Benzothiazole-tetraphenyl ethylene derivative as well as preparation method and anti-counterfeiting application thereof
By preparing benzothiazole-tetrastyrene derivatives, the problem of insufficient chromic properties of existing fluorescent anti-counterfeiting materials is solved, and high-contrast force-induced fluorescent discoloration is achieved, and it is used in fields such as anti-counterfeiting, fluorescent inks and information security.
Patent Information
- Application Number
- CN202510722158.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-30
- Publication Date
- 2025-09-02
AI Technical Summary
The existing fluorescent anti-counterfeiting materials have problems such as insufficient aggregation-induced luminescence properties in terms of force-discoloration properties, small force-discoloration displacement, high synthesis cost and complex operation.
Compound 1-1 and Compound 1-2 were prepared by using benzothiazole-tetrastyrene derivatives as fluorescent material, and high contrast mechanical force fluorescence discoloration was achieved by reacting 4-(1,2,2-triphenylvinyl)acetophenone with anthranothiophenol and a catalyst, and then reacting with malonitrile and base.
The prepared materials have high contrast force fluorescence discoloration effect, high force response sensitivity and low cost. They are suitable for the fields of anti-counterfeiting, fluorescent inks, pressure sensor materials and information security, and have expanded the anti-counterfeiting applications of force color discoloration materials.
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Figure CN120574191A_ABST
Abstract
Description
Technical Field
[0001] The invention is applicable to fields such as printing and dyeing, inks, and cosmetics. The synthesis method can also be used in the synthesis of fine organic chemical fields such as luminescent materials and trace detection technology. Specifically, it relates to benzothiazole-tetraphenylethylene derivatives, their preparation methods, and anti-counterfeiting applications. Background Art
[0002] In recent years, as consumer awareness of product safety and brand protection has grown, anti-counterfeiting technology has gained increasing attention in the packaging industry. The development and application of multi-layered anti-counterfeiting technologies not only effectively prevents the circulation of counterfeit and substandard products but also helps enhance brand competitiveness. Fluorescent anti-counterfeiting marking technology utilizes the fluorescence emission properties of fluorescent materials under ultraviolet light. Compared to conventional anti-counterfeiting technologies such as watermarks, lasers, and color-shifting inks, fluorescent anti-counterfeiting markings are transparent under visible light, do not affect the original appearance of the item, and provide excellent privacy. Under ultraviolet light, they exhibit a characteristic fluorescence, enabling anti-counterfeiting identification. Mechanochromic fluorescent materials can also provide a secondary layer of security: pressing or rubbing the fluorescent material coating causes the fluorescent color to change. Materials with a significant mechanochromic fluorescence color change are considered excellent candidates for multi-layered anti-counterfeiting materials. The reported structure (Chin. J. Org. Chem. 2023, 43, 3876-3887) does not exhibit aggregation-induced emission (AIE) and exhibits a small mechanochromic shift (<30 nm). Other acrylonitrile-based bridging groups are aromatic rings, which are inherently nonfluorescent. Alternatively, they may be connected to a fluorophore on one side and an aromatic ring on the other. Furthermore, their emission wavelength is relatively short, and their mechanochromic shift is relatively small (Chemical Engineering Journal, 2025, 515, 163597). This invention utilizes carbonyl groups and malononitrile to bridge a highly twisted tetraphenylethylene and planar benzothiazole fluorescent backbone. The connecting structural fragments are all classical fluorescent backbones. The twisted tetraphenylethylene and planar benzothiazole effectively balance the molecular mechanochromic properties, including the AIE effect, resulting in significant mechanochromism (i.e., large mechanochromic shift). Therefore, anti-counterfeiting fluorescent dyes must be easy to print and dye, have high fluorescence intensity, and exhibit high mechanochromic contrast. Furthermore, low synthesis cost, simple and efficient preparation methods, and ease of use are also of general concern.
