CN115724834A - Indenoquinolinone or chromene quinolinone derivative and preparation method and application thereof - Google Patents

Abstract

The patent application discloses indenoquinolinone or chromene quinolinone derivatives, and a preparation method and application thereof. The indenoquinolinone or chromene quinolinone derivative in the patent application is based on quinoline methyl ketone as an electron-withdrawing group, and is prepared into the indenoquinolinone or chromene quinolinone derivative organic light-emitting micromolecules by virtue of the electron-donating capability of N in a heterocyclic ring. The quinolinone derivative containing arylamine group provided by the patent application has unique aggregation induced luminescence effect, high luminous intensity, good thermal stability and good solubility, and can be used as a novel solid luminescent molecule with good performance, lower cost and highly distorted spatial structure. The quinolinone derivative containing arylamine groups has obvious economic value in the aspects of preparing luminescent materials, luminescent devices or intelligent materials and the like, and has good application prospect in the fields of full-color display and solid-state lighting.

Description

A kind of indenoquinolinone or chromene quinolinone derivative and its preparation method and application

technical field

This patent application relates to the field of organic luminescent materials, more specifically, to an indenoquinolinone or chromene quinolinone derivative and its preparation method and application.

Background technique

With the rise of high-tech technologies such as large-screen smartphones, tablet computers, and wearable devices, Organic Light-Emitting Diodes (OLEDs) have self-illumination, wide viewing angles, low power consumption, fast response time, and thin thickness. , can realize the advantages of flexibility, etc., it is regarded as a new generation of display products with great development prospects in the diversified flat panel display market, and is known as "dream display".

Compared with traditional LED technology, OLED technology has significant advantages in realizing large-area high-quality display and lighting, ultra-high resolution, ultra-fast response speed, and flexible electronics applications. And solid-state luminescence and other fields have great application potential, which has attracted extensive attention from the global academic and industrial circles. However, at present, the existing luminescent materials have problems such as insufficient luminous color purity, insufficient thermal stability, and poor solubility.

Contents of the invention

In order to overcome one of the problems in the above-mentioned prior art, this patent application provides an indenoquinolinone or chromene quinolinone derivative. The indenoquinolinone or chromene quinolinone derivatives can be used as an organic luminescent material, and have unique aggregation-induced luminescent effect, high luminous intensity, good thermal stability and good solubility.

Another object of this patent application is to provide a preparation method of the above-mentioned indenoquinolinone or chromene quinolinone derivatives.

Another object of this patent application is to provide the application of the above-mentioned indenoquinolinone or chromene quinolinone derivatives.

In order to solve the problems of the technologies described above, the technical solution adopted in this patent application is:

An indenoquinolinone or chromene quinolinone derivative, the indenoquinolinone or chromene quinolinone derivative has a quinolinone structure as the core, and has the following general structural formula:

Wherein R in the formulas (1) and (2) is selected from hydrogen and polycyclic aromatic groups containing heteroatoms, and the heteroatoms are one or more of N, O and S.

Preferably, the structural formula of the heteroatom-containing polycyclic aromatic group in the indenoquinolinones or chromene quinolinone derivatives in this patent application is selected from one of the following structural formulas:

Preferably, the indenoquinolinone or chromene quinolinone derivatives in this patent application are selected from one of the following structural formulas:

More preferably, the indenoquinolinone or chromene quinolinone derivatives in this patent application are selected from one of the following structural formulas:

This patent application also provides the preparation method of above-mentioned indenoquinolinones or chromene quinolinone derivatives, including:

S1. Preparation of 3-bromoindenoquinolinone: first, anthranilic aldehyde and 6-bromoindanone undergo a cyclization reaction under the action of ammonium acetate to generate the corresponding 3-bromoindenoquinolinone, which is then oxidized by oxygen to generate For the corresponding 3-bromoindenoquinolinone, the reaction equation involved in the step S1 is as follows:

S2. Preparation of chromene quinolinone compound: firstly heat hydroxyaniline and chromone formaldehyde compound in toluene solution to 75°C to generate chromone formaldehyde aniline compound, and then close the ring to obtain chromene quinolinone compound under the action of diethylamine , the reaction equation involved in the step S2 is as follows:

S3. Preparation of indenoquinolinone or chromene quinolinone derivatives: first weigh 3-bromoindenoquinolinone compound or 3-bromochromene quinolinone compound and 10H-phenoxazine, and use toluene Dissolve; then add Pd ₂ (dba) ₃ , potassium carbonate; under an inert atmosphere, react the mixed solution of the above reactants at a reaction temperature of 110-120°C for 12-24 hours, cool and filter the reaction solution, and rotate the filtrate to evaporate. Pass through a silica gel column to obtain the target product, and the reaction equation involved in the step S3 is as follows:

Preferably, the molar ratio of 6-bromoindanone to anthranilaldehyde in the step S1 is 1:(1.5-2.0).

