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (DCM as eluent), and recrystallized with DCM and methanol to obtain compound 2-3.

[0053] Compound 2-3, Pd(OAc)2 (compound 2-3:Pd(OAc)2 = 25:1), PCy3HBF4 (compound 2-3:PCy3HBF4 = 12.5:1), and K2CO3 (compound 2-3:K2CO3 = 1:3) were dispersed in DMAc under N2 atmosphere, and reacted at 130°C for 24h. After cooling to room temperature, the filter cake was obtained by filtration under reduced pressure, and the crude product was purified by silica gel column chromatography (DCM as eluent) to obtain compound 2-4.

[0054] Br2 (compound 2-4:Br2 = 1:10) was added to a DCM solution of compound 2-4 at room temperature. K2CO3 (compound 2-4:K2CO3 = 1:2) was added after 2h, and stirred for another 22h. The reaction was quenched with saturated sodium sulfite solution, and the water layer was washed with DCM 3 times. The organic layer was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (DCM as eluent), and recrystallized with DCM and methanol to obtain important intermediate 2-5.

[0055]

[0056] When X1 is a carbonyl group, under a N2 atmosphere, the borane-tetrahydrofuran complex (compound 2-5':borane-tetrahydrofuran complex = 1:2) was slowly added dropwise to a dry THF solution of compound 2-5', and refluxed for 2 hours. After cooling to room temperature, the reaction was quenched with H2O, and the aqueous layer was washed three times with DCM. The organic solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (DCM as eluent). Recrystallization with DCM and methanol yielded the important intermediate 2-6 (compound 2-5' with a carbonyl group as X1 also serves as an important intermediate).

[0057] When X1 is a carbonyl group, under a N2 atmosphere, a t-BuPh solution of lithium reagent (compound 2-5':lithium reagent = 1:2.1) is slowly added dropwise to a t-BuPh solution of compound 2-5', and then the mixture is allowed to naturally warm to room temperature. The reaction is quenched with H2O, the organic solvent layer is removed by rotary evaporation, the crude product is purified by column chromatography (DCM / petroleum ether, 1:10), and recrystallized from DCM and MeOH to obtain the intermediate. HCl was slowly added dropwise to the CH3COOH solution of the intermediate. After stirring for 10 min under N2 atmosphere, the mixture was rapidly vacuum filtered to obtain a filter cake, which was washed with MeOH and then recrystallized from DCM and MeOH to obtain the important intermediate 2-6' (X1' indicates direct bonding). One of them).

[0058]

[0059] Y1 2 Independently Important intermediates 2-6 are not compounds of this invention and require further reaction.

[0060] Under a nitrogen atmosphere, n-BuLi (important intermediate: n-BuLi = 1:1.1) was slowly added dropwise to a dry t-BuPh solution of the important intermediate. The reaction was carried out at 0°C for 2 h. Then, a t-BuPh solution containing a ketone structure (important intermediate: ketone structure compound = 1:1.1) was slowly added dropwise, and the mixture was allowed to warm naturally to room temperature. The reaction was quenched with H2O, and the organic solvent layer was removed by rotary evaporation. The crude product was purified by Al2O3 column chromatography (ethyl acetate / petroleum ether, 1:10 (v / v)) and recrystallized with THF and MeOH to give intermediate compound 1. HCl was slowly added dropwise to a CH3COOH solution of the intermediate (important intermediate: intermediate compound 1 = 1:1). After stirring for 10 min under N2 atmosphere, the mixture was rapidly vacuum filtered to obtain a filter cake, which was washed with MeOH and then recrystallized with THF and MeOH to obtain intermediate compound 2.

[0061] Next, intermediate compound 2 was subjected to the following reactions to obtain the compounds of the present invention.

[0062] (1) n-BuLi (intermediate 2: n-BuLi = 1:1.1) was slowly dropped into a dry t-BuPh solution of intermediate 2 under N2 atmosphere, and reacted at 0°C for 2 h. A solution of the ketone-containing compound (intermediate 2: ketone-containing compound = 1:1.1) was slowly dropped, and then naturally warmed to room temperature. The reaction was quenched with H2O, and the organic layer solvent was removed by rotary evaporation. The crude product was purified by column chromatography on Al2O3 (ethyl acetate / petroleum ether, 1:10 (volume ratio)), and recrystallized with THF and MeOH to obtain intermediate 2-1-1 HCl was slowly dropped into a CH3COOH solution of intermediate 2-1-1, and stirred under N2 atmosphere for 10 min. The filter cake was quickly filtered under vacuum, washed with MeOH, and recrystallized with THF and MeOH to obtain the compound of the present application (Y1 1 independently is

[0063] ).

[0064] (2) n-BuLi (intermediate 2: n-BuLi = 1:1.1) was slowly dropped into a dry t-BuPh solution of intermediate 2 under N2 atmosphere, and reacted at 0°C for 2 h. Dry ice was added at -50°C, and maintained at -50°C for 2 h, and then naturally warmed to room temperature. The reaction was quenched with water, and the organic phase was washed with water three times, and the water phases were combined. HCl was added dropwise to the water phase until the pH value was 1, and stirred for 30 min. The carboxylic acid intermediate 2-1-2 was obtained by filtration under reduced pressure A catalytic amount of DMF was added to a dry DCM solution of the carboxylic acid intermediate 2-1-2 under N2 atmosphere, and oxalyl chloride (carboxylic acid intermediate: oxalyl chloride = 1:1.1) was added dropwise. The reaction was refluxed for 3 h. The temperature was lowered to room temperature, and SnCl4 (carboxylic acid intermediate 2-1-2: SnCl4 = 1:1.1) was added dropwise. The reaction was refluxed for 3 h. The reaction was quenched with ice water, and washed with DCM three times. The organic layer solvent was removed by rotary evaporation, and the crude product was purified by column chromatography on silica gel (DCM as the eluent), and recrystallized with DCM and methanol to obtain the compound of the present application (Y1 1 is ).

[0065]

[0066] Further, the aforementioned compound of the present application, malononitrile (compound of the present application: malononitrile = 1:20) was dispersed in acetic anhydride, and refluxed for 12 h. The organic layer solvent was removed by rotary evaporation, and the crude product was purified by column chromatography on silica gel (ethyl acetate / DCM, 2:1 (volume ratio)), and recrystallized with DCM and methanol to obtain the compound of the present application (Y1 1 is ).

[0067] (3) Under N2atmosphere, THF solution of LaCl3.2LiCl (Intermediate 2: LaCl3.2LiCl = 1 : 2.2) was kept at -50°C for 15 min, then n-BuLi (Intermediate 2: n-BuLi = 1 : 2.2) was added dropwise, and reacted at -50°C for 30 min. THF solution of Intermediate 2 was added dropwise into n-Bu2LaCl.4LiCl, kept at -50°C for 5 min, and reacted at 0°C for 30 min. Diphenyltin dichloride (Intermediate 2: diphenyltin dichloride = 1 : 1.5) was added, and reacted at room temperature for 1 h. The reaction was quenched with water, washed with DCM for three times, and the organic solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography (DCM / petroleum ether, 1 : 20), and recrystallized with DCM and methanol to obtain the compound of the present application (Y1 1 To ).

[0068] (4) Under N2atmosphere, THF solution of LaCl3.2LiCl (Intermediate 2: LaCl3.2LiCl = 1 : 1.1) was kept at -50°C for 15 min, then n-BuLi (Intermediate 2: n-BuLi = 1 : 1.1) was added dropwise, and reacted at -50°C for 30 min. THF (10 mL) solution of Intermediate 2 was added dropwise into n-Bu2LaCl.4LiCl, kept at -50°C for 5 min, and reacted at 0°C for 30 min. I2 (Intermediate 2: I2 = 1 : 10) was added, and reacted at room temperature for 1 h. The reaction was quenched with water, washed with DCM for three times, and the organic solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography (DCM / petroleum ether, 1 : 5 (volume ratio)), and recrystallized with DCM and methanol to obtain Intermediate 2-1-4 Under N2atmosphere, Intermediate 2-1-4, sulfur powder or selenium powder (Intermediate 2-1-4: sulfur powder or selenium powder = 1 : 2), KOH (Intermediate 2-1-4: KOH = 1 : 4) were dispersed in DMSO, and reacted at 110°C for 24 h. The reaction was quenched with water, washed with DCM for three times, and the organic solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography (DCM / petroleum ether, 1 : 10 (volume ratio)), and recrystallized with DCM and methanol to obtain the compound of the present application (Y1 1 To ).