[0003] This paper invented a new method to synthesize benzothiazole-tetraphenylethylene derivatives that have not been reported so far. The method has obvious advantages: the raw materials are easily available, the price is low, and the operation is simple. Summary of the Invention
[0004] The purpose of the present invention is to provide a high-contrast mechanical force-induced fluorescent color-changing material and its preparation method and application. The preparation method is simple, easy to operate, and low-cost. The material has high force response sensitivity and can produce color response when the material undergoes obvious force changes. It is used in fluorescent inks, pressure sensor materials, information security, anti-counterfeiting and other fields.
[0005] The present invention discloses a mechanochromic fluorescent material. The molecular structure of the mechanochromic fluorescent material is shown in Formula I:
[0006] Formula I Wherein, the R group is either oxygen or malononitrile.
[0007] Preferably, when the R group is an oxygen atom, the mechanical force-induced fluorescent color-changing material is compound 1-1, and its molecular structure is shown in Formula II:
[0008] Formula II Compound 1-1 undergoes a mechanical force-induced red-shift in fluorescence.
[0009] Preferably, when the R group is malononitrile, the mechanical force-induced fluorescent color-changing material is compound 1-2, and its molecular structure is shown in Formula III:
[0010] Formula III Compound 1-2 undergoes a mechanical force-induced red-shift in fluorescence.
[0011] The present invention also provides a method for preparing the above-mentioned mechanochromic material, comprising the following steps: Step (1), dissolving 4-(1,2,2-triphenylvinyl)acetophenone, o-aminothiophenol and a catalyst in a solvent, and heating the mixture to react to obtain compound 1-1; Step (2), reacting the compound 1-1 prepared in step (1) with malononitrile in the presence of a base and a solvent, heating the reaction, and separating and purifying to obtain compound 1-2.
[0012] Preferably, the catalyst in step (1) is I2, and the base in step (2) is pyridine.
[0013] Preferably, the solvent in step (1) is dimethyl sulfoxide, and the solvent in step (2) is ethanol.
[0014] The heating reaction temperature in step (1) is 110-120° C., and the reaction time is 3-6 hours; the heating reaction temperature in step (2) is 60-80° C., and the reaction time is 3-4 days.
[0015] Preferably, the heating reaction temperature in step (1) is 110° C., and the reaction time is 5.5 h; the heating reaction temperature in step (2) is 80° C., and the reaction time is 4 days.
[0016] In the step (1), the molar ratio of 4-(1,2,2-triphenylvinyl)acetophenone, o-aminothiophenol and the catalyst is 1:2-5:0.1-0.6; in the step (2), the molar ratio of compound 1-1, malononitrile and the base is 1:5-10:20-40.
[0017] Preferably, in step (1), the molar ratio of 4-(1,2,2-triphenylvinyl)acetophenone, o-aminothiophenol and the catalyst is 1:3.7:0.46.
[0018] In step (2), the molar ratio of compound 1-1, malononitrile and base is 1:7:36.
[0019] On the other hand, the present invention also provides a mechanochromic material, wherein the mechanochromic material is or .
[0020] On the other hand, the present invention also provides a mechanical force-induced fluorescent color-changing material with reversible luminescent color change, the material is or .
[0021] The present invention also provides a solid-state luminescent material, which is or .
[0022] The mechanical force-induced fluorescence color-changing material is compound 1-1, which transforms between crystal states under the action of force, causes the fluorescence to red-shift and change color, and the luminescent color can change reversibly.
[0023] The mechanical force-induced fluorescence color-changing material is a compound 1-2 that transforms between a crystalline form and an amorphous form, and the mechanical force-induced fluorescence color-changing red shifts, and the luminescent color can be reversibly changed.
[0024] The mechanical force-induced fluorescence color-changing sensor material provided by the present invention is used in the fields of anti-counterfeiting, fluorescent ink, pressure sensor material, and information security. At the same time, the synthesis method can be used for the synthesis of luminescent materials and fine organic chemical fields such as printing and dyeing technology.