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

Preferably, the molar ratio of 3-bromoindenoquinolinone to heterocyclic aromatic amine compound in step S3 is 1: (1.2-1.5), Pd ₂ (dba) ₃ and 3-bromoindenoquinolinone The mol ratio of compound or 3-bromochromene quinolinone compound is (0.04～0.08): 1, and the mol ratio of potassium carbonate and 3-bromoindenoquinolinone compound or 3-bromochromene quinolinone compound is ( 2.0～4.0):1.

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

This patent application also provides the application of the above-mentioned indenoquinolinone or chromene quinolinone derivatives in the preparation of luminescent materials, organic electroluminescent devices, smart materials, and display materials.

Compared with prior art, the beneficial effect of this patent application is:

The indenoquinolinone or chromene quinolinone derivatives containing polycyclic aromatic groups provided in this patent application have a unique aggregation-induced luminescent effect, high luminous intensity, good thermal stability and good Solubility, it can be used as a new type of soluble luminescent molecule with good performance, low cost and highly distorted spatial structure. The indenoquinolinone or chromene quinolinone derivatives containing polycyclic aromatic groups have significant economic value in the preparation of light-emitting materials, light-emitting devices or smart materials, and are used in full-color displays and solid-state lighting It has a good application prospect in the field.

Description of drawings

Figure 1 is ^{the 1} HMNR chart of 3-(10H-phenoxazin-10-yl)-11H-indeno[1,2-b]quinolin-11-one prepared in Example 1.

Fig. 2 is ^{the 1} HMNR chart of 3-(10H-phenothiazin-10-yl)-11H-indeno[1,2-b]quinolin-11-one prepared in Example 2.

Figure 3 is the ¹ HMNR of 3-(9,9-dimethylacridin-10(9H)-yl)-11H-indeno[1,2-b]quinolin-11-one prepared in Example 3 picture.

Fig. 4 is ^{the 1} HMNR chart of 3-(10H-phenoxazin-10-yl)-12H-chromen[2,3-b]quinolin-12-one prepared in Example 4.

Fig. 5 is ^{the 1} HMNR chart of 3-(10H-phenothiazin-10-yl)-12H-chromen[2,3-b]quinolin-12-one prepared in Example 5.

Figure 6 is ^{the 1} HMNR of 3-(9,9-dimethylacridin-10(9H)-yl)-12H-chromen[2,3-b]quinolin-12-one prepared in Example 6 picture.

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

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

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

Figure 10 is the mass spectrum of 3-(10H-phenoxazin-10-yl)-12H-chromen[2,3-b]quinolin-12-one prepared in Example 4.

Figure 11 is the mass spectrum of 3-(10H-phenothiazin-10-yl)-12H-chromen[2,3-b]quinolin-12-one prepared in Example 5.

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

Figure 13 is the UV-Vis of 3-(9,9-dimethylacridin-10(9H)-yl)-11H-indeno[1,2-b]quinolin-11-one prepared in Example 3 Absorption spectrum graph.

Figure 14 is the 3-(9,9-dimethylacridin-10(9H)-yl)-11H-indeno[1,2-b]quinolin-11-one obtained in Example 3 in different Emission spectra in solutions with water content.

Detailed ways

Embodiments of the present patent application will be described in detail below in conjunction with examples, but those skilled in the art will understand that the following examples are only used to illustrate the present patent application, and should not be considered as limiting the scope of the present patent application. Those who do not indicate the specific conditions in the examples are carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used were not indicated by the manufacturer, and they were all conventional products that could be purchased from the market.

It should be noted:

In this patent application, unless otherwise specified, all the implementation modes and preferred implementation methods mentioned herein can be combined with each other to form new technical solutions.

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

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

In this patent application, unless otherwise stated, the numerical range "a~b" represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "2-8" means that all the real numbers between "2-8" have been listed in this article, and "2-8" is just an abbreviated representation of these numerical combinations.