[0069]

[0070] Further, mCPBA (Invention Compound:mCPBA = 1:5) was slowly added to a DCM solution of the Invention Compound, and stirred at room temperature overnight. The reaction was quenched with saturated sodium hydroxide solution, and the aqueous phase was washed with DCM three times. The organic layer was combined, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography (ethyl acetate / DCM, 2:1 (volume ratio)), and recrystallized with DCM and methanol to obtain the Invention Compound (Y1 1 To ).

[0071] (5) n-BuLi (Intermediate 2:n-BuLi = 1:1.1) was slowly added dropwise to a dry t-BuPh solution of Intermediate 2 at 0°C, and reacted for 2h. BBr3 (Intermediate 2:BBr3 = 1:4) was added, and reacted for 1h at room temperature. DIEA (Intermediate 2:DIEA = 1:4.8) was added at 0°C, and reacted for 10h while increasing the temperature to 180°C. Amidyl magnesium bromide (Intermediate 2:amidyl magnesium bromide = 1:4) was added at room temperature, and stirred overnight. The reaction was quenched with water, and the aqueous phase was washed with DCM three times. The solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (DCM / petroleum ether, 1:6 (volume ratio)), and recrystallized with DCM and methanol to obtain the Invention Compound (Y1 1 To ). (6)

[0073]

[0074] Intermediate 2-1-6 was obtained from important Intermediate 2-6 through a similar series of reactions as described above. Intermediate 2-1-6 was dispersed in a mixed solvent of DCM, dioxane, and water (DCM:dioxane:water = 10:5:1 (volume ratio)), and cooled to 0°C. DDQ (Intermediate 2-1:DDQ = 1:6) was slowly added, and then naturally increased to room temperature, and stirred overnight. The reaction was quenched with saturated sodium bicarbonate solution, and the aqueous phase was washed with DCM three times. The solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (ethyl acetate / DCM, 2:1), and recrystallized with DCM and methanol to obtain the Invention Compound (Y2 1 To ).

[0075]

[0076]

[0077] Intermediate 2-1-7 was obtained from important intermediates through partial carbonylation and reduction reactions as described above.

[0078] Under N2atmosphere, intermediate 2-1-7 and CuCN (intermediate 2-1-7:CuCN = 1:20) were dispersed in DMF and refluxed for 48 h. CuCN was removed by filtration under reduced pressure, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography (petroleum ether / DCM, 4:1 (volume ratio)) and recrystallized with DCM and methanol to obtain intermediate 2-2-1.

[0079] Further, intermediate 2-2-1 is subjected to carbonylation to obtain the compound of the present application.

[0080] Under N2atmosphere, n-BuLi (2 mmol) was slowly added to a dry t-BuPh solution of intermediate 2-1-7 at 0°C and reacted for 2 h. Dimethyl disulfide or selenoether (intermediate 2-1-7:dimethyl disulfide or selenoether = 1:1.1) was slowly added to the reaction system, and the temperature was naturally increased to room temperature and stirred overnight. The reaction was quenched by adding water, and the aqueous phase was washed with DCM three times. The organic phases were combined, dried, and the crude product was purified by column chromatography (ethyl acetate / petroleum ether, 1:10 (volume ratio)) and recrystallized with THF and MeOH to obtain intermediate 2-2-1.

[0081] Further, intermediate 2-2-1 is subjected to carbonylation to obtain the compound of the present application. 1-1 The present application also includes a pharmaceutical composition comprising a compound of the present application and a pharmaceutically acceptable carrier. ) and a pharmaceutically acceptable carrier.

[0082]

[0083] Under N2atmosphere, intermediate 2-2-2 and CuCN (intermediate 2-2-2:CuCN = 1:20) were dispersed in DMF and refluxed for 48 h. CuCN was removed by filtration under reduced pressure, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography (petroleum ether / DCM, 4:1 (volume ratio)) and recrystallized with DCM and methanol to obtain the compound of the present application.

[0084] Further, intermediate 2-2-2 is subjected to carbonylation to obtain the compound of the present application. 2 The present application also includes a pharmaceutical composition comprising a compound of the present application and a pharmaceutically acceptable carrier. ) and a pharmaceutically acceptable carrier.

[0085]

[0086] Further, intermediate 2-2-1 is subjected to carbonylation to obtain the compound of the present application. 1-1 The present application also includes a pharmaceutical composition comprising a compound of the present application and a pharmaceutically acceptable carrier. ) and a pharmaceutically acceptable carrier.

[0087] The key intermediate is substituted with amidoboron as described above to obtain the compound of the present invention (wherein X). 1-1 It also includes ).

[0088]

[0089]

[0090] The important intermediates are subjected to the carbonylation reaction described above to obtain the compounds of the present invention.

[0091] Under a nitrogen atmosphere, the THF solution of LaCl3·2LiCl (important intermediate: LaCl3·2LiCl = 1:1.1) was kept at -50℃ for 15 min, and then n-BuLi (important intermediate: n-BuLi = 1:1.1) was added dropwise, and the reaction was carried out at -50℃ for 30 min. The THF solution of the important intermediate (10 mL) was added dropwise to n-Bu2LaCl·4LiCl, kept at -50℃ for 5 min, and then reacted at 0℃ for 30 min. I2 (important intermediate: I2 = 1:10) was added, and the reaction was carried out at room temperature for 1 h. The reaction was quenched with water, washed three times with DCM, and the organic solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography (DCM / petroleum ether, 1:5 (volume ratio)), and recrystallized with DCM and methanol to obtain intermediate 2-2-3. Under a nitrogen atmosphere, intermediate 2-2-3, sulfur powder or selenium powder (intermediate 2-2-3: sulfur powder or selenium powder) were added.

[0092] =1:2), KOH (intermediate 2-2-3:KOH = 1:4) was dispersed in DMSO and reacted at 110℃ for 24 h. The reaction was quenched with water, washed three times with DCM, and the organic solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography (DCM / petroleum ether, 1:10 (v / v)), and recrystallized from DCM and methanol to obtain the compound of the present invention (wherein X) 1-1 It also includes The thiolated product is further sulfonated to obtain the compound of the present invention.

[0093] Those skilled in the art can obtain the general formulas for preparing the remaining compounds of this invention based on the above-described reaction formulas and in conjunction with common synthetic methods in the field. Therefore, the general formulas for preparing the remaining compounds of this invention will not be described in detail here.

[0094] The technical advantages of this invention are that the rigid framework of the compound solves the technical problems in the prior art, such as the vibrational coupling between the ground state and the first excited singlet state of fluorescent molecules and the structural relaxation of the excited state leading to spectral broadening and reduced efficiency; the compound of this invention has a large steric hindrance protecting group, which can greatly reduce the aggregation quenching effect, and correspondingly increase the doping concentration of the guest, which is beneficial to the fabrication of the device. Detailed Implementation

[0095] The present invention will be described in detail below with several specific embodiments. The compounds of the present invention can be synthesized with reference to the specific synthesis examples shown below. However, it should be noted that obtaining the compounds is not limited to the synthesis methods and raw materials used in the present invention. Those skilled in the art can also select other methods or routes to obtain the novel compounds proposed in the present invention. The compounds for which synthesis methods are not mentioned in the present invention are all raw material products obtained through commercial means, or self-made using these raw material products according to known methods.

