Preparation of a nitrogen-containing heptanoic fluorine-boron compound and its application in fluorescent anti-counterfeiting films.

Abstract

This invention discloses the preparation of a nitrogen-containing seven-membered fluoroboron compound and its application in fluorescent anti-counterfeiting films. The compound structure is as follows: The dye is produced by a Knoevenagel condensation reaction of 2,3,3-trimethylindole and dibromo-2-pyrrolecarboxaldehyde in the presence of acetic acid, piperidine, and toluene to generate a dibromo seven-membered fluoroboron fluorescent dye. This dibromo seven-membered fluoroboron fluorescent dye is then reacted with phenylboronic acid, 4-cyanophenylboronic acid, p-methoxyphenylboronic acid, and triphenylaminephenylboronic acid to obtain the final compound. This compound can react with acrylic resin to form a film on a thin film, exhibiting color under natural light and clear fluorescence under ultraviolet light (365nm). Furthermore, this fluorescent dye is simple and readily available, has low manufacturing costs, forms a film quickly with acrylic resin or polyvinyl alcohol solution, has a high anti-counterfeiting coefficient, and is difficult to counterfeit, showing great potential in fluorescent anti-counterfeiting packaging films and OLDE (Optically Variable Interaction) technology.

Description

Technical Field

[0001] This invention relates to the field of materials technology, and more specifically, to the preparation of a nitrogen-containing seven-membered fluorine-boron compound. This type of compound has high fluorescence intensity and can be widely used in the field of fluorescent anti-counterfeiting films. Background Technology

[0002] Ultraviolet fluorescent ink is a relatively mature anti-counterfeiting ink on the market. It is made by adding corresponding visible fluorescent compounds to the ink. Under ultraviolet light, the anti-counterfeiting label can display or emit various colors of fluorescence or change color. This technology uses special fluorescent ink to bond to the label, and the serial number, text, or pattern cannot be found with the naked eye or touch. It can only be seen when exposed to a fluorescent lamp, that is, an ultraviolet lamp, which has a good anti-counterfeiting effect.

[0003] This invention designs and synthesizes a novel nitrogen-containing seven-membered fluorine-boron compound, which, as a dye, exhibits excellent penetrability and has great potential in the fields of fluorescent anti-counterfeiting films and OLDE. Summary of the Invention

[0004] This invention provides a method for preparing a nitrogen-containing seven-membered fluorine-boron compound and its application in fluorescent anti-counterfeiting films. This compound is not only simple and readily available, with low manufacturing costs and high fluorescence intensity, but also causes minimal environmental pollution.

[0005] A nitrogen-containing seven-membered fluorine-boron compound and its application in fluorescent anti-counterfeiting films, wherein the chemical structural formula of the compound is as follows:

[0006]

[0007] The substituent R is selected from any one of hydrogen, cyano, methoxy, and diphenylamino.

[0008] As a preliminary option, the chemical structural formula of the compound is:

[0009] Any one of them.

[0010] A method for synthesizing the nitrogen-containing seven-membered fluorine-boron compound, the method comprising the following synthetic route:

[0011] The method specifically includes the following steps: (1) Add dibromoheptafluoroboron compound 1 to the reaction flask at room temperature, then add compound 2, tetra(triphenylphosphine)palladium, and cesium carbonate in sequence, dissolve in toluene and water, and react at 120°C under nitrogen protection to obtain the reaction solution; (2) The reaction solution in step (1) is extracted, dried, and evaporated by rotary evaporation, then separated by silica gel chromatography and evaporated to obtain solid product I.

[0012] Compound 1 is a dibromoheptafluoroboron compound, and compound 2 is phenylboronic acid containing different substituents, including any one of hydrogen, cyano, methoxy, and diphenylamino. The feed ratio of compound 1 to compound 2 is 1:6 to 10, the feed ratio of compound 1 to tetrakis(triphenylphosphine)palladium is 1:0.05 to 0.1, and the feed ratio of compound 1 to cesium carbonate is 1:1 to 2.

[0013] The feeding sequence of step (1) is as follows: compound 1, compound 2, tetrakis(triphenylphosphine)palladium, cesium carbonate, dissolved in a small amount of water, and finally dissolved in toluene.

[0014] The heating temperature in step (1) is 100~130℃ and the heating time is 15~17 hours to ensure that the reaction proceeds fully and to reduce the generation of by-products.

