Preparation and application of a tetraphenyl ethene-chalcone derivative

Abstract

The application discloses a kind of tetraphenyl ethylene-chalcone derivative preparation and its application preparation and its application.The structure is as follows: the method includes: 4-(1,2,2-triphenyl ethenyl) acetophenone, aldehyde derivative, sodium hydroxide (provides alkaline condition, pH=8.3~8.5), is placed in anhydrous ethanol, under the condition that heating temperature is 80 DEG C, reflux reaction 12h, after reaction is ended, the functional organic material is separated and purified.The functional organic material synthesized according to the above method has larger conjugated system, and has significant pressure-induced color change characteristics.The functional organic material disclosed in the application has low preparation cost, simple operation, simple method, and the material shows significant pressure-induced color change characteristics, can be applied to pressure-induced color change, luminescent material, printing and dyeing, color printing and anti-counterfeiting technical field.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis, specifically relating to a method for preparing a tetraphenylethylene-chalcone derivative. Background Technology

[0002] Chalcone derivatives are important reactive intermediates in organic synthesis. They are natural compounds found in medicinal plants such as licorice and safflower, serving as precursors for flavonoid synthesis in plants and representing natural, non-toxic drugs. Chalcones and their derivatives contain numerous reactive centers and have wide applications in many important chemical reactions. Chalcones and their derivatives also possess a wide range of pharmacological effects, exhibiting antiviral, antibacterial, anti-inflammatory, antioxidant, and anti-fibrotic properties.

[0003] Tetraphenylene (TPE) is a typical AIE organic fluorescent dye. Its structure contains a benzene ring that can rotate freely around the carbon-carbon double bond. In the aggregated state, this prevents π-π stacking and restricts intramolecular rotation and vibration, thus giving it good solid-state luminescence properties. By modifying the structure of TPE, its fluorescence properties can also be changed, such as giving it good fluorescence emission in solvents and a redshift.

[0004] Chalcones, due to their structure enabling intramolecular charge transfer (ICT) processes, have been widely used in fluorescent materials due to their push-pull structure composed of a donor-acceptor (D-π-A) framework. By introducing chalcone structures onto TPE units, DAD-framework-based TPE functional organic materials have been constructed. These D-π-A framework derivatives consist of three parts: a TPE group, various substituted aromatic rings, and a chalcone structure. Based on the ICT process and different π-π stacking modes of these compounds, these functional organic materials exhibit unique fluorescent properties.

[0005] This invention combines tetraphenylethylene and chalcone, modifies the chalcone skeleton, and proposes a new method to synthesize tetraphenylethylene-chalcone derivatives. This method utilizes the highly conjugated reactant 4-(1,2,2-triphenylvinyl)acetophenone with various aromatic aldehyde derivatives, sodium hydroxide (providing alkaline conditions, pH = 8.3–8.5), and anhydrous ethanol as the solvent (for optimal results). The conditions are mild. Compared to previous methods for synthesizing chalcone derivatives, this method offers advantages such as readily available and inexpensive raw materials and simple operation. Summary of the Invention

[0006] The purpose of this invention is to provide a method for preparing and applying a tetraphenylethylene-chalcone derivative, which exhibits significant pressure-induced color-changing properties.

[0007] The objective of this invention is achieved through the following technical solution:

[0008] A pressure-sensitive color-changing organic material based on tetraphenylethylene-chalcone derivatives, the molecular structure of which is as follows:

[0009]

[0010] The preparation method of the pressure-induced color-changing functional organic material includes the following steps: 4-(1,2,2-triphenylvinyl)acetophenone, an aromatic aldehyde derivative, and sodium hydroxide (providing alkaline conditions, pH = 8.3–8.5) are placed in anhydrous ethanol and subjected to a reflux reaction. After the reaction is completed, the functional organic material is obtained by separation and purification.

