CN116478031B - 1, 5-Dihydroxynaphthalene-2, 6-dichalcone derivative and preparation method and application thereof - Google Patents

1, 5-Dihydroxynaphthalene-2, 6-dichalcone derivative and preparation method and application thereof Download PDF

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CN116478031B
CN116478031B CN202310302002.5A CN202310302002A CN116478031B CN 116478031 B CN116478031 B CN 116478031B CN 202310302002 A CN202310302002 A CN 202310302002A CN 116478031 B CN116478031 B CN 116478031B
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dihydroxynaphthalene
derivative
dichalcone
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laser
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CN116478031A (en
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廖良生
王雪东
闫长存
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Suzhou University
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Abstract

The invention relates to a 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative, and a preparation method and application thereof, and belongs to the technical field of chalcone derivatives. The structural formula of the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative isWherein Ar is selected from substituted or unsubstituted aryl; the unsubstituted aryl is selected from benzene, biphenyl, a condensed aromatic ring or an aromatic heterocyclic ring; the substituent group of the substituted aromatic group is selected from alkyl, alkoxy, amino, alkylthio or carbazole. The 1, 5-dihydroxynaphthalene-2, 6-dichalchalcone derivative can establish two pairs of excited intramolecular proton transfer centers, realize excited intramolecular double proton transfer, bring more possibility for the regulation and control of laser performance, and improve the laser performance.

