An organic compound, a preparation method thereof, and an organic electroluminescent device

Abstract

The application belongs to the technical field of luminescent materials, and particularly relates to an organic compound, a preparation method thereof and an organic electroluminescent device. The application has the beneficial effects that a new high-efficiency organic compound and a preparation method thereof are provided. The molecular structure has a more flat spatial conformation, has better crystallinity, and is beneficial to forming a dense and uniform thin film. The organic electroluminescent device prepared by using the organic compound has a prolonged service life, improved luminous efficiency and reduced required driving voltage.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of light-emitting materials, and relates to an organic compound, a preparation method thereof and an organic electroluminescent device. BACKGROUND

[0002] OLED materials are divided into light-emitting materials, hole transport materials, electron transport materials and the like. Among them, the hole transport material usually has a low highest occupied molecular orbital (HOMO) value, and the excitons generated in the light-emitting layer diffuse to the hole transport layer interface or the hole transport layer side, finally resulting in light emission at the interface in the light-emitting layer or charge imbalance in the light-emitting layer, so that the color purity and efficiency of the organic electroluminescent device are low, and the service life is short.

[0003] Introducing a light-emitting auxiliary layer between the light-emitting layer and the hole transport layer can effectively avoid the above technical problems.

[0004] At present, the materials as the light-emitting auxiliary layer are limited, and most of such materials adopt a fluorene ring structure. They have high hole mobility, high T1 energy, block the outdiffusion of excitons after recombination to the transport layer, improve the overall efficiency of the device, and suitable HOMO value reduces the transport potential barrier of holes from the transport layer to the light-emitting layer, so that the driving voltage of the device is reduced and the service life is improved.

[0005] Therefore, there is an urgent need for a new organic compound to solve the problems in the prior art. SUMMARY

[0006] One of the purposes of the application is to provide a new compound; the second purpose is to provide a synthesis method of the new compound; and the third purpose is to provide an organic electroluminescent device applying the new compound.

[0007] The application discloses an organic compound, the molecular formula of which is shown in the general formula (I):

[0008]

[0009] Among them:

[0010] selected from any one of the chemical bonds;

[0011] Y1-Y8 are selected from any one of C and N, at least one of Y1-Y8 is different from the others, and 1-4 of Y1-Y8 are selected from N;

[0012] R1 is selected from any one of substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C1-C30 alkylmercapto, and substituted or unsubstituted silyl;

[0013] R2-R6 are independently selected from any one of substituted or unsubstituted C5-C30 aryl, substituted or unsubstituted 3-30 membered heteroaromatic ring, substituted or unsubstituted C10-C30 fused ring group, substituted or unsubstituted C5-C30 spiro ring group, monocyclic or polycyclic C3-C30 aliphatic ring, and monocyclic or polycyclic C6-C30 aromatic ring, or a group in which at least one carbon atom in the above group is replaced with another non-metallic atom;

[0014] L1, L2 are independently selected from any one of substituted or unsubstituted C5-C30 aryl, substituted or unsubstituted 3-30 membered heteroaromatic ring, substituted or unsubstituted C10-C30 fused ring group, substituted or unsubstituted C5-C30 spiro ring group, and monocyclic or polycyclic C3-C30 aliphatic ring or C6-C30 aromatic ring formed by connecting adjacent substituents, or a group in which at least one carbon atom in the above group is replaced with another non-metallic atom;

[0015] Ar1, Ar2 are independently selected from any one of substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-30 membered heteroaromatic ring, substituted or unsubstituted C10-C30 fused ring group, substituted or unsubstituted C5-C30 spiro ring group, and monocyclic or polycyclic C3-C30 aliphatic ring or C6-C30 aromatic ring formed by connecting adjacent substituents, or a group in which at least one carbon atom in the above group is replaced with another non-metallic atom.

[0016] Preferably, R1 is selected from an alkyl group.

[0017] More preferably, R1 is selected from at least one of a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, an alkoxy group, an alkylmercapto group, and a silyl group.

[0018] Preferably, in the group selected by L1 and L2, the other non-metallic atom replacing the carbon atom is selected from at least one of nitrogen, oxygen, sulfur, and silicon.

[0019] More preferably, L1 and L2 are independently selected from a phenyl group, a thiophene group, a furan group, a naphthalene group, or a derivative of the above groups.

[0020] Preferably, in the group selected by Ar1 and Ar2, the other non-metallic atom replacing the carbon atom is selected from at least one of nitrogen, oxygen, sulfur, and silicon.

[0021] More preferably, Ar1, Ar2 are independently selected from naphthyl, phenanthryl, phenyl, methylphenyl, dimethylphenyl, terphenyl, biphenyl, dibenzofuranyl, dibenzothiophenyl, cyclopentadithiophenyl, cyclopentadithiophenyl, dimethylfluorenyl, or derivatives of the above groups.

[0022] Preferably, in the general formula (I), The structure is selected from at least one of quinoxaline, pyrrolopyridine, pyridopyrazine, pyrazinopyrazine, quinoline, naphthridine, and cinnoline.