[0015] Another technical solution of the present invention is the application of the aforementioned nitrogen-containing seven-membered fluorine-boron compound as a fluorescent anti-counterfeiting film. This compound exhibits excellent fluorescence properties and chemical stability, making it suitable for high-security anti-counterfeiting labels.

[0016] The present invention also provides a fluorescent anti-counterfeiting film, comprising the aforementioned nitrogen-containing heptanodic fluorine-boron compound.

[0017] The preparation of fluorescent anti-counterfeiting film involves dissolving a compound in a solvent to prepare a mother liquor, then adding acrylic resin to prepare a film-forming solution. Finally, the film-forming solution is coated onto the anti-counterfeiting object to form a film, achieving the fluorescent anti-counterfeiting effect. By adjusting the concentration of the mother liquor and the ratio of acrylic resin, the performance of the fluorescent anti-counterfeiting film, such as fluorescence intensity, durability, and adhesion, can be further optimized.

[0018] The solvents include ethyl acetate, dichloromethane, dimethyl sulfoxide, acetonitrile, toluene, etc.

[0019] The beneficial effects of this invention are as follows: (1) The nitrogen-containing seven-membered fluorine-boron compound synthesized in this invention has high fluorescence intensity, is easy to obtain, has low manufacturing cost, and is low-pollution.

[0020] (2) The compound provided by this invention is mixed with acrylic resin or polyvinyl alcohol solution, and a film can be formed quickly on a glass plate. It is colored under natural light and has clear fluorescence under ultraviolet light. The best effect is achieved when the volume ratio of mother liquor to acrylic resin is 1:1 to 1.5. It is especially suitable for fluorescent anti-counterfeiting packaging film, or when combined with anode, cathode and semiconductor materials for use in OLDE. Attached Figure Description

[0021] Figure 1This is the proton NMR spectrum of compound I-1 obtained in Example 1.

[0022] Figure 2 This is the proton NMR spectrum of compound I-2 obtained in Example 8.

[0023] Figure 3 This is the proton NMR spectrum of compound I-3 obtained in Example 9.

[0024] Figure 4 This is the proton NMR spectrum of compound I-4 obtained in Example 10.

[0025] Figure 5 The compound I-1 from Example 11-1 was mixed with a polyvinyl alcohol solution to form a film on a glass plate. The film was then photographed with a VIVO S1 mobile phone under a UV lamp (365nm) to obtain a clear fluorescence image.

[0026] Figure 6 , Figure 7 , Figure 8 Compound I-1 from Examples 11-2, 11-3, and 11-4 was mixed with acrylic resin to form a film on a glass plate. The film was then photographed with a VIVO S1 mobile phone under a UV lamp (365nm) to obtain a clear fluorescence image.

[0027] Figure 9 The compound I-2 from Examples 11-4 was formed into a film with acrylic resin on a glass plate. The film was then photographed with a VIVO S1 mobile phone under a UV lamp (365nm) to obtain a clear fluorescence image.

[0028] Figure 10 The compound I-3 from Examples 11-6 was formed into a film with acrylic resin on a glass plate. The film was then photographed with a VIVO S1 mobile phone under a UV lamp (365nm) to obtain a clear fluorescence image.

[0029] Figure 11 The compound I-4 from Examples 11-7 was formed into a film with acrylic resin on a glass plate. The film was then photographed with a VIVO S1 mobile phone under a UV lamp (365nm) to obtain a clear fluorescence image. Detailed Implementation

[0030] 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.

[0031] Example 1 Weigh out compound 1, dibromoheptafluoroboron fluorescent dye (436.3 mg, 1 mmol), then add compound 2, p-cyanobenzoboric acid (1.17 g, 8 mmol), tetrakis(triphenylphosphine)palladium (57.8 mg, 0.05 mmol), and cesium carbonate (325.8 mg, 1 mmol) sequentially. Dissolve in a small amount of water, then add 15 mL of toluene to dissolve. Under nitrogen protection, heat to 120 °C. The reaction was heated and stirred at C for 17 hours until complete. The reactants were extracted, rotary evaporated, and then subjected to column chromatography to give an orange solid compound I-1 in 56.8% yield.

[0032] .