Description

1, 5-Dihydroxynaphthalene-2, 6-dichalcone derivative and preparation method and application thereof
Technical Field
The invention belongs to the technical field of chalcone derivatives, and particularly relates to a 1, 5-dihydroxynaphthalene-2, 6-dichlorlone derivative, and a preparation method and application thereof.
Background
The laser mainly consists of three parts: pump source, resonant cavity and gain medium. Organic materials can be used as ideal gain media (chem. Rev.2016,116, 12823) due to their large stimulated emission cross section, tunable emission wavelength, and good processability. For most organic laser active molecules, however, stimulated emission is based primarily on a quasi-four energy level system consisting of vibrational energy levels. The stokes shift caused by the quasi-four energy level process is small, resulting in severe self-absorption loss and thus high lasing threshold.
2' -Hydroxy chalcone compounds are receiving extensive attention because they can build a true four-level system by excited state intramolecular proton transfer. CN103242180 discloses 2' -hydroxy chalcone derivative crystals and their use in amplifying spontaneous emissions. There have also been recent reports of organic solid lasers based on 1 '-hydroxy-2' -naphthalene chalcone derivatives (J.Am. Chem. Soc.2015,137, 9289). However, there is no document report on derivatization and laser performance of centrosymmetric naphthalene chalcone. The centrally symmetrical naphthalene chalcone derivative has two pairs of excited state intramolecular proton transfer structural units, and can theoretically generate twice excited state intramolecular proton transfer, thereby providing more possibility for regulating and controlling the laser performance, and therefore, the derivatization of the centrally symmetrical 1, 5-dihydroxynaphthalene-2, 6-dichalcanone has important significance for developing high-performance organic laser active materials.
Disclosure of Invention
Therefore, the invention aims to solve the technical problems that the laser threshold of the organic laser active material is high, near infrared laser is difficult to realize and the like in the prior art.
In order to solve the technical problems, the invention provides a1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative, and a preparation method and application thereof.
The first object of the invention is to provide a1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative, the structure of which is shown as the formula (I):
wherein Ar is selected from substituted or unsubstituted aryl; the unsubstituted aryl is selected from benzene, biphenyl, a condensed aromatic ring or an aromatic heterocyclic ring; the substituent group of the substituted aromatic group is selected from alkyl, alkoxy, amino, alkylthio or carbazole.
In one embodiment of the invention, the unsubstituted aryl is selected from benzene, biphenyl, naphthalene, pyridine, furan, pyrrole, thiophene, benzofuran, benzothiophene, indole, or carbazole; the substituent of the substituted aryl group is selected from C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C1-C20 dialkyl amino, diphenylamino or carbazole.
In one embodiment of the invention, the C1-C20 alkyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl or n-hexyl; the C1-C20 alkoxy is selected from methoxy or ethoxy; the C1-C20 alkylthio is selected from methylthio or ethylthio; the C1-C20 dialkyl amino is selected from dimethylamino or diethylamino.
In one embodiment of the invention, the 1, 5-dihydroxynaphthalene-2, 6-dicarboxyl chalcone derivative is selected from the following compounds:
the second object of the present invention is to provide a process for the preparation of said 1, 5-dihydroxynaphthalene-2, 6-dicarboxyl chalcone derivative comprising the steps of,
S1, carrying out substitution reaction and oxidation reaction on a compound with a structure shown in a formula (II) to obtain a compound with a structure shown in a formula (III);
S2, connecting the compound with the structure shown in the formula (III) in the S1 through claisen-Schmidt reaction, and then deprotecting the compound to obtain the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative shown in the structure shown in the formula (I);
Wherein the structures of the general formulae (I) - (III) are as follows:
wherein X is selected from halogen;
r is selected from C1-C20 alkyl;
ar is selected from substituted or unsubstituted aryl; the unsubstituted aryl is selected from benzene, biphenyl, a condensed aromatic ring or an aromatic heterocyclic ring; the substituent group of the substituted aromatic group is selected from alkyl, alkoxy, amino, alkylthio or carbazole.
The third object of the invention is to provide the application of the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative in organic solid laser and luminescence.
A fourth object of the present invention is to provide a polystyrene microsphere comprising the 1, 5-dihydroxynaphthalene-2, 6-dicarboxyl chalcone derivative.
In one embodiment of the invention, the doping concentration of the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative is greater than 0.1wt%.
Further, the doping concentration of the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative is 0.1wt% to 10wt%.
A fifth object of the present invention is to provide an application of the polystyrene microsphere in organic solid laser.
In one embodiment of the invention, the polystyrene microsphere has a laser or luminescence wavelength of 650nm-2500nm.
Further, the laser wavelength of the polystyrene microsphere is 650nm-760nm.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative disclosed by the invention is based on a1, 5-dihydroxynaphthalene-2, 6-dichalcone structure, has the activity of proton transfer in an excited state molecule, and can construct an effective four-level system, so that the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative has excellent laser performance, and the laser wavelength is in a red light to near infrared light region (650 nm-2500 nm).
(2) The 1, 5-dihydroxynaphthalene-2, 6-dichalchalcone derivative can establish two pairs of excited intramolecular proton transfer centers, realize excited intramolecular double proton transfer, bring more possibility for the regulation and control of laser performance, and improve the laser performance.
(3) The 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative can realize effective regulation and control of HOMO and LUMO energy levels by introducing different electron donating and accepting groups, so that the laser wavelength can be regulated and controlled by regulating intramolecular charge transfer.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which:
FIG. 1 is a graph showing absorption and emission spectra of Compound 3 of the present invention.
FIG. 2 is a graph showing absorption and emission spectra of Compound 4 of the present invention.
FIG. 3 is a graph showing absorption and emission spectra of Compound 5 of the present invention.
FIG. 4 is a scanning electron micrograph of polystyrene microspheres of the present invention.
FIG. 5 is a laser spectrum of a polystyrene microsphere doped with the compound 3 according to the present invention.
FIG. 6 is a laser spectrum of a polystyrene microsphere doped with compound 4 according to the present invention.
FIG. 7 is a laser spectrum of a polystyrene microsphere doped with the compound 5 of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Example 1
A1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative and a preparation method thereof specifically comprise the following steps:
To a 500mL reaction flask was added intermediate 1 (10 g,62 mmol), acetic acid (300 mL), and then liquid bromine (7 mL,137 mmol) was added dropwise, and after the addition was completed, the mixture was heated to 80℃and stirred for 2 hours. After the reaction solution was filtered, the obtained solid was recrystallized from acetic acid to obtain colorless needle-like crystals (intermediate 2, 14.5 g), yield: 73%.
A500 mL reaction flask was charged with intermediate 2 (10 g,31 mmol), anhydrous potassium carbonate (26 g,189 mmol) and acetone (300 mL). Methyl iodide (4.4 g,31 mmol) was then added and the reaction was heated at reflux for 12h. The reaction solution was filtered, and the solid was washed with dichloromethane (3X 100 mL), and the filtrates were combined, desolventized under reduced pressure and diluted with dichloromethane (300 mL). The resulting solution was washed with water (3×10 mL), saturated sodium bicarbonate solution (20 mL), dried over anhydrous sodium sulfate, pressure desolventized, washed with n-hexane, and dried in vacuo to give a pale yellow solid (intermediate 3,9.5 g), yield: 87%.