[0023] Further, the "substituted or unsubstituted" means substituted with at least one substituent selected from deuterium, halogen group, nitrile group, hydroxyl group, carbonyl group, ester group, silyl group, boron group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylamine group, substituted or unsubstituted heterocyclic amine group, substituted or unsubstituted arylamine group, substituted or unsubstituted aryl group, and substituted or unsubstituted heterocyclic group, or substituted with two or more substituents connected to each other, or without substituent.

[0024] For example, the "two or more substituents connected to each other" can include biphenyl. In other words, the biphenyl can be an aryl group, or can be interpreted as two phenyl groups connected to each other.

[0025] Preferably, the organic compound is a molecule having a structure shown in the following formulae 1 to 135:

[0026]

[0027]

[0028]

[0029]

[0030]

[0031] at least one of the following formulae:

[0032] The present application also discloses a preparation method of the organic compound, and the synthesis path is as follows:

[0033]

[0034] Step 1: preparation of intermediate C

[0035] The reactant B is added to a reaction container, anhydrous tetrahydrofuran is added and replaced with nitrogen three times, and then the reaction system is cooled to -78°C, n-BuLi is added dropwise, and stirred for 2h;

[0036] The reactant A is dissolved in tetrahydrofuran and added dropwise into the reaction system, and after the dropwise addition is completed, the temperature is increased to room temperature and stirred for 10 hours;

[0037] The reaction is terminated by adding distilled water, and the organic phase is collected by liquid separation, and dried by adding anhydrous sodium sulfate. The rotary evaporation is performed to obtain the intermediate C;

[0038] Step 2: Preparation of intermediate D

[0039] The intermediate C is added into a reaction container, the temperature is decreased to-10℃, triethylsilane is added, stirred for 30 minutes, methanesulfonic acid is added, the temperature is increased to room temperature and stirred overnight, water is added to terminate the reaction, liquid separation is performed, and the organic phase is collected. The aqueous phase is extracted with dichloromethane for three times, the organic phases are combined, anhydrous sodium sulfate is added for drying, and rotary evaporation is performed to obtain a white solid powder D;

[0040] Step 3: Preparation of intermediate F

[0041] The intermediate D is added into a reaction container, tetrahydrofuran is added and stirred until it is completely dissolved, potassium tert-butoxide is added and stirred for 2 hours, E is slowly added dropwise, and stirred at reflux overnight. The temperature is cooled to room temperature, saturated ammonium chloride solution is added to quench the reaction, liquid separation is performed, and the organic phase is collected. The aqueous phase is extracted with dichloromethane for three times, the organic phases are combined, anhydrous sodium sulfate is added for drying, and rotary evaporation is performed to obtain a white solid powder F;

[0042] Step 4: Preparation of product

[0043] The intermediates F and G are added into a reaction container, toluene is added and stirred, nitrogen is replaced for three times, sodium tert-butoxide, tris(dibenzylideneacetone)dipalladium and tri-tert-butylphosphine are sequentially added, and the temperature is increased to 110℃ and stirred overnight;

[0044] The temperature is cooled to room temperature, water is added to terminate the reaction, liquid separation is performed, and the organic phase is collected. The aqueous phase is extracted with dichloromethane for three times, the organic phases are combined, anhydrous sodium sulfate is added for drying, and column chromatography is performed to obtain the product of the general formula.

[0045] The application further discloses an organic electroluminescent device, and the organic compound is used as an auxiliary light-emitting layer material.

[0046] The application has the following beneficial effects:

[0047] 1. The molecular structure of the compound has a more flat spatial conformation, has better crystallinity, and is beneficial to the formation of a dense and uniform thin film.

[0048] 2. The organic electroluminescent device prepared from the organic compound has a longer service life, higher luminous efficiency and lower required driving voltage. BRIEF DESCRIPTION OF DRAWINGS

[0049] Figure 1 NMR spectrum of compound 1;

[0050] Figure 2 NMR spectrum of compound 28;

[0051] Figure 3 NMR spectrum of compound 26;

[0052] Figure 4 NMR spectrum of compound 51;

[0053] Figure 5 NMR spectrum of compound 98;

[0054] Figure 6 NMR spectrum of compound 43;

[0055] Figure 7 NMR spectrum of compound 21;

[0056] Figure 8 NMR spectrum of compound 67. DETAILED DESCRIPTION

[0057] The specific embodiments of the present application will be further described with reference to the following examples. The following examples are provided to more clearly illustrate the technical embodiments of the present application, and cannot be used to limit the protection scope of the present application.

[0058] Example 1

[0059] Preparation of compound 1:

[0060] The reaction equation is as follows

[0061]

[0062] The intermediate B1 200mmol was added into a three-neck flask, THF was added and stirred until fully dissolved, replaced with nitrogen for three times, cooled to -78℃, slowly added n-butyllithium 183mmol, stirred for 2h, A1 166mmol was dissolved in THF, slowly added into the reaction system, after the dropwise addition was completed, the temperature was raised to room temperature and stirred overnight. The reaction was terminated by slowly adding dilute hydrochloric acid, the organic phase was collected, the aqueous phase was extracted with dichloromethane for three times, the organic phases were combined, anhydrous sodium sulfate was added for drying, and white solid powder C1 55g was obtained after rotary evaporation.

