A dithiophene-tetraphenylstilbene derivative, preparation method and application thereof

Abstract

The application discloses a dioxobenzothiophene-tetraphenylethylene derivative, a preparation method and application thereof, and belongs to the technical field of organic synthesis. 4-(1,2,2-triphenylvinyl) benzaldehyde or a derivative thereof, benz[b]thiophene-3(2)H-ketone-1,1-dioxide and a catalyst are dissolved in a solvent, and a dioxobenzothiophene-tetraphenylethylene derivative is prepared by heating reaction at a high temperature. The dioxobenzothiophene-tetraphenylethylene derivative, the preparation method and the application thereof have the advantages that the preparation method is simple, the operation is simple and convenient, the cost is low, the prepared dioxobenzothiophene-tetraphenylethylene derivative has fluorescence characteristics, and the dioxobenzothiophene-tetraphenylethylene derivative can be applied to the fields of anti-counterfeiting, textile and garment printing and dyeing, cosmetics, pressure sensor materials, information security and the like. Meanwhile, the synthesis method can be used for synthesis in the fields of fine organic chemical industry such as luminescent materials and printing and dyeing technology.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, and in particular to a dioxobenzothiophene-tetraphenylene derivative, its preparation method, and its application. Background Technology

[0002] In recent years, with consumers' increasing awareness of product safety and brand protection, anti-counterfeiting technology has become increasingly important in the packaging industry. To address the growing problem of counterfeit and substandard products, the development and application of multiple anti-counterfeiting technologies have gradually become a mainstream trend in the industry. These technologies can not only effectively curb the circulation of counterfeit products but also significantly enhance a company's brand competitiveness and market trust. Meanwhile, fluorescent dyes have also been widely used in the cosmetics, textile and apparel printing and dyeing industries.

[0003] Fluorescent anti-counterfeiting technology is an anti-counterfeiting method based on the specific fluorescence emission characteristics of fluorescent materials under ultraviolet light. Compared with traditional technologies such as watermarks, laser anti-counterfeiting, and color-changing inks, fluorescent anti-counterfeiting marks are transparent under visible light conditions, do not affect the original appearance of the item, and have good privacy and concealment. When exposed to ultraviolet light, their surface exhibits unique fluorescent characteristics, thus enabling rapid and convenient anti-counterfeiting identification. In addition, mechanochromic fluorescent materials, as a second anti-counterfeiting mechanism, change color under pressure or friction, further enhancing the anti-counterfeiting effect. Due to their significant mechanochromic fluorescence change characteristics, these materials are considered excellent candidates among multi-layered anti-counterfeiting materials.

[0004] Reference 1 (Chem. Eur. J. 2023, 29, e202203772) reports a method using 4,5-bis(triphenylvinyl)pyrazole as the basic structure, where the direction of the mechanochromic shift is altered by changing the substituent at position 2 (pyridine or quinoline); Reference 2 (Chem. Commun., 2018, 54, 5598-5601) reports a method to regulate the direction of the mechanochromic material of the target product by changing the connection position of tetraphenylethylene (TPE) and benzo[9,10-d]imidazole (PI); and Patent Claim (202510639100.7) proposes a conjugated molecular structure containing triphenylethylene, benzimidazole, and dicyanoethylene fragments, where the direction of the mechanochromic shift is altered by changing the substituent (hydrogen atom or methyl group) on one of the N atoms of the benzimidazole heterocycle. Summary of the Invention

[0005] The purpose of this invention is to provide a dioxobenzothiophene-tetraphenylethylene derivative, its preparation method, and its applications. The preparation method is simple, easy to operate, and low in cost. The prepared dioxobenzothiophene-tetraphenylethylene derivative has fluorescent properties and can be applied in fields such as anti-counterfeiting, textile and clothing printing and dyeing, cosmetics, pressure sensor materials, and information security. At the same time, this synthesis method can be used in the synthesis of luminescent materials and fine organic chemical technologies such as printing and dyeing technology.

[0006] To achieve the above objectives, the present invention provides a dioxobenzothiophene-tetraphenylethylene derivative, the structural formula of which is:

[0007] R is either H or OH.