[0033] Example 2 Weigh out compound 1, dibromoheptafluoroboron fluorescent dye (436.3 mg, 1 mmol), then add compound 2, p-cyanobenzoboric acid (1.17 g, 8 mmol), tetrakis(triphenylphosphine)palladium (57.8 mg, 0.05 mmol), and cesium carbonate (325.8 mg, 1 mmol) sequentially. Dissolve in a small amount of water, then add 15 mL of toluene to dissolve again. Under nitrogen protection, 100 The reaction was heated and stirred at temperature C for 17 hours. Compared to Example 1, the temperature was 20°C lower, resulting in incomplete reaction of the starting materials. The reactants were extracted, rotary evaporated, and then subjected to column chromatography to obtain an orange solid compound I-1 in 40.6% yield.

[0034] .

[0035] Example 3 Weigh out compound 1, dibromoheptafluoroboron fluorescent dye (436.3 mg, 1 mmol), then add compound 2, p-cyanobenzoboric acid (1.17 g, 8 mmol), tetrakis(triphenylphosphine)palladium (57.8 mg, 0.05 mmol), and cesium carbonate (325.8 mg, 1 mmol) sequentially. Dissolve in a small amount of water, then add 15 mL of toluene to dissolve. Under nitrogen protection, heat to 130 °C. The reaction was heated and stirred at temperature C for 17 hours. Compared to Example 1, the temperature was increased by 10°C, resulting in a complete reaction, but with more byproducts. The reactants were extracted, rotary evaporated, and then subjected to column chromatography to obtain the product in 35.4% yield. .

[0036] Example 4 Weigh out compound 1, dibromoheptafluoroboron fluorescent dye (436.3 mg, 1 mmol), then add compound 2, p-cyanobenzonic acid (1.47 g, 10 mmol), tetrakis(triphenylphosphine)palladium (57.8 mg, 0.05 mmol), and cesium carbonate (325.8 mg, 1 mmol) sequentially. Dissolve in a small amount of water, then add 15 mL of toluene to dissolve. Under nitrogen protection, heat to 120 °C. The reaction was carried out under heating and stirring for 17 hours until complete. Compared to Example 1, Compound 2 had a two-fold increase in equivalent yield, with a yield of 69.1%.

[0037] .

[0038] Example 5 Weigh out compound 1, dibromoheptafluoroboron fluorescent dye (436.3 mg, 1 mmol), then add compound 2, p-cyanobenzoboric acid (881.6 mg, 6 mmol), tetrakis(triphenylphosphine)palladium (57.8 mg, 0.05 mmol), and cesium carbonate (325.8 mg, 1 mmol) sequentially. Dissolve in a small amount of water, then add 15 mL of toluene to dissolve. Under nitrogen protection, incubate at 120 °C. The reaction was carried out under heating and stirring for 17 hours until complete. Compared to Example 1, compound 2 was reduced by two-fold equivalents, and the reactants did not react completely. The reactants were extracted, rotary evaporated, and column chromatography was performed to give an orange solid compound I-1, with a yield of 31.1%.

[0039] .

[0040] Example 6 Weigh out compound 1, dibromoheptafluoroboron fluorescent dye (436.3 mg, 1 mmol), then add compound 2, p-cyanobenzonic acid (1.47 g, 10 mmol), tetrakis(triphenylphosphine)palladium (57.8 mg, 0.05 mmol), and cesium carbonate (651 mg, 2 mmol) sequentially. Dissolve in a small amount of water, then add 15 mL of toluene to dissolve. Under nitrogen protection, heat to 120 °C. The reaction was carried out under heating and stirring at C for 17 hours until complete. Compared to Example 4, the amount of cesium carbonate was increased by 1 equivalent. After extraction of the reactants, rotary evaporation and column chromatography were performed to obtain an orange solid compound I-1, with a yield of 72.8%.

[0041] .

[0042] Example 7 Weigh out compound 1, dibromoheptafluoroboron fluorescent dye (436.3 mg, 1 mmol), then add compound 2, p-cyanobenzoboric acid (1.17 g, 10 mmol), tetrakis(triphenylphosphine)palladium (115.6 mg, 0.1 mmol), and cesium carbonate (651 mg, 2 mmol) sequentially. Dissolve in a small amount of water, then add 15 mL of toluene to dissolve further. Under nitrogen protection, heat to 120 °C. The reaction was carried out under heating and stirring for 15 hours until complete. Compared with Example 6, the catalyst tetra(triphenylphosphine)palladium was increased by 0.05 equivalents, the reaction time was shortened by 2 hours, and the reactants were extracted, rotary evaporated, and column chromatography was performed to give an orange solid compound I-1 with a yield of 72.8%.

[0043] .