[0063] The intermediate C1 160mmol was added into a three-neck flask, dichloromethane was added and stirred until fully dissolved, cooled to -10℃, triethylsilane 800mmol was added, stirred for 30min, methanesulfonic acid 800mmol was added, the temperature was raised to room temperature and stirred overnight, water was added to terminate the reaction, the organic phase was collected, the aqueous phase was extracted with dichloromethane for three times, the organic phases were combined, anhydrous sodium sulfate was added for drying, and white solid powder D1 50g was obtained after rotary evaporation.

[0064] Intermediate D1 152 mmol was added into a three-neck flask, THF was added to stir until fully dissolved, potassium tert-butoxide 304 mmol was added to stir for 2 h, iodomethane 760 mmol was added dropwise slowly, stirred at reflux overnight, cooled to room temperature, saturated ammonium chloride solution was added to quench the reaction, separated, collected the organic phase, the aqueous phase was extracted with dichloromethane for 3 times, combined the organic phase, anhydrous sodium sulfate was added to dry, white solid powder F1 49 g was obtained after rotary evaporation.

[0065] Intermediate F1 58 mmol, G1 62 mmol was added into a three-neck flask, toluene was added to stir, replaced with nitrogen for 3 times, sodium tert-butoxide 117 mmol, tris(dibenzylideneacetone)dipalladium 0.6 mmol, tri-tert-butylphosphine 3 mmol were added in turn, heated to 110 °C to stir overnight. Cooled to room temperature, added water to terminate the reaction, separated, collected the organic phase, the aqueous phase was extracted with dichloromethane for 3 times, combined the organic phase, anhydrous sodium sulfate was added to dry, column chromatography to obtain the product 36 g (yield: 92%).

[0066] The product was characterized by NMR as shown in the following: Figure 1

[0067] 1 H NMR (400 MHz, CDC13), δ (ppm): 8.50 (d, 1H), 8.34 (m, 2H), 7.90 (d, 1H), 7.73 (m, 1H), 7.61 (d, 1H), 7.59 (m, 2H), 7.55 (d, 4H), 7.47 (m, 1H), 7.43 (m, 2H), 7.39 (m, 7H), 7.29 (m, 2H), 7.22 (m, 1H), 7.19 (d, 2H), 6.95 (d, 1H), 1.83 (s, 3H), 1.56 (s, 6H).

[0068] Example 2

[0069] Preparation of compound 28:

[0070] The reaction equation is as follows

[0071]

[0072] Intermediate B1 183 mmol was added into a three-neck flask, THF was added to stir until fully dissolved, replaced with nitrogen for 3 times, cooled to -78 °C, n-butyllithium 168 mmol was added dropwise slowly, stirred for 2 h, A1 153 mmol was dissolved in THF, added to the reaction system slowly, after dropwise addition, stirred at room temperature overnight. Added dilute hydrochloric acid to terminate the reaction, separated, collected the organic phase, the aqueous phase was extracted with dichloromethane for 3 times, combined the organic phase, anhydrous sodium sulfate was added to dry, white solid powder C1 53 g was obtained after rotary evaporation.​

[0073] Intermediate CI 147 mmol was added into a three-neck flask, dichloromethane was added to stir until fully dissolved, cooled to -10 °C, triethylsilane 735 mmol was added, stirred for 30 min, methanesulfonic acid 735 mmol was added, warmed to room temperature and stirred overnight, water was added to terminate the reaction, separated, collected the organic phase, the aqueous phase was extracted with dichloromethane three times, the organic phase was combined, anhydrous sodium sulfate was added to dry, rotary evaporation to obtain white solid powder Dl 49 g.

[0074] Intermediate Dl 142 mmol was added into a three-neck flask, tetrahydrofuran was added to stir until fully dissolved, potassium tert-butoxide 284 mmol was added and stirred for 2 h, iodomethane 711 mmol was added dropwise, stirred at reflux overnight, cooled to room temperature, saturated ammonium chloride solution was added to quench the reaction, separated, collected the organic phase, the aqueous phase was extracted with dichloromethane three times, the organic phase was combined, anhydrous sodium sulfate was added to dry, rotary evaporation to obtain white solid powder F1 48 g.

[0075] Intermediate F1 56 mmol, G1 60 mmol was added into a three-neck flask, toluene was added to stir, replaced with nitrogen three times, sodium tert-butoxide 112 mmol, tris(dibenzylideneacetone)dipalladium 0.6 mmol, tri-tert-butylphosphine 3 mmol were added in turn, warmed to 110 °C and stirred overnight. Cooled to room temperature, water was added to terminate the reaction, separated, collected the organic phase, the aqueous phase was extracted with dichloromethane three times, the organic phase was combined, anhydrous sodium sulfate was added to dry, column chromatography to obtain the product 34 g (yield: 94%).

[0076] The product was subjected to nuclear magnetic resonance characterization as shown in the following: Figure 2

[0077] 1 H NMR (400 MHz, CDC13), δ (ppm): 8.50 (s, 1H), 8.02 (m, 1H), 7.59 (m, 4H), 7.56 (d, 1H), 7.54 (d, 4H), 7.51 (t, 1H), 7.40 (m, 6H), 7.29 (m, 2H), 7.23 (d, 4H), 7.18 (m, 2H), 7.08 (m, 2H), 6.98 (m, 2H), 1.84 (s, 3H).

