Fluorine-containing seven-membered heterocyclic dye and application thereof in fluorescent anti-counterfeiting film

Abstract

The invention discloses a fluorine-containing seven-membered heterocyclic dye and application thereof on a fluorescent anti-counterfeiting film, the structure of the compound is shown in the following figure: # imgabs0 #, and the substituent group R is selected from N, N-dimethylamino phenyl, p-cyanophenyl and 3, 4, 5-trimethoxy phenyl. The dye is prepared by taking 5-bromo-2, 3, 3-trimethylindole and pyrrole-2-formaldehyde as raw materials to carry out condensation reaction and then carrying out Suzuki cross coupling. The dye and polymethyl methacrylate are combined on a film to form the film quickly, and strong fluorescence can be seen under an ultraviolet lamp (365nm). Meanwhile, the synthesis method is simple, separation and purification are convenient, the yield is high, the manufacturing cost is low, the solid / liquid fluorescent quantum yield is high, and the potential in the fields of fluorescent anti-counterfeiting packaging films and the like is huge.

Description

Technical Field

[0001] The invention relates to the field of fine chemicals, and more specifically to a fluorine-containing seven-membered heterocyclic dye and application thereof in a fluorescent anti-counterfeiting film. Background Art

[0002] In the modern commodity economy, the importance of anti-counterfeiting technology has become increasingly prominent, especially in areas with high security requirements such as currency, certificates, trademarks, and important documents. As an effective anti-counterfeiting method, fluorescent anti-counterfeiting film is widely used due to its unique visual effects and difficult-to-copy characteristics. Fluorescent dyes, as the core component of fluorescent anti-counterfeiting film, have a direct impact on the anti-counterfeiting effect and application scope of the anti-counterfeiting film.

[0003] The application of traditional fluorescent dyes in anti-counterfeiting films has certain limitations, such as fading and decreased fluorescence intensity under long-term illumination or in harsh environments. In addition, the excitation and emission wavelength ranges of traditional fluorescent dyes are relatively narrow, which limits their adaptability in specific application scenarios. In order to overcome these limitations, the development of new fluorescent dyes, especially dyes with excellent photostability, wide excitation and emission wavelength ranges, and high fluorescence quantum yields, is crucial to improving the performance of fluorescent anti-counterfeiting films.

[0004] The present invention relates to a fluorescent dye, which has excellent light stability and high fluorescence quantum yield, and can emit strong and lasting fluorescence under illumination of different wavelengths. The dye can be widely used in the preparation of fluorescent anti-counterfeiting films, which not only improves the anti-counterfeiting effect of the anti-counterfeiting film, but also broadens its scope of application. By using the fluorescent dye of the present invention, the fluorescent anti-counterfeiting film can display a unique fluorescent pattern or information under the irradiation of ultraviolet light or other light sources of specific wavelengths, effectively preventing forgery and tampering. In addition, the fluorescent dye of the present invention also has the advantages of being environmentally friendly and low in cost, and is suitable for large-scale production and application. With the growing demand for high-security anti-counterfeiting technology, the fluorescent dye of the present invention and its application in the fluorescent anti-counterfeiting film are expected to bring new progress to the field of anti-counterfeiting. Summary of the invention

[0005] The main purpose of the present invention is to provide a fluorine-containing seven-membered heterocyclic dye and its application in fluorescent anti-counterfeiting film. The technical solution of the present invention is as follows: A fluorine-containing seven-membered heterocyclic dye and its application in a fluorescent anti-counterfeiting film, wherein the chemical structural formula of the compound is:

[0006] Wherein, the substituent R is selected from any one of N,N-dimethylaminophenyl, p-cyanophenyl, and 3,4,5-trimethoxyphenyl. As a preferred embodiment, the chemical structure of the compound is:

[0007] Any of the three.

[0008] The method for synthesizing the fluorine-containing seven-membered heterocyclic dye and its application in fluorescent anti-counterfeiting film comprises the following synthesis path:

[0009] (1) Add compound I-1, DMF, and compound 2 to a reaction bottle at room temperature, dissolve them by magnetic stirring, then add tetrakistriphenylphosphine palladium and potassium hydroxide aqueous solution, and heat to obtain a reaction solution; (2) The reaction solution in step (1) is washed with water, extracted, dried, concentrated and purified to obtain product I, i.e., a fluorine-containing seven-membered heterocyclic compound.

