阅读说明：本技术 一种含有芳胺基团的喹啉酮类衍生物及其制备和应用 (Quinolinone derivative containing arylamine group and preparation and application thereof ) 是由 霍延平 吴晓慧 陈文铖 高杨 籍少敏 杨庆旦 于 2021-07-08 设计创作，主要内容包括：本发明提供了一种含有芳胺基团的喹啉酮类衍生物及其制备和应用。所述含有芳胺基团的喹啉酮类衍生物能发生明显的聚集诱导发光效应,从而具有较高的发光强度,且该喹啉酮类衍生物还具有良好的热稳定性,因此可用于发光材料的制备,为发光材料技术领域提供了一种新的材料来源。(The invention provides quinolinone derivatives containing arylamine groups, and preparation and application thereof. The quinolinone derivative containing arylamine group can generate obvious aggregation induced luminescence effect, so that the quinolinone derivative has higher luminescence intensity, and has good thermal stability, so that the quinolinone derivative can be used for preparing luminescent materials, and a new material source is provided for the technical field of luminescent materials.)

1. A quinolinone derivative containing an arylamine group, characterized in that the quinolinone derivative has a chemical structure represented by the following formula (I), formula (II) or formula (III):

2. the process for producing quinolinone derivatives according to claim 1, wherein the quinolinone derivatives are obtained by reacting (4-fluorobenzene) (quinolin-3-yl) methanone with Compound A; the compound A comprises 10H-phenoxazine, 10H-phenothiazine or 9, 10-dihydro-9, 9-dimethylacridine.

3. The preparation method according to claim 2, wherein the molar ratio of the (4-fluorobenzene) (quinolin-3-yl) methanone to the compound A is 1: 1 to 1.2.

4. The preparation method according to claim 3, wherein the molar ratio of the (4-fluorobenzene) (quinolin-3-yl) methanone to the compound A is 1: 1.1.

5. the preparation method according to claim 2, wherein the (4-fluorobenzene) (quinolin-3-yl) methanone and the compound A are stirred and react for 12-15 hours at 70-75 ℃ in an organic solvent, an alkaline reagent and an inert atmosphere.

6. The method according to claim 5, wherein the organic solvent comprises N, N-dimethylformamide; the basic agent comprises potassium tert-butoxide.

7. The method of claim 5, wherein the reaction temperature is 75 ℃; the reaction time was 15 h.

8. Use of the quinolinone derivative of claim 1 for producing a luminescent material.

9. A luminescent material, comprising the quinolinone derivative of claim 1 or prepared from the quinolinone derivative of claim 1.

10. Use of the luminescent material according to claim 9 for the preparation of a light emitting device.

Technical Field

The invention belongs to the technical field of luminescent materials. More particularly, relates to quinolinone derivatives containing arylamine groups, and preparation and application thereof.

Background

With the rise of high technology such as large-screen smart phones, tablet computers, wearable devices, etc., Organic Light-Emitting diodes (OLEDs for short) have the advantages of self-luminescence, wide viewing angle, low power consumption, fast response time, thin thickness, and flexible realization, etc., and are regarded as a new generation of display products with great development prospects in the diversified tablet display market, and are known as "dream displays". 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-state lighting and the like, and attracts wide attention of the global academic world and industrial industry (Wu Qingyang OLED technology and the research of the facing technical problems [ J ] computer fan, 2017(25):209,138.DOI: 10.3969/j.snis.1672-528 X.2017.25.195.).

In the prior art, researches have found that quinolinone derivatives show better potential when used as luminescent materials, for example, patent CN201811158821.2 discloses an application of a compound taking quinolinone derivatives as a core in OLEDs, and patent CN201480059773.5 discloses a luminescent material based on benzimidazolyl xanthene isoquinolinone derivatives, which all show that quinolinone derivatives can be used as excellent luminescent materials, but in general, the types of quinolinone derivatives which can be used as luminescent materials are few, and therefore, there is a need to develop more novel quinolinone derivatives which can be used as luminescent materials.

Disclosure of Invention

The invention aims to provide quinolinone derivatives containing arylamine groups, and preparation and application thereof. The quinolinone derivative containing arylamine group can generate obvious aggregation induced luminescence effect, so that the quinolinone derivative has high luminescence intensity and good thermal stability, and a novel organic luminescent material is provided.