[0078] Example 3

[0079] Preparation of compound 26:

[0080] The reaction equation is as follows

[0081]

[0082] ​Intermediate B4 200 mmol was added into a three-neck flask, THF was added to stir until fully dissolved, replaced with nitrogen for three times, cooled to -78 °C, slowly added n-butyllithium 183 mmol dropwise, stirred for 2 h, A4 166 mmol was dissolved in THF, slowly added into the reaction system, after the dropwise addition was completed, the temperature was raised to room temperature and stirred overnight. The reaction was terminated by slowly adding dilute hydrochloric acid, separated, the organic phase was collected, the aqueous phase was extracted with dichloromethane for three times, the organic phases were combined, anhydrous sodium sulfate was added for drying, and white solid powder C4 54 g was obtained after rotary evaporation.

[0083] Intermediate C4 157 mmol was added into a three-neck flask, dichloromethane was added to stir until fully dissolved, cooled to -10 °C, triethylsilane 783 mmol was added, stirred for 30 min, methanesulfonic acid 313 mmol was added, the temperature was raised to room temperature and stirred overnight, water was added to terminate the reaction, separated, the organic phase was collected, the aqueous phase was extracted with dichloromethane for three times, the organic phases were combined, anhydrous sodium sulfate was added for drying, and white solid powder D4 48 g was obtained after rotary evaporation.

[0084] Intermediate D4 145 mmol was added into a three-neck flask, tetrahydrofuran was added to stir until fully dissolved, potassium tert-butoxide 292 mmol was added and stirred for 2 h, 2-iodopropane 730 mmol was slowly added dropwise, stirred at reflux overnight, cooled to room temperature, saturated ammonium chloride solution was added to quench the reaction, separated, the organic phase was collected, the aqueous phase was extracted with dichloromethane for three times, the organic phases were combined, anhydrous sodium sulfate was added for drying, and white solid powder F4 53 g was obtained after rotary evaporation.

[0085] Intermediate F4 52 mmol and G4 55 mmol were added into a three-neck flask, toluene was added to stir, replaced with nitrogen for three times, sodium tert-butoxide 104 mmol, tris(dibenzylideneacetone)dipalladium 0.5 mmol, tri-tert-butylphosphine 2.5 mmol were added in turn, the temperature was raised to 110 °C and stirred overnight. The temperature was cooled to room temperature, water was added to terminate the reaction, separated, the organic phase was collected, the aqueous phase was extracted with dichloromethane for three times, the organic phases were combined, anhydrous sodium sulfate was added for drying, and the product 34 g (yield: 92%) was obtained after column chromatography.

[0086] The product was subjected to nuclear magnetic resonance characterization as shown in the following: Figure 3

[0087] 1 ​H NMR (400 MHz, CDC13), δ (ppm): 8.51 (s, 1H), 8.04 (m, 1H), 7.90 (m, 1H), 7.73 (m, 1H), 7.63 (d, 1H), 7.57 (d, 2H), 7.51 (d, 1H), 7.49 (m, 1H), 7.47 (m, 5H), 7.43 (m, 3H), 7.39 (m, 2H), 7.37 (m, 8H), 7.22 (m, 1H), 1.57 (d, 6H), 1.25 (s, 9H).

[0088] Example 4

[0089] Preparation of compound 51:

[0090] The reaction equation is as follows

[0091]

[0092] The intermediate B5 200 mmol was added into a three-neck flask, THF was added and stirred until fully dissolved, replaced with nitrogen for three times, cooled to -78 °C, slowly added n-butyllithium 183 mmol, stirred for 2 h, A5 166 mmol was dissolved in THF, slowly added into the reaction system, after the dropwise addition was completed, it was stirred at room temperature overnight. The reaction was terminated by slowly adding dilute hydrochloric acid, separated, the organic phase was collected, the aqueous phase was extracted with dichloromethane for three times, the organic phases were combined, anhydrous sodium sulfate was added for drying, and white solid powder C5 54 g was obtained after rotary evaporation.

[0093] The intermediate C5 157 mmol was added into a three-neck flask, dichloromethane was added and stirred until fully dissolved, cooled to -10 °C, triethylsilane 783 mmol was added, stirred for 30 min, methanesulfonic acid 313 mmol was added, stirred at room temperature overnight, water was added to terminate the reaction, separated, the organic phase was collected, the aqueous phase was extracted with dichloromethane for three times, the organic phases were combined, anhydrous sodium sulfate was added for drying, and white solid powder D5 48 g was obtained after rotary evaporation.

[0094] The intermediate D5 145 mmol was added into a three-neck flask, tetrahydrofuran was added and stirred until fully dissolved, potassium tert-butoxide 290 mmol was added and stirred for 2 h, iodomethane 725 mmol was slowly added dropwise, stirred at reflux overnight, cooled to room temperature, saturated ammonium chloride solution was added to quench the reaction, separated, the organic phase was collected, the aqueous phase was extracted with dichloromethane for three times, the organic phases were combined, anhydrous sodium sulfate was added for drying, and white solid powder F4 44 g was obtained after rotary evaporation.