[0008] Furthermore, when R is H, the structural formula is: (1-1); When R is OH, the structural formula is: (1-2); Compound 1-1 undergoes intercrystalline transformation under the action of force, resulting in a force-induced blue shift in fluorescence color, with the emission color changing from orange-yellow to yellow. Compounds 1-2 transform between crystalline and amorphous forms, and mechanical force causes a red shift in fluorescence color, changing the emission color from pale yellow to deep red.

[0009] The present invention also provides a method for preparing dioxobenzothiophene-tetraphenylethylene derivative, the steps of which are as follows: the reactants, benzo[b]thiophene-3(2)H-one-1,1-dioxide and catalyst are dissolved in a solvent, and the reaction is carried out by heating to obtain dioxobenzothiophene-tetraphenylethylene derivative.

[0010] Preferably, the molar ratio of the reactant to benzo[b]thiophene-3(2)H-one-1,1-dioxide is 1:1-5.

[0011] Preferably, the reactant is one of 4-(1,2,2-triphenylvinyl)benzaldehyde and 2-hydroxy-4-(1,2,2-triphenylvinyl)benzaldehyde.

[0012] Preferably, the solvent is one of methanol, anhydrous ethanol, acetonitrile, and toluene.

[0013] Preferably, the heating reaction temperature is 70-110℃ and the reaction time is 4-72h.

[0014] Preferably, when the solvent is anhydrous ethanol, the heating reaction temperature is 75-80℃ and the reaction time is 4-48h; when the solvent is toluene, the heating reaction temperature is 100-110℃ and the reaction time is 24-72h.

[0015] Preferably, the catalyst is one of pyridine, piperidine, and sodium tert-butoxide.

[0016] Furthermore, when the reactant is 4-(1,2,2-triphenylvinyl)benzaldehyde, the solvent is anhydrous ethanol and the catalyst is pyridine; When the reactant is 2-hydroxy-4-(1,2,2-triphenylvinyl)benzaldehyde, the solvent is toluene and the catalyst is pyridine.

[0017] This invention also provides an application of a dioxobenzothiophene-tetraphenylethylene derivative, which is used as a mechanotropic fluorescent color-changing material or a solid-state luminescent material in textile and apparel printing and dyeing, cosmetics, pressure sensor materials, information security, and anti-counterfeiting fields.

[0018] This invention utilizes the Brainwell condensation reaction to form a carbon-carbon double bond connecting a highly twisted tetraphenylethylene and a planar dioxobenzothiophene fluorescent backbone, resulting in a class of dioxobenzothiophene-tetraphenylethylene derivatives. Both structural fragments are classic fluorescent backbones. The twisted tetraphenylethylene and planar dioxobenzothiophene structures balance the molecular mechanochromic properties. The product exhibits characteristics including the AIE effect and significant mechanochromic shift (i.e., a large mechanochromic shift). The direction of the mechanochromic shift is regulated through hydroxyl substitution (-H or -OH). This dioxobenzothiophene-tetraphenylethylene derivative is easy to print and dye, exhibits high fluorescence intensity and high mechanochromic contrast, effectively meeting the basic needs of society and industry for fluorescent dyes. Furthermore, it boasts advantages such as low synthesis cost, simple and efficient preparation method, and ease of use.

[0019] Therefore, the present invention, by employing the above-mentioned dioxobenzothiophene-tetraphenylethylene derivative, its preparation method, and its application, has the following beneficial effects: (1) The mechanical force-induced color-changing sensor material preparation method of the present invention is simple, easy to operate, and low in cost. It can be applied to anti-counterfeiting, textile and clothing printing and dyeing, cosmetics, pressure sensor materials, information security and other fields. 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) In this invention, tetraphenylethylene and benzo[b]thiophene-3(2)H-one-1,1-dioxide, which have better effects on the preparation of mechanically induced fluorescent color-changing materials, are selected as molecular structural fragments. At the same time, compared with the planar structural fragments and other structural fragments that do not have aggregation-induced emission characteristics added to the fluorescent color-changing materials in the past, this invention uses tetraphenylethylene structural fragments, which have aggregation-induced emission characteristics, thus ensuring the solid-state emission of the target material. Moreover, the mechanically induced fluorescent color-changing material compounds 1-2 provided by this invention exhibit high contrast (mechanical color-changing shift > 80nm). The key is that the micro-structural changes cause the mechanically induced fluorescent color-changing direction to change. Among them, compound 1-1 mechanically induced fluorescence blue shift and compound 1-2 mechanically induced fluorescence red shift, which greatly expands the anti-counterfeiting field of mechanically induced fluorescent materials.