[0044] Example 8 Weigh out compound 1, dibromoheptafluoroboron fluorescent dye (436.3 mg, 1 mmol), then add compound 2, phenylboronic acid (1.2 g, 10 mmol), tetrakis(triphenylphosphine)palladium (57.8 mg, 0.05 mmol), and cesium carbonate (651 mg, 2 mmol) sequentially. Dissolve in a small amount of water, then add 15 mL of toluene to dissolve further. Under nitrogen protection, heat to 120 °C. The reaction was heated and stirred at C for 17 hours until complete. The reactants were extracted, rotary evaporated, and then subjected to column chromatography to give an orange solid compound I-1 in 52.9% yield.

[0045] .

[0046] Example 9 Weigh out compound 1, dibromoheptafluoroboron fluorescent dye (436.3 mg, 1 mmol), then add compound 2, p-methoxyphenylboronic acid (1.5 g, 10 mmol), tetrakis(triphenylphosphine)palladium (57.8 mg, 0.05 mmol), and cesium carbonate (651 mg, 2 mmol) sequentially. Dissolve in a small amount of water, then add 15 mL of toluene to dissolve further. Under nitrogen protection, heat to 120 °C. The reaction was heated and stirred at C for 17 hours until complete. The reactants were extracted, rotary evaporated, and then subjected to column chromatography to give an orange-red solid compound I-1 in 67.6% yield.

[0047] .

[0048] Example 10 Weigh out compound 1, dibromoheptafluoroboron fluorescent dye (436.3 mg, 1 mmol), then add compound 2, triphenylamine phenylboronic acid (2.9 g, 10 mmol), tetrakis(triphenylphosphine)palladium (57.8 mg, 0.05 mmol), and cesium carbonate (651 mg, 2 mmol) sequentially. Dissolve in a small amount of water, then add 15 mL of toluene to dissolve further. Under nitrogen protection, heat to 120 °C. The reaction was heated and stirred at C for 17 hours until complete. The reactants were extracted, rotary evaporated, and then subjected to column chromatography to give a purple-red solid compound I-1 in 61.8% yield.

[0049] .

[0050] Example 11 Preparation of Fluorescent Anti-counterfeiting Film Example 11-1 Weigh 4.8 mg (0.01 mmol) of compound I prepared in Example 1, dissolve it in 1 mL of ethyl acetate to prepare a 0.01 mol / L stock solution, then dissolve 5 μL of the stock solution in 10 μL of polyvinyl alcohol solution and evenly coat it onto a glass plate. Dry the plate at 30°C, place it under natural light, and take a clear picture using a VIVO S1 mobile phone. See details below. Figure 5 As shown, the surface of the anti-counterfeiting film is uneven, with obvious air bubbles, slow film formation, and weak fluorescence. Adjusting the volume ratio of the mother liquor to the polyvinyl alcohol solution to 1:1 further weakens the fluorescence intensity, which is detrimental to the preparation of the anti-counterfeiting film.

[0051] Example 11-2 Weigh 4.8 mg (0.01 mmol) of compound I prepared in Example 1, dissolve it in 1 mL of ethyl acetate to prepare a 0.01 mol / L stock solution, then dissolve 5 μL of the stock solution in 10 μL of acrylic resin and evenly coat it onto a glass plate. Dry the plate at 30°C, place it under natural light, and take a clear picture using a VIVO S1 mobile phone. See details below. Figure 6 As shown, the surface of the anti-counterfeiting film is uneven and contains air bubbles. Because the film formed by the mother liquor and acrylic resin is relatively thin, uneven heating is likely to occur in the oven, which is not conducive to the preparation of the anti-counterfeiting film.

[0052] Examples 11-3 Weigh 4.8 mg (0.01 mmol) of compound I from Example 1, dissolve it in 1 mL of ethyl acetate to prepare a 0.01 mol / L stock solution, then dissolve 5 μL of the stock solution in 10 μL of acrylic resin and evenly coat it onto a glass plate. Allow it to air dry at room temperature (25°C). Place the glass plate under a 365 nm UV lamp and take a picture using a VIVO S1 mobile phone to obtain a clear fluorescence image, as shown below. Figure 7As shown, the surface of the anti-counterfeiting film is smooth, which is beneficial for its preparation.

