Indenoquinolinone or chromenequinolinone derivatives and preparation method and application thereof

Abstract

This patent application discloses an indenoquinolinone or chromenequinolinone derivative and its preparation method and application. The indenoquinolinone or chromenequinolinone derivative in this patent application is based on quinoline methyl ketone as an electron-withdrawing group, and with the help of the electron-donating ability of N in the heterocyclic ring, an indenoquinolinone or chromenequinolinone derivative organic luminescent small molecule is prepared. The quinolinone derivative containing aromatic amine groups provided in this patent application has a unique aggregation-induced emission effect, high luminous intensity, good thermal stability and good solubility, and can be used as a new type of solid luminescent molecule with good performance, low cost and highly distorted spatial structure. The quinolinone derivative containing aromatic amine groups has significant economic value in the preparation of luminescent materials, luminescent devices or smart materials, and has good application prospects in the fields of full-color display and solid-state lighting.

Description

Technical Field

[0001] The present patent application relates to the field of organic light-emitting materials, and more specifically, to an indenoquinolinone or chromenequinolinone derivative and a preparation method and application thereof. Background Art

[0002] With the rise of high-tech such as large-screen smartphones, tablets, and wearable devices, organic light-emitting diodes (OLED) are regarded as a promising new generation of display products in the diversified flat panel display market due to their advantages such as self-luminescence, wide viewing angle, low power consumption, fast response time, thin thickness, and flexibility. They are known as "dream displays."

[0003] Compared with traditional LED technology, OLED technology has great application potential in flat panel display, smart phones and solid-state light-emitting due to its significant advantages in achieving large-area high-quality display and lighting, ultra-high resolution, ultra-fast response speed and flexible electronics applications, and has attracted extensive attention from the global academic and industrial communities. However, existing luminescent materials currently have problems such as insufficient luminescent color purity, insufficient thermal stability and poor solubility. Summary of the invention

[0004] In order to overcome one of the problems existing in the above-mentioned prior art, the present patent application provides an indenoquinolinone or chromenequinolinone derivative. The indenoquinolinone or chromenequinolinone derivative can be used as an organic light-emitting material, and has a unique aggregation-induced emission effect, high luminous intensity, good thermal stability and good solubility.

[0005] Another object of the present patent application is to provide a method for preparing the above-mentioned indenoquinolinone or chromenequinolinone derivatives.

[0006] Another object of the present patent application is to provide the application of the above-mentioned indenoquinolinone or chromenequinolinone derivatives.

[0007] In order to solve the above technical problems, the technical solution adopted by this patent application is:

[0008] An indenoquinolinone or chromenequinolinone derivative, wherein the indenoquinolinone or chromenequinolinone derivative has a quinolinone structure as a core and has the following general structural formula:

[0009]

[0010] Wherein R in formula (1) and (2) is selected from hydrogen and a polycyclic aromatic group containing a heteroatom, and the heteroatom is one or more of N, O, and S.

[0011] Preferably, the structural formula of the polycyclic aromatic group containing heteroatoms in the indenoquinolinone or chromenequinolinone derivatives in the present patent application is selected from one of the following structural formulas:

[0012]

[0013] Preferably, the indenoquinolinone or chromenequinolinone derivatives in the present patent application are selected from one of the following structural formulas:

[0014]

[0015]

[0016] More preferably, the indenoquinolinone or chromenequinolinone derivatives in the present patent application are selected from one of the following structural formulas:

[0017]

[0018] This patent application also provides a method for preparing the above-mentioned indenoquinolinone or chromenequinolinone derivatives, comprising:

[0019] S1. Preparation of 3-bromoindenoquinolinone: firstly, o-aminobenzaldehyde and 6-bromoindanone are subjected to a cyclization reaction under the action of ammonium acetate to generate the corresponding 3-bromoindenoquinoline, and then oxidized by oxygen to generate the corresponding 3-bromoindenoquinolinone. The reaction equation involved in step S1 is as follows:

[0020]

[0021] S2. Preparation of chromene quinolinone compound: firstly, hydroxyaniline and chromene formaldehyde compound are heated to 75°C in a toluene solution to generate chromene formaldehyde phenylamino compound, and then, under the action of diethylamine, the ring is closed to obtain chromene quinolinone compound. The reaction equation involved in step S2 is as follows:

[0022]

[0023] S3. Preparation of indenoquinolinone or chromenequinolinone derivatives: first weigh 3-bromoindenoquinolinone compound or 3-bromochromenequinolinone compound and 10H-phenoxazine, dissolve in toluene; then add Pd2(dba)3 and potassium carbonate; under an inert atmosphere, react the mixed solution of the above reactants at a reaction temperature of 110 to 120° C. for 12 to 24 hours, cool and filter the reaction solution, and rotary evaporate the filtrate and pass it through a silica gel column to obtain the target product. The reaction equation involved in step S3 is as follows:

[0024]

[0025] Preferably, the molar ratio of 6-bromoindanone to o-aminobenzaldehyde in step S1 is 1:(1.5-2.0).