[0025] Therefore, the present invention uses the above-mentioned mechanical force-induced fluorescent color-changing material and its preparation method and anti-counterfeiting application, which has the following beneficial effects: 1. The preparation method of the mechanochromic sensor material of the present invention is simple, easy to operate, and low-cost. It can be applied to the fields of anti-counterfeiting, dyes, and sensors. At the same time, the synthesis method can be used for the synthesis of luminescent materials and fine organic chemical fields such as printing and dyeing technology. 2. The present invention selects tetraphenylethylene and benzothiazole as molecular structure fragments, which are more effective in preparing mechanochromic fluorescent materials. At the same time, compared with the planar structure fragments and other structure fragments added to the fluorescent materials in the past that do not have the aggregation-induced emission characteristics, the present invention adopts tetraphenylethylene structure fragments and aggregation-induced emission to provide a guarantee for the solid-state luminescence of the target material. In addition, the mechanochromic fluorescent material compound 1-2 provided by the present invention exhibits high contrast (mechanochromic displacement > 70 nm), which greatly expands the anti-counterfeiting field of mechanochromic materials. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Figure 1 This is a flow chart for preparing a mechanical force-induced fluorescent color-changing material of the present invention.
[0027] Figure 2 This is the hydrogen spectrum of compound 1-1 prepared in Example 1 of the present invention.
[0028] Figure 3 This is the carbon spectrum of compound 1-1 prepared in Example 1 of the present invention.
[0029] Figure 4 This is a high-resolution mass spectrum of compound 1-1 prepared in Example 1 of the present invention.
[0030] Figure 5 It is the hydrogen spectrum of compound 1-2 prepared in Example 2 of the present invention.
[0031] Figure 6 This is the carbon spectrum of compound 1-2 prepared in Example 2 of the present invention.
[0032] Figure 7 This is a high-resolution mass spectrum of compound 1-2 prepared in Example 2 of the present invention.
[0033] Figure 8 It is a single crystal structure diagram of the target compound crystal prepared from compound 1-1 of the present invention.
[0034] Figure 9 It is a single crystal structure diagram of the target compound crystal prepared from compound 1-2 of the present invention.
[0035] Figure 10 1-1 is the AIE property diagram of compound 1-1 of the present invention, wherein is the maximum emission peak intensity diagram.
[0036] Figure 11: is the AIE property diagram of compound 1-2 of the present invention, wherein is the maximum emission peak intensity diagram.
[0037] Figure 12 This is the mechanochromic spectrum of compound 1-1 of the present invention, wherein the inserted figure is the fluorescence color photograph at 365nm before and after grinding and fumigation.
[0038] Figure 13 This is the mechanochromic spectrum of compound 1-2 of the present invention, wherein the inserted figure is the fluorescence color photograph at 365nm before and after grinding and fumigation.
[0039] Figure 14 These are the powder X-ray diffraction experimental pictures of compound 1-1 of the present invention before and after grinding.
[0040] Figure 15 These are the X-ray diffraction experimental diagrams of the powder of compound 1-2 of the present invention before and after grinding and fumigation sample.
[0041] Figure 16 For anti-counterfeiting applications of 1-2 fluorescent dye molecules. DETAILED DESCRIPTION
[0042] The present invention is further described below with reference to the following examples. However, the scope of protection claimed in the present invention is not limited to the scope described in the examples.