[0095] Intermediate F5 52 mmol, G5 60 mmol were added into a three-necked flask, toluene was added for stirring, nitrogen was replaced for three times, sodium tert-butoxide 104 mmol, tris(dibenzylideneacetone)dipalladium 0.5 mmol, tri-tert-butylphosphine 2.5 mmol were added in turn, the temperature was raised to 110°C for stirring overnight. The temperature was cooled to room temperature, water was added to terminate the reaction, the liquid was separated, the organic phase was collected, the aqueous phase was extracted with dichloromethane for three times, the organic phases were combined, anhydrous sodium sulfate was added for drying, column chromatography was performed to obtain Example 37g (yield: 90%).

[0096] The product was subjected to nuclear magnetic resonance characterization as shown in the following: Figure 4

[0097] 1 H NMR (400 MHz, CDC13), δ (ppm): 8.54 (s, 1H), 8.40 (s, 1H), 7.90 (t, 1H), 7.74 (m, 4H), 7.63 (d, 2H), 7.55 (d, 2H), 7.47 (m, 5H), 7.39 (m, 7H), 7.34 (m, 5H), 1.85 (s, 3H), 1.57 (s, 6H).

[0098] Example 5

[0099] Preparation of compound 98:

[0100] The reaction equation is as follows

[0101]

[0102] Intermediate B3 162 mmol was added into a three-necked flask, THF was added for stirring until it was fully dissolved, nitrogen was replaced for three times, the temperature was lowered to -78°C, n-butyllithium 148 mmol was slowly added dropwise, stirring was performed for 2 h, A1 135 mmol was dissolved in THF, and then slowly added into the reaction system, after the dropwise addition was completed, the temperature was raised to room temperature for stirring overnight. Dilute hydrochloric acid was slowly added to terminate the reaction, the liquid was separated, the organic phase was collected, the aqueous phase was extracted with dichloromethane for three times, the organic phases were combined, anhydrous sodium sulfate was added for drying, and then white solid powder C1 50 g was obtained after rotary evaporation.

[0103] Intermediate C3 130 mmol was added into a three-necked flask, dichloromethane was added for stirring until it was fully dissolved, the temperature was lowered to -10°C, triethylsilane 648 mmol was added, stirring was performed for 30 min, methanesulfonic acid 648 mmol was added, the temperature was raised to room temperature for stirring overnight, water was added to terminate the reaction, the liquid was separated, the organic phase was collected, the aqueous phase was extracted with dichloromethane for three times, the organic phases were combined, anhydrous sodium sulfate was added for drying, and then white solid powder D3 45 g was obtained after rotary evaporation.

[0104] ​Intermediate D3 120 mmol was added into a three-necked flask, THF was added to stir until fully dissolved, potassium tert-butoxide 243 mmol was added to stir for 2 h, 2-iodopropane 608 mmol was added dropwise slowly, and the mixture was stirred at reflux overnight. The mixture was cooled to room temperature, saturated ammonium chloride solution was added to quench the reaction, and the organic phase was collected. The aqueous phase was extracted with dichloromethane for 3 times, and the organic phases were combined and dried over anhydrous sodium sulfate. After rotary evaporation, white solid powder F1 45 g was obtained.

[0105] Intermediate F3 48 mmol and G3 62 mmol were added into a three-necked flask, toluene was added to stir, and the mixture was replaced with nitrogen for 3 times. Sodium tert-butoxide 117 mmol, tris(dibenzylideneacetone)dipalladium 0.6 mmol, and tri-tert-butylphosphine 3 mmol were added in sequence, and the mixture was stirred at 110 ℃ overnight. The mixture was cooled to room temperature, water was added to terminate the reaction, and the mixture was separated. The organic phase was collected, the aqueous phase was extracted with dichloromethane for 3 times, and the organic phases were combined and dried over anhydrous sodium sulfate. Column chromatography was performed to obtain the product 33 g (yield: 89%).

[0106] The product was subjected to nuclear magnetic resonance characterization as shown in FIG. 1, and the characterization data are as follows: Figure 5

[0107] 1 H NMR (400 MHz, CDCl3), δ (ppm): 8.64 (d, 1H), 7.96 (m, 2H), 7.89 (m, 3H), 7.73 (m, 1H), 7.63 (d, 1H), 7.58 (m, 4H), 7.47 (m, 6H), 7.34 (m, 2H), 7.25 (m, 1H), 7.19 (d, 2H), 7.13 (m, 4H), 7.00 (m, 4H), 2.64 (m, 1H), 1.57 (s, 6H), 1.05 (d, 6H).

[0108] Example 6

[0109] Preparation of compound 43:

[0110] The reaction equation is as follows:

[0111]

[0112] Intermediate B6 108 mmol was added into a three-necked flask, THF was added to stir until fully dissolved, and the mixture was replaced with nitrogen for 3 times. The mixture was cooled to -78 ℃, and n-butyllithium 108 mmol was added dropwise slowly. After stirring for 2 h, A6 90 mmol was dissolved in THF and added to the reaction system slowly. After the addition was completed, the mixture was stirred at room temperature overnight. Dilute hydrochloric acid was added slowly to terminate the reaction, and the mixture was separated. The organic phase was collected, the aqueous phase was extracted with dichloromethane for 3 times, and the organic phases were combined and dried over anhydrous sodium sulfate. After rotary evaporation, white solid powder C6 33 g was obtained. ​

[0113] 85 mmol of intermediate C6 was added to a three-necked flask, and dichloromethane was added and stirred until fully dissolved. The mixture was cooled to -10 °C, and 425 mmol of triethylsilane was added. The mixture was stirred for 30 min, and 425 mmol of methanesulfonic acid was added. The mixture was then heated to room temperature and stirred overnight. The reaction was terminated by adding water. The mixture was separated, and the organic phase was collected. The aqueous phase was extracted three times with dichloromethane. The organic phases were combined, dried with anhydrous sodium sulfate, and evaporated to dryness to obtain 30 g of white solid powder D6.