[0026] Preferably, in step S2, the molar ratio of the chromone formaldehyde compound to hydroxyaniline is 1:(1-1.2), and the molar ratio of the chromone formaldehyde phenylamino compound to diethylamine is 1:(1-1.5).

[0027] Preferably, the molar ratio of 3-bromoindenoquinolinone to the heterocyclic aromatic amine compound in step S3 is 1:(1.2-1.5), the molar ratio of Pd2(dba)3 to the 3-bromoindenoquinolinone compound or the 3-bromochromenequinolinone compound is (0.04-0.08):1, and the molar ratio of potassium carbonate to the 3-bromoindenoquinolinone compound or the 3-bromochromenequinolinone compound is (2.0-4.0):1.

[0028] Preferably, in step S1, the solvent selected for the cyclization reaction is ethanol, and the solvent selected for the oxidation reaction is N,N-dimethylformamide.

[0029] This patent application also provides the use of the above-mentioned indenoquinolinone or chromenequinolinone derivatives in the preparation of luminescent materials, organic electroluminescent devices, smart materials, and display materials.

[0030] Compared with the prior art, the beneficial effects of this patent application are:

[0031] The indenoquinolinone or chromenequinolinone derivatives containing polycyclic aromatic groups provided in the present patent application have unique aggregation-induced emission effect, high luminous intensity, good thermal stability and good solubility, and can be used as a new type of soluble luminescent molecule with good performance, low cost and highly distorted spatial structure. The indenoquinolinone or chromenequinolinone derivatives containing polycyclic aromatic groups have significant economic value in the preparation of luminescent materials, luminescent devices or smart materials, and have good application prospects in the fields of full-color display and solid-state lighting. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 3-(10H-phenoxazine-10-yl)-11H-indeno[1,2-b]quinolin-11-one prepared in Example 1 1 HMNR diagram.

[0033] Figure 2 3-(10H-phenothiazine-10-yl)-11H-indeno[1,2-b]quinolin-11-one prepared in Example 2 1 HMNR diagram.

[0034] Figure 33-(9,9-dimethylacridin-10(9H)-yl)-11H-indeno[1,2-b]quinolin-11-one prepared in Example 3 1 HMNR diagram.

[0035] Figure 4 3-(10H-phenoxazine-10-yl)-12H-chromeno[2,3-b]quinolin-12-one prepared in Example 4 1 HMNR diagram.

[0036] Figure 5 3-(10H-phenothiazin-10-yl)-12H-chromeno[2,3-b]quinolin-12-one prepared in Example 5 1 HMNR diagram.

[0037] Figure 6 3-(9,9-dimethylacridin-10(9H)-yl)-12H-chromeno[2,3-b]quinolin-12-one prepared in Example 6 1 HMNR diagram.

[0038] Figure 7 This is the mass spectrum of 3-(10H-phenoxazine-10-yl)-11H-indeno[1,2-b]quinolin-11-one prepared in Example 1.

[0039] Figure 8 This is the mass spectrum of 3-(10H-phenothiazin-10-yl)-11H-indeno[1,2-b]quinolin-11-one obtained in Example 2.

[0040] Fig. 9 This is the mass spectrum of 3-(9,9-dimethylacridin-10(9H)-yl)-11H-indeno[1,2-b]quinolin-11-one obtained in Example 3.

[0041] Fig.10 This is the mass spectrum of 3-(10H-phenoxazine-10-yl)-12H-chromeno[2,3-b]quinolin-12-one prepared in Example 4.

[0042] Fig.11 This is the mass spectrum of 3-(10H-phenothiazin-10-yl)-12H-chromeno[2,3-b]quinolin-12-one obtained in Example 5.

[0043] Fig.12 This is the mass spectrum of 3-(9,9-dimethylacridin-10(9H)-yl)-12H-chromeno[2,3-b]quinolin-12-one prepared in Example 6.

[0044] Fig.13This is the UV-visible absorption spectrum of 3-(9,9-dimethylacridin-10(9H)-yl)-11H-indeno[1,2-b]quinolin-11-one prepared in Example 3.

[0045] Fig.14 This is an emission spectrum of 3-(9,9-dimethylacridin-10(9H)-yl)-11H-indeno[1,2-b]quinolin-11-one prepared in Example 3 in solutions with different water contents. DETAILED DESCRIPTION

[0046] The embodiments of the present patent application will be described in detail below in conjunction with the examples, but those skilled in the art will appreciate that the following examples are only used to illustrate the present patent application and should not be considered to limit the scope of the present patent application. If the specific conditions are not specified in the examples, they are carried out according to the normal conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0047] It should be noted that:

[0048] In this patent application, unless otherwise specified, all implementation methods and preferred implementation methods mentioned herein can be combined with each other to form a new technical solution.

[0049] In the present patent application, unless otherwise specified, percentage (%) or part refers to the weight percentage or weight part relative to the composition.

[0050] In this patent application, unless otherwise specified, the components or preferred components involved can be combined with each other to form a new technical solution.