The first purpose of the invention is to provide quinolinone derivatives containing arylamine groups.

The second purpose of the invention is to provide a preparation method of the quinolinone derivative.

The third purpose of the invention is to provide the application of the quinolinone derivative in preparing luminescent materials.

It is a fourth object of the present invention to provide a luminescent material.

The fifth purpose of the invention is to provide the application of the luminescent material in the preparation of a luminescent device.

The above purpose of the invention is realized by the following technical scheme:

the invention provides quinolinone derivatives containing arylamine groups, which have chemical structures shown in a formula (I), a formula (II) or a formula (III):

a compound of formula (I): (4- (10H-phenoxazin-10-yl) phenyl) (quinolin-3-yl) methanone;

a compound of formula (II): (4- (10H-phenothiazin-10-yl) phenyl) (quinolin-3-yl) methanone;

a compound of formula (III): (4- (9, 9-dimethylacridin-10 (9H) -yl) phenyl) (quinolin-3-yl) methanone.

The quinolinone derivative containing arylamine groups forms a larger conjugated plane due to the introduction of a bridged benzene ring in a hydrogenated phenoxazine group, a hydrogenated phenothiazine group or a 9, 10-dihydro-9, 9-dimethylacridine group, and is favorable for molecular luminescence due to the existence of C-H-pi accumulation, so that higher fluorescence quantum yield can be obtained.

In addition, after a hydrogenated phenoxazine group, a hydrogenated phenothiazine group or a 9, 10-dihydro-9, 9-dimethylacridine group is introduced on the basis of (4-fluorobenzene) (quinoline-3-yl) ketone, the quinolinone derivative containing the aromatic amine group can generate an aggregation-induced luminescence effect, the phenomenon of exciton annihilation can be effectively inhibited, and molecules have stronger fluorescence emission under a high-concentration aggregation state than under a low concentration state, so that the quinolinone derivative has higher luminescence intensity. In addition, the quinolinone derivative containing the aromatic amine group has relatively large molecular weight, and a conjugation condition exists between the N-containing heterocyclic structure and the aromatic amine structure, so that the quinolinone derivative also has the advantage of good thermal stability.

Based on the structural characteristics of the quinolinone derivative containing arylamine groups, the quinolinone derivative can generate an obvious aggregation-induced emission effect, so that the quinolinone derivative has high luminous intensity, has good thermal stability, and can be suitable for preparation of luminescent materials.

Preferably, the light emitting material comprises an organic light emitting diode.

The invention also provides a preparation method of the quinolinone derivative, which is specifically obtained by reacting (4-fluorobenzene) (quinoline-3-yl) ketone with the compound A; the compound A comprises 10H-phenoxazine, 10H-phenothiazine or 9, 10-dihydro-9, 9-dimethylacridine.

Wherein: the compound of the formula (I) is obtained by reacting (4-fluorobenzene) (quinoline-3-yl) ketone with 10H-phenoxazine; the compound of the formula (II) is obtained by reacting (4-fluorobenzene) (quinoline-3-yl) ketone with 10H-phenothiazine; the compound of the formula (III) is obtained by reacting (4-fluorobenzene) (quinoline-3-yl) ketone with 9, 10-dihydro-9, 9-dimethylacridine.

Preferably, the molar ratio of the (4-fluorobenzene) (quinolin-3-yl) methanone to the compound a is 1: 1 to 1.2.

Most preferably, the molar ratio of the (4-fluorobenzene) (quinolin-3-yl) methanone to the compound a is 1: 1.1, see example 1.

Preferably, the (4-fluorobenzene) (quinolin-3-yl) ketone and the compound A are stirred and react for 12-15 hours at 70-75 ℃ in an organic solvent, an alkaline reagent and an inert atmosphere.

Further preferably, the organic solvent comprises N, N dimethylformamide; the basic agent comprises potassium tert-butoxide.

Further preferably, the inert atmosphere includes a nitrogen atmosphere, an argon atmosphere, or a helium atmosphere.

Most preferably, the temperature of the reaction is 75 ℃ and the time of the reaction is 15 h. See example 1.