[0096] Preparation Example 1: Synthesis of Compound 1

[0097]

[0098] Synthesis of intermediate 1-b

[0099] Without alkyl or phenyl substitution, the product was prepared directly from the starting materials: Acridinone (8.89 g, 45.54 mmol), 1,4-diiodobenzene (9.1 g, 27.32 mmol), CuI (1.73 g, 9.11 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (3.57 g, 18.21 mmol), and Cs₂CO₃ (12.59 g, 91.07 mmol) were dispersed in DMF (70 mL) under a nitrogen atmosphere and refluxed for 8 h. After cooling to room temperature, the product was filtered under reduced pressure to obtain a filter cake. The crude product was purified by silica gel column chromatography (using DCM as the eluent), and recrystallized from DCM and methanol to give a white powder 1-b (9.39 g, 74%).

[0100] Synthesis of intermediate 1-c

[0101] At room temperature, Br2 (25.41 g, 160.00 mmol) was added to a 160 mL solution of DCM (7.43 g, 16.00 mmol) containing 1-b. After 2 h, K2CO3 (4.42 g, 32 mmol) was added, and the mixture was stirred for another 22 h. The reaction was quenched with saturated sodium sulfite solution, and the aqueous layer was washed three times with DCM. The organic solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (using DCM as the eluent). Recrystallization from DCM and methanol yielded a yellow powder, 1-c (6.97 g, 70%).

[0102] Synthesis of intermediate 1-d

[0103] 1-c (6.62 g, 10.63 mmol), Pd(OAc)2(95 mg, 0.43 mmol), PCy3HBF4(313 mg, 0.85 mmol) and K2CO3(4.71 g, 31.89 mmol) were dispersed in DMAc (50 mL) and reacted at 130 °C for 24 h under N2atmosphere. After cooling to room temperature, the filter cake was obtained by filtration under reduced pressure, and the crude product was purified by silica gel column chromatography (DCM as eluent) to obtain yellow powder 1-d (3.23 g, 66%).

[0104] Synthesis of intermediate 1-e

[0105] Br2(18.55 g, 116.80 mmol) was added to a solution of 1-d (2.69 g, 5.84 mmol) in DCM (120 mL) at room temperature. After 2 h, K2CO3(1.61 g, 11.68 mmol) was added and stirred for another 22 h. The reaction was quenched with saturated sodium sulfite solution and washed with DCM three times. The organic layer was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (DCM as eluent) and recrystallized with DCM and methanol to obtain yellow powder 1-e (2.89 g, 80%).

[0106] Synthesis of intermediate 1-f

[0107] Borane-tetrahydrofuran complex (1 M, 8.31 mL) was slowly added dropwise to a solution of 1-e (2.57 g, 4.15 mmol) in dry THF (80 mL) under N2atmosphere and refluxed for 2 h. After cooling to room temperature, the reaction was quenched with H2O and the aqueous layer was washed with DCM three times. The organic layer was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (DCM as eluent) and recrystallized with DCM and methanol to obtain yellow powder 1-f (2.33 g, 95%).

[0108] Synthesis of intermediate 1-g

[0109] n-BuLi (1.6 M, 2.30 mL) was slowly added to a solution of 1-f (2.17 g, 3.68 mmol) in dry t-BuPh (80 mL) at 0 °C for 2 h, a solution of benzophenone (664 mg, 3.68 mmol) in t-BuPh (20 mL) was slowly added and then allowed to warm to room temperature naturally. The reaction was quenched with H2O and the organic layer solvent was removed by rotary evaporation. The crude product was purified by column chromatography on Al2O3 (ethyl acetate / petroleum ether, 1 : 10, by volume, same below) and recrystallized from THF and MeOH to give the intermediate (3.01 g). HCl (3.7 mL) was slowly added to a solution of the intermediate in CH3COOH (370 mL) and stirred under N2for 10 min. The filter cake was obtained by rapid vacuum filtration, washed with MeOH and recrystallized from THF and MeOH to give yellow powder 1-g (1.62 g, 65%).

[0110] Synthesis of intermediate 1-h

[0111] n-BuLi (1.6 M, 0.625 mL) was slowly added to a solution of 1-g (0.68 g, 1.00 mmol) in dry t-BuPh (20 mL) at 0 °C for 2 h, a solution of benzophenone (182 mg, 1.00 mmol) in t-BuPh (5 mL) was slowly added and then allowed to warm to room temperature naturally. The reaction was quenched with H2O and the organic layer solvent was removed by rotary evaporation. The crude product was purified by column chromatography on Al2O3 (ethyl acetate / petroleum ether, 1 : 10) and recrystallized from THF and MeOH to give the intermediate (0.93 g). HCl (1 mL) was slowly added to a solution of the intermediate in CH3COOH (100 mL) at room temperature and stirred under N2for 10 min. The filter cake was obtained by rapid vacuum filtration, washed with MeOH and recrystallized from THF and MeOH to give intermediate 1-h (0.52 g, 65%).

[0112] Synthesis of compound 1

[0113] 1-h (0.53 g, 0.69 mmol) was dispersed in a mixture of DCM (10 mL), dioxane (5 mL) and water (1 mL), cooled to 0 °C and then DDQ (0.94 g, 4.14 mmol) was slowly added and then allowed to warm to room temperature naturally. The reaction was stirred overnight. The reaction was quenched with saturated sodium bicarbonate solution and the aqueous layer was washed with DCM three times. The organic layer solvent was removed by rotary evaporation. The crude product was purified by column chromatography on silica gel (ethyl acetate / DCM, 2: 1) and recrystallized from DCM and methanol to give compound 1 (0.35 g, 63%). The relevant data of the target compound obtained are shown in Table 1.

[0114] Preparation Example 2: Synthesis of compound 2

[0115]

[0116] Compound 1 was prepared according to the procedure described above.

[0117] Synthesis of intermediate 2-a

[0118] n-BuLi (1.6 M, 2.30 mL) was slowly added dropwise to a solution of 1-f (2.17 g, 3.68 mmol) in dry t-BuPh (80 mL) under N2atmosphere at 0°C for 2 h. Dry ice was added at -50°C and maintained at -50°C for 2 h and then allowed to warm up to room temperature. The reaction was quenched with water and the organic phase was washed with water three times and the aqueous phases were combined. HCl was added dropwise to the aqueous phase until pH 1 was reached, stirred for 30 min and filtered under reduced pressure to obtain the carboxylic acid intermediate 1.98 g. To a solution of the carboxylic acid intermediate in dry DCM (30 mL) was added a catalytic amount of DMF and oxalyl chloride (2 M, 1.82 mL) was added dropwise under N2atmosphere at reflux for 3 h. The reaction was cooled to room temperature and SnCl4(1 M, 3.64 mL) was added dropwise at reflux for 3 h. The reaction was quenched with ice water and washed with DCM three times. The organic layer was removed by rotary evaporation and the crude product was purified by column chromatography on silica gel (DCM as eluent) and recrystallized from DCM and methanol to obtain 2-a as a yellow powder (1.38 g, 70%).

[0119] Synthesis of intermediate 2-b

[0120] Borane-tetrahydrofuran complex (1 M, 2.49 mL) was slowly added dropwise to a solution of 2-a (1.34 g, 2.49 mmol) in dry THF (50 mL) under N2atmosphere at reflux for 2 h. After cooling to room temperature, the reaction was quenched with H2O and the aqueous layer was washed with DCM three times. The organic layer was removed by rotary evaporation and the crude product was purified by column chromatography on silica gel (DCM as eluent) and recrystallized from DCM and methanol to obtain 2-b as a yellow powder (1.24 g, 95%).

[0121] Synthesis of intermediate 2-c

[0122] n-BuLi (1.6 M, 1.42 mL) was slowly added to a solution of 2-b (1.19 g, 2.27 mmol) in dry t-BuPh (50 mL) under N2atmosphere at 0 °C for 2 h. Dry ice was added at -50 °C and kept at -50 °C for 2 h, then allowed to warm up to room temperature. The reaction was quenched with water and the organic phase was washed with water three times. The water phases were combined. HCl was added dropwise to the water phase until the pH value was 1. The mixture was stirred for 30 min and filtered under reduced pressure to obtain the carboxylic acid intermediate 1.02 g. To a solution of the carboxylic acid intermediate in dry DCM (20 mL) was added a catalytic amount of DMF, then oxalyl chloride (2 M, 1.02 mL) was added dropwise under N2atmosphere. The mixture was refluxed for 3 h. The temperature was allowed to cool down to room temperature and SnCl4(1 M, 2.04 mL) was added dropwise. The mixture was refluxed for 3 h. The reaction was quenched with ice water and washed with DCM three times. The solvent was removed from the organic layer by rotary evaporation. The crude product was purified by silica gel column chromatography (DCM as eluent) and recrystallized from DCM and methanol to obtain yellow powder 2-c (0.77 g, 72%).