[0051] In this patent application, unless otherwise specified, the numerical range "a-b" represents an abbreviation of any real number combination between a and b, where a and b are real numbers. For example, the numerical range "2-8" means that all real numbers between "2-8" have been listed in this document, and "2-8" is just an abbreviation of these numerical combinations.

[0052] The “range” disclosed in this patent application is in the form of a lower limit and an upper limit, which can be one or more lower limits, and one or more upper limits, respectively.

[0053] In this patent application, unless otherwise specified, each reaction or operation step can be carried out in sequence or in accordance with the sequence. Preferably, the reaction method herein is carried out in sequence.

[0054] Unless otherwise specified, the professional and scientific terms used herein are the same as those familiar to those skilled in the art. In addition, any method or material similar or equivalent to the described content may also be applied to this patent application.

[0055] The present patent application provides an indenoquinolinone or chromenequinolinone derivative, which has a quinolinone structure as the core and has the following general structural formula:

[0056]

[0057] Wherein R in formula (1) and (2) is selected from hydrogen and a polycyclic aromatic group containing a heteroatom, and the heteroatom is one or more of N, O, and S.

[0058] The indenoquinolinone or chromenequinolinone derivatives in the present patent application contain amino compounds and can be used as organic light-emitting materials, and have unique aggregation-induced emission effect, high luminous intensity, good thermal stability and good solubility.

[0059] In some embodiments, the structural formula of the polycyclic aromatic group containing heteroatoms in the indenoquinolinone or chromenequinolinone derivatives of the present patent application is selected from one of the following structural formulas:

[0060]

[0061] In some preferred embodiments, the indenoquinolinone or chromenequinolinone derivatives in the present patent application are selected from one of the following structural formulas:

[0062]

[0063]

[0064] More preferably, the indenoquinolinone or chromenequinolinone derivatives provided in the present patent application have one of the following molecular structures:

[0065]

[0066] This patent application also provides a method for synthesizing the above-mentioned indenoquinolinone or chromenequinolinone derivatives. The method comprises the following steps:

[0067] S1. Preparation of 3-bromoindenoquinolinone: firstly, o-aminobenzaldehyde and 6-bromoindanone are subjected to a cyclization reaction under the action of ammonium acetate to generate the corresponding 3-bromoindenoquinoline, and then oxidized by oxygen to generate the corresponding 3-bromoindenoquinolinone. The reaction equation involved in step S1 is as follows:

[0068]

[0069] S2. Preparation of chromene quinolinone compound: firstly, hydroxyaniline and chromene formaldehyde compound are heated to 75°C in a toluene solution to generate chromene formaldehyde phenylamino compound, and then, under the action of diethylamine, the ring is closed to obtain chromene quinolinone compound. The reaction equation involved in step S2 is as follows:

[0070]

[0071] S3. Preparation of indenoquinolinone or chromenequinolinone derivatives: first weigh 3-bromoindenoquinolinone compound or 3-bromochromenequinolinone compound and 10H-phenoxazine, dissolve in toluene; then add Pd2(dba)3 and potassium carbonate; under an inert atmosphere, react the mixed solution of the above reactants at a reaction temperature of 110 to 120° C. for 12 to 24 hours, cool and filter the reaction solution, and rotary evaporate the filtrate and pass it through a silica gel column to obtain the target product. The reaction equation involved in step S3 is as follows:

[0072]

[0073] In some preferred embodiments of the present patent application, the molar ratio of 6-bromoindanone to o-aminobenzaldehyde in step S1 is 1:(1.5-2.0), and the molar ratio of ammonium acetate to 6-bromoindanone is (10-12):1; more preferably, the molar ratio of 6-bromoindanone to o-aminobenzaldehyde is 1:1.5, and the molar ratio of ammonium acetate to 6-bromoindanone is 10:1.

[0074] In some preferred embodiments of the present patent application, the molar ratio of the chromone methanol compound to hydroxyaniline in step S2 is 1:(1~1.2), and the molar ratio of the chromone formaldehyde phenylamino compound to diethylamine is 1:(1~1.5); more preferably, the molar ratio of the chromone methanol compound to hydroxyaniline is 1:1.2, and the molar ratio of the chromone formaldehyde phenylamino compound to diethylamine is 1:1.1.

[0075] In some preferred embodiments of the present patent application, in step S3, the molar ratio of 3-bromoindenoquinolinone to the heterocyclic aromatic amine compound is 1:(1.2-1.5), the molar ratio of Pd2(dba)3 to the 3-bromoindenoquinolinone compound or the 3-bromochromenequinolinone compound is (0.04-0.08):1, the molar ratio of potassium carbonate to the 3-bromoindenoquinolinone compound or the 3-bromochromenequinolinone compound is (2.0-4.0):1, and the molar ratio of Pd2(dba)3 to tri-tert-butylphosphine (abbreviated as TTBP) is 1:(1.5 ~2); more preferably, the molar ratio of 3-bromoindenoquinolinone to the heterocyclic aromatic amine compound is 1:1.2, the molar ratio of Pd2(dba)3 to the 3-bromoindenoquinolinone compound or the 3-bromochromenequinolinone compound is 0.04:1, the molar ratio of potassium carbonate to the 3-bromoindenoquinolinone compound or the 3-bromochromenequinolinone compound is 2.0:1; the molar ratio of Pd2(dba)3 to the 3-bromoindenoquinolinone compound or the 3-bromochromenequinolinone compound is 0.08:1, and the molar ratio of Pd2(dba)3 to TTBP is 1:2.