To a 250mL reaction flask was added intermediate 3 (3.5 g,10 mmol), tetrahydrofuran (100 mL), and n-butyllithium solution (2.5M, 10mL,25 mmol) was slowly added dropwise at low temperature, followed by stirring at low temperature for 2 minutes, and then acetaldehyde in tetrahydrofuran (5.0M, 10mL,50 mmol) was added at once, and the mixture was naturally warmed to room temperature and stirred for 1 hour. The reaction mixture was quenched by careful addition of water (50 mL), then slowly diluted hydrochloric acid (pH paper monitor) and extracted with dichloromethane (3X 100 mL). The organic phases were combined, washed with water (3X 100 mL), washed with saturated brine (200 mL), dried over anhydrous sodium sulfate, filtered and desolventized under reduced pressure to give the crude product (intermediate 4) which was used directly in the next step.
A500 mL reaction flask was charged with the crude intermediate 4, methylene chloride (200 mL), and then with dess-Martin oxidant (11 g,25 mmol), and the reaction was stirred at room temperature for 10h. The reaction was quenched by the addition of saturated sodium bicarbonate solution (100 mL) and sodium thiosulfate solution (100 mL) and continued to stir at room temperature for 30min. The solution was separated and the aqueous phase was extracted with dichloromethane (3X 50 mL). The organic phases were combined, washed with water (3×100 mL), washed with saturated brine (100 mL), dried over anhydrous sodium sulfate, and subjected to atmospheric column chromatography (oil ether: ethyl acetate=20:1 elution) to give a pale yellow solid (intermediate 5,2.1 g), yield: 76%.
To a 250mL reaction flask was added intermediate 5 (1.4 g,5 mmol), intermediate 6 (15 g,10 mmol), sodium hydroxide (2 g,50 mmol) and ethanol (100 mL), and the mixture was stirred at room temperature for 10h to give a orange-red precipitate, the reaction mixture was diluted with water, filtered, the orange-red solid was washed with clear water, and the crude intermediate 7 was dried in vacuo. The crude product was further purified by normal pressure column chromatography (dichloromethane: ethyl acetate=10:1 elution) to give an orange-red solid (intermediate 7,2.2 g). Yield rate ：81％;1H NMR(400MHz,CDCl3)δ8.07(d,J＝8.4Hz,2H),7.73(d,J＝8.4Hz,2H),7.68(d,J＝15.6Hz,2H),7.54(d,J＝8.8Hz,4H),7.34(d,J＝15.6Hz,2H),6.69(d,J＝8.8Hz,4H),3.97(s,6H),3.05(s,12H).
To a 100mL reaction flask was added intermediate 7 (1.1 g,2.0 mmol), methylene chloride (20 mL), and then a methylene chloride solution of boron tribromide (1.0M, 5.0mL,5.0 mmol) was slowly added dropwise with stirring at room temperature, and after the addition was completed, the reaction was continued with stirring at room temperature for 1h. The reaction was quenched by the addition of saturated sodium bicarbonate solution (10 mL). The solution was separated and the aqueous phase was extracted with dichloromethane (3X 5 mL). The combined organic phases were washed with water (3×10 mL), saturated brine (20 mL), dried over anhydrous sodium sulfate, and subjected to atmospheric column chromatography (petroleum ether: dichloromethane=1:1 elution) to give a dark red solid (compound 1,0.57 g), yield ：56％.1H NMR(400MHz,CDCl3)δ14.94(s,2H),8.03(d,J＝15.2Hz,2H),7.96(d,J＝15.2Hz,2H),7.65(d,J＝8.8Hz,4H),7.60(d,J＝14.8Hz,2H),7.31(d,J＝14.8Hz,2H),6.75(d,J＝8.8Hz,4H),3.11(s,12H).
Example 2
A1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative and a preparation method thereof specifically comprise the following steps:
Substantially the same as in example 1, except that intermediate 6 was 9-aldehyde julolidine, was obtained as a dark solid (compound 4,0.75 g), yield ：61％.1H NMR(400MHz,CDCl3)δ15.09(s,2H),7.99–7.90(m,6H),7.51(d,J＝15.2Hz,2H),7.21(s,4H),3.31(t,J＝5.6Hz,8H),2.82(t,J＝6.4Hz,8H),2.07–1.96(m,8H).
Example 3
A1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative and a preparation method thereof specifically comprise the following steps:
substantially the same as in example 1, except that intermediate 6 was 4-diphenylaminobenzaldehyde, was obtained in the form of a dark red solid (compound 5,1.19 g), yield ：79％.1H NMR(400MHz,CDCl3)δ14.72(s,2H),7.97(d,J＝15.2Hz,2H),7.94(d,J＝8.4Hz,2H),7.91(d,J＝8.4Hz,2H),7.62(d,J＝15.2Hz,2H),7.56(d,J＝8.8Hz,4H),7.36–7.29(m,8H),7.20–7.11(m,12H),7.05(d,J＝8.8Hz,4H).
Test example 1
Absorption and emission spectroscopy test of 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative (Compound 3-5):
(1) Sample preparation: a methylene chloride solution of the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative was prepared at a concentration of about 1X 10 -5 mol/L and 5mL.
(2) Ultraviolet-visible absorption spectroscopy test: the ultraviolet-visible absorption spectrum of the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative solution was tested using an ultraviolet-visible spectrophotometer.
(3) Fluorescence spectrum test: the fluorescence emission spectrum of the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative solution was measured by a fluorescence spectrometer, and the excitation light was 500nm xenon lamp light source, as shown in FIGS. 1-3.
As can be seen from fig. 1, the methylene chloride solution of compound 3 has a maximum absorption wavelength of 500nm and a maximum emission wavelength of 655nm.
As can be seen from fig. 2, the methylene chloride solution of compound 4 has a maximum absorption wavelength of 535nm and a maximum emission wavelength of 680nm.
As can be seen from fig. 3, the maximum absorption wavelength of the dichloromethane solution of the compound 5 was 500nm, and the maximum emission wavelength was 670nm.
Test example 2
Preparation of 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative doped (Compound 3-5) polystyrene microsphere and test of laser Performance:
(1) Preparing mother solution: 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative (1.0 mg), polystyrene powder (M W:260000, 100 mg) were accurately weighed, a 2mL dichloromethane solution was prepared, and the solution was completely dissolved by ultrasonic vibration, and the obtained solution was used as a mother liquor for standby.
(2) Preparation of CTAB solution: CTAB (14.6 mg) was accurately weighed, dissolved in 20mL of deionized water to prepare a 2mM aqueous solution, and sonicated until all was dissolved for use.
(3) Preparation of polystyrene microspheres: CTAB solution (2 mL) was added to the clean sample bottle, mother liquor (0.2 mL) was added under vigorous stirring, stirring was continued for 20min, stirring was stopped, and the mixture was allowed to stand for 12h. Filtering, washing the solid with deionized water, and obtaining the solid, namely the polystyrene microsphere. The doping concentration of the compound in the polystyrene was 1.0wt%.
(4) Characterization of polystyrene microspheres: dispersing the obtained polystyrene microsphere into absolute ethyl alcohol, taking a drop of dispersion liquid to be dripped on a clean glass sheet, a quartz sheet or a silicon wafer, and obtaining a sample for testing laser performance after the solvent is completely volatilized.
A Scanning Electron Microscope (SEM) image of the compound 3-doped polystyrene microsphere is shown in fig. 4, from which it can be seen that the 1, 5-dihydroxynaphthalene-2, 6-dicarboxyl chalcone derivative-doped polystyrene microsphere has a regular morphology and a smooth surface, and the polystyrene microsphere with a smooth surface can realize light reflection, thus being used as a resonant cavity.
(5) Laser performance test: the laser spectrum of the polystyrene microsphere doped with the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative can be obtained by utilizing a micro-region spectrum system under the excitation of 532nm pulse laser (pulse width: 10ns, frequency: 10 Hz), and is shown in figures 5-7.
As can be seen from fig. 5, the compound 3-doped polystyrene microsphere can achieve laser emission with a center wavelength of 720nm and a threshold of 26.6 μj/cm 2.
As can be seen from fig. 6, the compound 4-doped polystyrene microsphere can achieve laser emission with a center wavelength of 720nm, and a threshold of 16.7 μj/cm 2.
As can be seen from FIG. 7, the compound 5-doped polystyrene microsphere can realize laser emission with a center wavelength of 730nm and a threshold of 18.4 mu J/cm 2.
From the test results, the invention can effectively realize the laser emission with low threshold value, and can realize the laser from red light to near infrared.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.

