CN115724834A - Indenoquinolinone or chromene quinolinone derivative and preparation method and application thereof - Google Patents
Indenoquinolinone or chromene quinolinone derivative and preparation method and application thereof Download PDFInfo
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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
Technical Field
The patent application relates to the field of organic luminescent materials, in particular to indenoquinolinone or chromene quinolinone derivatives, and a preparation method and application thereof.
Background
With the development of high technology such as large-screen smart phones, tablet computers, wearable devices, etc., organic Light-Emitting diodes (OLEDs) are regarded as a new generation of display products with great development prospects in the diversified tablet display market, and are known as "illusion displays" because of their advantages of self-luminescence, wide viewing angle, low power consumption, fast response time, thin thickness, and flexibility.
Compared with the traditional LED technology, the OLED technology has the remarkable advantages in the aspects of large-area high-quality display and illumination, ultrahigh resolution, ultra-fast response speed, flexible electronics application and the like, has huge application potential in the fields of flat panel display, smart phones, solid light emitting and the like, and attracts the wide attention of the global academic and industrial fields. However, the conventional luminescent materials have problems of insufficient luminescent color purity, insufficient thermal stability, poor solubility, and the like.
Disclosure of Invention
To overcome one of the problems of the prior art, the present patent application provides an indenoquinolinone or chromene quinolinone derivative. The indenoquinolinone or chromene quinolinone derivative can be used as an organic luminescent material, and has a unique aggregation-induced emission effect, high luminous intensity, good thermal stability and good solubility.
It is another object of the present application to provide a method for preparing the indenoquinolinone or chromene quinolinone derivatives.
It is another object of the present application to provide the use of the above indenoquinolinone or chromene quinolinone derivatives.
In order to solve the technical problem, the technical scheme adopted by the patent application is as follows:
an indenoquinolinone or chromene quinolinone derivative, which 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.
Preferably, the structural formula of the polycyclic aromatic group containing a heteroatom in the indenoquinolinone or chromenoquinolinone derivatives of the present application is selected from one of the structural formulae shown below:
preferably, the indenoquinolinone or chromenoquinolinone derivative in the present application is selected from one of the following structural formulae:
more preferably, the indenoquinolinone or chromene quinolinone derivatives of the present application are selected from one of the following structural formulae:
the application also provides a preparation method of the indenoquinolinone or chromene quinolinone derivative, which comprises the following steps:
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 a 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:
preferably, the molar ratio of the 6-bromoindanone to the o-aminobenzaldehyde in the step S1 is 1 (1.5-2.0).
Preferably, the molar ratio of the chromone formaldehyde compound to the hydroxyaniline in step S2 is 1: (1-1.2), the molar ratio of the chromone formaldehyde phenylamino compound to the diethylamine is 1: (1-1.5).
Preferably, the molar ratio of the 3-bromoindenoquinolinone to the heterocyclic aromatic amine compound in the step S3 is 1: (1.2-1.5), pd 2 (dba) 3 The mol ratio of the compound to the 3-bromoindenoquinolinone compound or the 3-bromochromene quinolinone compound is (0.04-0.08): 1, the molar ratio of the potassium carbonate to the 3-bromoindenoquinolinone compound or the 3-bromochromene quinolinone compound is (2.0-4.0): 1.
preferably, the solvent selected for the cyclization reaction in step S1 is ethanol, and the solvent selected for the oxidation reaction is N, N-dimethylformamide.
The application also provides the application of the indenoquinolinone or chromene quinolinone derivative in the preparation of luminescent materials, organic electroluminescent devices, intelligent materials and display materials.
Compared with the prior art, the beneficial effect of this patent application is:
the indenoquinolinone or chromenoquinolinone derivative containing polycyclic aromatic groups provided by the patent application has unique aggregation-induced emission effect, high luminous intensity, good thermal stability and good solubility, and can be used as a novel soluble light-emitting molecule with good performance, low cost and highly distorted spatial structure. The indenoquinolinone or chromenoquinolinone derivative containing polycyclic aromatic groups has remarkable economic value in the application 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.
Drawings
FIG. 1 is 3- (10H-phenoxazin-10-yl) -11H-indeno [1,2-b prepared in example 1]Process for preparing quinolin-11-ones 1 HMNR graph.