[0076] In some preferred embodiments of the present patent application, the solvent selected for the cyclization reaction in step S1 is ethanol, and the solvent selected for the oxidation reaction is N,N-dimethylformamide.

[0077] In some preferred embodiments of the present patent application, the solvent selected for the condensation rearrangement reaction in step S2 is toluene, and the solvent selected for the ring-closing reaction is ethanol.

[0078] In some preferred embodiments of the present patent application, the solvent selected for the Heck reaction in step S3 is toluene.

[0079] In some preferred embodiments of the present patent application, the reaction conditions for the cyclization reaction in step S1 are room temperature and stirring for 5 days, and the reaction conditions for the oxidation reaction are 120° C. and stirring for 24 hours.

[0080] In some preferred embodiments of the present patent application, the reaction conditions of the condensation rearrangement reaction in step S2 are 75° C. and stirring for 12 h, and the reaction conditions of the ring-closing reaction are 95° C. and stirring for 12 h.

[0081] In some preferred embodiments of the present patent application, the reaction conditions of the Heck reaction in step S3 are 110-120° C., and the reaction is stirred for 12-24 hours. More preferably, the reaction conditions of the Heck reaction in step S3 are 120° C., and the reaction is stirred for 24 hours.

[0082] In some preferred embodiments of the present patent application, the oxidation reaction in step S1 should be carried out under an oxygen atmosphere.

[0083] In some preferred embodiments of the present patent application, the Heck reaction in step S3 should be carried out under an inert atmosphere, and more preferably, the inert atmosphere is nitrogen.

[0084] In some preferred embodiments of the present patent application, the post-treatment of the cyclization reaction in step S1 is concentration, extraction, drying, and separation. Concentration and collection to obtain a solid, the solid is extracted three times with water and ethyl acetate, the organic phases obtained three times are combined, dried with anhydrous magnesium sulfate, and the organic phases are distilled under reduced pressure to obtain a crude product; finally, ethyl acetate and petroleum ether are used as eluents for silica gel column chromatography to separate the product; the post-treatment of the oxidation reaction is cooling, extraction, drying, concentration, and separation. Cooling and collection to obtain an orange turbid liquid, the orange turbid liquid is extracted three times with water and ethyl acetate, the organic phases obtained three times are combined, dried with anhydrous magnesium sulfate, and the organic phases are distilled under reduced pressure to obtain a crude product; finally, ethyl acetate and petroleum ether are used as eluents for silica gel column chromatography to separate the compound.

[0085] In some preferred embodiments of the present patent application, the post-treatment of the condensation rearrangement reaction in step S2 is extraction, concentration, drying, and separation. The yellow turbid liquid is extracted three times with water and ethyl acetate, the organic phases obtained three times are combined, dried with anhydrous magnesium sulfate, and the organic phases are distilled under reduced pressure to obtain a crude product; finally, ethyl acetate and petroleum ether are used as eluents for silica gel column chromatography to separate the compound, and the post-treatment of the closed-loop reaction is cooling, concentration, extraction, drying, concentration, and separation. Cooling and collecting to obtain a yellow turbid liquid, concentrating and collecting to obtain a solid, the solid is extracted three times with water and ethyl acetate, the organic phases obtained three times are combined, dried with anhydrous magnesium sulfate, and the organic phases are distilled under reduced pressure to obtain a crude product; finally, ethyl acetate and petroleum ether are used as eluents for silica gel column chromatography to separate the product.

[0086] In some preferred embodiments of the present patent application, the post-treatment of the Heck reaction in step S3 is cooling, extraction, drying, concentration, and separation. The brown-black turbid liquid is collected by cooling, and the brown-black turbid liquid is extracted three times with water and ethyl acetate, and the organic phases obtained three times are combined, dried with anhydrous magnesium sulfate, and then the organic phase is distilled under reduced pressure to obtain a crude product; finally, ethyl acetate and petroleum ether are used as eluents to perform silica gel column chromatography to separate the compound.

[0087] At the same time, this patent application also provides the application of the above-mentioned indenoquinolinone or chromenequinolinone derivatives in the preparation of luminescent materials, organic electroluminescent devices, smart materials, and display materials.

[0088] Next, this patent application takes indenoquinolinone or chromenequinolinone derivatives A01-A03, A25-A26 as examples to introduce in detail the preparation method of indenoquinolinone or chromenequinolinone derivatives in this patent application.

