Fluorine-containing seven-membered heterocyclic dye and its use in fluorescent security film

Abstract

The application discloses a fluorine-containing seven-membered heterocyclic dye and application thereof to a fluorescent anti-counterfeiting film, and the structure of the compound is as shown in the following figure: wherein the substituent group R is selected from N,N-dimethylaminophenyl, p-cyanophenyl and 3,4,5-trimethoxyphenyl. The dye is synthesized through condensation reaction of 5-bromo-2,3,3-trimethylindole and pyrrole-2-carboxaldehyde and then through Suzuki cross coupling. The dye can be combined with polymethyl methacrylate on a film to form a film rapidly, and strong fluorescence can be observed under an ultraviolet lamp (365 nm). Meanwhile, the synthesis method is simple, separation and purification are convenient, the yield is high, the manufacturing cost is low, the solid / liquid fluorescence quantum yield is high, and the dye has great potential in the field of fluorescent anti-counterfeiting packaging films and the like.

Description

Technical Field

[0001] This invention relates to the field of fine chemicals, and more specifically, to a fluorine-containing seven-membered heterocyclic dye and its application in fluorescent anti-counterfeiting films. Background Technology

[0002] In modern commodity economy, the importance of anti-counterfeiting technology is increasingly prominent, especially in areas with high security requirements such as currency, certificates, trademarks, and important documents. Fluorescent anti-counterfeiting film, as an effective anti-counterfeiting method, is widely used due to its unique visual effects and difficulty in replication. Fluorescent dyes, as the core component of fluorescent anti-counterfeiting film, directly affect the anti-counterfeiting effect and application scope of the film.

[0003] The application of traditional fluorescent dyes in anti-counterfeiting films has certain limitations, such as fading and decreased fluorescence intensity under prolonged light exposure or harsh environments. Furthermore, the narrow excitation and emission wavelength ranges of traditional fluorescent dyes limit their applicability in specific application scenarios. To overcome these limitations, developing novel fluorescent dyes, especially those with excellent photostability, wide excitation and emission wavelength ranges, and high fluorescence quantum yield, is crucial for improving the performance of fluorescent anti-counterfeiting films.

[0004] This invention relates to a fluorescent dye possessing excellent photostability and a high fluorescence quantum yield, capable of emitting strong and persistent fluorescence under illumination of different wavelengths of light. This dye can be widely used in the preparation of fluorescent security films, not only improving the anti-counterfeiting effect of the films but also broadening their application range. By using the fluorescent dye of this invention, the fluorescent security film can display unique fluorescent patterns or information under ultraviolet light or other specific wavelength light sources, effectively preventing counterfeiting and tampering. Furthermore, the fluorescent dye of this invention is environmentally friendly and low-cost, suitable for large-scale production and application. With the increasing demand for high-security anti-counterfeiting technologies, the fluorescent dye of this invention and its application in fluorescent security films are expected to bring new progress to the anti-counterfeiting field. Summary of the Invention

[0005] The main objective of this invention is to provide a fluorine-containing seven-membered heterocyclic dye and its application in fluorescent anti-counterfeiting films. The technical solution of this invention is as follows:

[0006] A fluorine-containing seven-membered heterocyclic dye and its application in fluorescent anti-counterfeiting films, wherein the chemical structural formula of the compound is as follows:

[0007]

[0008] 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 structural formula of the compound is:

[0009]

[0010] Any one of the three.

[0011] The method for synthesizing the aforementioned fluorine-containing seven-membered heterocyclic dye and its application in fluorescent anti-counterfeiting films includes the following synthetic route:

[0012]

[0013] (1) Compound I-1, DMF and compound 2 were added to the reaction flask at room temperature and dissolved by magnetic stirring. Then tetraphenylphosphine palladium and potassium hydroxide aqueous solution were added and heated to obtain the reaction solution.

[0014] (2) The reaction solution in step (1) was washed with water, extracted, dried, concentrated and purified to obtain product I, which is a fluorine-containing seven-membered heterocyclic compound.