[0020] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0021] Figure 1 This is a flowchart illustrating the preparation process of compound 1-1 of the present invention; Figure 2 This is the proton NMR spectrum of compound 1-1 of this invention; Figure 3 This is the carbon spectrum of compound 1-1 of the present invention; Figure 4 This is the high-resolution mass spectrum of compound 1-1 of the present invention; Figure 5 These are the proton NMR spectra of compounds 1-2 of this invention; Figure 6 These are the carbon spectra of compounds 1-2 of this invention; Figure 7 These are the high-resolution mass spectra of compounds 1-2 of this invention; Figure 8 This is a single-crystal structure diagram of the target compound crystal obtained from compound 1-1 of the present invention; Figure 9 This is a single-crystal structure diagram of the target compound crystals obtained from compounds 1-2 of the present invention; Figure 10 This is the AIE property diagram of compound 1-1 of the present invention; Figure 11 This is the mechanochromic spectrum of compound 1-1 of the present invention; Figure 12 These are the mechanochromic spectra of compounds 1-2 of this invention; Figure 13 These are X-ray diffraction images of compound 1-1 before and after grinding. Figure 14 These are X-ray diffraction images of compounds 1-2 before and after grinding, representing the powders of this invention. Figure 15These are images showing the anti-counterfeiting application results of compounds 1-2 of this invention. Detailed Implementation

[0022] The technical solution of the present invention will be further described below with reference to the accompanying drawings and embodiments.

[0023] Unless otherwise defined, the technical or scientific terms used in this invention shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.

[0024] Example 1 This invention provides a dioxobenzothiophene-tetraphenylethylene derivative with the following structural formula: (1-1).

[0025] like Figure 1 As shown, the preparation method of compound 1-1 includes the following steps: In a 25 mL reaction flask, 400 mg and 1.10 mmol of 4-(1,2,2-triphenylvinyl)benzaldehyde, 286 mg and 1.57 mmol of benzo[b]thiophene-3(2)H-one-1,1-dioxide, and 2.50 mL of pyridine were added sequentially. 8 mL of anhydrous ethanol was added, and the mixture was reacted at 80 °C for 26 h. A precipitate was formed, dried, and subjected to column chromatography (petroleum ether: dichloromethane volume ratio of 2:3) to obtain compound 1-1.

[0026] Compound 1-1 has a yield of 64%, and its proton NMR spectrum is shown below. Figure 2 As shown, the carbon spectrum is as follows Figure 3 As shown, the high-resolution mass spectrum is as follows: Figure 4 As shown.

[0027] Its proton NMR data are as follows: 1 H NMR (400 MHz, DMSO- d 6) δ 8.26 (d, J = 7.3 Hz, 1H), 8.12 (m, 3H), 8.00 (t, J = 9.4 Hz, 3H), 7.24 – 7.13 (m, 11H), 7.02 (m, 6H).

[0028] Its carbon spectrum data are as follows: 13 C NMR (100 MHz, DMSO- d6) δ 178.6, 149.8, 144.2, 143.8,143.3, 143.1, 143.0, 142.8, 134.0, 138.1, 135.6, 133.6, 132.1, 132.0, 131.2,131.2, 131.1, 130.6, 128.8, 128.6, 128.6, 128.3, 127.7, 127.4, 125.3,122.1.

[0029] HRMS(ESI):m / z C 35 H 24 O3NaS[M+Na] + :547.1344;Found: 547.1346.

[0030] Example 2 This invention provides a dioxobenzothiophene-tetraphenylethylene derivative with the following structural formula: (1-2).

[0031] The preparation method of compounds 1-2 includes the following steps: 2-hydroxy-4-(1,2,2-triphenylvinyl)benzaldehyde (250 mg, 0.67 mmol), benzo[b]thiophene-3(2)H-one-1,1-dioxide (120 mg, 0.66 mmol), 2.00 mL of pyridine, and 4 mL of toluene were added sequentially to a 25 mL reaction flask. After reacting at 110 °C for 32 h, a precipitate was formed, dried, and subjected to column chromatography (petroleum ether: ethyl acetate volume ratio of 5:2) to obtain compounds 1-2.