[0123] Synthesis of compound 2

[0124] 2-c (0.66 g, 1.4 mmol) was dispersed in a mixture of DCM (20 mL), dioxane (10 mL) and water (2 mL) and cooled to 0 °C. DDQ (2.94 g, 13 mmol) was added slowly, then the temperature was allowed to warm up to room temperature and the mixture was stirred overnight. The reaction was quenched with saturated sodium bicarbonate solution and the water layer was washed with DCM three times. The solvent was removed from the organic layer by rotary evaporation. The crude product was purified by silica gel column chromatography (ethyl acetate / DCM, 2:1) and recrystallized from DCM and methanol to obtain yellow powder compound 2 (0.60 g, 88%). The relevant data of the target compound obtained are shown in Table 1.

[0125] Preparation Example 3: Synthesis of compound 4

[0126]

[0127] 1-f was obtained according to the preparation method of compound 1.

[0128] Synthesis of intermediate 4-a

[0129] To a solution of 4-a (1.21 g, 1.29 mmol) in DMSO (20 mL) was added powdered sulfur (0.17 g, 5.17 mmol) and KOH (0.58 g, 10.34 mmol) under N2atmosphere. The reaction was stirred at 110 °C for 24 h. The reaction was quenched with water and washed with DCM three times. The organic solvent was removed by rotary evaporation and the crude product was purified by silica gel column chromatography (DCM / petroleum ether, 1 : 10) and recrystallized with DCM and methanol to give yellow powder 4-b (0.48 g, 76%).

[0130] Synthesis of intermediate 4-b

[0131] To a solution of 4-a (1.21 g, 1.29 mmol) in DMSO (20 mL) was added powdered sulfur (0.17 g, 5.17 mmol) and KOH (0.58 g, 10.34 mmol) under N2atmosphere. The reaction was stirred at 110 °C for 24 h. The reaction was quenched with water and washed with DCM three times. The organic solvent was removed by rotary evaporation and the crude product was purified by silica gel column chromatography (DCM / petroleum ether, 1 : 10) and recrystallized with DCM and methanol to give yellow powder 4-b (0.48 g, 76%).

[0132] Synthesis of compound 4

[0133] Compound 4 was prepared from 4-b in a similar manner as compound 1. The obtained target compound was recrystallized with DCM and methanol to give yellow powder 4 (92%). The relevant data of the obtained target compound are shown in Table 1.

[0134] Preparation Example 4: Synthesis of compound 5

[0135]

[0136] Synthesis of compound 5

[0137] To a solution of compound 4 (0.70 g, 1.34 mmol) in DCM (10 mL) was added mCBPA (1.16 g, 6.71 mmol) slowly and stirred at room temperature overnight. The reaction was quenched with saturated NaOH solution and the aqueous phase was washed with DCM three times. The organic solvent was removed by rotary evaporation and the crude product was purified by silica gel column chromatography (ethyl acetate / DCM, 2: 1) and recrystallized with DCM and methanol to give yellow powder 5 (0.65, 83%). The relevant data of the obtained target compound are shown in Table 1.

[0138] Preparation Example 5: Synthesis of compound 7 To a solution of 4-a (1.21 g, 1.29 mmol) in DMSO (20 mL) was added powdered sulfur (0.17 g, 5.17 mmol) and KOH (0.58 g, 10.34 mmol) under N2atmosphere. The reaction was stirred at 110 °C for 24 h. The reaction was quenched with water and washed with DCM three times. The organic solvent was removed by rotary evaporation and the crude product was purified by silica gel column chromatography (DCM / petroleum ether, 1 : 10) and recrystallized with DCM and methanol to give yellow powder 4-b (0.48 g, 76%).

[0139]

[0140] After alkylation, intermediate 7-a was obtained analogously to the preparation of compound 1.

[0141] Synthesis of intermediate 7-c

[0142] n-BuLi (1.6 M, 2.30 mL) was slowly added dropwise to a solution of 7-a (2.17 g, 3.68 mmol) in dry t-BuPh (80 mL) under N2atmosphere for 2 h at 0 °C, a solution of thioxanthone (782 mg, 3.68 mmol) in t-BuPh (20 mL) was slowly added dropwise and then allowed to warm up to room temperature spontaneously. The reaction was quenched with H2O and the organic layer was removed by rotary evaporation. The crude product was purified by column chromatography on Al2O3(eluent: ethyl acetate / petroleum ether, 1 : 10, v / v, same below) and recrystallized from THF and MeOH to give an intermediate (2.83 g). HCl (3.7 mL) was slowly added dropwise to a solution of the intermediate in CH3COOH (370 mL) and after stirring for 10 min under N2atmosphere, the filter cake was obtained by rapid vacuum filtration, washed with MeOH and recrystallized from THF and MeOH to give yellow powder 7-b (1.88 g, 67%).

[0143] Intermediate 7-c was prepared from intermediate 7-b according to the reaction described above.

[0144] Synthesis of compound 7

[0145] Compound 7 was prepared from intermediate 7-c analogously to the preparation of compound 1 (87%). The data related to the target compound obtained are reported in Table 1.

[0146] Preparation Example 6: Synthesis of compound 11

[0147]

[0148] Alkylation

[0149] 9(10H)-Acridinone (10 g, 51.22 mmol) and AlCl3(15.03 g, 112.69 mmol) were dispersed in dry DCM (250 mL) under N2atmosphere and chloroiso-propane (16.09 g, 204.9 mmol) was slowly added dropwise. The reaction was stirred at -40 °C for 4 h. The reaction was quenched with ice water and the liquid phase was removed by filtration under reduced pressure. The crude product was purified by column chromatography on silica gel (eluent: DCM) and concentrated to 100 mL in DCM. The yellow powder 11-a (13.59 g, 95%) was obtained by precipitation and filtration.

[0150] Intermediate 11-f was prepared from intermediate a by a series of reactions, then reacted with compound 2 to give intermediate 11-h.

[0151] Synthesis of intermediate 11-I

[0152] n-BuLi (1.6 M, 1.83 mL) was slowly added to a solution of 11-h (2.03 g, 2.93 mmol) in dry t-BuPh (50 mL) under N2atmosphere at 0 °C for 2 h. BBr3(1.47 g, 5.86 mmol) was added and stirred at room temperature for 1 h. DIEA (1.23 mL, 7.03 mmol) was added at 0 °C and the reaction mixture was heated to 180 °C for 10 h. Amidomagnesium bromide (1 M, 5.86 mL) was added at room temperature and stirred overnight. The reaction was quenched by water and the aqueous phase was washed with DCM three times. The solvent was removed by rotary evaporation and the crude product was purified by silica gel column chromatography (DCM / petroleum ether, 1 :6) and recrystallized with DCM and methanol to give yellow powder 11-I (0.69 g, 32%).

[0153] Synthesis of compound 11

[0154] 11-I (0.65 g, 0.88 mmol) was dispersed in a mixture of DCM (10 mL), dioxane (5 mL) and water (1 mL) and cooled to 0 °C. DDQ (1.91 g, 8.43 mmol) was added slowly and then the reaction mixture was allowed to warm to room temperature and stirred overnight. The reaction was quenched by saturated sodium bicarbonate solution and the aqueous phase was washed with DCM three times. The solvent was removed by rotary evaporation and the crude product was purified by silica gel column chromatography (ethyl acetate / DCM, 2:1) and recrystallized with DCM and methanol to give yellow powder 11 (0.61 g, 89%). The relevant data of the target compound obtained are shown in Table 1.

[0155] Preparation Example 7: Synthesis of compound 12

[0156]

[0157] Intermediate 11-h was prepared according to the previous reaction.