[0015] In step (1), the ratio of compound I-1, compound 2, and tetratriphenylphosphine palladium is 1:1-10:0.01-1.

[0016] In step (1), the concentration of potassium hydroxide in the potassium hydroxide aqueous solution is 0.1 mol / mL to 10 mol / mL.

[0017] The feeding sequence of step (1) is compound I-1, DMF, compound 2, tetratriphenylphosphine palladium, and potassium hydroxide aqueous solution.

[0018] The heating reaction temperature in step (1) is 30~150℃ and the heating time is 2~18 hours.

[0019] In step (1), the ratio of compound I-1 to potassium hydroxide is 1:1-10.

[0020] The beneficial effects of this invention are as follows:

[0021] (1) The compound of the present invention is a fluorine-containing seven-membered heterocyclic dye that can be rapidly formed into a film by combining with polymethyl methacrylate and can be seen to have strong fluorescence under ultraviolet light (365nm).

[0022] (2) The method for preparing the fluorine-containing seven-membered heterocyclic compound described in this invention is simple and has high solid and liquid fluorescence quantum yields. Attached Figure Description

[0023] Figure 1 This is the absorption spectrum of compound I-2 obtained in Example 5.

[0024] Figure 2This is the emission spectrum of compound I-2 obtained in Example 5.

[0025] Figure 3 This is the hydrogen spectrum of I-1 obtained in Example 1.

[0026] Figure 4 This is the hydrogen spectrum of I-2 obtained in Example 5.

[0027] Figure 5 These are photographs taken under sunlight after film formation in I-2 at different film-forming ratios in Example 10.

[0028] Figure 6 These are UV-lit images taken after film formation in I-2 at different film-forming ratios in Example 10.

[0029] Figure 7 These are photographs taken under sunlight after film formation in I-3 at different film-forming ratios in Example 10.

[0030] Figure 8 These are UV-lit images taken after film formation in I-3 at different film-forming ratios in Example 10.

[0031] Figure 9 These are photographs of the solid powders of compounds I-2, I-3, and E in Example 11 taken under a UV lamp. Detailed Implementation

[0032] 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.

[0033] Example 1

[0034]

[0035] Compound I-1 (439 mg, 1 mmol) was weighed and dissolved in 30.00 mL of DMF. Then, 4-diphenylaminophenylboronic acid (289 mg, 1 mmol), tetrakis(triphenylphosphine)palladium (11.6 mg, 0.001 mmol), and potassium hydroxide (1 mmol) aqueous solution were added sequentially. The mixture was stirred and heated to 60 °C in a water bath. The reaction was completed after 8 hours, with a yield of 39.5%.

[0036] Example 2

[0037]

[0038] Compound I-1 (439 mg, 1 mmol) was weighed and dissolved in 30.00 mL of DMF. Then, 4-diphenylaminophenylboronic acid (578 mg, 2 mmol), tetrakis(triphenylphosphine)palladium (11.6 mg, 0.001 mmol), and potassium hydroxide (1 mmol) aqueous solution were added sequentially. The mixture was stirred and heated to 60°C in a water bath, and the reaction was completed after 8 hours. When the amount of 4-diphenylaminophenylboronic acid was increased by 1 time compared to Example 1, the yield increased by 15.1%.

[0039] Example 3

[0040]

[0041] Compound I-1 (439 mg, 1 mmol) was weighed and dissolved in 30.00 mL of DMF. Then, 4-diphenylaminophenylboronic acid (578 mg, 2 mmol), tetrakis(triphenylphosphine)palladium (11.6 mg, 0.001 mmol), and potassium hydroxide (1 mmol) aqueous solution were added sequentially. The mixture was stirred and heated to 90°C in a water bath. The reaction was completed after 6 hours. When the reaction temperature was increased by 30°C compared to Example 2, the reaction time was reduced by 2 hours, and the yield increased by 22.2%.