FIG. 2 is a 3- (10H-phenothiazin-10-yl) -11H-indeno [1,2-b, prepared in example 2]Process for preparing quinolin-11-ones 1 HMNR graph.
FIG. 3 is the 3- (9,9-dimethylacridin-10 (9H) -yl) -11H-indeno [1,2-b preparation of example 3]Process for preparing quinolin-11-ones 1 HMNR graph.
FIG. 4 is the 3- (10H-phenoxazin-10-yl) -12H-chromene [2,3-b prepared in example 4]Process for preparing quinolin-12-ones 1 HMNR graph.
FIG. 5 is the 3- (10H-phenothiazin-10-yl) -12H-chromene [2,3-b prepared in example 5]Process for preparing quinolin-12-ones 1 HMNR graph.
FIG. 6 is a 3- (9,9-dimethylacridin-10 (9H) -yl) -12H-chromene [2,3-b preparation of example 6]Process for preparing quinolin-12-ones 1 HMNR graph.
FIG. 7 is a mass spectrum of 3- (10H-phenoxazin-10-yl) -11H-indeno [1,2-b ] quinolin-11-one obtained in example 1.
FIG. 8 is a mass spectrum of 3- (10H-phenothiazin-10-yl) -11H-indeno [1,2-b ] quinolin-11-one obtained in example 2.
FIG. 9 is a mass spectrum of 3- (9,9-dimethylacridin-10 (9H) -yl) -11H-indeno [1,2-b ] quinolin-11-one obtained in example 3.
FIG. 10 is a mass spectrum of 3- (10H-phenoxazin-10-yl) -12H-chromene [2,3-b ] quinolin-12-one obtained in example 4.
FIG. 11 is a mass spectrum of 3- (10H-phenothiazin-10-yl) -12H-chromene [2,3-b ] quinolin-12-one obtained in example 5.
FIG. 12 is a mass spectrum of 3- (9,9-dimethylacridin-10 (9H) -yl) -12H-chromene [2,3-b ] quinolin-12-one obtained in example 6.
FIG. 13 is a chart of the UV-VIS absorption spectrum of 3- (9,9-dimethylacridin-10 (9H) -yl) -11H-indeno [1,2-b ] quinolin-11-one obtained in example 3.
FIG. 14 is a graph of the emission spectra of 3- (9,9-dimethylacridin-10 (9H) -yl) -11H-indeno [1,2-b ] quinolin-11-one prepared in example 3 in solutions having different water contents.
Detailed Description
Embodiments of the present patent application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present patent application and should not be construed as limiting the scope of the present patent application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
It should be noted that:
all embodiments and preferred methods mentioned herein can be combined with each other to form new solutions, if not specifically stated in the present patent application.
In this patent application, percentages (%) or parts refer to percentages or parts by weight relative to the composition, if not otherwise specified.
In the present patent application, the components referred to or the preferred components thereof may be combined with each other to form new solutions, if not specifically stated.
In this patent application, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "2 to 8" indicates that all real numbers between "2 to 8" have been listed herein, and "2 to 8" is only a shorthand representation of the combination of these numbers.
The "range" disclosed in this patent application may be in the form of one or more lower limits and one or more upper limits, respectively, in the form of lower limits and upper limits.
In this application, unless otherwise indicated, individual reactions or process steps may be performed sequentially or in sequence. Preferably, the reaction processes herein are carried out sequentially.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. Moreover, any methods or materials similar or equivalent to those described herein can also be used in the present application.
The application provides an indenoquinolinone or chromene quinolinone derivative, which 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 comprising a heteroatom which is one or more of N, O, S.
The indenoquinolinone or chromene quinolinone derivative contains an amino compound, can be used as an organic luminescent material, and has a unique aggregation-induced luminescent effect, 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 chromenoquinolinone derivatives of the present application is selected from one of the structural formulas shown below:
in some preferred embodiments, the indenoquinolinone or chromene quinolinone derivatives of the present application are selected from one of the following structural formulae:
more preferably, the indenoquinolinone or chromenoquinolinone derivatives provided in this patent application have one of the following molecular structures:
the application also provides a synthetic method of the indenoquinolinone or chromene quinolinone derivative. The method comprises the following steps:
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 a 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:
in some preferred embodiments of the present application, the molar ratio of 6-bromoindanone to o-aminobenzaldehyde in step S1 is 1 (1.5-2.0), 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.