The "range" disclosed in this patent application is in the form of lower limit and upper limit, and may be one or more lower limits, and one or more upper limits, respectively.

In this patent application, unless otherwise specified, each reaction or operation step can be carried out sequentially or in sequence. Preferably, the reaction methods herein are performed sequentially.

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

This patent application provides an indenoquinolinone or chromene quinolinone derivative, the indenoquinolinone or chromene quinolinone derivative has a quinolinone structure as the core, and has the following General structural formula:

Wherein R in the formulas (1) and (2) is selected from hydrogen and polycyclic aromatic groups containing heteroatoms, and the heteroatoms are one or more of N, O and S.

The indenoquinolinone or chromene quinolinone derivatives in this patent application contain amino compounds, which can be used as organic light-emitting materials, and have unique aggregation-induced luminescence effects, high luminous intensity, good thermal stability and Good solubility.

In some embodiments, the structural formula of the heteroatom-containing polycyclic aromatic group in the indenoquinolinone or chromene quinolinone derivatives in this patent application is selected from one of the following structural formulas :

In some preferred embodiments, the indenoquinolinone or chromene quinolinone derivatives in this patent application are selected from one of the following structural formulas:

More preferably, the indenoquinolinones or chromene quinolinone derivatives provided by this patent application have one of the following molecular structures:

This patent application also provides a synthesis method of the above-mentioned indenoquinolinone or chromene quinolinone derivatives. The method includes the following steps:

S1. Preparation of 3-bromoindenoquinolinone: first, anthranilic aldehyde and 6-bromoindanone undergo a cyclization reaction under the action of ammonium acetate to generate the corresponding 3-bromoindenoquinolinone, which is then oxidized by oxygen to generate For the corresponding 3-bromoindenoquinolinone, the reaction equation involved in the step S1 is as follows:

S2. Preparation of chromene quinolinone compound: firstly heat hydroxyaniline and chromone formaldehyde compound in toluene solution to 75°C to generate chromone formaldehyde aniline compound, and then close the ring to obtain chromene quinolinone compound under the action of diethylamine , the reaction equation involved in the step S2 is as follows:

S3. Preparation of indenoquinolinone or chromene quinolinone derivatives: first weigh 3-bromoindenoquinolinone compound or 3-bromochromene quinolinone compound and 10H-phenoxazine, and use toluene Dissolve; then add Pd ₂ (dba) ₃ , potassium carbonate; under an inert atmosphere, react the mixed solution of the above reactants at a reaction temperature of 110-120°C for 12-24 hours, cool and filter the reaction solution, and rotate the filtrate to evaporate. Pass through a silica gel column to obtain the target product, and the reaction equation involved in the step S3 is as follows:

In some preferred embodiments of this patent application, the mol ratio of 6-bromoindanone and anthranilaldehyde in step S1 is 1:(1.5～2.0), and the mol ratio of ammonium acetate and 6-bromoindanone is ( 10-12): 1; more preferably, the molar ratio of 6-bromoindanone to anthranilaldehyde is 1:1.5, and the molar ratio of ammonium acetate to 6-bromoindanone is 10:1.

In some preferred embodiments of this patent application, the molar ratio of chromone methanol compound and hydroxyaniline in step S2 is 1:(1～1.2), and the molar ratio of chromone formaldehyde aniline compound and diethylamine is 1:( 1～1.5); More preferably, the molar ratio of chromone methanol compound to hydroxyaniline is 1:1.2, and the molar ratio of chromone formaldehyde aniline compound to diethylamine is 1:1.1.

In some preferred embodiments of this patent application, in step S3, the molar ratio of 3-bromoindenoquinolinone to heterocyclic aromatic amine compound is 1:(1.2～1.5), Pd ₂ (dba) ₃ and 3- The molar ratio of bromoindenoquinolinone compound or 3-bromochromene quinolinone compound is (0.04～0.08):1, potassium carbonate and 3-bromoindenoquinolinone compound or 3-bromochromene quinolinone The molar ratio of the compound is (2.0～4.0):1, and the molar ratio of Pd ₂ (dba) ₃ to tri-tert-butylphosphine (abbreviated as TTBP) is 1:(1.5～2); more preferably, 3-bromoindeno The molar ratio of quinolinone to heterocyclic aromatic amine compound is 1:1.2, and the molar ratio of Pd ₂ (dba) ₃ to 3-bromoindenoquinolinone compound or 3-bromochromene quinolinone compound is 0.04:1 , the mol ratio of potassium carbonate and 3-bromoindenoquinolinone compound or 3-bromochromene quinolinone compound is 2.0:1; Pd ₂ (dba) ₃ and 3-bromoindenoquinolinone compound or 3- The molar ratio of bromochromene quinolinone compound is 0.08:1, and the molar ratio of Pd ₂ (dba) ₃ to TTBP is 1:2.