[0043] Example 1: Synthesis of 1-1 molecule In a 50 mL reaction flask, 1.0 g, 2.7 mmol of 4-(1,2,2-triphenylvinyl)acetophenone, 1.25 g, 10 mmol of o-aminothiophenol, 325 mg, 1.25 mmol of iodine, and 20 mL of dimethyl sulfoxide were added sequentially. The mixture was heated at 110°C for 5.5 h, extracted with ethyl acetate, filtered, dried, concentrated, and purified by column chromatography (petroleum ether: dichloromethane = 5:1) to obtain compound 1-1 in a 62% yield. Its hydrogen spectrum is shown in FIG. Figure 2 As shown, the carbon spectrum is as Figure 3 As shown in the high-resolution mass spectrum Figure 4 As shown, 1 H NMR (400 MHz, DMSO) δ 8.26 (dd, J = 8.8, 4.0 Hz, 4H), 7.62-7.68(m, 2H), 7.23 (d, J = 8.4 Hz, 2H), 7.13-7.19 (m, 9H), 7.09-6.97 (m, 2H). 13CNMR (100 MHz, DMSO) δ 184.5, 167.3, 153.7, 149.9, 143.2, 143.1, 143.0, 142.9,140.1, 136.7, 132.8, 131.4, 131.2, 131., 128.6, 128.5, 128.3, 127.9, 127.5,127.4, 125.8, 123.3. HRMS(ESI): m / z C 24 H 24 NOS [M+H] + :494.1579; Found: 494.1578. Example 2: Synthesis of 1-2 molecules This embodiment provides a mechanochromic fluorescent material, the preparation method of which is as follows: In a 25 mL reaction flask, 250 mg, 0.5 mmol of compound 1-1 prepared in Example 1, 231 mg, 3.5 mmol of malononitrile, 1.5 mL of pyridine (added in batches), and 3 mL of ethanol were added in sequence. The mixture was heated to 80°C and reacted for 4 days. A precipitate was precipitated and washed with ethanol and then n-hexane to obtain the molecular compound 1-2 with a yield of 81%. Its hydrogen spectrum is shown in FIG. Figure 5 As shown, the carbon spectrum is as Figure 6 As shown in the high-resolution mass spectrum Figure 7 As shown, 1 H NMR (400 MHz, DMSO-d6)δ 8.26 (dd, J = 8.8, 4.0 Hz, 4H), 7.62-7.68 (m, 2H), 7.23 (d, J = 8.4 Hz, 2H), 7.13-7.19 (m, 9H), 7.09-6.97 (m, 2H). 13 C NMR (100 MHz, DMSO-d6) δ 184.5,167.3, 153.7, 149.9, 143.2, 143.1, 143.0, 142.9, 140.1, 136.7, 132.8, 131.4,131.2, 131., 128.6, 128.5, 128.3, 127.9, 127.5, 127.4, 125.8, 123.3. HRMS(ESI): m / z C 37 H 24 N3S [M+H] + :542.1691; Found: 542.1688. Example 3: Synthesis of 1-2 molecules To a 25 mL reaction bottle, 10 mg, 0.02 mmol of compound 1-1 prepared in Example 1, 10 mg, 0.15 mmol of malononitrile, 1 drop of piperidine, and 3 mL of ethanol were added in sequence. The mixture was heated to 80° C. and reacted for 26 hours. TLC monitoring showed that the molecular compound 1-2 was not obtained, and the yield was 0%.
[0044] Example 4: Synthesis of 1-2 molecules To a 25 mL reaction vial were added 10 mg, 0.02 mmol of compound 1-1 prepared in Example 1, 10 mg, 0.15 mmol of malononitrile, 14 mg, 0.1 mmol of potassium carbonate, and 5 mL of ethanol in sequence. The mixture was heated to 80° C. and reacted for 26 hours. TLC monitoring revealed that no molecular compound 1-2 was obtained, with a yield of 0%.
[0045] Example 5: Synthesis of 1-2 molecules To a 25 mL reaction vial were added 10 mg, 0.02 mmol of compound 1-1 prepared in Example 1, 10 mg, 0.15 mmol of malononitrile, 10 mg, 0.1 mmol of sodium tert-butoxide, and 5 mL of ethanol in sequence. The mixture was heated to 80° C. and reacted for 26 hours. TLC monitoring revealed that no molecular compound 1-2 was obtained, with a yield of 0%.
[0046] Example 6: Synthesis of 1-2 molecules To a 25 mL reaction bottle, 10 mg, 0.02 mmol of compound 1-1 prepared in Example 1, 10 mg, 0.15 mmol of malononitrile, 2 drops of pyridine, and 3 mL of acetonitrile were added in sequence. The reaction was heated to 80° C. for 26 hours. TLC monitoring showed that the molecular compound 1-2 was not obtained, and the yield was 32%.