[0089] Example 1 Preparation of 3-(10H-phenoxazin-10-yl)-11H-indeno[1,2-b]quinolin-11-one (A01)

[0090] S1. Preparation of 3-bromoindenoquinolinone

[0091] Take 181.7 mg of o-aminobenzaldehyde and 211.0 mg of 6-bromoindanone and react with 770.8 mg of ammonium acetate to generate 265 mg of the corresponding indenoquinoline with a yield of 90%, and then oxidize with oxygen to generate 255 mg of the corresponding 3-bromoindanone with a yield of 92%. The reaction equation is:

[0092]

[0093] Preparation of S3.A01 compound

[0094] Weigh 308 mg of 3-bromoindenylquinolinone, 220 mg of 10H-phenoxazine, 276 mg of potassium carbonate, 336.6 mg of Pd2(dba), 160 mg of TTBP, and 3 mL of toluene in a sealed tube, stir to remove the air in the device and fill with nitrogen protection, heat and stir under reflux at 120 ° C for 24 hours under nitrogen protection, and after the reaction, cool, extract, dry, concentrate and separate the crude product. Cool and collect to obtain a brown-black turbid liquid, extract the turbid liquid with water and ethyl acetate three times, combine the organic phases obtained three times, dry with anhydrous magnesium sulfate, and then distill the organic phase under reduced pressure to obtain a crude product; finally, use ethyl acetate and petroleum ether as eluents for silica gel column chromatography. The obtained pure product solution is distilled under reduced pressure and vacuum dried to obtain 156 mg of dark red solid, which is the formula A01 compound with a purity of 98% and a yield of 38%. The reaction equation is:

[0095]

[0096] Example 2 Preparation of 3-(10H-phenothiazin-10-yl)-11H-indeno[1,2-b]quinolin-11-one (A02)

[0097] S1.3-bromoindenoquinolinone was prepared in the same manner as in Example 1;

[0098] Preparation of S3.A02 compound

[0099] Weigh 308 mg of 3-bromoindenoquinolinone, 239 mg of 10H-phenothiazine, 276 mg of potassium carbonate, 336.6 mg of Pd2(dba), 160 mg of TTBP, and 3 mL of toluene in a sealed tube, stir to remove the air in the device and fill with nitrogen protection, heat and stir under reflux at 120°C under nitrogen protection for 24 hours, and after the reaction, cool, extract, dry, concentrate, and separate the crude product. Cool and collect to obtain a brown-black turbid liquid, extract the turbid liquid three times with water and ethyl acetate, combine the organic phases obtained three times, dry with anhydrous magnesium sulfate, and then distill the organic phase under reduced pressure to obtain a crude product; finally, use ethyl acetate and petroleum ether as eluents for silica gel column chromatography separation. The obtained pure product solution is distilled under reduced pressure and dried in vacuo to obtain 278 mg of brown-yellow solid, which is the compound of formula (II), with a purity of 98% and a yield of 65%. The reaction equation is:

[0100]

[0101] Example 3 Preparation of 3-(9,9-dimethylacridin-10(9H)-yl)-11H-indeno[1,2-b]quinolin-11-one (A03)

[0102] S1.3-bromoindenoquinolinone was prepared in the same manner as in Example 1;

[0103] Preparation of S3.A03 compound

[0104] Weigh 308 mg of 3-bromoindenoquinolinone, 251 mg of 9,10-dihydro-9,9-dimethylacridine, 276 mg of potassium carbonate, 336.6 mg of Pd2(dba), 160 mg of TTBP, and 3 mL of toluene in a sealed tube, stir to remove the air in the device and fill with nitrogen protection, heat and stir under reflux at 120°C under nitrogen protection for 24 hours, and after the reaction, cool, extract, dry, concentrate, and separate the crude product. Cool and collect to obtain a brown-black turbid liquid, extract the turbid liquid three times with water and ethyl acetate, combine the organic phases obtained three times, dry with anhydrous magnesium sulfate, and then distill the organic phase under reduced pressure to obtain a crude product; finally, use ethyl acetate and petroleum ether as eluents for silica gel column chromatography separation. The obtained pure product solution is distilled under reduced pressure and dried in vacuo to obtain 183 mg of yellow solid, which is the compound of formula (III), with a purity of 98% and a yield of 42%. The reaction equation is:

[0105]

[0106] Example 4 Preparation of 3-(10H-phenoxazin-10-yl)-12H-chromeno[2,3-b]quinolin-12-one (A025)

[0107] S2. Preparation of Brominated Chromene Quinolinone Compounds

[0108] First, 131 mg of hydroxyaniline and 252 mg of chromone formaldehyde compound were heated to 75°C in a toluene solution to undergo condensation rearrangement reaction to generate 281.8 mg of chromone formaldehyde phenylamino compound with a yield of 82%. Then, 80 mg of diethylamine was added to close the ring to obtain 189.8 mg of chromone quinolinone compound with a yield of 71%. The reaction equation is:

[0109]