[0158] Synthesis of intermediate 12-a

[0159] To a solution of 11-h (1.38 g, 2 mmol) in THF (10 mL) was added dropwise n-Bu2LaCl-4LiCl under N2atmosphere at -50 °C for 15 min, then n-BuLi (1.6 M, 2.75 mL) was added dropwise at -50 °C for 30 min. To the solution of 11-h (1.38 g, 2 mmol) in THF (10 mL) was added dropwise n-Bu2LaCl-4LiCl under N2atmosphere at -50 °C for 15 min, then n-BuLi (1.6 M, 2.75 mL) was added dropwise at -50 °C for 30 min. Diphenyltin dichloride (1.03 g, 3 mmol) was added at room temperature for 1 h. The reaction was quenched with water and washed with DCM three times. The organic solvent was removed by rotary evaporation and the crude product was purified by silica gel column chromatography (DCM / petroleum ether, 1 :20) and recrystallized with DCM and methanol to give yellow powder 12-a (1.38 g, 78%).

[0160] Synthesis of compound 12

[0161] Compound 12 was prepared from intermediate 12-a in a similar manner to that described for compound 1 (85%). The data obtained for the target compound are shown in Table 1.

[0162] Preparation Example 8: Synthesis of compound 13

[0163]

[0164] Intermediate 11-h was obtained according to the previous reaction.

[0165] Synthesis of intermediate 13-a

[0166] Intermediate 13-a was obtained from intermediate 11-h in a similar manner to that described for compound 4.

[0167] Synthesis of intermediate 13-b

[0168] Intermediate 13-b was obtained from intermediate 13-a in a similar manner to that described for compound 4.

[0169] Synthesis of compound 13

[0170] Compound 13 was prepared from intermediate 13-b in a similar manner to that described for compound 1 (77%). The data obtained for the target compound are shown in Table 1.

[0171] Preparation Example 9: Synthesis of compound 28

[0172]

[0173] Synthesis of intermediate 28-a

[0174] Intermediate 28-a was obtained from intermediate 1-f in a similar manner to that described for compound 1.

[0175] Synthesis of intermediate 28-b

[0176] Intermediate 28-b was obtained from intermediate 28-a, similarly to the method described in the preparation of compound 2.

[0177] Synthesis of compound 28

[0178] Compound 28 was obtained from intermediate 28-b, similarly to the method described in the preparation of compound 1. The data related to the compound of interest obtained are shown in Table 1.

[0179] Preparation Example 10: Synthesis of compound 58

[0180]

[0181] Intermediate 58-a was obtained, similarly to the synthesis described in compound 2.

[0182] Synthesis of compound 58

[0183] Intermediate 58-a (0.57 g, 1 mmol), malononitrile (1.32 g, 20 mmol) were dispersed in 10 mL of acetic anhydride and refluxed for 12 h. The organic layer was removed by rotary evaporation and the crude product was purified by column chromatography on silica gel (ethyl acetate / DCM, 2:1) and recrystallized with DCM and methanol to obtain compound 58 (0.34 g, 45%), the data related to the compound of interest obtained are shown in Table 1.

[0184] Preparation Example 11: Synthesis of compound 62

[0185]

[0186] After alkylation, intermediate 62-a was obtained, similarly to the synthesis described in compound 1.

[0187] Synthesis of compound 62

[0188] Intermediate 62-a (0.96 g, 1 mmol), malononitrile (1.30 g, 19.7 mmol) were dispersed in 10 mL of acetic anhydride and refluxed for 12 h. The organic layer was removed by rotary evaporation and the crude product was purified by column chromatography on silica gel (ethyl acetate / DCM, 2:1) and recrystallized with DCM and methanol to obtain compound 62 (0.55 g, 52%), the data related to the compound of interest obtained are shown in Table 1.

[0189] Preparation Example 12: Synthesis of compound 117

[0190]

[0191] After alkylation, the synthesis method in compound 1 was followed to prepare intermediate 117-e

[0192] Synthesis of compound 117

[0193] Compound 117 was prepared from intermediate 117-e (17%) in analogy to the method described for the preparation of compound 11. The data related to the target compound obtained are reported in Table 1.

[0194] Preparation Example 13: Synthesis of compound 120

[0195]

[0196] Intermediate 120-a was prepared following the procedure described above.

[0197] Synthesis of compound 120

[0198] Compound 120 was prepared from intermediate 120-a (60%) as a white powder in analogy to the method described for the preparation of compound 1. The data related to the target compound obtained are reported in Table 1.

[0199] Preparation Example 14: Synthesis of compound 172

[0200]

[0201] After arylation, intermediate 172-a was prepared in analogy to the method described for the preparation of intermediate 117-e.

[0202] Synthesis of intermediate 172-b

[0203] Intermediate 172-b was obtained from intermediate 172-a in analogy to the method described for the preparation of compound 1-g.

[0204] Synthesis of intermediate 172-c

[0205] Intermediate 172-c was obtained from intermediate 172-b in analogy to the method described for the preparation of compound 4.

[0206] Synthesis of compound 172

[0207] Compound 172 was obtained from intermediate 172-c (71%) in analogy to the method described for the preparation of compound 4. The data related to the target compound obtained are reported in Table 1.

[0208] Preparation Example 15: Synthesis of compound 174

[0209]

[0210] Intermediate 174-a was prepared following the procedure described above.

[0211] Synthesis of compound 174

[0212] Compound 174 was prepared from intermediate 174-a as a white powder (70%) in analogy to the procedure described for compound 2. The data related to the compound of interest are reported in Table 1.

[0213] Preparation Example 16: Synthesis of compound 175

[0214]

[0215] Intermediate 175-a was prepared in analogy to the procedure described for compound 174.

[0216] Synthesis of compound 175

[0217] Compound 175 was prepared from intermediate 175-a (13%) in analogy to the procedure described for compound 11. The data related to the compound of interest are reported in Table 1.

[0218] Preparation Example 17: Synthesis of compound 183

[0219]

[0220] After alkylation, intermediate 183-a was prepared in analogy to the procedure described for compound 172.

[0221] Synthesis of intermediate 183-b

[0222] Intermediate 183-b was obtained from intermediate 183-a in analogy to the procedure described for compound 1.

[0223] Synthesis of compound 183

[0224] Compound 183 was prepared from intermediate 183-b (68%) in analogy to the procedure described for compound 2. The data related to the compound of interest are reported in Table 1.

[0225] Preparation Example 18: Synthesis of compound 187

[0226]

[0227] After alkylation, intermediate 187-a was prepared in analogy to the procedure described for compound 1.

[0228] Synthesis of intermediate 187-b

[0229] To a solution of intermediate 187-a (2.80 g, 3.56 mmol) in t-BuPh (60 mL) was added dropwise at 0 °C under N2atmosphere and the reaction was allowed to warm to room temperature. The reaction was quenched with H2O and the organic layer was removed by rotary evaporation. The crude product was purified by column chromatography on Al2O3(ethyl acetate / petroleum ether, 1 :10) and recrystallized from THF and MeOH to give the intermediate (3.30 g). To a solution of the intermediate in CH3COOH (350 mL) was added dropwise HCl (7 mL) and stirred for 10 min under N2atmosphere. The filter cake was obtained by rapid vacuum filtration, washed with MeOH and recrystallized from THF and MeOH to give yellow powder 187-b (2.38 g, 63%).

[0230] Synthesis of compound 187

[0231] Compound 187 was prepared from intermediate 187-b in a similar manner to that described for compound 2 (72%). The data obtained for the target compound are shown in Table 1.

[0232] Preparation Example 19: Synthesis of compound 189

[0233]

[0234] Intermediate 189-a was obtained in a similar reaction to that described previously.

[0235] Synthesis of compound 189

[0236] Compound 189 was prepared from intermediate 189-a in a similar manner to that described for compound 175 (16%). The data obtained for the target compound are shown in Table 1.

[0237] Preparation Example 20: Synthesis of compound 202

[0238]

[0239] Synthesis of intermediate 202-a

[0240] Intermediate 202-a was obtained from intermediate 1-e in a similar manner to that described for compound 187.

[0241] Synthesis of intermediate 202-b

[0242] Intermediate 202-b was obtained from intermediate 202-a in a similar manner to that described for compound 5.