[0114] 80 mmol of intermediate D6 was added to a three-necked flask, tetrahydrofuran was added and stirred until fully dissolved, 160 mmol of potassium tert-butoxide was added and stirred for 2 h, 400 mmol of iodomethane was slowly added dropwise, the mixture was refluxed and stirred overnight, cooled to room temperature, and saturated ammonium chloride solution was added to quench the reaction. The mixture was separated, the organic phase was collected, and the aqueous phase was extracted three times with dichloromethane. The organic phases were combined, dried with anhydrous sodium sulfate, and evaporated to dryness to obtain 30 g of white solid powder F6.

[0115] Intermediates F6 (78 mmol) and G6 (86 mmol) were added to a three-way valve, toluene was added and stirred, and the mixture was purged with nitrogen three times. Sodium tert-butoxide (155 mmol), tris(dibenzylacetone)dipalladium (0.8 mmol), and tri-tert-butylphosphine (4 mmol) were added sequentially. The mixture was heated to 110 °C and stirred overnight. After cooling to room temperature, water was added to terminate the reaction. The mixture was separated, and the organic phase was collected. The aqueous phase was extracted three times with dichloromethane. The combined organic phases were dried over anhydrous sodium sulfate and subjected to column chromatography to obtain 52 g of the product (yield: 93%).

[0116] As attached Figure 6 As shown, the product underwent NMR characterization, and the characterization data are as follows:

[0117] 1 H NMR (400MHz, CDCl3), δ (ppm): 8.58 (d, 1H), 8.42 (s, 1H), 8.03 (m, 2H), 7.9 (m, 1H), 7.78 (d, 1H), 7.73 (m, 1H), 7.67 ( m,1H),7.63(m,1H),7.54(m,1H),7.45(m,3H),7.42(m,3H),7.29(m,1H),7.12(m,8H),2.95(s,3H),1.58(d,12H).

[0118] Example 7

[0119] Preparation of compound 21:

[0120] The reaction equation is as follows:

[0121]

[0122] Intermediate B7 162 mmol was added into a three-neck flask, THF was added to stir until fully dissolved, replaced with nitrogen for three times, cooled to -78 °C, slowly added n-butyllithium 162 mmol dropwise, stirred for 2 h, A7 135 mmol was dissolved in THF, slowly added into the reaction system, after the dropwise addition was completed, the temperature was raised to room temperature and stirred overnight. The reaction was terminated by slowly adding dilute hydrochloric acid, separated, the organic phase was collected, the aqueous phase was extracted with dichloromethane for three times, the organic phases were combined, anhydrous sodium sulfate was added for drying, and white solid powder C7 50 g was obtained after rotary evaporation.

[0123] Intermediate C7 130 mmol was added into a three-neck flask, dichloromethane was added to stir until fully dissolved, cooled to -10 °C, triethylsilane 650 mmol was added, stirred for 30 min, methanesulfonic acid 650 mmol was added, the temperature was raised to room temperature and stirred overnight, water was added to terminate the reaction, separated, the organic phase was collected, the aqueous phase was extracted with dichloromethane for three times, the organic phases were combined, anhydrous sodium sulfate was added for drying, and white solid powder D7 45 g was obtained after rotary evaporation.

[0124] Intermediate D7 122 mmol was added into a three-neck flask, tetrahydrofuran was added to stir until fully dissolved, potassium tert-butoxide 240 mmol was added and stirred for 2 h, iodomethane 600 mmol was slowly added dropwise, stirred at reflux overnight, cooled to room temperature, saturated ammonium chloride solution was added to quench the reaction, separated, the organic phase was collected, the aqueous phase was extracted with dichloromethane for three times, the organic phases were combined, anhydrous sodium sulfate was added for drying, and white solid powder F7 48 g was obtained after rotary evaporation.

[0125] Intermediate F7 80 mmol, G7 86 mmol were added into a three-neck flask, toluene was added to stir, replaced with nitrogen for three times, sodium tert-butoxide 155 mmol, tris(dibenzylideneacetone)dipalladium 0.8 mmol, tri-tert-butylphosphine 4 mmol were added in turn, the temperature was raised to 110 °C and stirred overnight. The temperature was cooled to room temperature, water was added to terminate the reaction, separated, the organic phase was collected, the aqueous phase was extracted with dichloromethane for three times, the organic phases were combined, anhydrous sodium sulfate was added for drying, and the product 50 g was obtained by column chromatography (yield: 94%).

[0126] The product was subjected to nuclear magnetic resonance characterization as shown in the following: Figure 7

[0127] 1 H NMR (400 MHz, CDCl3), δ (ppm): 8.77 (d, 1H), 7.58 (s, 4H), 7.54 (m, 5H), 7.38 (m, 6H), 7.32 (m, 1H), 7.28 (m, 2H), 7.17 (m, 8H), 7.08 (m, 4H), 1.73 (s, 3H), 1.55 (s, 6H).