In some preferred embodiments of the present application, the molar ratio of the chromone carbinol compound to the 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 chromone carbinol compound to hydroxyaniline is 1.2 and the molar ratio of chromone formaldehyde phenylamino compound to diethylamine is 1.1.
In some preferred embodiments of the present patent application, in step S3, 3-bromoThe mol ratio of the indenoquinolinone to the heterocyclic arylamine compound is 1 (1.2-1.5), 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, the molar ratio of the potassium carbonate to the 3-bromoindenoquinolinone compound or the 3-bromochromene quinolinone compound is (2.0-4.0): 1, pd 2 (dba) 3 The molar ratio of the compound to tri-tert-butylphosphine (abbreviated as TTBP) is 1 (1.5-2); more preferably, the molar ratio of 3-bromoindenoquinolinone to heterocyclic aromatic amine compound is 1:1.2, pd 2 (dba) 3 And 3-bromoindenoquinolinone compound or 3-bromochromene quinolinone compound at a molar ratio of 0.04 to 1, and a molar ratio of potassium carbonate to 3-bromoindenoquinolinone compound or 3-bromochromene quinolinone compound of 2.0; pd 2 (dba) 3 And the molar ratio of the 3-bromoindenoquinolinone compound or the 3-bromochromene quinolinone compound is 0.08 2 (dba) 3 Molar ratio to TTBP 1:2.
in some preferred embodiments of the present 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.
In some preferred embodiments of the present application, the solvent selected for the condensation rearrangement reaction in step S2 is toluene and the solvent selected for the ring closure reaction is ethanol.
In some preferred embodiments of the present patent application, the solvent selected for the Heck reaction in step S3 is toluene.
In some preferred embodiments of the present application, the cyclization reaction in step S1 is performed under normal temperature and stirring for 5d, and the oxidation reaction is performed under 120 ℃ and stirring for 24h.
In some preferred embodiments of the present application, the condensation rearrangement reaction in step S2 is performed at 75 deg.C under stirring for 12h, and the ring-closure reaction is performed at 95 deg.C under stirring for 12h.
In some preferred embodiments of the present application, the Heck reaction in step S3 is performed under a reaction condition of 110 to 120 ℃ and the stirring reaction is performed for 12 to 24 hours, and more preferably, the Heck reaction in step S3 is performed under a reaction condition of 120 ℃ and the stirring reaction is performed for 24 hours.
In some preferred embodiments of the present patent application, the oxidation reaction of step S1 should be carried out under an oxygen atmosphere.
In some preferred embodiments of the present 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 the present patent application, the cyclization reaction post-treatment of step S1 is concentration, extraction, drying, isolation. Concentrating and collecting to obtain solid, extracting the solid with water and ethyl acetate for three times, combining organic phases obtained in the three times, drying with anhydrous magnesium sulfate, and distilling the organic phase under reduced pressure to obtain a crude product; finally, separating the product by silica gel column chromatography by using ethyl acetate and petroleum ether as eluent; the post-treatment of the oxidation reaction comprises cooling, extraction, drying, concentration and separation. Cooling and collecting to obtain orange turbid liquid, extracting the orange turbid liquid with water and ethyl acetate for three times, combining organic phases obtained by the three times, drying with anhydrous magnesium sulfate, and distilling the organic phase under reduced pressure to obtain a crude product; finally, the compound is separated by silica gel column chromatography by using ethyl acetate and petroleum ether as eluent.
In some preferred embodiments of the present application, the condensation rearrangement reaction of step S2 is followed by extraction, concentration, drying, and isolation. Extracting the yellow turbid liquid with water and ethyl acetate for three times, combining organic phases obtained in the three times, drying with anhydrous magnesium sulfate, and distilling the organic phase under reduced pressure to obtain a crude product; and finally, separating the compound by silica gel column chromatography by using ethyl acetate and petroleum ether as eluent, wherein the post-treatment of the ring-closing reaction comprises cooling, concentration, extraction, drying, concentration and separation. Cooling and collecting to obtain yellow turbid liquid, concentrating and collecting to obtain solid, extracting the solid with water and ethyl acetate for three times, combining organic phases obtained in the three times, drying with anhydrous magnesium sulfate, and distilling the organic phase under reduced pressure to obtain a crude product; finally, the product is separated by silica gel column chromatography by using ethyl acetate and petroleum ether as eluent.