Preferably, the quinolinone derivative is prepared by stirring the (4-fluorobenzene) (quinolin-3-yl) ketone and the compound A in an organic solvent, an alkaline reagent and an inert atmosphere at 70-75 ℃ to perform nucleophilic substitution reaction for 12-15 h, and performing post-treatment.

Preferably, the post-treatment is cooling, extraction, drying, concentration, separation.

Specifically, the method comprises the following steps: and the post-treatment comprises the steps of carrying out nucleophilic substitution reaction on the (4-fluorobenzene) (quinoline-3-yl) ketone and the compound A, 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, carrying out reduced pressure distillation on the organic phases, concentrating to obtain a crude product, and finally carrying out silica gel column chromatography separation by using ethyl acetate and petroleum ether as an eluent to obtain the quinolinone derivative.

As a preferable mode of execution, the reaction formula of the preparation process of the quinolinone derivative is as follows:

in the technical scheme of the invention, the (4-fluorobenzene) (quinolin-3-yl) methanone can be synthesized by a person skilled in the art by referring to the prior art, and any (4-fluorobenzene) (quinolin-3-yl) methanone prepared by the prior art can realize the technical scheme of the invention, and can also be obtained by a market.

As a preferred practical embodiment, the (4-fluorobenzene) (quinolin-3-yl) methanone may be prepared by: performing aza-Michael addition reaction on the anthranilic anhydride and the 4-fluoro acetophenone in the presence of potassium persulfate, and performing post-treatment to obtain the final product.

Preferably, the molar ratio of the anthranilic anhydride to the 4-fluoroacetophenone to the potassium persulfate is 1-1.1: 1: 2.3 to 2.5.

Most preferably, the molar ratio of anthranilic anhydride, 4-fluoroacetophenone to potassium persulfate is 1.1: 1: 2.5.

preferably, the solvent used in the aza-Michael addition reaction comprises dimethyl sulfoxide.

Preferably, the aza-Michael addition reaction is carried out under conditions of heating and stirring in a nitrogen atmosphere.

Further preferably, the heating and stirring temperature is 115-120 ℃, and the time is 22-24 hours.

Most preferably, the heating and stirring temperature is 120 ℃ and the time is 24 h. See example 1.

Preferably, in the above preparation method of (4-fluorobenzene) (quinolin-3-yl) methanone, the post-treatment is cooling, transferring, extracting, concentrating, separating; cooling the solution after the aza-Michael addition reaction to room temperature, transferring the brown-black turbid solution into a separating funnel, extracting with water, a saturated sodium chloride aqueous solution, a saturated sodium bicarbonate aqueous solution and ethyl acetate for three times respectively, combining organic phases obtained in the three times, drying with anhydrous magnesium sulfate, concentrating under reduced pressure to obtain a crude product, and finally performing silica gel column chromatography separation by using ethyl acetate and petroleum ether as an eluent to obtain the (4-fluorobenzene) (quinolin-3-yl) methanone.

In addition, the invention also claims a luminescent material containing the quinolinone derivative or prepared from the quinolinone derivative, and application of the luminescent material in preparing a luminescent device.

Preferably, the light emitting device comprises an organic light emitting diode.

The invention has the following beneficial effects:

the quinolinone derivative containing arylamine groups can generate obvious aggregation-induced emission effect, so that the quinolinone derivative has high luminous intensity, has good thermal stability, is suitable for preparing luminescent materials, and provides a new choice for the technical field of luminescent materials.

Drawings

FIG. 1 shows the product obtained in example 1¹HMNR graph.

FIG. 2 is an embodiment2 of the product obtained¹HMNR graph.

FIG. 3 shows the product obtained in example 3¹HMNR graph.

FIG. 4 is a mass spectrum of the product obtained in example 1.

FIG. 5 is a mass spectrum of the product obtained in example 2.

FIG. 6 is a mass spectrum of the product obtained in example 3.

FIG. 7 is a chart showing an ultraviolet-visible absorption spectrum of the product obtained in example 1.

FIG. 8 is a graph of the emission spectra of the product obtained in example 1 in solutions of different water contents.

FIG. 9 shows the results of thermogravimetric analysis of the product obtained in example 1.

Detailed Description

The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.