[0243] Synthesis of compound 202

[0244] Compound 202 was obtained from intermediate 202-b (81%) in analogy to the procedure described for compound 2. See Table 1 for data related to the target compound obtained.

[0245] Preparation Example 21 : Synthesis of compound 216

[0246]

[0247] Synthesis of intermediate 216-a

[0248] Intermediate 216-a was prepared in analogy to the procedure described for compound 1.

[0249] Intermediate 216-b

[0250] n-BuLi (1.6 M, 1.00 mL) was slowly added dropwise to a solution of 216-a (1.13 g, 1.67 mmol) in dry t-BuPh (30 mL) at 0 °C for 2 h. Dimethyl disulfide (0.17 g, 1.83 mmol) was added slowly to the reaction mixture and allowed to warm to room temperature overnight. The reaction was quenched with water and the aqueous phase was washed with DCM three times. The organic phases were combined and the crude product was purified by column chromatography on AI2O3 (ethyl acetate / petroleum ether, 1 : 10) and recrystallized from THF and MeOH to give intermediate 216-b as a yellow powder (0.97 g, 90%).

[0251] Synthesis of compound 216

[0252] Compound 216 was obtained from intermediate 216-b (90%) in analogy to the procedure described for compound 1. See Table 1 for data related to the target compound obtained.

[0253] Preparation Example 22: Synthesis of compound 236

[0254]

[0255] Synthesis of intermediate 236-a

[0256] After alkylation, intermediate 236-a was prepared in analogy to the previous reaction.

[0257] Synthesis of compound 236

[0258] mCBPA (0.20 g, 1.14 mmol) was slowly added to a 20 mL solution of 236-a (0.96 g, 1.15 mmol) in DCM, and stirred overnight at room temperature. The reaction was quenched with saturated sodium hydroxide solution. The aqueous phase was washed three times with DCM, and the organic phases were combined. The solvent in the organic layer was removed by rotary evaporation. The crude product was purified by silica gel column chromatography (ethyl acetate / DCM, 2:1), and recrystallized from DCM and methanol to give a yellow powder 236 (0.82 g, 83%). The relevant data of the target compound obtained are shown in Table 1.

[0259] Preparation Example 23: Synthesis of Compound 246

[0260]

[0261] Synthesis of intermediate 246-a

[0262] After arylation, intermediate 246-a was prepared in a similar manner to the aforementioned reaction.

[0263] Synthesis of Compound 246

[0264] mCBPA (0.48 g, 2.79 mmol) was slowly added to a 20 mL solution of 246-a (1.12 g, 1.15 mmol) in DCM, and stirred overnight at room temperature. The reaction was quenched with saturated sodium hydroxide solution. The aqueous phase was washed three times with DCM, and the organic phases were combined. The solvent in the organic layer was removed by rotary evaporation. The crude product was purified by silica gel column chromatography (ethyl acetate / DCM, 2:1), and recrystallized from DCM and methanol to give a yellow powder 246 (0.98 g, 85%). The relevant data of the target compound obtained are shown in Table 1.

[0265] Preparation Example 24: Synthesis of Compound 256

[0266]

[0267] After alkylation, intermediate 256-a was obtained in a similar manner to that used in the preparation of compound 1.

[0268] Synthesis of intermediate 256-b

[0269] Under a nitrogen atmosphere, intermediate 256-a (1.2 g, 1.64 mmol) and CuCN (2.94 g, 32.82 mmol) were dispersed in DMF (20 mL) and refluxed for 48 h. CuCN was removed by vacuum filtration, and the solvent in the intermediate layer was removed by rotary evaporation. The crude product was purified by silica gel column chromatography (petroleum ether / DCM, 4:1), and recrystallized from DCM and methanol to give intermediate 256-b (0.64 g, 58%) as a yellow powder.

[0270] Synthesis of Compound 256

[0271] Compound 256 was obtained as a yellow powder (92%) from intermediate 256-b in analogy to the procedure described for the preparation of compound 1. The data related to the compound obtained are reported in Table 1.

[0272] Preparation Example 25: synthesis of compound 303

[0273]

[0274] Synthesis of intermediate 303-a

[0275] Intermediate 303-a was obtained from intermediate 1-f in analogy to the procedure described for the preparation of compound 172.

[0276] Synthesis of intermediate 303-b

[0277] Intermediate 303-b was obtained from intermediate 303-a in analogy to the procedure described for the preparation of compound 256.

[0278] Synthesis of intermediate 303-c

[0279] Intermediate 303-c was obtained from intermediate 303-b in analogy to the procedure described for the preparation of compound 1.

[0280] Synthesis of compound 303

[0281] Intermediate 303 was obtained as a yellow powder (50%) from intermediate 303-c in analogy to the procedure described for the preparation of compound 58. The data related to the compound obtained are reported in Table 1.

[0282] Preparation Example 26: synthesis of compound 320

[0283]

[0284] Synthesis of intermediate 320-a

[0285] Intermediate 320-a was obtained from intermediate 117-e in analogy to the procedure described for the preparation of compound 5.

[0286] Synthesis of compound 320

[0287] n-BuLi (1.6 M, 2.00 mL) was slowly added to a solution of 320-a (1.50 g, 1.67 mmol) in dry t-BuPh (60 mL) at 0 °C under N2atmosphere for 2 h. Dimethyl diselenide (0.69 g, 3.67 mmol) was added slowly to the reaction mixture, which was allowed to warm to room temperature and stirred overnight. The reaction was quenched with water and the aqueous phase was washed with DCM three times. The organic phases were combined and the crude product was purified by column chromatography on Al203(ethyl acetate / petroleum ether, 1 : 10) and recrystallized from THF and MeOH to give compound 320 (1.34 g, 88%). See Table 1 for compound data obtained.

[0288] Preparation Example 27: Synthesis of compound 350

[0289]

[0290] Synthesis of intermediate 350-a

[0291] Intermediate 350-a was prepared from intermediate 174-a in analogy to the procedure described for compound 11.

[0292] Synthesis of compound 350

[0293] Compound 350 was prepared from intermediate 350-a in analogy to the procedure described for compound 256 (87%). See Table 1 for compound data obtained.

[0294] Preparation Example 28: Synthesis of compound 352

[0295]

[0296] Intermediate 325-a was obtained in analogy to the procedure described for compound 1.

[0297] Synthesis of intermediate 352-b

[0298] Intermediate 352-b was obtained from intermediate 352-a in analogy to the procedure described for compound 11.

[0299] Synthesis of compound 352

[0300] Compound 352 was prepared from intermediate 352-b in analogy to the procedure described for compound 256 (52%). See Table 1 for compound data obtained.

[0301] Preparation Example 29: Synthesis of compound 359

[0302]

[0303] After alkylation, intermediate 359-a was prepared in analogy to the preparation of compound 1.

[0304] Intermediate 359-b was prepared from intermediate 359-a in analogy to the preparation of compound 187.

[0305] Intermediate 359-c was prepared from intermediate 359-b in analogy to the preparation of compound 2.

[0306] Intermediate 359-d was prepared from intermediate 359-c in analogy to the preparation of compound 216.

[0307] Synthesis of compound 359

[0308] Compound 359 was prepared from intermediate 359-d in analogy to the preparation of compound 236 (54%), the compound of interest was obtained. See Table 1 for data related to the compound of interest.

[0309] Preparation Example 30: Synthesis of compound 390

[0310]

[0311] After alkylation, intermediate 390-a was prepared in analogy to the preparation of compound 1.

[0312] Synthesis of intermediate 390-b

[0313] n-BuLi (1.6 M, 2.00 mL) was slowly added to a solution of 390-a (1.31 g, 1.67 mmol) in dry t-BuPh (60 mL) at 0 °C under N2atmosphere and stirred for 2 h. Dimethyl diselenide (0.69 g, 3.67 mmol) was added slowly to the reaction mixture and allowed to warm to room temperature overnight. The reaction was quenched with water and the aqueous phase was washed with DCM three times. The organic phases were combined and the crude product was purified by column chromatography on Al203(ethyl acetate / petroleum ether, 1 : 10) and recrystallized from THF and MeOH to give intermediate 390-b (1.25 g, 91%),

[0314] Synthesis of compound 390

[0315] Compound 390 was prepared from intermediate 390-b in analogy to the preparation of compound 1 (88%). See Table 1 for data related to the compound of interest.