Claims (7)

1.1, 5-Dihydroxynaphthalene-2, 6-dichalcone derivative is characterized in that the structure is shown as a formula (I):
，
wherein Ar is selected from Or (b)。
2. A process for the preparation of a 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative according to claim 1, comprising the steps of,
S1, carrying out substitution reaction and oxidation reaction on a compound with a structure shown in a formula (II) to obtain a compound with a structure shown in a formula (III);
S2, connecting the compound with the structure shown in the formula (III) in the S1 through claisen-Schmidt reaction, and then deprotecting the compound to obtain the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative shown in the structure shown in the formula (I);
wherein the structures of the general formulae (I) - (III) are as follows:
，，，
wherein X is selected from halogen;
r is selected from C1-C20 alkyl;
Ar is selected from Or (b)。
3. Use of the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative according to claim 1 in organic solid state lasers.
4. A polystyrene microsphere comprising the 1, 5-dihydroxynaphthalene-2, 6-dicarboxyl chalcone derivative of claim 1.
5. The polystyrene microsphere according to claim 4, wherein the doping concentration of the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative is greater than 0.1 wt%.
6. Use of the polystyrene microsphere of claim 4 or 5 in an organic solid laser.
7. The use according to claim 6, wherein the polystyrene microsphere has a laser wavelength of 650 nm-2500 nm.
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CN115466187A (en) * 2022-09-15 2022-12-13 苏州大学 1 '-hydroxy-2' -anthracene chalcone derivative and preparation method and application thereof

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