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

In some preferred embodiments of this patent application, the selected solvent for the condensation rearrangement reaction in step S2 is toluene, and the selected solvent for the ring closure reaction is ethanol.

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

In some preferred embodiments of this patent application, the reaction conditions of the cyclization reaction in step S1 are normal temperature, the stirring reaction is 5d, and the reaction conditions of the oxidation reaction are 120°C, and the stirring reaction is 24h.

In some preferred embodiments of the present patent application, the reaction conditions of the condensation rearrangement reaction in step S2 are 75° C., stirred for 12 hours, and the reaction conditions of the ring closure reaction are 95° C., stirred for 12 hours.

In some preferred embodiments of this patent application, the reaction condition of the Heck reaction in step S3 is 110-120°C, and the stirring reaction is 12-24h. More preferably, the reaction condition of the Heck reaction in step S3 is 120°C, and the stirring reaction is 24h .

In some preferred embodiments of this patent application, the oxidation reaction in step S1 should be performed under an oxygen atmosphere.

In some preferred embodiments of this patent application, the step S3 Heck reaction should be performed under an inert atmosphere, more preferably, the inert atmosphere is nitrogen.

In some preferred embodiments of this patent application, the post-processing of the cyclization reaction in step S1 includes concentration, extraction, drying, and separation. Concentrate and collect the obtained solid, extract the solid with water and ethyl acetate three times, combine the organic phases obtained three times, dry over 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 Silica gel column chromatography is carried out to separate the product; post-treatment of the oxidation reaction is cooling, extraction, drying, concentration and separation. Cool and collect the orange turbid liquid, extract the orange turbid liquid with water and ethyl acetate three times, combine the organic phase obtained three times, dry with anhydrous magnesium sulfate, and then distill the organic phase under reduced pressure to obtain the crude product; finally use ethyl acetate and petroleum ether The compounds were isolated by silica gel column chromatography as eluent.

In some preferred embodiments of the present patent application, the post-processing of the condensation rearrangement reaction in step S2 includes extraction, concentration, drying, and separation. Extract the yellow turbid liquid with water and ethyl acetate three times, combine the organic phase obtained three times, dry with anhydrous magnesium sulfate, and then distill the organic phase under reduced pressure to obtain the crude product; finally use ethyl acetate and petroleum ether as eluents for silica gel column The compound is separated by chromatography, and the post-processing of the ring-closing reaction is cooling, concentration, extraction, drying, concentration and separation. Cool and collect to obtain a yellow turbid liquid, concentrate and collect to obtain a solid, extract the solid 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 The product was isolated by silica gel column chromatography with petroleum ether as eluent.

In some preferred embodiments of this patent application, the post-treatment of the Heck reaction in step S3 includes cooling, extraction, drying, concentration, and separation. The brown-black turbid liquid was collected by cooling, and the brown-black turbid liquid was extracted three times with water and ethyl acetate, and the organic phases obtained three times were combined, dried with anhydrous magnesium sulfate, and then the organic phase was distilled under reduced pressure to obtain a crude product; finally, ethyl acetate was mixed with The compounds were separated by silica gel column chromatography using petroleum ether as eluent.

At the same time, this patent application also provides the application of the above indenoquinolinone or chromene quinolinone derivatives in the preparation of luminescent materials, organic electroluminescent devices, smart materials, and display materials.

Next, this patent application takes indenoquinolinones or chromene quinolinone derivatives A01-A03, A25-A26 as examples, and introduces indenoquinolinones or chromene quinolines in this patent application in detail Preparation method of ketone derivatives.