[0316] Preparation Example 31: Synthesis of compound 412

[0317]

[0318] Compound 412-b was prepared from intermediate 412-a in analogy to the preparation of compound 390.

[0319] Compound 412-c was prepared from intermediate 412-b in analogy to the preparation of compound 216 and then in analogy to the preparation of compound 246.

[0320] Compound 412-d was prepared from intermediate 412-c in analogy to the preparation of compound 1.

[0321] Synthesis of compound 412

[0322] Compound 412 was prepared from intermediate 412-d in analogy to the preparation of compound 62 (49%). Data related to the compound of interest are given in Table 1.

[0323] Preparation Example 32: Synthesis of compound 421

[0324]

[0325] Synthesis of intermediate 421-a

[0326] Compound 421-a was prepared from intermediate 172-a in analogy to the preparation of compound 246.

[0327] Synthesis of compound 421

[0328] Compound 421 was prepared from intermediate 421-a in analogy to the preparation of compound 256 (50%). Data related to the compound of interest are given in Table 1.

[0329] Preparation Example 33: Synthesis of compound 432

[0330]

[0331] Synthesis of intermediate 432-a

[0332] Compound 432-a was prepared from intermediate 183-a in analogy to the preparation of compound 216.

[0333] Synthesis of compound 432

[0334] Compound 432 was prepared from intermediate 432-a in analogy to the preparation of compound 256 (90%). Data related to the compound of interest are given in Table 1.

[0335] Preparation Example 34: Synthesis of compound 434

[0336]

[0337] Prepared analogously to the preparation of compound 187 from intermediate 434-a.

[0338] Synthesis of compound 434

[0339] Prepared analogously to the preparation of compound 256 from intermediate 434-a. Compound 434 was obtained in 56% yield. See Table 1 for data related to the compound of interest.

[0340] Preparation Example 35: Synthesis of compound 456

[0341]

[0342] After alkylation, prepared analogously to the preparation of compound 1 to obtain intermediate 456-a.

[0343] Synthesis of intermediate 456-b

[0344] n-BuLi (1.6 M, 0.625 mL) was slowly added to a solution of 1-g (0.73 g, 1.00 mmol) in dry t-BuPh (20 mL) under N2atmosphere at 0 °C for 2 h. The reaction was quenched with H2O and the organic layer was removed by rotary evaporation. The crude product was purified by column chromatography on Al2O3(ethyl acetate / petroleum ether, 1:10) and recrystallized from THF and MeOH to obtain intermediate 456-b (0.59 g, 90%).

[0345] Synthesis of compound 456

[0346] Prepared analogously to the preparation of compound 1 from intermediate 456-b. Compound 456 was obtained in 87% yield. See Table 1 for data related to the compound of interest.

[0347] Preparation Example 36: Synthesis of compound 464

[0348]

[0349] Synthesis of intermediate 464-a

[0350] Prepared analogously to the preparation of compound 4 from intermediate 11-f to obtain intermediate 464-a

[0351] Synthesis of intermediate 464-b

[0352] Prepared analogously to the preparation of compound 456 from intermediate 464-a to obtain intermediate 464-b

[0353] Synthesis of compound 464

[0354] Compound 464 was prepared from intermediate 464-b (51%) in a similar manner as in the preparation of compound 58. See Table 1 for data relating to the target compound obtained.

[0355] Preparation Example 37: Synthesis of compound 472

[0356]

[0357] Intermediate 472-f was prepared in a similar manner as in the preparation of compound 174.

[0358] Intermediate 472-h was prepared in a similar manner as in the preparation of compound 456.

[0359] Synthesis of compound 472

[0360] n-BuLi (1.6 M, 1.0 mmol) was slowly added to a solution of 472-h (1.47 g, 1.6 mmol) in dry t-BuPh (30 mL) at 0 °C under N2atmosphere and stirred for 2 h. BBr3(1.64 g, 6.5 mmol) was added and stirred for 1 h at room temperature. DIEA (1.01 g, 7.8 mmol) was added at 0 °C and the reaction mixture was heated to 180 °C for 10 h. Amidomagnesium bromide (1 M, 5.86 mL) was added at room temperature and stirred overnight. The reaction was quenched with water and the aqueous phase was washed with DCM three times. The organic layer was removed by rotary evaporation and the crude product was purified by silica gel column chromatography (DCM / pet. ether, 1 :6) and recrystallized with DCM and methanol to give compound 472 (0.28 g, 18%). See Table 1 for data relating to the target compound obtained.

[0361] Preparation Example 38: Synthesis of compound 481

[0362]

[0363] Synthesis of intermediate 481-a

[0364] Intermediate 464-a was prepared from intermediate 7-a in a similar manner as in the preparation of compound 12

[0365] Synthesis of intermediate 481-b

[0366] Intermediate 481-b was prepared from intermediate 481-a in a similar manner as in the preparation of compound 456

[0367] Synthesis of compound 481

[0368] Compound 481 was prepared from intermediate 481-b in a similar manner as in the preparation of compound 456 (87%). See Table 1 for data relating to the target compound obtained.

[0369] Preparation Example 39: Synthesis of compound 483

[0370]

[0371] After alkylation, intermediate 483-a was prepared in a similar manner as in the preparation of compound 1.

[0372] Intermediate 483-b was prepared from intermediate 483-a in a similar manner as in the preparation of compound 472.

[0373] Intermediate 483-c was prepared from intermediate 483-b in a similar manner as in the preparation of compound 256.

[0374] Synthesis of compound 483

[0375] Compound 483 (0.64 g, 88%) was prepared from intermediate 483-c in a similar manner as in the preparation of compound 1. The data related to the compound obtained are reported in Table 1.

[0376] Preparation Example 40: Synthesis of compound 491

[0377]

[0378] After alkylation, intermediate 491-a was prepared in a similar manner as in the preparation of compound 1.

[0379] Intermediate 491-b was prepared from intermediate 491-a in a similar manner as in the preparation of compound 472.

[0380] Intermediate 491-c was prepared from intermediate 491-b in a similar manner as in the preparation of compound 216.

[0381] Intermediate 491-d was prepared from intermediate 491-c in a similar manner as in the preparation of compound 1.

[0382] Synthesis of compound 491

[0383] Compound 491 (60%) was prepared from intermediate 491-d in a similar manner as in the preparation of compound 62. The data related to the compound obtained are reported in Table 1.

[0384] Preparation Example 41: Synthesis of compound 518

[0385]

[0386] After alkylation, intermediate 518-a was prepared in a similar manner as in the preparation of compound 1.

[0387] Compound 518-b was prepared from intermediate 518-a in analogy to the preparation of compound 472.

[0388] Compound 518-c was prepared from intermediate 518-b in analogy to the preparation of compound 412.

[0389] Compound 518-d was prepared from intermediate 518-c in analogy to the preparation of compound 1.

[0390] Synthesis of compound 518

[0391] Compound 491 was prepared from intermediate 491-d in analogy to the preparation of compound 187 (61%), see Table 1 for data related to the obtained target compound.

[0392] Table 1. Summary of product data for synthesis examples

[0393]

[0394]

[0395] Application examples 1-28

[0396] The present application provides an organic electroluminescent device comprising the compound of the above examples. The following uses OLED as an example of organic electroluminescent device, but it should be noted that the following detailed description is not a limitation of the present application, and those skilled in the art can extend the following detailed description to other organic electroluminescent devices.

[0397] The OLED is composed of an anode layer, an organic functional layer and a cathode layer; the organic functional layer includes a hole transport layer, a light-emitting layer, an electron transport region, etc.

[0398] In specific embodiments, glass or polymer material can be used as a substrate under the anode layer. In addition, the substrate for display can also be provided with a thin film transistor (TFT).

[0399] The anode layer material can use indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO) and other oxide transparent conductive materials and any combination thereof. The cathode layer material can also use magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) and other metals or alloys and any combination thereof.