[0053] Examples 11-4 Weigh 4.8 mg (0.01 mmol) of compound I from Example 1, dissolve it in 1 mL of ethyl acetate to prepare a 0.01 mol / L stock solution, then dissolve 5 μL of the stock solution in 5 μL of acrylic resin and evenly coat it onto a glass plate. Allow it to air dry at room temperature (25°C). Place the glass plate under a 365 nm UV lamp and take a picture using a VIVO S1 mobile phone to obtain a clear fluorescence image, as shown below. Figure 8 As shown, when the volume ratio of mother liquor to acrylic resin is 1:1, the fluorescence intensity is enhanced compared to Example 12-2, and the film formation rate is faster.

[0054] Examples 11-5 Weigh 4.4 mg (0.01 mmol) of compound I from Example 8, dissolve it in 1 mL of ethyl acetate to prepare a 0.01 mol / L stock solution, then dissolve 5 μL of the stock solution in 5 μL of acrylic resin and evenly coat it onto a glass plate. Allow it to air dry at room temperature (25°C). It will turn orange under natural light. Place the glass plate under a 365 nm UV lamp and take a picture using a VIVO S1 mobile phone to obtain a clear fluorescence image, as shown below. Figure 9 As shown.

[0055] Examples 11-6 Weigh 4.9 mg (0.01 mmol) of compound I from Example 9, dissolve it in 1 mL of ethyl acetate to prepare a 0.01 mol / L stock solution, then dissolve 5 μL of the stock solution in 5 μL of acrylic resin and evenly coat it onto a glass plate. Allow it to air dry at room temperature (25°C). Under natural light, it appears orange-red. Place the glass plate under a 365 nm UV lamp and take a picture using a VIVO S1 mobile phone to obtain a clear fluorescence image, as shown below. Figure 10 As shown.

[0056] Examples 11-7 Weigh out 7.7 mg (0.01 mmol) of compound I from Example 10, dissolve it in 1 mL of ethyl acetate to prepare a 0.01 mol / L stock solution, then dissolve 5 μL of the stock solution in 5 μL of acrylic resin and evenly coat it onto a glass plate. Allow it to air dry at room temperature (25°C). It will turn red under natural light. Place the glass plate under a 365 nm UV lamp and take a picture using a VIVO S1 mobile phone to obtain a clear fluorescence image, as shown below. Figure 11 As shown. The anti-counterfeiting film described in this patent can also be used in materials such as plastic wrap.

[0057] The above embodiments are merely preferred technical solutions of the present invention and should not be considered as limitations on the present invention. The embodiments and features described in these embodiments can be arbitrarily combined without conflict. The scope of protection of the present invention should be limited to the technical solutions described in the claims, including equivalent substitutions of the technical features described in the claims. That is, equivalent substitutions and improvements within this scope are also within the scope of protection of the present invention.

Claims

1. The application of nitrogen-containing seven-membered fluorine-boron compound in the preparation of fluorescent anti-counterfeiting film, characterized in that, The structural formulas of nitrogen-containing seven-membered fluorine-boron compounds are shown below: Ⅰ Wherein, the substituent R is selected from any one of hydrogen, cyano, methoxy or diphenylamino; The compound is dissolved in a solvent to prepare a mother liquor, and then an acrylic resin solution is added to prepare a film-forming solution. The volume ratio of the acrylic resin solution to the mother liquor is 1:

1. Finally, the film-forming solution is coated on the anti-counterfeiting object to form a film, and then air-dried at 25°C to achieve a fluorescent anti-counterfeiting effect. The solvent is selected from ethyl acetate, dichloromethane, dimethyl sulfoxide, acetonitrile, or toluene.

2. The application according to claim 1, characterized in that, The preparation method of nitrogen-containing seven-membered fluorine-boron compound includes the following steps: (1) Compound 1, compound 2, tetrakis(triphenylphosphine)palladium, cesium carbonate, toluene and water were added to the reaction flask at room temperature and the reaction was carried out under nitrogen protection to obtain the reaction solution. (2) The reaction solution in step (1) was extracted with dichloromethane and water. The extract was dried with anhydrous sodium sulfate and then rotary evaporated. After separation by silica gel column chromatography, solid product I, i.e., a nitrogen-containing seven-membered fluorine-boron compound, was obtained. The reaction formula is as follows: ； Wherein, the substituent R is selected from any one of hydrogen, cyano, methoxy or diphenylamino.

3. The application according to claim 2, characterized in that, In step (1), the molar ratio of compound 1 to compound 2 is 1:6~10.

4. The application according to claim 2, characterized in that, The heating temperature in step (1) is 100~130℃ and the heating time is 15~17 hours.

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