In some preferred embodiments of the present patent application, the Heck post-reaction treatment of step S3 is cooling, extraction, drying, concentration, isolation. Cooling and collecting to obtain a brownish black turbid liquid, extracting the brownish black turbid liquid with water and ethyl acetate for three times, combining organic phases obtained by the three times, drying with anhydrous magnesium sulfate, and distilling the organic phases under reduced pressure to obtain a crude product; finally, the compound is separated by silica gel column chromatography by using ethyl acetate and petroleum ether as eluent.
Meanwhile, the application also provides the application of the indenoquinolinone or chromene quinolinone derivative in the preparation of luminescent materials, organic electroluminescent devices, intelligent materials and display materials.
Next, the present patent application takes indenoquinolinone or chromene quinolinone derivatives A01-A03 and A25-A26 as examples, and details of the preparation method of the indenoquinolinone or chromene quinolinone derivatives in the present patent application are described.
Example 1 preparation of 3- (10H-Phenoxazin-10-yl) -11H-indeno [1,2-b ] quinolin-11-one (A01)
S1.3 preparation of bromoindenoquinolinones
Taking 181.7mg of anthranilic aldehyde and 5363 mg of 6-bromoindanone 211.0mg to carry out cyclization reaction under the action of 770.8mg of ammonium acetate to generate 265mg of corresponding indenoquinoline, wherein the yield is 90%, and then generating 255mg of corresponding 3-bromoindenoquinolinone through oxygen oxidation, wherein the yield is 92%. The reaction equation is as follows:
s3. Preparation of A01 Compounds
Weighing 3-bromoindenoquinolinone 308mg, 10H-phenoxazine 220mg, potassium carbonate 276mg, pd 2 (dba) 3 Putting 36.6mg, TTBP 160mg and 3mL of toluene in a sealed tube, stirring, pumping out air in the device, filling nitrogen for protection, heating, stirring and refluxing for reaction for 24 hours at 120 ℃ under the protection of nitrogen, and after the reaction is finished, cooling, extracting, drying, concentrating and separating a crude product. Cooling and collecting to obtain a brownish black turbid liquid, extracting the turbid liquid with water and ethyl acetate for three times, combining organic phases obtained by the three times, drying with anhydrous magnesium sulfate, and distilling the organic phase under reduced pressure to obtain a crude product; and finally, separating by silica gel column chromatography by using ethyl acetate and petroleum ether as eluent. The pure product obtainedThe resulting solution was distilled under reduced pressure and dried in vacuo to obtain 156mg of a dark red solid, i.e., a compound of formula A01, having a purity of 98% and a yield of 38%, according to the reaction equation:
example 2 preparation of 3- (10H-phenothiazin-10-yl) -11H-indeno [1,2-b ] quinolin-11-one (A02)
S1.3 preparation of bromoindenoquinolinone as in example 1;
s3.preparation of A02 Compounds
3-bromoindeno quinolinone 308mg, 10H-phenothiazine 239mg, potassium carbonate 276mg and Pd are weighed in 2 (dba) 3 Putting 36.6mg, TTBP 160mg and 3mL of toluene in a sealed tube, stirring, pumping out air in the device, filling nitrogen for protection, heating, stirring and refluxing for reaction for 24 hours at 120 ℃ under the protection of nitrogen, and after the reaction is finished, cooling, extracting, drying, concentrating and separating a crude product. Cooling and collecting to obtain a brownish black turbid liquid, extracting the turbid liquid with water and ethyl acetate for three times, combining organic phases obtained by the three times, drying with anhydrous magnesium sulfate, and distilling the organic phase under reduced pressure to obtain a crude product; and finally, performing silica gel column chromatography separation by using ethyl acetate and petroleum ether as eluent. The resulting pure product solution was distilled under reduced pressure and dried in vacuo to yield 278mg of a tan solid, a compound of formula (ii), 98% pure, 65% yield, according to the equation:
example 3- (9,9-dimethylacridin-10 (9H) -yl) -11H-indeno [1,2-b ] quinolin-11-one (A03)
S1.3 preparation of bromoindenoquinolinone as in example 1;
s3. Preparation of A03 Compounds