[0400] The organic functional layer can be formed by vacuum evaporation, spin coating, printing and the like.

[0401] The hole transport zone between the anode layer and the light emitting layer can be a single layer hole transport layer (HTL) including a single layer hole transport layer containing only one compound and a single layer hole transport layer containing multiple compounds. The hole transport zone can also be a combination of a hole injection layer (HIL) and a hole transport layer (HTL).

[0402] The hole injection layer (HIL) is a host-guest doped material, the host material is selected from HT-1 to HT-30, and the guest material is selected from HI1-HI3, the doping ratio of the guest material in the host-guest material is 3-5wt%;

[0403]

[0404] The material of the hole transport layer (HTL) can be selected from, but not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or conductive dopant-containing polymers such as polyphenylene vinylene, polyaniline / dodecylbenzenesulfonic acid (PANI / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphor sulfonic acid (PANI / CSA), polyaniline / poly(4-styrenesulfonate) (Pani / PSS), aromatic amine derivatives as shown in HT-1 to HT-30, or any combination thereof.

[0405]

[0406]

[0407] The light emitting layer includes light emitting dyes (i.e. dopants) and host materials that can emit different wavelengths of light. The light emitting layer can be a single color light emitting layer that emits a single color such as red, green, blue, etc. Multiple single color light emitting layers of different colors can be arranged in a planar pattern according to a pixel pattern, or stacked together to form a color light emitting layer. When different color light emitting layers are stacked together, they can be separated from each other or connected to each other. The light emitting layer can also be a single color light emitting layer that can emit different colors such as red, green, blue, etc. at the same time.

[0408] Depending on the technology, the light emitting layer material can use different materials such as fluorescent electroluminescent materials, phosphorescent electroluminescent materials, thermally activated delayed fluorescence light emitting materials, etc. In an OLED device, a single light emitting technology can be used, or a combination of multiple different light emitting technologies can be used. These different light emitting materials classified by technology can emit the same color of light, or different colors of light.

[0409] In the present application, the light-emitting layer adopts the technology of blue fluorescent electroluminescence. The host material of the light-emitting layer is selected from, but not limited to, a combination of one or more of BFH-1 to BFH-16, and the guest material of the light-emitting layer is the compound 1 to compound 497 described in the present application. In the host-guest material, the doping ratio of the guest material is 10wt%;

[0410]

[0411] The OLED organic functional layer can also include an electron transport layer between the light-emitting layer and the cathode. The electron transport layer can be a single-layer electron transport layer (ETL) including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing multiple compounds.

[0412] In the present application, the electron transport layer material can be selected from, but not limited to, a combination of one or more of ET-1 to ET-18 listed below.

[0413]

[0414]

[0415] The device can also include an electron injection layer between the electron transport layer and the cathode layer, and the electron injection layer material includes, but is not limited to, a combination of one or more of the following.

[0416] LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca.

[0417] The present application also discloses a display screen or display panel, wherein the display screen or display panel adopts the organic electroluminescent device as described above; as a preferred, the display screen or display panel is an OLED display.

[0418] The present application also discloses an electronic device, wherein the electronic device has a display screen or display panel, and the display screen or display panel adopts the organic electroluminescent device as described above.

[0419] In application example 1, the device structure is as follows: a glass substrate with ITO (thickness 185 nm) transparent conductive layer is ultrasonically treated in a commercial cleaning agent (30 min / 2 times), rinsed in deionized water, then ultrasonically treated in solvents of acetone and isopropanol (30 min / 2 times), baked in a clean environment until the solvents are completely removed, cleaned with ultraviolet light and ozone, and the surface is bombarded with a low-energy cation beam. The ITO transparent conductive layer after the above treatment is used as an anode layer, and the glass plate with the anode layer is placed in the vacuum chamber of an evaporation device, vacuumed to 1 x 10"5 Pa, and vacuum evaporated HT-10:HI-2 (95:5 wt%) as a hole injection layer, HT-10 as a hole transport layer, with film thicknesses of 10 nm and 40 nm, respectively. BFH-5:compound 1 (90:10 wt%) is vacuum evaporated as a light-emitting layer on the hole transport layer, with a film thickness of 30 nm. ET-8 is vacuum evaporated as an electron transport layer on the light-emitting layer, with a film thickness of 20 nm. LiF 1 nm is vacuum evaporated as an electron injection layer on the electron transport layer, and Al 100 nm is vacuum evaporated as a cathode.

[0420] The device structure of the above device example 1 is briefly summarized as follows: ITO (185 nm) / HT-10:HI-2 (10 nm, 95:5 wt%) / HT-10 (40 nm) / BFH-5:compound 1 (30 nm, 10% wt) / ET-8 (20 nm) / LiF (1 nm) / Al (100 nm).

[0421] Device examples 2-28 are the same as device example 1, except that the light-emitting layer guest material compound 1 is replaced by compound 2, compound 4, compound 5, compound 7, compound 11, compound 12, compound 13, compound 28, compound 58, compound 62, compound 117, compound 120, compound 172, compound 174, compound 175, compound 183, compound 187, compound 189, compound 202, compound 216, compound 236, compound 246, compound 256, compound 303, compound 320, compound 350, compound 352, compound 359, compound 390, compound 412, compound 421, compound 432, compound 434, compound 456, compound 472, compound 481, compound 483, compound 491, and compound 518.

[0422] The driving voltage and current efficiency of the organic electroluminescent devices in application examples 1-28 and the service life of the devices are measured using a digital source table and a luminance meter at the same brightness. Specifically, the voltage is increased at a rate of 0.1 V per second, and the driving voltage at which the brightness of the organic electroluminescent device reaches 1000 cd / m2is measured. 2The voltage at this time is the driving voltage, and the current density at this time is measured, and the ratio of brightness to current density is the current efficiency; the lifetime test of LT95 is as follows: using a luminance meter, keeping a constant current, measuring the time for the brightness of the organic electroluminescent device to decrease to 950 cd / m 2 FWHM represents the half peak width of the light emission peak, and the detailed data are shown in Table 2.

[0423] Table 2: Device data of application examples

[0424]

[0425]

[0426] As can be seen from the above Table 2, when the compound of the present application is used as the guest material of the light-emitting layer, the device has the performance of low operating voltage, high efficiency, narrow spectrum and long lifetime. Since the compound of the present application has large rigidity, the vibration coupling of the ground state and the first excited singlet state and the excited state structure relaxation are inhibited, which leads to the spectrum broadening and the decrease of fluorescence quantum yield (PLQY), and at the same time, the large steric hindrance protection avoids the aggregation quenching and spectrum broadening under high voltage.

Claims

1. A high-efficiency narrow-band organic electroluminescent material, the structure general formula of which is shown as one of the following formulas I, II, III, IV, V: wherein X is independently selected from: represents the position of the bond; Y 1 , Y 2 are the same or different, independently selected from: represents the position of the bond; Z 1 , Z 2 are the same or different, independently selected from represents the position of the bond; and at least one of X, Y 1 , Y 2 , Z 1 , Z 2 is one of the groups having electron withdrawing properties; R is selected from hydrogen, C1-C10 alkyl, C1-C10 alkoxy, C6-C10 aromatic group.

2. The high-efficiency narrow-band electroluminescent material as described in claim 1, characterized in that: R is hydrogen, C1-C4 alkyl or phenyl.

3. The high-efficiency narrow-band electroluminescent material as described in claim 2, characterized in that: the structure of which is shown as one of the following formulas, 4. Use of a high-efficiency, narrow-band organic electroluminescent material according to claim 1, 2 or 3 for the production of an electroluminescent device, characterized in that: for preparing a light-emitting layer.

5. Use of a highly efficient, narrow-band organic electroluminescent material according to claim 4 for the production of an electroluminescent device, characterized in that: The light-emitting layer host material is selected from a combination of one or more of BFH-1 to BFH-16, and the light-emitting layer guest material is one or more of the high-efficiency narrow-band organic electroluminescent materials described in any one of claims 1 to 3; in the host-guest material, the doping ratio of the guest material is 10 wt%.

Images