[0047] Example 7: Synthesis of 1-2 molecules To a 25 mL reaction bottle, 10 mg, 0.02 mmol of compound 1-1 prepared in Example 1, 10 mg, 0.15 mmol of malononitrile, 2 drops of pyridine, and 3 mL of toluene were added in sequence. The reaction was heated to 80° C. for 26 hours. TLC monitoring showed that the molecular compound 1-2 was not obtained, and the yield was 16%.
[0048] Example 8: Synthesis of 1-2 molecules To a 25 mL reaction bottle, 10 mg, 0.02 mmol of compound 1-1 prepared in Example 1, 10 mg, 0.15 mmol of malononitrile, 2 drops of pyridine, and 3 mL of tetrahydrofuran were added in sequence. The reaction was heated to 80° C. and reacted for 26 hours. TLC monitoring showed that the molecular compound 1-2 was not obtained, and the yield was 22%.
[0049] Example 9 The compound 1-1 prepared in Example 1 was naturally evaporated in a mixed solvent of ethyl acetate and methanol to obtain crystals of the target compound, as shown in FIG. Figure 8 Its crystal data are shown in Table 1.
[0050] Table 1 Crystal data of compound 1-1
[0051] Example 10 The compound 1-2 prepared in Example 2 was naturally evaporated in dichloromethane and petroleum ether to obtain crystals of the target compound, as shown in FIG. Figure 9 Its crystal data are shown in Table 2.
[0052] Table 2 Crystal data of compound 1-2
[0053] Example 11 A certain amount of compound 1-1 and compound 1-2 prepared in Example 1 and Example 2 were weighed and dissolved in N,N-dimethylformamide to prepare a mother solution with a concentration of 5 mM, which was then sealed and refrigerated.
[0054] Preparation of the AIE system solution: 0, 0.3, 0.6, 0.9, 1.2, 1.5, 1.8, 2.1, 2.4, and 2.7 ml of aqueous solution were pipetted, followed by 3, 2.7, 2.4, 2.1, 1.8, 1.5, 1.2, 0.9, 0.6, and 0.3 ml of ethanol solution. These were mixed to a total volume of 3 ml. Ethanol-water mixtures with water volume fractions of 0, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90% were prepared. 6 μL of the stock solution was added to 3 mL of the solution, and the AIE properties of the dye molecule at a concentration of 10 μM were tested.
[0055] Study the AIE properties of compound 1-1 and test the fluorescence spectrum, such as Figure 10As shown in the figure, there is almost no fluorescence in pure ethanol. With the increase of water content (0-60%), its fluorescence intensity and emission wavelength do not change significantly. When the water content increases to 60%-90%, the fluorescence intensity increases significantly, resulting in a significant AIE effect. Study the AIE properties of 1-2 and test the fluorescence spectrum, such as Figure 11 Compound 1-2 also has similar AIE properties to compound 1-1.
[0056] Example 12 A certain amount of compound 1-1 prepared in Example 1 was weighed and put into a mortar. After being fully ground, the fluorescence changed from green to yellow. The ground yellow dye was washed with petroleum ether to obtain a green dye (such as Figure 12 (As shown in the insert figure). The fluorescent colors of compound 1-1 before and after grinding were green and yellow, respectively. After fumigation with dichloromethane, the fluorescent color returned to green. Therefore, it can be used in anti-counterfeiting, fluorescent inks, pressure sensor materials, information security and other fields. Solid-state fluorescence spectroscopy was performed on samples of compound 1-1 before and after grinding and after stirring in the solvent. The results are as follows Figure 12 As shown in the figure, it can be seen that after grinding, the maximum emission peak of compound 1-1 red-shifted from 506 nm to 530 nm.
[0057] Weigh a certain amount of compound 1-2 prepared in Example 2 into a mortar and Figure 13 It can be seen that compound 1-2 also changes before and after grinding and after fluorescence spectrum detection with different excitation wavelengths. The difference from compound 1-1 is that a red shift change occurs before and after grinding (561nm to 635nm).