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

Preparation of S1.3-bromoindenoquinolinone

Take 181.7 mg of anthranilaldehyde and 211.0 mg of 6-bromoindanone under the action of 770.8 mg of ammonium acetate to undergo a cyclization reaction to generate 265 mg of the corresponding indenoquinoline, with a yield of 90%, and then oxidize with oxygen to generate the corresponding 3 -Bromoindenoquinolinone 255mg, the yield is 92%. Its reaction equation is:

Preparation of S3.A01 compound

Weigh 308 mg of 3-bromoindenoquinolinone, 220 mg of 10H-phenoxazine, 276 mg of potassium carbonate, 36.6 mg of Pd ₂ (dba) ₃ , 160 mg of TTBP, and 3 mL of toluene in a sealed tube, stir to remove the air in the device and fill it with Protected by nitrogen, heated and stirred under reflux at 120°C for 24 hours. After the reaction, the crude product was cooled, extracted, dried, concentrated and separated. Cool and collect the brown-black turbid liquid, extract the turbid liquid three times with water and ethyl acetate, combine the organic phase obtained three times, dry with anhydrous magnesium sulfate, and then distill the organic phase under reduced pressure to obtain the crude product; finally use ethyl acetate and petroleum ether Silica gel column chromatography was used as the eluent. The resulting pure product solution was distilled under reduced pressure and dried in vacuo to obtain 156 mg of a dark red solid, which is a compound of formula A01 with a purity of 98% and a yield of 38%. The reaction equation is:

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

The preparation of S1.3-bromoindenoquinolinone is the same as in Example 1;

Preparation of S3.A02 compound

Weigh 308 mg of 3-bromoindenoquinolinone, 239 mg of 10H-phenothiazine, 276 mg of potassium carbonate, 36.6 mg of Pd ₂ (dba) ₃ , 160 mg of TTBP, and 3 mL of toluene in a sealed tube, stir to remove the air in the device and fill it with Protected by nitrogen, heated and stirred under reflux at 120°C for 24 hours. After the reaction, the crude product was cooled, extracted, dried, concentrated and separated. Cool and collect the brown-black turbid liquid, extract the turbid liquid three times with water and ethyl acetate, combine the organic phase obtained three times, dry with anhydrous magnesium sulfate, and then distill the organic phase under reduced pressure to obtain the crude product; finally use ethyl acetate and petroleum ether Silica gel column chromatography was used as the eluent. The obtained pure product solution is distilled under reduced pressure and vacuum-dried to obtain 278mg brownish-yellow solid, which is the compound of formula (II), with a purity of 98%, and a yield of 65%. Its reaction equation is:

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

The preparation of S1.3-bromoindenoquinolinone is the same as in Example 1;

Preparation of S3.A03 compound

Weigh 308 mg of 3-bromoindenoquinolinone, 251 mg of 9,10-dihydro-9,9-dimethylacridine, 276 mg of potassium carbonate, 36.6 mg of Pd ₂ (dba) ₃ , 160 mg of TTBP, and 3 mL of toluene in Seal the tube, stir to remove the air in the device and fill it with nitrogen protection, heat, stir and reflux reaction at 120°C under nitrogen protection for 24 hours. After the reaction, the crude product is cooled, extracted, dried, concentrated and separated. Cool and collect the brown-black turbid liquid, extract the turbid liquid three times with water and ethyl acetate, combine the organic phase obtained three times, dry with anhydrous magnesium sulfate, and then distill the organic phase under reduced pressure to obtain the crude product; finally use ethyl acetate and petroleum ether Silica gel column chromatography was used as the eluent. The resulting pure product solution was distilled under reduced pressure and dried in vacuo to obtain 183 mg of a yellow solid, which is the compound of formula (Ⅲ), with a purity of 98%, and a yield of 42%. The reaction equation is:

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

S2. Preparation of chromene quinolinone brominated compounds

Firstly, 131 mg of hydroxyaniline and 252 mg of chromone-formaldehyde compound were heated to 75°C in toluene solution to generate condensation and rearrangement reaction to produce 281.8 mg of chromone-formaldehyde aniline compound, with a yield of 82%. Then, 80 mg of diethylamine was added to close the ring Obtain chromene quinolinone compound 189.8mg, yield rate is 71%, and its reaction equation is:

Preparation of S3.A025 compound

Weigh 325 mg of chromene quinolinone bromide compound, 220 mg of 10H-phenoxazine, 276 mg of potassium carbonate, 36.6 mg of Pd ₂ (dba) ₃ , 160 mg of TTBP, and 3 mL of toluene in a sealed tube, stir to remove the air in the device and fill it with Protected by nitrogen, heated and stirred under reflux at 120°C for 24 hours. After the reaction, the crude product was cooled, extracted, dried, concentrated and separated. Cool and collect the brown-black turbid liquid, extract the turbid liquid three times with water and ethyl acetate, combine the organic phase obtained three times, dry with anhydrous magnesium sulfate, and then distill the organic phase under reduced pressure to obtain the crude product; finally use ethyl acetate and petroleum ether Silica gel column chromatography was used as the eluent. The obtained pure product solution was distilled under reduced pressure and vacuum-dried to obtain 269mg red solid, which was the compound of formula (I), with a purity of 98%, and a yield of 63%. The reaction equation was:

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

S2. The preparation of chromene quinolinone brominated compound is the same as in Example 4;

Preparation of S3.A026 compound

Weigh 325 mg of chromene quinolinone brominated compound, 239 mg of 10H-phenothiazine, 276 mg of potassium carbonate, 36.6 mg of Pd ₂ (dba) ₃ , 160 mg of TTBP, and 3 mL of toluene in a sealed tube, stir to remove the air in the device and fill it with Protected by nitrogen, heated and stirred under reflux at 120°C for 24 hours. After the reaction, the crude product was cooled, extracted, dried, concentrated and separated. Cool and collect the brown-black turbid liquid, extract the turbid liquid three times with water and ethyl acetate, combine the organic phase obtained three times, dry with anhydrous magnesium sulfate, and then distill the organic phase under reduced pressure to obtain the crude product; finally use ethyl acetate and petroleum ether Silica gel column chromatography was used as the eluent. The obtained pure product solution was distilled under reduced pressure and vacuum-dried to obtain 133mg yellow solid, which was the compound of formula (II), with a purity of 98%, and a yield of 30%. The reaction equation was:

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

S2. The preparation of chromene quinolinone brominated compound is the same as in Example 4;

Preparation of S3.A027 compound

Weigh 325 mg of chromene quinolinone brominated compound, 251 mg of 9,10-dihydro-9,9-dimethylacridine, 276 mg of potassium carbonate, 36.6 mg of Pd ₂ (dba) ₃ , 160 mg of TTBP, and 3 mL of toluene in Seal the tube, stir to remove the air in the device and fill it with nitrogen protection, heat, stir and reflux reaction at 120°C under nitrogen protection for 24 hours. After the reaction, the crude product is cooled, extracted, dried, concentrated and separated. Cool and collect the brown-black turbid liquid, extract the turbid liquid three times with water and ethyl acetate, combine the organic phase obtained three times, dry with anhydrous magnesium sulfate, and then distill the organic phase under reduced pressure to obtain the crude product; finally use ethyl acetate and petroleum ether Silica gel column chromatography was used as the eluent. The resulting pure product solution was distilled under reduced pressure and dried in vacuo to obtain 245 mg of a yellow solid, which is the compound of formula (Ⅲ), with a purity of 98%, and a yield of 54%. The reaction equation is:

Characterization and Performance Testing

The indenoquinolinone or chromene quinolinone derivatives A01-A03 and A25-A27 obtained in Examples 1-6 were characterized and tested for performance.

The test method is as follows:

Compound structure detection: Bruker 400MHz superconducting nuclear magnetic resonance instrument is used, and the solvent is deuterated chloroform or deuterated dimethyl sulfoxide;

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 mass spectrometer LCMS-2020.

Ultraviolet absorption spectrum detection: using Shimadzu UV-visible spectrophotometer UV-2700, dissolve indenoquinolinones or chromene quinolinone derivatives in THF to prepare a mother liquor of 1×10 ^-3 molL ^-1 , When testing, it is diluted to 1×10 ^-5 molL ^-1 and the scanning range is 200-450nm;

Emission spectrum detection: use a steady-state/transient fluorescence spectrometer (FLS980), the excitation wavelength is 310nm, and the concentration of indenoquinolinones or chromene-quinolinone derivatives in the test solution is kept at 1×10 ^-5 molL ^-1 , adjust the ratio of tetrahydrofuran and water in the test solution. Dissolve indenoquinolinone or chromene quinolinone derivatives in tetrahydrofuran to prepare a mother solution of 1×10 ^-3 molL ^-1 , and keep the total volume of the test solution at 3 mL. For example: when the water content is 90%, the amount of each component added is mother liquor: water: tetrahydrofuran = 30uL: 2700uL: 270uL, under the protection of nitrogen, the test temperature is 300K.