[0042] Example 4

[0043]

[0044] Compound I-1 (439 mg, 1 mmol) was weighed and dissolved in 30.00 mL of DMF. Then, 4-diphenylaminophenylboronic acid (578 mg, 2 mmol), tetrakis(triphenylphosphine)palladium (23.2 mg, 0.002 mmol), and potassium hydroxide (1 mmol) aqueous solution were added sequentially. The mixture was stirred and heated to 90°C in a water bath, and the reaction was completed after 6 hours. When the amount of tetrakis(triphenylphosphine)palladium was increased by 1 time compared to Example 3, the yield increased by 6.7%.

[0045] Example 5

[0046]

[0047] Compound I-1 (439 mg, 1 mmol) was weighed and dissolved in 30.00 mL of DMF. Then, 4-diphenylaminophenylboronic acid (578 mg, 2 mmol), tetrakis(triphenylphosphine)palladium (23.2 mg, 0.002 mmol), and an aqueous solution of potassium hydroxide (2 mmol) were added sequentially. The mixture was stirred and heated to 90°C in a water bath, and the reaction was completed after 6 hours. When the amount of potassium hydroxide aqueous solution was doubled compared to Example 4, the yield increased by 5.4%.

[0048] Example 6

[0049]

[0050] Compound I-1 (439 mg, 1 mmol) was weighed and dissolved in 60.00 mL of DMF. Then, 4-diphenylaminophenylboronic acid (578 mg, 2 mmol), tetrakis(triphenylphosphine)palladium (23.2 mg, 0.002 mmol), and potassium hydroxide (2 mmol) aqueous solution were added sequentially. The mixture was stirred and heated to 90°C in a water bath, and the reaction was completed after 6 hours. When the amount of DMF was increased by 1 time compared to Example 5, the yield did not change significantly.

[0051] Example 7

[0052]

[0053] Weigh out compound I-1 (439 mg, 1 mmol), dissolve it in 30.00 mL of DMF, and then add 4-cyanobenzoic acid (293.8 mg, 2 mmol), tetrakis(triphenylphosphine)palladium (23.2 mg, 0.002 mmol), and potassium hydroxide (2 mmol) aqueous solution sequentially. Stir and heat to 90°C in a water bath. After 6 hours, the reaction is complete, and the product has the following structural formula: (E).

[0054] Example 8

[0055]

[0056] Weigh out compound I-1 (439 mg, 1 mmol), dissolve it in 30.00 mL of DMF, and then add 3,4,5-trimethoxyphenyl (424.02 mg, 2 mmol), tetrakis(triphenylphosphine)palladium (23.2 mg, 0.002 mmol), and potassium hydroxide (2 mmol) aqueous solution sequentially. Stir and heat to 90 °C in a water bath, and the reaction is complete after 6 hours.

[0057] Example 9

[0058] Compound I-2 (6.0 mg, 0.01 mmol) from Example 5 was weighed and dissolved in 0.1 mL of dichloromethane to prepare a solution with a concentration of 10. -1 The mother liquor of M was prepared by dissolving 3 μL of each of the five mother liquors in 3 mL of toluene, dichloromethane, acetone, acetonitrile, and dimethyl sulfoxide to prepare a concentration of 1×10⁻⁶. -4 The test solution of M is subjected to ultraviolet and fluorescence tests, such as... Figure 1 and Figure 2As shown, the maximum emission wavelength of this compound is 580 nm, and the redshift and blueshift phenomena in different solvents are not obvious. The test results show that the optical properties of this substance are basically unaffected by different solvents.