[0058] Therefore, the fluorescent materials of 1-1 and 1-2 of the present invention both have a reversible mechanochromic effect and can respond in color when a significant force change occurs in the material.
[0059] Example 13 Powder X-ray diffraction experiments were performed on compound 1-1 before and after grinding and after stirring in the solvent. It was found that diffraction peaks were generated before and after grinding, indicating that the compound was in a microcrystalline state before and after grinding ( Figure 14 ),according to Figure 14 It can be seen that the process of transformation from crystalline state to crystalline state occurs before and after grinding.
[0060] Powder X-ray diffraction experiments were conducted on compound 1-2 before grinding, after grinding and after fumigation. Figure 15 It can be seen that there is a transformation process from crystalline to amorphous before and after grinding.
[0061] Example 14 Figure 16For the application of dye molecule 1-2, the specific implementation process is: spread the yellow dye molecule flatly on it, then write an "A" on paper, and then under a 365nm fluorescent light, it is found that the "A" is red. It can be seen that this dye molecule can be used well as a read-write device and has potential anti-counterfeiting applications.
[0062] Therefore, the present invention adopts the above-mentioned mechanical force-induced chromic fluorescent material, all of which have a reversible force-induced chromic effect. Material compound 1-1 mainly causes the luminous color to change reversibly due to the transformation of dye molecules between crystalline states; and material compound 1-2 mainly causes the luminous color to change reversibly due to the transformation of dye molecules between crystalline and amorphous forms; this type of material has a high force response sensitivity and can respond in color when the material undergoes a significant force change, and is used in anti-counterfeiting, fluorescent inks, pressure sensor materials, information security and other fields.
[0063] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention. It should be understood that the above description is only a specific implementation method of the present invention and does not limit the scope of protection of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.
Claims
1. A benzothiazole-tetraphenylethylene derivative, characterized in that: Its structural formula is shown in Formula 1: Formula I Wherein, the R group is oxygen or malononitrile.
2. A method for preparing a benzothiazole-tetraphenylethylene derivative according to claim 1, characterized in that: The following steps are involved: Step (1), dissolving 4-(1,2,2-triphenylvinyl)acetophenone, o-aminothiophenol and a catalyst in a solvent, and heating the mixture to react to obtain compound 1-1; Step (2), reacting the compound 1-1 prepared in step (1) with malononitrile in the presence of a base and a solvent, heating the reaction, and separating and purifying to obtain compound 1-2.
3. The method for preparing a benzothiazole-tetraphenylethylene derivative according to claim 2, wherein: The catalyst in step (1) is iodine, and the base in step (2) is one of pyridine, piperidine and sodium tert-butoxide.
4. The method for preparing a benzothiazole-tetraphenylethylene derivative according to claim 2, wherein: The solvent in step (1) is dimethyl sulfoxide, and the solvent in step (2) is one of ethanol, acetonitrile and toluene.
5. The method for preparing a benzothiazole-tetraphenylethylene derivative according to claim 2, wherein: The heating reaction temperature in step (1) is 110-120°C, and the reaction time is 3-6 hours; the heating reaction temperature in step (2) is 60-80°C, and the reaction time is 3-4 days.
6. The method for preparing a benzothiazole-tetraphenylethylene derivative according to claim 2, wherein: In step (1), the molar ratio of 4-(1,2,2-triphenylvinyl)acetophenone, o-aminothiophenol and the catalyst is 1:2-5:0.1-0.6; in step (2), the molar ratio of compound 1-1, malononitrile and the base is 1:5-10:20-40.
7. A mechanochromic material characterized by: The mechanical force-induced fluorescent color changing material is or .
8. A mechanoluminescent material with reversible luminescent color change, characterized in that: The material is or .
9. A solid-state luminescent material, characterized in that: The material is or .
10. Use of the mechanochromic material according to claim 7, the mechanochromic material with reversible luminescent color change according to claim 8, or the solid-state luminescent material according to claim 9 in the fields of anti-counterfeiting, printing and dyeing, pressure sensor materials, and information security.