[0110] Preparation of S3.A025 compound

[0111] Weigh 325 mg of bromochromene quinolinone compound, 220 mg of 10H-phenoxazine, 276 mg of potassium carbonate, 336.6 mg of Pd2(dba), 160 mg of TTBP, and 3 mL of toluene in a sealed tube, stir to remove the air in the device and fill with nitrogen protection, heat and stir under reflux at 120°C under nitrogen protection for 24 hours, and after the reaction, cool, extract, dry, concentrate, and separate the crude product. Cool and collect to obtain a brown-black turbid liquid, extract the turbid liquid three times with water and ethyl acetate, combine the organic phases obtained three times, dry with anhydrous magnesium sulfate, and then distill the organic phase under reduced pressure to obtain a crude product; finally, use ethyl acetate and petroleum ether as eluents for silica gel column chromatography separation. The obtained pure product solution is distilled under reduced pressure and dried in vacuo to obtain 269 mg of red solid, which is the compound of formula (I), with a purity of 98% and a yield of 63%. The reaction equation is:

[0112]

[0113] Example 5 Preparation of 3-(10H-phenothiazin-10-yl)-12H-chromeno[2,3-b]quinolin-12-one (A026)

[0114] S2. Preparation of bromochromene quinolinone compound is the same as in Example 4;

[0115] Preparation of S3.A026 compound

[0116] Weigh 325 mg of bromochromene quinolinone compound, 239 mg of 10H-phenothiazine, 276 mg of potassium carbonate, 336.6 mg of Pd2(dba), 160 mg of TTBP, and 3 mL of toluene in a sealed tube, stir to remove air from the device and fill with nitrogen protection, heat and stir under reflux at 120°C under nitrogen protection for 24 hours, and after the reaction, cool, extract, dry, concentrate, and separate the crude product. Cool and collect to obtain a brown-black turbid liquid, extract the turbid liquid three times with water and ethyl acetate, combine the organic phases obtained three times, dry with anhydrous magnesium sulfate, and then distill the organic phase under reduced pressure to obtain a crude product; finally, use ethyl acetate and petroleum ether as eluents for silica gel column chromatography separation. The obtained pure product solution is distilled under reduced pressure and dried in vacuo to obtain 133 mg of yellow solid, which is the compound of formula (II), with a purity of 98% and a yield of 30%. The reaction equation is:

[0117]

[0118] Example 6 Preparation of 3-(9,9-dimethylacridin-10(9H)-yl)-12H-chromeno[2,3-b]quinolin-12-one (A027)

[0119] S2. Preparation of bromochromene quinolinone compound is the same as in Example 4;

[0120] Preparation of S3.A027 compound

[0121] Weigh 325 mg of bromochromene quinolinone compound, 251 mg of 9,10-dihydro-9,9-dimethylacridine, 276 mg of potassium carbonate, 336.6 mg of Pd2(dba), 160 mg of TTBP, and 3 mL of toluene in a sealed tube, stir to remove the air in the device and fill with nitrogen protection, heat and stir under reflux at 120°C under nitrogen protection for 24 hours, and after the reaction, cool, extract, dry, concentrate, and separate the crude product. Cool and collect to obtain a brown-black turbid liquid, extract the turbid liquid with water and ethyl acetate three times, combine the organic phases obtained three times, dry with anhydrous magnesium sulfate, and then distill the organic phase under reduced pressure to obtain a crude product; finally, use ethyl acetate and petroleum ether as eluents for silica gel column chromatography separation. The obtained pure product solution is distilled under reduced pressure and dried in vacuo to obtain 245 mg of yellow solid, which is the compound of formula (III) with a purity of 98% and a yield of 54%. The reaction equation is:

[0122]

[0123] Characterization and performance testing

[0124] The indenoquinolinone or chromenequinolinone derivatives A01-A03 and A25-A27 obtained in Examples 1-6 were characterized and their performance tested.

[0125] The test method is as follows:

[0126] Compound structure detection: using a Bruker 400MHz superconducting nuclear magnetic resonance spectrometer, the solvent is deuterated chloroform or deuterated dimethyl sulfoxide;

[0127] Mass spectrometry detection: A01-A03 and A25-A27 prepared in Examples 1-6 were dissolved in dichloromethane to prepare a solution with a concentration of 1 mg / mL, and mass spectrometry was performed using a liquid spectrometer LCMS-2020.

[0128] UV absorption spectrum detection: Shimadzu UV-visible spectrophotometer UV-2700 was used to dissolve indenoquinolinone or chromenequinolinone derivatives in THF to prepare 1×10 -3 molL -1 The mother solution was diluted to 1×10 -5 molL -1 The scanning range is 200-450nm;

[0129] Emission spectrum detection: Steady-state / transient fluorescence spectrometer (FLS980) was used, with an excitation wavelength of 310 nm, and the concentration of indenoquinolinone or chromenequinolinone derivatives in the test solution was kept at 1×10 -5 molL -1 , adjust the ratio of tetrahydrofuran and water in the test solution. First, dissolve the indenoquinolinone or chromenequinolinone derivatives in tetrahydrofuran to make 1×10 -3 molL -1 The total volume of the test solution is maintained at 3mL. For example, when the water content is 90%, the amount of each component added is mother solution: water: tetrahydrofuran = 30uL: 2700uL: 270uL. Under nitrogen protection, the test temperature is 300K.