The test results are as follows:

The H NMR spectrum of the indenoquinolinone or chromene quinolinone derivative A01 prepared in Example 1 is shown in FIG. 1 . It can be seen that: ¹ H NMR (400MHz, Chloroform-d) δ8.42(s, 1H), 8.21(s, 1H), 8.14(d, J=8.4Hz, 1H), 7.97(d, J=7.9Hz ,1H),7.87(d,J=8.0Hz,1H),7.75(t,J=7.7Hz,1H),7.53(t,J=7.5Hz,1H),7.47(dd,J=7.9,1.5Hz , 1H), 6.71–6.64 (m, 4H), 6.62–6.57 (m, 2H), 6.13 (d, J=7.8Hz, 2H).[0067], the molecular hydrogen spectrum peak energy corresponds to the target product one by one, The quantity is reasonable; as can be seen from the mass spectrogram (Figure 7), the relative molecular mass in the figure is 412.12, which is consistent with the relative molecular mass of the synthesized A01. In conjunction with the results of the above NMR and mass spectrometry, it can be known that the product obtained in Example 1 is 3-(10H-phenoxazin-10-yl)-11H-indeno[1,2-b]quinolin-11-one (A01 ).

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

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

The H NMR spectrum of the indenoquinolinone or chromene quinolinone derivative A25 prepared in Example 4 is shown in Figure 4 . It can be seen that: ¹ H NMR (400MHz, Chloroform-d) δ9.26 (s, 1H), 8.44 (d, J = 8.4Hz, 1H), 8.05 (t, J = 7.7Hz, 2H), 7.89–7.84 (m,1H),7.62–7.54(m,2H),7.36(dd,J＝8.4,1.9Hz,1H),6.76–

6.68 (m, 4H), 6.67–6.60 (m, 2H), 6.22–6.15 (m, 2H)., the molecular proton spectrum peak energy corresponds to the target product one by one, and the number is reasonable; from the mass spectrum (Figure 10) it can be It can be seen that the relative molecular mass in the figure is 428.12, which is consistent with the relative molecular mass of the synthesized A25. In conjunction with the results of the above NMR and mass spectrometry, it can be known that the product obtained in Example 4 is 3-(10H-phenoxazin-10-yl)-12H-chromen[2,3-b]quinolin-12-one (A25 ).

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

The H NMR spectrum of the indenoquinolinone or chromene quinolinone derivative A27 prepared in Example 6 is shown in FIG. 6 . It can be seen that: ¹ H NMR (400MHz, Chloroform-d) δ9.29(s, 1H), 8.41(d, J=8.7Hz, 1H), 8.09(d, J=8.5Hz, 2H), 7.90(ddd ,J＝8.4,6.9,1.4Hz,1H),7.64–7.59(m,2H),7.51(dd,J＝7.6,1.7Hz,2H),7.40(dd,J＝8.7,2.1Hz,1H), 7.13(dqd, J＝14.7, 7.3, 1.6Hz, 4H), 6.90(dd, J＝7.8, 1.5Hz, 2H), 1.64(s, 6H), the molecular hydrogen spectrum peak energy corresponds to the target product one by one, the quantity Reasonable; as can be seen from the mass spectrogram (Figure 11), the relative molecular mass in the figure is 454.17, which is consistent with the relative molecular mass of the synthesized A27. In combination with the results of the above NMR and mass spectrometry, it can be seen that the product obtained in Example 6 is 3-(9,9-dimethylacridin-10(9H)-yl)-12H-chromene[2,3-b]quinone Lin-12-one (A27).

In addition, the applicant of this patent also tested the photophysical properties of the indenoquinolinone or chromene quinolinone derivative A03. The absorption spectrum and emission spectrum of indenoquinolinone or chromene quinolinone derivative A03 are shown in Figure 13 and Figure 14 respectively.

As shown in FIG. 13, the position of the main absorption peak of the indenoquinolinone or chromene quinolinone derivative A03 compound is 404 nm.

From Figure 14, the emission wavelength of indenoquinolones or chromene quinolinone derivatives A03 compound is 622nm; when the water content is lower than 95%, the indenoquinolones or chromene quinolinones The fluorescence emission wavelength of the derivative A03 compound in the solution has an obvious red shift; and when the water content exceeds 90%, the corresponding fluorescence intensity is greatly enhanced, which shows that indenoquinolinones containing polycyclic aromatic groups Or chromene quinolinone derivatives have obvious aggregation-induced luminescence phenomenon.