[0010] In the step (1), the feed ratio of compound I-1, compound 2 and tetrakistriphenylphosphine palladium is 1: 1-10: 0.01-1.

[0011] In the step (1), the concentration of the compound potassium hydroxide in the potassium hydroxide aqueous solution is 0.1 mol / mL-10 mol / mL.

[0012] The order of adding materials in step (1) is compound I-1, DMF, compound 2, tetrakistriphenylphosphine palladium, and potassium hydroxide aqueous solution.

[0013] The heating reaction temperature of step (1) is 30-150° C., and the heating time is 2-18 hours.

[0014] In the step (1), the feed ratio of compound I-1 to potassium hydroxide is 1:1-10.

[0015] The beneficial effects of the present invention are as follows: (1) The compound of the present invention is a fluorine-containing seven-membered heterocyclic dye, which can form a film quickly by combining with polymethyl methacrylate and can be observed to have strong fluorescence under ultraviolet light (365nm).

[0016] (2) The fluorine-containing seven-membered heterocyclic compound of the present invention has a simple preparation method and has a high solid and liquid fluorescence quantum yield. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is the absorption spectrum of compound I-2 obtained in Example 5.

[0018] Figure 2 It is the emission spectrum of compound I-2 obtained in Example 5.

[0019] Figure 3 This is the hydrogen spectrum of I-1 obtained in Example 1.

[0020] Figure 4 This is the hydrogen spectrum of I-2 obtained in Example 5.

[0021] Figure 5 These are photos taken under sunlight after I-2 film formation at different film forming ratios in Example 10.

[0022] Figure 6 These are photographs taken under ultraviolet light after I-2 film formation at different film formation ratios in Example 10.

[0023] Figure 7 These are photos taken under sunlight after I-3 film formation at different film formation ratios in Example 10.

[0024] Figure 8 These are photographs taken under ultraviolet light after I-3 film formation at different film formation ratios in Example 10.

[0025] Fig. 9 This is a photograph of the solid powder of compounds I-2, I-3, and E in Example 11 under ultraviolet light. DETAILED DESCRIPTION

[0026] The present invention is further described below with reference to embodiments, but the scope of protection claimed by the present invention is not limited to the scope described in the embodiments.

[0027] Example 1

[0028] Weigh compound I-1 (439 mg, 1 mmol), dissolve it in 30.00 mL DMF, and then add 4-diphenylaminophenylboronic acid (289 mg, 1 mmol), tetrakistriphenylphosphine palladium (11.6 mg, 0.001 mmol) and potassium hydroxide (1 mmol) aqueous solution in sequence. Stir and heat to 60 ° C in a water bath. The reaction is complete after 8 hours, and the yield is 39.5%.

[0029] Example 2

[0030] Weigh compound I-1 (439 mg, 1 mmol), dissolve it in 30.00 mL DMF, and then add 4-diphenylaminophenylboronic acid (578 mg, 2 mmol), tetrakistriphenylphosphine palladium (11.6 mg, 0.001 mmol) and potassium hydroxide (1 mmol) aqueous solution in sequence. Stir and heat to 60 ° C in a water bath, and the reaction is complete after 8 hours. When the amount of 4-diphenylaminophenylboronic acid is increased by 1 times relative to Example 1, its yield increases by 15.1%.

[0031] Example 3

[0032] Weigh compound I-1 (439 mg, 1 mmol), dissolve it in 30.00 mL DMF, and then add 4-diphenylaminophenylboronic acid (578 mg, 2 mmol), tetrakistriphenylphosphine palladium (11.6 mg, 0.001 mmol) and potassium hydroxide (1 mmol) aqueous solution in sequence. Stir and heat to 90 ° C in a water bath, and the reaction is complete after 6 hours. When the reaction temperature is increased by 30 ° C relative to Example 2, the reaction time is reduced by 2 hours, and the yield is increased by 22.2%.