[0130] The test results are as follows:

[0131] The H NMR spectrum of the indenoquinolinone or chromenequinolinone derivative A01 prepared in Example 1 is as follows: Figure 1 As shown. It can be seen that: 1H NMR (400MHz, Chloroform-d) δ8.42 (s, 1H), 8.21 (s, 1H), 8.14 (d, J = 8.4 Hz, 1H), 7.97 (d, J = 7.9 Hz, 1H), 7.87 (d, J = 8.0 Hz, 1H), 7.75 (t, J = 7.7 Hz, 1H), 7.53 (t, J = 7.5 Hz, 1H), 7.47 (dd, J = 7.9, 1.5 Hz, 1H), 6.71–6.64 (m, 4H), 6.62–6.57 (m, 2H), 6.13 (d, J = 7.8 Hz, 2H). The molecular hydrogen spectrum peaks can correspond to the target product one by one, and the number is reasonable; from the mass spectrum ( Figure 7 ) can be seen in the figure, the relative molecular mass is 412.12, which is consistent with the relative molecular mass of the synthesized A01. Combining the above NMR and mass spectrometry results, it can be seen that the product obtained in Example 1 is 3-(10H-phenoxazine-10-yl)-11H-indeno[1,2-b]quinolin-11-one (A01).

[0132] The H NMR spectrum of the indenoquinolinone or chromenequinolinone derivative A02 prepared in Example 2 is as follows: Figure 2 As shown. It can be seen that: 1 H NMR (400MHz, Chloroform-d) δ8.32 (s, 1H), 8.11 (s, 1H), 7.86 (d, J = 7.8 Hz, 1H), 7.80–7.67 (m, 3H), 7.55–7.45 (m, 5H), 7.39 (t, J = 7.3 Hz, 2H), 7.26–7.20 (m, 2H), 7.13 (d, J = 8.4 Hz, 1H). The molecular hydrogen spectrum peaks can correspond to the target product one by one, and the number is reasonable; from the mass spectrum ( Figure 8 ) can be seen in the figure, the relative molecular mass is 428.10, which is consistent with the relative molecular mass of the synthesized A02. Combining the above NMR and mass spectrometry results, it can be seen that the product obtained in Example 2 is 3-(10H-phenothiazine-10-yl)-11H-indeno[1,2-b]quinolin-11-one (A02).

[0133] The H NMR spectrum of the indenoquinolinone or chromenequinolinone derivative A03 prepared in Example 3 is as follows: Figure 3 As shown. It can be seen that: 1H NMR (400MHz, Chloroform-d) δ8.40 (s, 1H), 8.12 (s, 1H), 8.04 (dd, J = 16.4, 8.1 Hz, 2H), 7.87 (d, J = 7.9 Hz, 1H), 7.74 (t, J = 7.4 Hz, 1H), 7.55–7.47 (m, 4H), 7.06–6.97 (m, 4H), 6.58 (d, J = 7.6 Hz, 2H), 1.69 (s, 6H), molecular hydrogen spectrum peaks can correspond to the target product one by one, and the number is reasonable; from the mass spectrum ( Fig. 9 ) can be seen in the figure, the relative molecular mass is 438.17, which is consistent with the relative molecular mass of the synthesized A03. Combining the above NMR and mass spectrometry results, it can be seen that the product obtained in Example 3 is 3-(9,9-dimethylacridin-10(9H)-yl)-11H-indeno[1,2-b]quinolin-11-one (A03).

[0134] The H NMR spectrum of the indenoquinolinone or chromenequinolinone derivative A25 prepared in Example 4 is as follows: Figure 4 As shown. It can be seen that: 1 H NMR (400MHz, Chloroform-d) δ9.26 (s, 1H), 8.44 (d, J = 8.4 Hz, 1H), 8.05 (t, J = 7.7 Hz, 2H), 7.89–7.84 (m, 1H), 7.62–7.54 (m, 2H), 7.36 (dd, J = 8.4, 1.9 Hz, 1H), 6.76–6.68 (m, 4H), 6.67–6.60 (m, 2H), 6.22–6.15 (m, 2H). The molecular hydrogen spectrum peaks can correspond to the target product one by one, and the number is reasonable; from the mass spectrum ( Fig.10 ) can be seen in the figure, the relative molecular mass is 428.12, which is consistent with the relative molecular mass of the synthesized A25. Combining the above NMR and mass spectrometry results, it can be seen that the product obtained in Example 4 is 3-(10H-phenoxazine-10-yl)-12H-chromeno[2,3-b]quinoline-12-one (A25).