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

In the description of this specification, descriptions referring to the terms "one embodiment", "some embodiments", "exemplary embodiments", "examples", "specific examples", or "some examples" etc. mean that the embodiments are combined A specific feature, structure, material, or characteristic described or exemplified is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the described specific features, structures, materials or characteristics may be combined in any suitable manner in any one or more embodiments or examples.

Although several implementations of the present patent application have been shown and described, those skilled in the art can understand that various changes, modifications and substitutions can be made to these implementations without departing from the principle and spirit of the present invention. and modifications, the scope of the invention is defined by the claims and their equivalents.

Claims (10)

1. An indenoquinolinone or chromene quinolinone derivative, which is characterized in that the indenoquinolinone or chromene quinolinone derivative takes a quinolinone structure as a core and has the following structural general formula:

wherein R in formulas (1) and (2) is selected from hydrogen and a polycyclic aromatic group containing heteroatoms of one or more of N, O, S.

2. The indenoquinolinone or chromenoquinolinone derivative of claim 1, wherein said polycyclic aromatic group containing a heteroatom has a formula selected from one of the formulae shown below:

3. the indenoquinolinone or chromene-quinolinone derivative of claim 2, wherein said indenoquinolinone or chromene-quinolinone derivative is selected from one of the following structural formulas:

4. the indenoquinolinone or chromene-quinolinone derivative of claim 3, wherein said indenoquinolinone or chromene-quinolinone derivative is selected from one of the following structural formulas:

5. the method for preparing indenoquinolinone or chromene quinolinone derivatives of claim 4, comprising:

s1, preparing 3-bromoindenoquinolinone: firstly, o-aminobenzaldehyde and 6-bromoindenone are subjected to cyclization reaction under the action of ammonium acetate to generate corresponding 3-bromoindenoquinoline, and then the corresponding 3-bromoindenoquinolinone is generated through oxygen oxidation, wherein the reaction equation related to the step S1 is as follows:

s2, preparing the chromene quinolinone compound: heating hydroxyaniline and a chromone formaldehyde compound in a toluene solution to 75 ℃ to generate a chromone formaldehyde phenylamino compound, and then carrying out ring closure under the action of diethylamine to obtain a chromene quinolinone compound, wherein the reaction equation related to the step S2 is as follows:

s3, preparing indenoquinolinone or chromene quinolinone derivatives: firstly, weighing a 3-bromoindenoquinolinone compound or a 3-bromochromene quinolinone compound and 10H-phenoxazine, and dissolving the 3-bromoindenoquinolinone compound or the 3-bromochromene quinolinone compound and the 10H-phenoxazine by using toluene; then adding Pd ₂ (dba) ₃ Potassium carbonate; reacting the mixed solution of the reactants at the reaction temperature of 110-120 ℃ for 12-24 hours under an inert atmosphere, cooling, filtering the reaction solution, performing rotary evaporation on the filtrate, and passing through a silica gel column to obtain a target product, wherein the reaction equation related to the step S3 is as follows:

6. the method for preparing indenoquinolinone or chromenoquinolinone derivatives according to claim 5, characterized in that: the molar ratio of the 6-bromoindanone to the o-aminobenzaldehyde in the step S1 is 1 (1.5-2.0).

7. The method for preparing indenoquinolinone or chromenoquinolinone derivatives according to claim 5, characterized in that: the molar ratio of the chromone formaldehyde compound to the hydroxyaniline in the step S2 is 1 (1-1.2), and the molar ratio of the chromone formaldehyde phenylamino compound to the diethylamine is 1 (1-1.5).

8. The indenoquinolinone of claim 5The preparation method of the derivatives of the analog or chromene quinolinone is characterized in that: the mol ratio of the 3-bromoindenoquinolinone to the heterocyclic arylamine compound in the step S3 is 1 (1.2-1.5), and Pd ₂ (dba) ₃ The molar ratio of the compound to the 3-bromoindenoquinolinone compound or the 3-bromochromene quinolinone compound is (0.04-0.08): 1, and the molar ratio of the potassium carbonate to the 3-bromoindenoquinolinone compound or the 3-bromochromene quinolinone compound is (2.0-4.0): 1.

9. The method of claim 6, wherein the solvent selected for the cyclization reaction in step S1 is ethanol and the solvent selected for the oxidation reaction is N, N-dimethylformamide.

10. The indenoquinolinone or chromenoquinolinone derivative of claim 1, for use in the preparation of luminescent materials, organic electroluminescent devices, intelligent materials, and display materials.

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