[0032] The yield of compounds 1-2 was 34%, and their proton NMR spectra are shown below. Figure 5 As shown, the carbon spectrum is as follows Figure 6 As shown, the high-resolution mass spectrum is as follows: Figure 7 As shown.

[0033] Its proton NMR data are as follows: 1 H NMR (400 MHz, DMSO- d6) δ 11.03 (s, 1H), 8.39 (s, 1H), 8.23 ​​(d, J = 7.5 Hz, 1H), 8.10 (dd, J = 11.4, 7.8 Hz, 2H), 7.99 (dd, J =14.6, 7.8 Hz, 2H), 7.26 – 7.12 (m, 9H), 7.09 – 6.93 (m, 6H), 6.72 (s, 1H), 6.62 (d, J = 8.2 Hz, 1H).

[0034] Its carbon spectrum data are as follows: 13 C NMR (100 MHz, DMSO- d 6) δ 178.8, 160.6, 152.8, 143.7,143.1, 143.0, 142.8, 139.9, 137.9, 137.9, 137.9, 135.4, 132.1, 131.5, 131.2,131.1, 131.1, 131.1, 128.6, 128.6, 128.3, 128.3, 128.3, 127.8, 127.4, 125.1,123.2, 121.9, 119.2, 116.1.

[0035] HRMS(ESI): m / z C 35 H 25 O4S [M+H] + :541.1474; Found: 541.1472.

[0036] I. Compound 1-1 prepared in Example 1 was allowed to evaporate naturally in dichloromethane and n-hexane to obtain crystals of the target compound, as shown below. Figure 8 As shown, its crystal data is shown in Table 1.

[0037] Table 1 Crystal data for compound 1-1 ;

[0038] The compounds 1-2 prepared in Example 2 were allowed to evaporate naturally in a mixed solvent of dichloromethane and n-hexane to obtain crystals of the target compound, such as... Figure 9 As shown, its crystal data is shown in Table 2.

[0039] Table 2 Crystal data for compounds 1-2 ;

[0040] 2. Weigh a certain amount of compounds 1-1 and 1-2 prepared in Example 1 and Example 2, dissolve them in DMSO, prepare a mother liquor with a concentration of 0.5 mM, seal it and store it in the refrigerator.

[0041] Preparation of AIE system solutions: Using a pipette, pipette 0, 0.3, 0.6, 0.9, 1.2, 1.5, 1.8, 2.1, 2.4, and 2.7 mL of aqueous solution, respectively. Then pipette 3, 2.7, 2.4, 2.1, 1.8, 1.5, 1.2, 0.9, 0.6, and 0.3 mL of ethanol solution, mixing them to a total volume of 3 mL. This prepares ethanol-water mixed solutions with water volume fractions of 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90%. Add 30 μL of the stock solution to each 3 mL solution and test the AIE properties of the dye molecules at a concentration of 5 μM.

[0042] The AIE properties of compound 1-1 were studied, and the fluorescence spectrum was measured as follows: Figure 10 As shown, by Figure 10 It is known that there is almost no fluorescence in pure ethanol. As the water (poor solvent) content increases (0-90%), its fluorescence intensity and emission wavelength do not change significantly. When the water content increases to 90%, the fluorescence intensity increases significantly, producing a significant AIE effect.

[0043] III. A certain amount of compound 1-1 prepared in Example 1 was weighed and placed in a mortar. After thorough grinding, the fluorescence changed from orange to yellow. This indicates that compound 1-1 can be applied in fields such as anti-counterfeiting, fluorescent inks, pressure sensor materials, and information security. Solid-state fluorescence spectroscopy was performed on samples of compound 1-1 before and after grinding, and the results are as follows... Figure 11 As shown in the figure, after grinding, the maximum emission peak of compound 1-1 shifted from 592 nm to 574 nm.

[0044] Weigh a certain amount of compounds 1-2 prepared in Example 2 and place them in a mortar. Figure 12 It can be seen that compounds 1-2 also undergo changes after being excited by fluorescence spectroscopy before and after grinding. The difference between compounds 1-2 and compounds 1-1 is that they undergo a red shift (from 566nm to 648nm) before and after grinding.