3-bromoindeno quinolinone 308mg,9, 10-dihydro-9,9-dimethylacridine 251mg, potassium carbonate 276mg, pd 2 (dba) 3 36.6mg, TTBP 160mg,3mL of tolueneStirring and pumping out air in the device in a sealed tube, filling nitrogen for protection, heating, stirring and refluxing for reaction for 24 hours at the temperature of 120 ℃ under the protection of nitrogen, and cooling, extracting, drying, concentrating and separating a crude product after the reaction is finished. Cooling and collecting to obtain a brownish black turbid liquid, extracting the turbid liquid with water and ethyl acetate for three times, combining organic phases obtained by the three times, drying with anhydrous magnesium sulfate, and distilling the organic phase under reduced pressure to obtain a crude product; and finally, performing silica gel column chromatography separation by using ethyl acetate and petroleum ether as eluent. The resulting pure product solution was distilled under reduced pressure and dried in vacuo to yield 183mg of a yellow solid, which was the compound of formula (III) with 98% purity and 42% yield according to the equation:
example 4 preparation of 3- (10H-phenoxazin-10-yl) -12H-chromene [2,3-b ] quinolin-12-one (A025)
S2, preparation of chromene quinolinone bromo-compound
Firstly, 131mg of hydroxyaniline and 252mg of chromone formaldehyde compound are heated to 75 ℃ in a toluene solution to carry out condensation rearrangement reaction to generate 281.8mg of chromone formaldehyde phenylamino compound with the yield of 82%: and then under the action of 80mg of diethylamine, ring closure is carried out to obtain 189.8mg of chromene quinolinone compound with the yield of 71 percent, and the reaction equation is as follows:
s3. Preparation of A025 Compounds
Weighing 325mg, 10H-phenoxazine as chromene quinolinone bromo-compound, 276mg, pd as potassium carbonate 2 (dba) 3 Putting 36.6mg, TTBP 160mg and 3mL of toluene in a sealed tube, stirring, pumping out air in the device, filling nitrogen for protection, heating, stirring and refluxing for reaction for 24 hours at 120 ℃ under the protection of nitrogen, and after the reaction is finished, cooling, extracting, drying, concentrating and separating a crude product. Cooling and collecting to obtain a brownish black turbid liquid, and extracting the turbid liquid with water and ethyl acetate for three timesCombining the organic phases obtained in the three steps, drying by using anhydrous magnesium sulfate, and then distilling the organic phase under reduced pressure to obtain a crude product; and finally, performing silica gel column chromatography separation by using ethyl acetate and petroleum ether as eluent. The resulting pure product solution was distilled under reduced pressure and dried in vacuo to yield 269mg of a red solid, the compound of formula (I), 98% pure, 63% yield, according to the equation:
example 5 preparation of 3- (10H-phenothiazin-10-yl) -12H-chromene [2,3-b ] quinolin-12-one (A026)
S2, preparing the chromene quinolinone bromo-compound in the same way as in example 4;
s3. Preparation of A026 Compound
Weighing 325mg, 10H-phenothiazine 239mg, potassium carbonate 276mg and Pd of chromene quinolinone bromo-compound 2 (dba) 3 Placing 36.6mg, TTBP 160mg, and 3mL of toluene in a sealed tube, stirring and pumping out the air in the device, filling nitrogen for protection, heating, stirring and refluxing for reaction for 24 hours at 120 ℃ under the protection of nitrogen, and after the reaction is finished, cooling, extracting, drying, concentrating and separating the crude product. Cooling and collecting to obtain a brownish black turbid liquid, extracting the turbid liquid with water and ethyl acetate for three times, combining organic phases obtained in the three times, drying with anhydrous magnesium sulfate, and distilling the organic phases under reduced pressure to obtain a crude product; and finally, performing silica gel column chromatography separation by using ethyl acetate and petroleum ether as eluent. The resulting pure product solution was distilled under reduced pressure and dried under vacuum to give 133mg of a yellow solid, which was the compound of formula (II) with 98% purity and 30% yield according to the equation:
example 6 preparation of 3- (9,9-dimethylacridin-10 (9H) -yl) -12H-chromene [2,3-b ] quinolin-12-one (A027)
S2, preparing the chromene quinolinone bromo-compound in the same way as in example 4;
s3. Preparation of A027 Compounds
Weighing 325mg of chromene quinolinone bromo-compound, 251mg of 9, 10-dihydro-9,9-dimethylacridine, 276mg of potassium carbonate, pd 2 (dba) 3 Putting 36.6mg, TTBP 160mg and 3mL of toluene in a sealed tube, stirring, pumping out air in the device, filling nitrogen for protection, heating, stirring and refluxing for reaction for 24 hours at 120 ℃ under the protection of nitrogen, and after the reaction is finished, cooling, extracting, drying, concentrating and separating a crude product. Cooling and collecting to obtain a brownish black turbid liquid, extracting the turbid liquid with water and ethyl acetate for three times, combining organic phases obtained by the three times, drying with anhydrous magnesium sulfate, and distilling the organic phase under reduced pressure to obtain a crude product; and finally, performing silica gel column chromatography separation by using ethyl acetate and petroleum ether as eluent. The pure product solution obtained is distilled under reduced pressure and dried in vacuo to give 245mg of a yellow solid, i.e., the compound of formula (III), 98% pure, 54% yield, according to the equation:
characterization and Performance testing
The indenoquinolinone or chromenoquinolinone derivatives A01-A03, A25-A27 obtained in examples 1-6 were characterized and tested for their properties.
The test method is as follows:
and (3) detecting the structure of the compound: using a Bruker 400MHz superconducting nuclear magnetic resonance instrument, wherein a solvent is deuterated chloroform or deuterated dimethyl sulfoxide;
mass spectrum detection: A01-A03 and A25-A27 obtained in examples 1 to 6 were dissolved in methylene chloride to prepare solutions having a concentration of 1mg/mL, and mass spectrometry was performed by using a liquid chromatograph LCMS-2020.
Detecting ultraviolet absorption spectrum: dissolving indenoquinolinone or chromene quinolinone derivatives in THF to obtain 1 × 10 solution by using Shimadzu ultraviolet-visible spectrophotometer UV-2700 -3 molL -1 The mother liquor of (1) is diluted to 1X 10 at the time of the test -5 molL -1 The scanning range is 200-450 nm;
and (3) emission spectrum detection: using steady stateTransient fluorescence spectrometer (FLS 980), excitation wavelength is 310nm, concentration of indenoquinolinone or chromene quinolinone derivative in test solution is maintained to be 1 × 10 -5 molL -1 The ratio of tetrahydrofuran to water in the test solution was adjusted. Firstly, indenoquinolinone or chromene quinolinone derivative is dissolved in tetrahydrofuran to prepare 1 × 10 -3 molL -1 Maintaining the total volume of the test solution at 3mL. For example: at a water content of 90%, the components are added in an amount of mother liquor, water, tetrahydrofuran =30uL, 2700uL, 270uL, and the test temperature is 300K under nitrogen protection.
The test results were as follows:
the NMR spectrum of the indenoquinolinone or chromenoquinolinone 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, and the quantity is reasonable; from the mass spectrum (FIG. 7), it can be seen that the relative molecular mass in the graph is 412.12, which is consistent with the relative molecular mass of A01 synthesized. The results of the above nuclear magnetic and mass spectrometry combined show that the product obtained in example 1 is 3- (10H-phenoxazin-10-yl) -11H-indeno [1,2-b]Quinolin-11-one (A01).
The NMR spectrum of the indenoquinolinone or chromenoquinolinone derivative A02 prepared in example 2 is shown in FIG. 2. It can be seen that: 1 h NMR (400MHz, chloroform-d) delta 8.32 (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), molecular hydrogen spectral peaks can correspond to target products one by one, and the number is reasonable; from the mass spectrum (FIG. 8), it can be seen that the relative molecular mass in the graph is 428.10, which is consistent with the relative molecular mass of A02 synthesized. The results of the above nuclear magnetic and mass spectrometry combined show that the product obtained in example 2 was 3- (10H-phenothiazin-10-yl) -11H-indeno [1,2-b]Quinolin-11-one (A02).