Unless otherwise indicated, reagents and materials used in the following examples are commercially available.

EXAMPLE 1 preparation of quinolinone derivatives containing an arylamine group-Compounds of formula (I)

First, experiment method

S1 preparation of (4-fluorobenzene) (quinolin-3-yl) methanone:

adding 138mg of 4-fluoroacetophenone, 131mg of anthranilic anhydride, 676mg of potassium persulfate and 3mL of dimethyl sulfoxide into a 50mL two-neck round-bottom flask, heating and stirring for 24 hours at 120 ℃ in a nitrogen atmosphere to complete aza-Michael addition reaction; cooling the solution after the aza-Michael addition reaction to room temperature, transferring the brown-black turbid solution into a separating funnel, extracting with water, a saturated sodium chloride aqueous solution, a saturated sodium bicarbonate aqueous solution and ethyl acetate for three times respectively, combining organic phases obtained in the three times, drying with anhydrous magnesium sulfate, concentrating under reduced pressure to obtain a crude product, and finally performing silica gel column chromatography separation by using ethyl acetate and petroleum ether (volume ratio is 1: 10) as an eluent to obtain the (4-fluorobenzene) (quinolin-3-yl) methanone, wherein the reaction equation is as follows:

s2. preparation of the compound of formula (I):

weighing 126mg of (4-fluorobenzene) (quinoline-3-yl) ketone, 100mg of 10H-phenoxazine, 84mg of potassium tert-butoxide and 3mL of N, N-dimethylformamide, adding into a sealed tube, wherein the molar ratio of the (4-fluorobenzene) (quinoline-3-yl) ketone to the 10H-phenoxazine is 1: 1.1, stirring and pumping out the air in the device, heating, stirring and refluxing at 75 ℃ under the protection of nitrogen for 15 hours, and thus completing the nucleophilic substitution reaction; cooling and collecting to obtain brownish black turbid liquid, extracting the turbid liquid with water and ethyl acetate for three times, combining organic phases obtained by three times, drying with anhydrous magnesium sulfate, distilling the organic phase under reduced pressure, concentrating to obtain a crude product, and finally performing silica gel column chromatography separation by using ethyl acetate and petroleum ether (volume ratio is 1: 10) as an eluent to obtain an orange solid.

Second, experimental results

The reaction gave 85mg of an orange-yellow solid in 41% yield, and the reaction equation for the above procedure is as follows:

EXAMPLE 2 preparation of quinolinone derivatives containing an arylamine group-Compounds of formula (II)

First, experiment method

The experimental procedure of example 1 was followed, except that 10H-phenoxazine was replaced with 10H-phenothiazine and the amount of 10H-phenothiazine was adjusted so that the molar ratio of (4-fluorobenzo) (quinolin-3-yl) methanone to 10H-phenoxazine was 1: 1.2; argon was used instead of nitrogen and the reaction was heated at 70 ℃ with stirring under reflux for 15 h.

Second, experimental results

The reaction gave 75mg of a pale yellow solid in 35% yield, and the reaction equation for the above procedure is as follows:

EXAMPLE 3 preparation of quinolinone derivatives containing an arylamine group-Compounds of formula (III)

First, experiment method

The same experimental procedure as in example 1, except that 9, 10-dihydro-9, 9-dimethylacridine was used in place of 10H-phenoxazine, and the amount of 9, 10-dihydro-9, 9-dimethylacridine was adjusted so that the molar ratio of (4-fluorobenzo) (quinolin-3-yl) methanone to 9, 10-dihydro-9, 9-dimethylacridine was 1: 1; helium gas protection is used for replacing nitrogen gas protection, and the reaction is heated, stirred and refluxed for 12 hours at the temperature of 75 ℃.

Second, experimental results

The reaction gave 66mg of a pale yellow solid in a yield of 30%, and the reaction equation for the above process is as follows:

example 4 structural characterization and Performance testing

(1) Nuclear magnetic resonance:

nuclear magnetic resonance scanning was performed on the products obtained in examples 1 to 3 using a Brooks 400MHz superconducting nuclear magnetic resonance spectrometer to obtain the products of FIGS. 1 to 3¹HMNR plot and assignment of hydrogen signals therein:

as can be seen from fig. 1, δ (ppm) of the compound obtained in example 1 is: δ 9.388.66, 8.24,8.11,7.99,7.89,7.71,7.56,6.69, 6.04.