[0045] In summary, both compound 1-1 and compound 1-2 prepared by this invention have a mechanochromic effect and can produce obvious color reactions when the material is subjected to stress changes.

[0046] IV. Powder X-ray diffraction experiments were performed on samples of compound 1-1 before and after grinding. Diffraction peaks were observed before and after grinding, indicating that the samples were in a microcrystalline state before and after grinding. Figure 13 ),according to Figure 13 It can be seen that the process of transformation from crystalline to crystalline state occurs before and after grinding.

[0047] Powder X-ray diffraction experiments were performed on samples of compounds 1-2 before and after grinding. Figure 14 It can be seen that the process of transformation from crystalline to amorphous state occurs before and after grinding.

[0048] V. Testing the applications of compounds 1-2: Figure 15 For the application of compound 1-2, the specific implementation process is as follows: Yellow dye molecules are laid flat on paper, and then the letter "A" is written on the paper. Under a 365nm fluorescent lamp, the "A" is found to be orange-red. It can be seen that the prepared compound 1-2 can be used as a reading and writing device and has potential anti-counterfeiting applications.

[0049] Therefore, this invention utilizes the aforementioned dioxobenzothiophene-tetraphenylethylene derivative, its preparation method, and its application. The prepared dioxobenzothiophene-tetraphenylethylene derivatives all exhibit reversible mechanochromic effects. Compound 1-1 primarily results in a color change due to the transformation of dye molecules between crystalline and amorphous states, while compound 1-2 primarily results in a color change due to the transformation of dye molecules between crystalline and amorphous states. This type of material exhibits high force response sensitivity and can produce a significant color reaction when the material undergoes a force change. It can be applied in fields such as anti-counterfeiting, textile and apparel printing and dyeing, cosmetics, pressure sensor materials, and information security.

[0050] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A dioxobenzothiophene-tetraphenylethylene derivative, characterized in that: The structural formula of the dioxobenzothiophene-tetraphenylethylene derivative is: R is either H or OH.

2. The method for preparing a dioxobenzothiophene-tetraphenylethylene derivative as described in claim 1, characterized in that: The steps are as follows: Dissolve the reactants, benzo[b]thiophene-3(2)H-one-1,1-dioxide and catalyst in a solvent, and heat the mixture to prepare dioxobenzothiophene-tetraphenylethylene derivative.

3. The method for preparing a dioxobenzothiophene-tetraphenylethylene derivative according to claim 2, characterized in that: The molar ratio of the reactant to benzo[b]thiophene-3(2)H-one-1,1-dioxide was 1:1-5.

4. The method for preparing a dioxobenzothiophene-tetraphenylethylene derivative according to claim 2, characterized in that: The reactant is one of 4-(1,2,2-triphenylvinyl)benzaldehyde and 2-hydroxy-4-(1,2,2-triphenylvinyl)benzaldehyde.

5. The method for preparing a dioxobenzothiophene-tetraphenylethylene derivative according to claim 2, characterized in that: The solvent is one of methanol, anhydrous ethanol, acetonitrile, and toluene.

6. The method for preparing a dioxobenzothiophene-tetraphenylethylene derivative according to claim 5, characterized in that: The heating reaction temperature is 70-110℃, and the reaction time is 4-72h.

7. The method for preparing a dioxobenzothiophene-tetraphenylethylene derivative according to claim 6, characterized in that: When the solvent is anhydrous ethanol, the heating temperature is 75-80℃ and the reaction time is 4-48h; when the solvent is toluene, the heating temperature is 100-110℃ and the reaction time is 24-72h.

8. The method for preparing a dioxobenzothiophene-tetraphenylethylene derivative according to claim 2, characterized in that: The catalyst is one of pyridine, piperidine, and sodium tert-butoxide.

9. An application of a dioxobenzothiophene-tetraphenylethylene derivative, characterized in that: The dioxobenzothiophene-tetraphenylphenyl derivative of claim 1 is used as a mechanotropic fluorescent color-changing material or a solid-state luminescent material in the fields of textile and apparel printing and dyeing, cosmetics, pressure sensor materials, information security, and anti-counterfeiting.

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