The NMR spectrum of the indenoquinolinone or chromenoquinolinone derivative A03 prepared in example 3 is shown in FIG. 3. It can be seen that: 1 h NMR (400mhz, chloroform-d) δ 8.40 (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), molecular hydrogen spectrum peaks can correspond to the target products one-to-one, in reasonable amounts; from the mass spectrum (FIG. 9), it can be seen that the relative molecular mass in the graph is 438.17, which is consistent with the relative molecular mass of the synthesized A03. Combining the results of the above nuclear magnetic and mass spectrometry, the product obtained in example 3 was 3- (9,9-dimethylacridin-10 (9H) -yl) -11H-indeno [1,2-b]Quinolin-11-one (A03).
The NMR spectrum of the indenoquinolinone or chromenoquinolinone derivative A25 prepared in example 4 is shown in FIG. 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 hydrogen spectrum peak energy corresponds to the target product one by one, and the quantity is reasonable; from the mass spectrum (FIG. 10), it can be seen that the relative molecular mass in the graph is 428.12, which is consistent with the relative molecular mass of A25 synthesized. The results of the above nuclear magnetic and mass spectrometry combined show that the product obtained in example 4 was 3- (10H-phenoxazin-10-yl) -12H-chromene [2,3-b ] quinolin-12-one (A25).
The NMR spectrum of the indenoquinolinone or chromenoquinolinone derivative A26 prepared in example 5 is shown in FIG. 5. It can be seen that: 1 h NMR (400mhz, chloroform-d) δ 9.15 (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), molecular hydrogen spectral peaks can correspond one-to-one to the target product, and the number is reasonable; from the mass spectrum (FIG. 11), it can be seen that the relative molecular mass in the graph is 444.09, which is consistent with the relative molecular mass of A26 synthesized. The results of the above nuclear magnetic and mass spectrometry combined show that the product obtained in example 5 is 3- (10H-phenoxazin-10-yl) -12H-chromene [2,3-b]Quinolin-12-one (A26).
The NMR spectrum of the indenoquinolinone or chromenoquinolinone derivative A27 prepared in example 6 is shown in FIG. 6. It can be seen that: 1 h NMR (400mhz, chloroform-d) δ 9.29 (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), molecular hydrogen spectral peaks can correspond one-to one for one, and in reasonable amounts to the target product; from the mass spectrum (FIG. 11), it can be seen that the relative molecular mass in the graph is 454.17, which is consistent with the relative molecular mass of A27 synthesized. The results of the above nuclear magnetic and mass spectrometry combined indicate that the product obtained in example 6 was 3- (9,9-dimethylacridin-10 (9H) -yl) -12H-chromene [2,3-b]Quinolin-12-one (A27).
In addition, the applicant also tests the photophysical properties of the indenoquinolinone or chromenoquinolinone derivatives A03. The absorption spectrum and the emission spectrum of the indenoquinolinone or chromenoquinolinone derivative A03 are respectively shown in FIG. 13 and FIG. 14.
As shown in FIG. 13, the main absorption peak position of the indenoquinolinone or chromene quinolinone derivative A03 compound is 404nm.
From FIG. 14, the emission wavelength of the A03 compound, which is an indenoquinolinone or chromenoquinolinone derivative, is 622nm; when the water content is lower than 95%, the fluorescence emission wavelength of the indenoquinolinone or chromene quinolinone derivative A03 compound in the solution is obviously red-shifted; when the water content exceeds 90%, the corresponding fluorescence intensity is greatly enhanced, and the indenoquinolinone or chromene quinolinone derivative containing polycyclic aromatic groups has obvious aggregation-induced luminescence phenomenon.
In summary, the quinolinone derivative containing arylamine group provided by the patent application has unique aggregation-induced emission effect, high luminous intensity, good thermal stability and good solubility, and can be used as a novel soluble luminescent molecule with good performance, low 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.
In the description of the present specification, reference to the description of the terms "one embodiment", "some embodiments", "an illustrative embodiment", "an example", "a specific example", or "some examples", etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example 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 particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While several embodiments of the present patent application have been shown and described, it will be appreciated by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which 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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