[0128] Example 8​

[0129] Preparation of compound 67:

[0130] The reaction equation is as follows:

[0131]

[0132] Intermediate B8 200mmol was added into a three-neck flask, THF was added and stirred until fully dissolved, replaced with nitrogen for three times, cooled to -78℃, slowly added n-butyllithium 200mmol dropwise, stirred for 2h, A8 167mmol was dissolved in THF, slowly added into the reaction system, after the dropwise addition was completed, the temperature was raised to room temperature and stirred overnight. The reaction was terminated by slowly adding dilute hydrochloric acid, separated, collected the organic phase, the aqueous phase was extracted with dichloromethane for three times, the organic phases were combined, anhydrous sodium sulfate was added for drying, and white solid powder C8 53g was obtained after rotary evaporation.

[0133] Intermediate C8 155mmol was added into a three-neck flask, dichloromethane was added and stirred until fully dissolved, cooled to -10℃, triethylsilane 770mmol was added, stirred for 30min, methanesulfonic acid 770mmol was added, the temperature was raised to room temperature and stirred overnight, water was added to terminate the reaction, separated, collected the organic phase, the aqueous phase was extracted with dichloromethane for three times, the organic phases were combined, anhydrous sodium sulfate was added for drying, and white solid powder D8 46g was obtained after rotary evaporation.

[0134] Intermediate D8 140mmol was added into a three-neck flask, tetrahydrofuran was added and stirred until fully dissolved, potassium tert-butoxide 280mmol was added and stirred for 2h, iodomethane 700mmol was slowly added dropwise, stirred at reflux overnight, cooled to room temperature, saturated ammonium chloride solution was added to quench the reaction, separated, collected the organic phase, the aqueous phase was extracted with dichloromethane for three times, the organic phases were combined, anhydrous sodium sulfate was added for drying, and white solid powder F8 42g was obtained after rotary evaporation.

[0135] Intermediate F8 80mmol, G8 86mmol were added into a three-neck flask, toluene was added and stirred, replaced with nitrogen for three times, sodium tert-butoxide 155mmol, tris(dibenzylideneacetone)dipalladium 0.8mmol, tri-tert-butylphosphine 4mmol were added in turn, the temperature was raised to 110℃ and stirred overnight. The temperature was cooled to room temperature, water was added to terminate the reaction, separated, collected the organic phase, the aqueous phase was extracted with dichloromethane for three times, the organic phases were combined, anhydrous sodium sulfate was added for drying, and the product 40g (yield: 75%) was obtained after column chromatography.

[0136] The product was subjected to nuclear magnetic resonance characterization as shown in the following: Figure 8 The characterization data are as follows:

[0137] 1H NMR (400 MHz, CDC13), δ (ppm): 7.88 (d, 1H), 7.77 (d, 1H), 7.68 (m, 2H), 7.54 (d, 2H), 7.32 (m, 21H), 7.22 (m, 2H), 1.84 (s, 3H), 1.59 (s, 6H).

[0138] Examples 9-21

[0139] The preparation of the compounds was accomplished according to the synthetic procedure of Examples 1-8.

[0140] The molecular formula and mass spectra are shown in Table 1:

[0141] Table 1 List of parameters for Examples 6-21

[0142]

[0143] In addition, it should be noted that other compounds of the present application can be obtained according to the synthetic procedures of the above listed examples, and therefore are not listed here.

[0144] In order to further illustrate the beneficial effects of the present application, the following application examples are provided:

[0145] Application Example 1

[0146] An organic electroluminescent device was prepared using the compound 1 obtained in Example 1 as a light-emitting auxiliary material:

[0147] An ITO glass substrate with a coating thickness of 150 nm from Fischer was cleaned in distilled water twice, ultrasonically washed for 30 min, and repeatedly washed with distilled water twice, ultrasonically washed for 10 min. After the distilled water washing was completed, the substrate was dried and transferred to a plasma cleaning machine, washed for 5 min, and then introduced into an evaporation machine. Compound HT and P-dopant (3%) were introduced into a chamber of a vacuum vapor deposition apparatus, and the pressure in the chamber of the apparatus was controlled to 10"6torr. Thereafter, an electric current was applied to the chamber to evaporate the above-introduced materials, thereby forming a hole injection layer having a thickness of 10 nm on the ITO substrate. A hole transport layer having a thickness of 35 nm of HT was vacuum deposited on the formed hole injection layer, and a light-emitting auxiliary layer was formed by vacuum depositing the compound of Example 1 of the present application on the hole transport layer to a thickness of 20 nm, thereby producing a light-emitting layer of an OLED light-emitting device. The light-emitting layer had a structure in which Host-R used in the OLED light-emitting layer was used as a host material, and Dopant-R was used as a dopant material, the doping ratio of the dopant material was 3% by weight, and the film thickness of the light-emitting layer was 40 nm.