[0011] The specific synthesis process is as follows:

[0012]

[0013] The structures of the aromatic aldehyde derivatives include any one of the following formulas:

[0014] The molar ratio of the 4-(1,2,2-triphenylvinyl)acetophenone and the aromatic aldehyde derivative is 1:1-1.1.

[0015] The reflux reaction temperature is 70-90℃ for 10-12 hours.

[0016] The reaction solvent is anhydrous ethanol. This application also attempted anhydrous methanol, but the reaction proceeded very poorly.

[0017] 4-(1,2,2-triphenylvinyl)acetophenone is practically insoluble in methanol. TLC monitoring showed no formation of the target product, and no target product was generated when dichloromethane was used either.

[0018] The innovation of this paper lies in using 4-(1,2,2-triphenylvinyl)acetophenone and various aromatic aldehydes with strong conjugation as substrates, sodium hydroxide (providing alkaline conditions, pH=8.3-8.5) and anhydrous ethanol as solvents. The raw materials are readily available, the reaction conditions are mild, the operation is simple, and the purification is easy.

[0019] The functional organic materials synthesized by this invention have a large conjugated system, and all material molecules have significant pressure-induced color change. The preparation method described in this invention is simple, easy to operate, and low in cost, and can be applied to the fields of luminescent materials, pressure-induced color change material printing and dyeing, color printing (fluorescent ink), and anti-counterfeiting. Attached Figure Description

[0020] Figure 1 This is the hydrogen NMR spectrum of B-1.

[0021] Figure 2This is the carbon NMR spectrum of B-1.

[0022] Figure 3 This is the hydrogen NMR spectrum of B-2.

[0023] Figure 4 This is the carbon NMR spectrum of B-2.

[0024] Figure 5 This is the hydrogen NMR spectrum of B-3.

[0025] Figure 6 This is the carbon NMR spectrum of B-3.

[0026] Figure 7 The images show the fluorescence spectra of B-1 before and after grinding.

[0027] Figure 8 The color change of B-1 before and after grinding.

[0028] Figure 9 The image shows the powder XRD patterns of B-1 before and after grinding.

[0029] Figure 10 Applications of functional organic material molecule B-1.

[0030] Figure 11 The images show the fluorescence spectra of B-3 before and after grinding.

[0031] Figure 12 The color change of B-3 before and after grinding.

[0032] Figure 13 The image shows the powder XRD patterns of B-3 before and after grinding.

[0033] Figure 14 Applications of functional organic material molecule B-3. Detailed Implementation

[0034] The present invention will be further illustrated below with reference to the embodiments, but the scope of protection of the present invention is not limited to the scope described in the embodiments.

[0035] Example 1: Synthesis of B-1 material molecules

[0036] 4-(1,2,2-triphenylvinyl)acetophenone (149.8 mg, 0.4 mmol), 4-(10H-phenthiazin-10-yl)benzaldehyde (108.5 mg, 0.4 mmol), sodium hydroxide (68.8 mg, 1.72 mmol), and 6 mL of anhydrous ethanol were added sequentially to a 25 mL reaction flask. After reacting at 80 °C for 12 h, the ethanol was evaporated, and the sample was subjected to column chromatography (PE:EA = 25:1) to obtain the yellow-orange material molecule, with a mass of 85.6 mg and a yield of 32.5%.

[0037] The structure is as follows:

[0038]

[0039] Example 2: Synthesis of B-2 material molecules

[0040] 4-(1,2,2-triphenylvinyl)acetophenone (149.8 mg, 0.4 mmol), 4-(9H-carbazole-9-yl)benzaldehyde (121.2 mg, 0.4 mmol), sodium hydroxide (68.8 mg, 1.72 mmol), and 6 mL of anhydrous ethanol were added sequentially to a 25 mL reaction flask. After reacting at 80 °C for 12 h, the ethanol was evaporated, and the sample was subjected to column chromatography (PE:EA = 20:1) to obtain the yellow-green material molecule with a mass of 92.3 mg and a yield of 36.8%.