[0033] Example 4

[0034] Weigh compound I-1 (439 mg, 1 mmol), dissolve it in 30.00 mL DMF, and then add 4-diphenylaminophenylboronic acid (578 mg, 2 mmol), tetrakistriphenylphosphine palladium (23.2 mg, 0.002 mmol) and potassium hydroxide (1 mmol) aqueous solution in sequence. Stir and heat to 90 ° C in a water bath, and the reaction is complete after 6 hours. When the amount of tetrakistriphenylphosphine palladium is increased by 1 times relative to Example 3, its yield increases by 6.7%.

[0035] Example 5

[0036] Weigh compound I-1 (439 mg, 1 mmol), dissolve it in 30.00 mL DMF, and then add 4-diphenylaminophenylboronic acid (578 mg, 2 mmol), tetrakistriphenylphosphine palladium (23.2 mg, 0.002 mmol) and potassium hydroxide (2 mmol) aqueous solution in sequence. Stir and heat to 90 ° C in a water bath, and the reaction is complete after 6 hours. When the amount of potassium hydroxide aqueous solution is increased by 1 times relative to Example 4, the yield increases by 5.4%.

[0037] Example 6

[0038] Weigh compound I-1 (439 mg, 1 mmol), dissolve it in 60.00 mL DMF, and then add 4-diphenylaminophenylboronic acid (578 mg, 2 mmol), tetrakistriphenylphosphine palladium (23.2 mg, 0.002 mmol) and potassium hydroxide (2 mmol) aqueous solution in sequence. Stir and heat to 90 ° C in a water bath, and the reaction is complete after 6 hours. When the amount of DMF is increased by 1 times compared with Example 5, the yield does not change significantly.

[0039] Example 7

[0040] Weigh compound I-1 (439 mg, 1 mmol), dissolve it in 30.00 mL DMF, and then add 4-cyanophenylboronic acid (293.8 mg, 2 mmol), tetrakistriphenylphosphine palladium (23.2 mg, 0.002 mmol) and potassium hydroxide (2 mmol) aqueous solution in sequence. Stir in a water bath and heat to 90 ° C. After 6 hours, the reaction is complete and the product structure is (E).

[0041] Example 8

[0042] Weigh compound I-1 (439 mg, 1 mmol), dissolve it in 30.00 mL DMF, then add 3,4,5-trimethoxyphenyl (424.02 mg, 2 mmol), tetrakistriphenylphosphine palladium (23.2 mg, 0.002 mmol) and potassium hydroxide (2 mmol) aqueous solution in sequence. Stir in a water bath and heat to 90°C. The reaction is complete after 6 hours.

[0043] Example 9 Weigh compound I-2 (6.0 mg, 0.01 mmol) from Example 5 and dissolve it in 0.1 mL of dichloromethane to a concentration of 10 -1 3 μL of each of the five mother solutions were dissolved in 3 mL of toluene, dichloromethane, acetone, acetonitrile and dimethyl sulfoxide to make a concentration of 1×10 -4 M test solution, and conduct UV and fluorescence tests on the test solution, such as Figure 1 and Figure 2 It can be observed that the maximum emission wavelength of the compound is 580nm, and the red shift and blue shift in different solvents are not obvious. The test results show that the optical properties of the substance are basically not affected by different solvents.

[0044] Example 10 Weigh the compounds I-2 (6.0 mg, 0.01 mmol) and I-3 (4.6 mg, 0.01 mmol) in Example 5 and Example 7 respectively and dissolve them in 0.1 mL of dichloromethane to a concentration of 10 -1Take 5 groups of two kinds of mother liquors, 10μL in each group, and mix them evenly with 10μL, 20μL, 30μL, 40μL, and 50μL of polymethyl methacrylate in a ratio of 1:1, 1:2, 1:3, 1:4:, and 1:5, respectively, and apply them evenly on the glass plate with a KTQ-II adjustable coater. Dry them in an oven at 30°C, place the glass plate under natural light, and take pictures with an iPhone 14 Pro to obtain clear pictures (from left to right, they are anti-counterfeiting films with mixing ratios of 1:1, 1:2, 1:3, 1:4:, and 1:5), as shown in the figure. Figure 5 and Figure 7 Then place the glass plate coated with dye under a 365nm ultraviolet lamp and take a photo with an iPhone 14 Pro phone to obtain a fluorescence image with strong fluorescence (from left to right, the anti-counterfeiting films with mixing ratios of 1:1, 1:2, 1:3, 1:4, and 1:5), as shown below. Figure 6 and Figure 8 shown.