[0148] On the above light emitting layer, 12 nm thick TPBi was vacuum evaporated as a hole blocking layer, and on the above hole blocking layer, ET was vacuum deposited as an electron transporting layer with a thickness of 40 nm; on the above electron transporting layer, 1.0 nm thick lithium quinolyl hydroxide (Liq) was vacuum evaporated as an electron injecting layer. On the electron injecting layer, an Al electrode layer with a thickness of 150 nm was prepared, which was a cathode layer.

[0149] After the OLED light emitting device was prepared as described above, the anode and the cathode were connected by a known driving circuit, and the current efficiency of the device and the service life of the device were measured.

[0150] The molecular structure of the related material is shown below:

[0151]

[0152] Application Example 2-21

[0153] The product corresponding to Example 2-21 was applied in the same manner as in Application Example 1

[0154] In order to further illustrate the advancement of the present application over the prior art, the following comparative examples are provided:

[0155] Comparative Example 1

[0156] Referring to the method of Application Example 1, the compound 1 used in the device of Application Example 1 was replaced by the comparative material as the light emitting auxiliary layer, and the corresponding organic electroluminescent device was prepared.

[0157]

[0158] The following performance tests were conducted on Application Examples 1-21 and Comparative Example 1:

[0159] The above prepared organic electroluminescent device was biased with a forward direct current voltage, and the organic electroluminescent characteristics were measured using a PR-650 luminosity measuring device of Photo Research Company, with a brightness of 6000 cd / m 2 The T95 life was measured under the conditions of Table 2-3 using a life measuring device of McScience Company. The results are shown in Table 2-3:

[0160] Table 2 Test Performance Parameter Table

[0161]

[0162]

[0163] Table 3 Device Performance Parameter Test Table

[0164]

[0165] As can be seen from Table 2,

[0166] The device performance shows that the application examples of the present application have significantly improved performance in terms of life, luminous efficiency, etc. compared with the comparative examples.

[0167] Under the condition of the same main body, the driving voltage is reduced by 0.1-0.2V, which embodies the progressiveness of the present application.

[0168] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the present application, but not to limit it; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. An organic compound characterized in that, The molecular formula is shown as general formula (I): Wherein: any one selected from the group consisting of a chemical bond, any one selected from the group consisting of a chemical bond, the structure is selected from at least one of quinoxaline, pyridopyrazine, pyrazinopyrazine, quinoline, naphthyridine, pteridine; R1 is selected from any one of methyl, ethyl, isopropyl, tert-butyl, C1 alkoxy, C1 alkylmercapto; L1, L2 are respectively selected from any one of phenyl, thienyl, furanyl, naphthyl; Ar1, Ar2 are respectively selected from any one of naphthyl, phenanthryl, phenyl, methylphenyl, dimethylphenyl, terphenyl, biphenyl, dibenzofuran, dibenzothiophene, cyclopentadithiophene, cyclopentadifuran, dimethylfluorene.

2. An organic compound, characterized by, The structural formula of the organic compound is any one of the following structural formula: At least one of the intermediates.

3. A method for the preparation of an organic compound, characterized in that, The organic compound of claim 1 is prepared according to the following steps: The synthesis path is as follows: Step 1: preparation of intermediate C The reactant B is added to the reaction container, anhydrous tetrahydrofuran is added and replaced with nitrogen three times, then the reaction system is cooled to-78℃, n-BuLi is added dropwise, and stirred for 2h; The reactant A is dissolved in tetrahydrofuran and added dropwise to the reaction system, and after the dropwise addition is completed, the temperature is raised to room temperature and stirred for 10h; Distilled water is added to terminate the reaction, the organic phase is collected by liquid separation, anhydrous sodium sulfate is added for drying, and rotary evaporation is performed to obtain intermediate C; Step 2: preparation of intermediate D Intermediate C is added to the reaction container, cooled to-10℃, triethylsilane is added, stirred for 30min, methanesulfonic acid is added, stirred at room temperature overnight, water is added to terminate the reaction, liquid separation is performed, the organic phase is collected, the aqueous phase is extracted with dichloromethane three times, the organic phases are combined, anhydrous sodium sulfate is added for drying, and rotary evaporation is performed to obtain white solid powder D; Step 3: preparation of intermediate F Intermediate D is added to the reaction container, tetrahydrofuran is added and stirred until it is completely dissolved, potassium tert-butoxide is added and stirred for 2h, E is slowly added dropwise, refluxed and stirred overnight, cooled to room temperature, saturated ammonium chloride solution is added to quench the reaction, liquid separation is performed, the organic phase is collected, the aqueous phase is extracted with dichloromethane three times, the organic phases are combined, anhydrous sodium sulfate is added for drying, and rotary evaporation is performed to obtain white solid powder F; Step 4: preparation of the product Intermediate F, G is added to the reaction container, toluene is added and stirred, replaced with nitrogen three times, sodium tert-butoxide, tris(dibenzylideneacetone)dipalladium, and tri-tert-butylphosphine are sequentially added, the temperature is raised to 110℃ and stirred overnight; Cool to room temperature, add water to terminate the reaction, separate the liquid, collect the organic phase, extract the aqueous phase with dichloromethane three times, combine the organic phases, add anhydrous sodium sulfate for drying, and column chromatography to obtain the product shown in general formula (1).

4. An organic electroluminescent device, characterized by comprising The organic compound of any one of claims 1-2 is used as an auxiliary light-emitting layer material.

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