[0041] The structure is as follows:

[0042]

[0043] Example 3: Synthesis of B-3 material molecules

[0044] 4-(1,2,2-triphenylvinyl)acetophenone (149.8 mg, 0.4 mmol), 4-(9,9-dimethyl-10(9H)-acrididine)benzaldehyde (125.2 mg, 0.4 mmol), sodium hydroxide (68.8 mg, 1.72 mmol), and 6 mL of anhydrous ethanol were added sequentially to a 25 mL reaction flask. After reacting at 80 °C for 12 h, the ethanol was evaporated, and the sample was subjected to column chromatography (PE:EA = 25:1) to obtain the yellow material molecule with a mass of 94.6 mg and a yield of 35.3%.

[0045] The structure is as follows:

[0046]

[0047] Example 4: Synthesis of B-4 material molecules

[0048] 4-(1,2,2-triphenylvinyl)acetophenone (149.8 mg, 0.4 mmol), 4-(10H-phenphenoxazine-10-yl)benzaldehyde (114.8 mg, 0.4 mmol), sodium hydroxide (68.8 mg, 1.72 mmol), and 6 mL of anhydrous ethanol were added sequentially to a 25 mL reaction flask. After reacting at 80 °C for 12 h, the ethanol was evaporated, and the sample was subjected to column chromatography (PE:EA = 25:1) to obtain the yellow-orange material molecule with a mass of 82.3 mg and a yield of 31.4%.

[0049] The structure is as follows:

[0050]

[0051] Example 5: Synthesis of B-5 material molecules

[0052] 4-(1,2,2-triphenylvinyl)acetophenone (149.8 mg, 0.4 mmol), 9-anthracarbaldehyde (82.4 mg, 0.4 mmol), sodium hydroxide (68.8 mg, 1.72 mmol), and 6 mL of anhydrous ethanol were added sequentially to a 25 mL reaction flask. After reacting at 80 °C for 12 h, the ethanol was evaporated, and the resulting product was obtained by column chromatography (PE:EA = 25:1) to yield the orange material molecule with a mass of 118.9 mg and a yield of 52.9%.

[0053]

[0054] Example 6

[0055] Five milligrams of the yellow-orange material molecule B-1 prepared in Example 1 were weighed and placed in a mortar. After grinding with a pestle for 1 minute, irradiation with a 365° UV lamp revealed that the dye molecule changed from yellow-orange to orange. The ground orange dye was then washed with n-hexane with stirring for 2 minutes to obtain yellow-orange molecules. The obtained yellow-orange molecules can be ground to orange again, and the orange dye can also be washed to yellow-orange; this process can be repeated indefinitely.

[0056] Figure 7 and Figure 8 The images show the fluorescence spectra and color changes of the yellow-orange material molecule B-1 before and after grinding. Figure 7 In this context, "pristine" represents the original solid powder (the solid before grinding), "ground" represents the ground solid powder, and "soaked" represents the solid powder washed with n-hexane after grinding; (The rest of the text appears to be a list of terms or keywords related to the powder.) Figure 8 It can be seen that the maximum emission wavelength of the dye molecules redshifts by 34 nm after grinding, and the fluorescence color changes from yellow-orange to orange. After washing the ground solid powder with n-hexane, the yellow-orange color can be restored, indicating that the dye molecules have good pressure-induced color change properties and good reversibility.

[0057] Figure 9 The images show the XRD patterns of B-1 powder before and after grinding. Figure 9 In the image, "pristine" represents the original solid powder and the solid before grinding (top), "ground" represents the ground solid powder (middle), and "soaked" represents the solid powder washed with petroleum ether after grinding (bottom); according to... Figure 9As can be seen, the dye molecules exhibited clear and sharp diffraction peaks before grinding, indicating ordered crystalline properties. However, the solid after grinding showed rather weak diffraction, indicating that the ground sample was amorphous. The forces disrupted or weakened the intermolecular interactions, and this transition from crystalline to amorphous state led to a red shift in the fluorescence color. However, washing with n-hexane significantly improved the crystallinity, resulting in sharp diffraction peaks that matched the original peaks well, and the fluorescence color returned to the yellow-orange color before grinding.