[0135] The H NMR spectrum of the indenoquinolinone or chromenequinolinone derivative A26 prepared in Example 5 is as follows: Figure 5 As shown. It can be seen that: 1H NMR (400MHz, Chloroform-d) δ9.15 (s, 1H), 8.00 (dd, J = 18.2, 8.7 Hz, 3H), 7.79 (t, J = 7.3 Hz, 1H), 7.54–7.45 (m, 5H), 7.36 (t, J = 7.3 Hz, 2H), 7.23 (t, J = 7.5 Hz, 2H), 7.03 (s, 1H), 6.94 (d, J = 9.0 Hz, 1H), molecular hydrogen spectrum peaks can correspond to the target product one by one, and the number is reasonable; from the mass spectrum ( Fig.11 ) can be seen in the figure, the relative molecular mass is 444.09, which is consistent with the relative molecular mass of the synthesized A26. Combining the above NMR and mass spectrometry results, it can be seen that the product obtained in Example 5 is 3-(10H-phenoxazine-10-yl)-12H-chromeno[2,3-b]quinolin-12-one (A26).

[0136] The H NMR spectrum of the indenoquinolinone or chromenequinolinone derivative A27 prepared in Example 6 is as follows: Figure 6 As shown. It can be seen that: 1 H NMR (400MHz, Chloroform-d) δ9.29 (s, 1H), 8.41 (d, J = 8.7 Hz, 1H), 8.09 (d, J = 8.5 Hz, 2H), 7.90 (ddd, J = 8.4, 6.9, 1.4 Hz, 1H), 7.64–7.59 (m, 2H), 7.51 (dd, J = 7.6, 1.7 Hz, 2H), 7.40 (dd, J = 8.7, 2.1 Hz, 1H), 7.13 (dqd, J = 14.7, 7.3, 1.6 Hz, 4H), 6.90 (dd, J = 7.8, 1.5 Hz, 2H), 1.64 (s, 6H). The molecular hydrogen spectrum peaks can correspond to the target product one by one, and the quantity is reasonable. From the mass spectrum ( Fig.11 ) can be seen in the figure, the relative molecular mass is 454.17, which is consistent with the relative molecular mass of the synthesized A27. Combining the above NMR and mass spectrometry results, it can be seen that the product obtained in Example 6 is 3-(9,9-dimethylacridin-10(9H)-yl)-12H-chromeno[2,3-b]quinolin-12-one (A27).

[0137] In addition, the applicant of the present invention also tested the photophysical properties of the indenoquinolinone or chromenequinolinone derivative A03. The absorption spectrum and emission spectrum of the indenoquinolinone or chromenequinolinone derivative A03 are shown in FIG. Fig.13 and Fig.14 shown.

[0138] like Fig.13As shown, the main absorption peak position of the indenoquinolinone or chromenequinolinone derivative A03 compound is 404 nm.

[0139] from Fig.14 In the experiment, the emission wavelength of the indenoquinolinone or chromenequinolinone derivative A03 compound was 622nm; when the water content was lower than 95%, the fluorescence emission wavelength of the indenoquinolinone or chromenequinolinone derivative A03 compound in the solution showed an obvious red shift; and when the water content exceeded 90%, the corresponding fluorescence intensity was greatly enhanced, indicating that the indenoquinolinone or chromenequinolinone derivatives containing polycyclic aromatic groups had obvious aggregation-induced emission phenomenon.

[0140] In summary, the quinolinone derivatives containing aromatic amine groups provided in this patent application have unique aggregation-induced emission effect, high luminescence intensity, good thermal stability and good solubility, and can be used as a new type of soluble luminescent molecule with good performance, low cost and highly distorted spatial structure. The quinolinone derivatives containing aromatic amine groups have significant economic value in the preparation of luminescent materials, luminescent devices or smart materials, and have good application prospects in the fields of full-color display and solid-state lighting.

[0141] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "illustrative embodiments", "examples", "specific examples", or "some examples" means that the specific features, structures, materials, or characteristics described in conjunction with the embodiments or examples are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described may be combined in any one or more embodiments or examples in a suitable manner.

[0142] Although several embodiments of the present patent application have been shown and described, those skilled in the art will appreciate that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the claims and their equivalents.

Claims

1. An indenoquinolinone derivative, characterized in that: The indenoquinolinone derivatives have the following structural formula:

2. The method for preparing the indenoquinolinone derivatives according to claim 1, characterized in that: include: S1. Preparation of 3-bromoindenoquinolinone: firstly, o-aminobenzaldehyde and 6-bromoindanone are subjected to a cyclization reaction under the action of ammonium acetate to generate the corresponding 3-bromoindenoquinoline, and then oxidized by oxygen to generate the corresponding 3-bromoindenoquinolinone. The reaction equation involved in step S1 is as follows: S2. Preparation of indenoquinolinones: The reaction equation involved in step S2 is as follows:

3. The method for preparing the indenoquinolinone derivatives according to claim 2, characterized in that: The molar ratio of 6-bromoindanone to o-aminobenzaldehyde in step S1 is 1:(1.5-2.0).

4. The method for preparing the indenoquinolinone derivatives according to claim 3, characterized in that: In step S1, the solvent selected for the cyclization reaction is ethanol, and the solvent selected for the oxidation reaction is N,N-dimethylformamide.

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