[0045] Embodiment 11 Weigh compounds I-2 (18.0 mg, 0.03 mmol) and I-3 (18.4 mg, 0.04 mmol) in Example 5 and Example 7 respectively, and ensure that the sample surface is flat to facilitate uniform irradiation and collection of light. Use the Quantaurus-QY fluorescence spectrometer equipped with an integrating sphere, adjust the integrating sphere reversal mirror to the "powder" position, and then place a blank plate inside the integrating sphere for testing to obtain background data. Measure the scattering and emission spectra of the blank sample and record them as Blank. Take out the blank plate and put in the solid fluorescent sample without changing other settings. Measure the scattering and emission spectra of samples I-2 and I-3 again and record them as Sample. Calculate the quantum yield according to the formula: . After completing the fluorescence quantum yield test, select the Manual Lifetime test option in the software. Set the excitation wavelength, emission wavelength, detector settings, and start data acquisition. Using TCSPC technology, the fluorescence decay curve is constructed by recording the arrival time of a single photon. By collecting a large amount of photon arrival time data, a fluorescence lifetime curve is constructed to obtain the corresponding solid fluorescence lifetime. Compared with compound E, the solid fluorescence quantum yield and solid fluorescence lifetime of compounds I-2 and I-3 are better. The fluorescence graphs of compound I-2, I-3, and E solid powders under 365nm light source irradiation ( Fig. 9 ) can prove this.

[0046]

Claims

1. A fluorine-containing seven-membered heterocyclic dye, characterized in that: The chemical structural formula of the compound is: I Wherein, the substituent R is selected from any one of N,N-dimethylaminophenyl, p-cyanophenyl and 3,4,5-trimethoxyphenyl.

2. The method for preparing a fluorine-containing seven-membered heterocyclic dye according to claim 1, characterized in that: The method comprises the following synthetic route: Wherein, the substituent R is selected from any one of N,N-dimethylaminophenyl, p-cyanophenyl, and 3,4,5-trimethoxyphenyl; (1) Adding compound I-1, DMF, and compound 2 to a reaction bottle at room temperature, dissolving them by magnetic stirring, then adding tetrakistriphenylphosphine palladium and potassium hydroxide aqueous solution, and heating to obtain a reaction solution, wherein the substituent R in the compound 2 is selected from any one of N,N-dimethylaminophenyl, p-cyanophenyl, and 3,4,5-trimethoxyphenyl; (2) The reaction solution in step (1) is washed with water, extracted, dried, concentrated and purified to obtain product I, i.e., a fluorine-containing seven-membered heterocyclic dye.

3. The method according to claim 2, characterized in that In the step (1), the feed ratio of compound I-1, compound 2 and tetrakistriphenylphosphine palladium is 1: 1-10: 0.01-1.

4. The method according to claim 2, characterized in that: In the step (1), the concentration of the potassium hydroxide aqueous solution in the potassium carbonate aqueous solution is 0.1 mol / mL-10 mol / mL.

5. The method according to claim 2, characterized in that: The order of adding materials in step (1) is compound I-1, DMF, compound 2, tetrakistriphenylphosphine palladium, and potassium hydroxide aqueous solution.

6. The method according to claim 2, characterized in that The heating reaction temperature of step (1) is 30-150° C., and the heating time is 2-18 hours.

7. The method according to claim 2, characterized in that In the step (1), the feed ratio of compound I-1 to potassium hydroxide is 1:1-10.

8. A fluorine-containing seven-membered heterocyclic dye as claimed in claim 1 and its use in fluorescent anti-counterfeiting film.

9. Fluorescent anti-counterfeiting film, characterized in that: The invention comprises the fluorine-containing seven-membered heterocyclic dye as claimed in claim 1.

10. The fluorescent anti-counterfeiting film according to claim 9, characterized in that: The fluorescent anti-counterfeiting film achieves an anti-counterfeiting effect under ultraviolet light.

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