[0058] Figure 10 The specific implementation process for the application of functional organic material molecule B-1 is as follows: Yellow-orange dye molecules are laid flat on it, and then the letter "A" is written on paper. Under a 365nm fluorescent lamp, the "A" will be found to be orange. It can be seen that this dye molecule can be used as a reading and writing device and has potential anti-counterfeiting applications.

[0059] Material molecule B-3 can also be ground using the same method; the specific color change can be observed... Figure 11 . Figure 11 and Figure 12 The images show the fluorescence spectra and color changes of B-3 before and after grinding. Figure 11 In the figure, pristine represents the original solid powder (the solid before grinding), ground represents the solid powder after grinding, and soaked represents the solid powder washed with n-hexane after grinding. As can be seen from the figure, the maximum emission wavelength of B-3 redshifts by 18 nm after grinding, and the fluorescence color changes from yellow-green to yellow. After washing the ground solid powder with n-hexane, it can return to yellow-green, indicating that the dye molecule has good pressure-induced color change properties and good reversibility.

[0060] Figure 13 The images show the powder XRD patterns of B-3 before and after grinding. Figure 13 In the image, "pristine" represents the original solid powder and the solid before grinding (top), "ground" represents the ground solid powder (middle), and "soaked" represents the solid powder washed with petroleum ether after grinding (bottom); according to... Figure 13 As can be seen, the dye molecules exhibited clear and sharp diffraction peaks before grinding, indicating ordered crystalline properties. However, the solid after grinding showed rather weak diffraction, indicating that the ground sample was amorphous. The forces disrupted or weakened the intermolecular interactions, and this transition from crystalline to amorphous state led to a red shift in the fluorescence color. However, washing with n-hexane significantly improved the crystallinity, resulting in sharp diffraction peaks that matched the original peaks well, and the fluorescence color returned to the yellow-green color before grinding.

[0061] Figure 14To enable the application of organic material molecule B-3, the specific implementation process is as follows: Yellow-green dye molecules are laid flat on it, and then the letter "F" is written on paper. Under a 365nm fluorescent lamp, it is found that the "F" is dark yellow, indicating that this dye molecule can be well used as a reading and writing device and has potential anti-counterfeiting applications.

[0062] The embodiments of the present invention have been described in detail above with reference to the examples, but the present invention is not limited to the described embodiments. For those skilled in the art, various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and these variations still fall within the protection scope of the present invention.

Claims

1. A tetraphenylethylene-chalcone derivative, characterized in that, The compound has a structural formula that includes any one of the following: 。 2. The method for preparing the tetraphenylethylene-chalcone derivative according to claim 1, characterized in that, The process includes the following steps: 4-(1,2,2-triphenylvinyl)acetophenone, aromatic aldehyde derivative, and sodium hydroxide (pH=8.3~8.5) are placed in a solvent and heated under reflux. After the reaction is completed, the tetraphenylethylene-chalcone derivative is obtained by separation and purification. The aromatic aldehyde derivatives are selected from 4-(10H-phenthiazin-10-yl)benzaldehyde or 4-(9,9-dimethyl-10(9H)-acridine)benzaldehyde.

3. The method for preparing the tetraphenylethylene-chalcone derivative according to claim 2, characterized in that, The molar ratio of the 4-(1,2,triphenylvinyl)acetophenone and the aromatic aldehyde derivative is 1:1-1.

1.

4. The method for preparing the tetraphenylethylene-chalcone derivative according to claim 2, characterized in that, The reflux reaction temperature is 70-90℃ for 10-12 hours.

5. The method for preparing the tetraphenylethylene-chalcone derivative according to claim 2, characterized in that, The solvent is anhydrous ethanol.

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