As can be seen from fig. 2, δ (ppm) of the compound obtained in example 2 is: δ 9.29,9.28,8.50,8.50,8.18,8.16,7.89,7.87,7.83,7.81,7.79,7.61,7.60,7.58,7.39,7.38,7.36,7.26,7.25,7.23,7.23,7.22,7.21,7.20,7.18,7.15,7.15,7.13,7.13, 7.12.

As can be seen from fig. 3, δ (ppm) of the compound obtained in example 3 is: δ 9.41,9.40,8.69,8.69,8.25,8.23,8.14,8.12,8.01,7.99,7.91,7.90,7.88,7.71,7.69,7.67,7.56,7.54,7.50,7.49,7.48,7.26,7.04,7.02,6.99,6.97,6.41,6.41,6.39, 1.70.

(2) Mass spectrum:

the product obtained in example 1 to 3 was dissolved in acetonitrile to prepare a solution having a concentration of 1 mg/mL^-1And (4) testing the solution by using a liquid chromatography-mass spectrometer LCMS-2020 to obtain the graph of 4-6. As can be seen from FIGS. 4 to 6, the relative molecular masses of the products obtained in examples 1 to 3 were 414.11, 430.08 and 440.16, respectively.

Therefore, based on the results of nuclear magnetic resonance and mass spectrometry, it can be determined that the structural formulas of the compounds prepared in examples 1 to 3 are respectively shown as the following formulas (i), (ii), and (iii):

(3) ultraviolet visible absorption spectrum:

the product obtained in example 1 was dissolved in THF to prepare 1X 10^-3mol·L^-1The mother liquor of (1) is diluted to 1 × 10 by adopting Shimadzu ultraviolet visible spectrophotometer UV-2700 for testing^-5mol·L^-1To give a compound of formula (I) at 1X 10 as shown in FIG. 7^-5Ultraviolet-visible absorption spectrum diagram in mol/L tetrahydrofuran.

As can be seen from FIG. 7, the compound of formula (I) has a main absorption peak position of 407 nm. Indicating that 407nm uv light was required to excite the compound.

(4) Emission spectrum:

the concentration of the product obtained in example 1 was maintained at 1X 10^-5mol·L^-1Adjusting the ratio of tetrahydrofuran to water in the test solution; the product obtained in example 1 was first dissolved in tetrahydrofuran to give a concentration of 1X 10^-3mol·L^-1Maintaining the total volume of the test solution at 3 mL. (for example, when the water content is 90%, the amounts of the respective components are adjusted so that the mother liquor of water: tetrahydrofuran is 30. mu.L: 2700. mu.L: 270. mu.L.)

The fluorescence spectrum of the product obtained in example 1 in a tetrahydrofuran-water solution containing 1% to 99% of water was measured with an FLS980 fluorometer, and fig. 8 was obtained. As can be seen from FIG. 8, the emission wavelength of the compound of formula (I) is 611 nm; when the water content is lower than 95%, the fluorescence emission wavelength of the compound of the formula (I) in the solution is obviously red-shifted; when the water content exceeds 90%, the corresponding fluorescence intensity is greatly enhanced, which shows that the product obtained in example 1 has obvious aggregation-induced luminescence phenomenon.

(5) Thermogravimetric analysis:

the high temperature synchronous thermal analyzer STA409PC was set with the conditions: the temperature rise rate was 10K/min, the temperature range was normal temperature to 600 ℃ and the gas protection was nitrogen, and thermogravimetric analysis was performed on the product obtained in example 1 to obtain FIG. 9.

As can be seen from fig. 9, the 5% weight loss temperature of the product obtained in example 1 is 336.89 ℃, which indicates that the product obtained in example 1 has good thermal stability and potential for being prepared into a luminescent material with good performance.

In conclusion, the quinolinone derivative containing arylamine groups can generate obvious aggregation-induced emission effect, so that the quinolinone derivative has high luminous intensity, has good thermal stability, can be suitable for preparing luminescent materials, and provides a new choice for the technical field of luminescent materials.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.