[0059] Example 10

[0060] Compounds I-2 (6.0 mg, 0.01 mmol) and I-3 (4.6 mg, 0.01 mmol) from Examples 5 and 7 were weighed and dissolved in 0.1 mL of dichloromethane to prepare a concentration of 10. -1 The mother liquor of M. Take 5 groups of each of the two mother liquors, 10 μL of each group, and mix them evenly with 10 μL, 20 μL, 30 μL, 40 μL, and 50 μL of polymethyl methacrylate at ratios of 1:1, 1:2, 1:3, 1:4, and 1:5, respectively. Apply the mixture evenly to a glass plate using a KTQ-II adjustable coater, dry it in a 30℃ oven, place the glass plate under natural light, and take a clear picture with an iPhone 14 Pro (from left to right, these are the anti-counterfeiting films with mixing ratios of 1:1, 1:2, 1:3, 1:4, and 1:5). See details below. Figure 5 and Figure 7 As shown. Next, the glass plate coated with dye is placed under a 365nm ultraviolet lamp, and a photo is taken with an iPhone 14 Pro. A fluorescence image with strong fluorescence can be obtained (from left to right, these are anti-counterfeiting films with mixing ratios of 1:1, 1:2, 1:3, 1:4, and 1:5), specifically as shown. Figure 6 and Figure 8 As shown.

[0061] Example 11

[0062] Compounds I-2 (18.0 mg, 0.03 mmol) and I-3 (18.4 mg, 0.04 mmol) from Examples 5 and 7, respectively, were weighed, ensuring the sample surface was flat to facilitate uniform light irradiation and collection. Using a Quantaurus-QY fluorescence spectrometer equipped with an integrating sphere, the integrating sphere's reversal mirror was adjusted to the "powder" setting. A blank plate was then placed inside the integrating sphere to obtain background data. The scattering and emission spectra of the blank sample were measured and recorded as Blank. The blank plate was removed, and a solid fluorescent sample was placed inside, without changing other settings. The scattering and emission spectra of samples I-2 and I-3 were measured again and recorded as Sample. The quantum yield was calculated 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, and detector settings, and start data acquisition. Using TCSPC technology, construct a fluorescence decay curve by recording the arrival time of a single photon. By collecting a large amount of photon arrival time data, construct a fluorescence lifetime curve to obtain the corresponding solid-state fluorescence lifetime. Compared with compound E, compounds I-2 and I-3 exhibit superior solid-state fluorescence quantum yield and solid-state fluorescence lifetime. Fluorescence images of solid powders of compounds I-2, I-3, and E under 365nm lamp illumination are shown below. Figure 9 This can be proven.

[0063]

Claims

1. The application of a fluorine-containing seven-membered heterocyclic dye in fluorescent anti-counterfeiting film, characterized in that, The chemical structural formula of a fluorine-containing seven-membered heterocyclic dye is: I Wherein, the substituent R is selected from any one of N,N-diphenylaminophenyl, p-cyanophenyl, and 3,4,5-trimethoxyphenyl; Fluorine-containing seven-membered heterocyclic dyes can be rapidly formed into films by combining with polymethyl methacrylate, and strong fluorescence can be seen under a 365nm UV lamp.

2. The application according to claim 1, characterized in that, The application includes the following synthesis path: (1) Compound I-1, DMF, and compound 2 were added to a reaction flask at room temperature and dissolved by magnetic stirring. Then tetratriphenylphosphine palladium and potassium hydroxide aqueous solution were added and heated to obtain a reaction solution. The substituent R in compound 2 was selected from any one of N,N-diphenylaminophenyl, 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, which is a fluorine-containing seven-membered heterocyclic dye.

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

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

5. The application according to claim 2, characterized in that, The feeding sequence of step (1) is compound I-1, DMF, compound 2, tetratriphenylphosphine palladium, and potassium hydroxide aqueous solution.

6. The application according to claim 2, characterized in that, The heating reaction temperature in step (1) is 30~150℃ and the heating time is 2~18 hours.

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

8. A fluorescent anti-counterfeiting film, characterized in that, The fluorine-containing seven-membered heterocyclic dye according to claim 1 has the following chemical structural formula: I。 9. The fluorescent anti-counterfeiting film according to claim 8, characterized in that, The fluorescent anti-counterfeiting film achieves its anti-counterfeiting effect under ultraviolet light.

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