Preparation of nitrogen-containing seven-membered fluorine boron compound and application of nitrogen-containing seven-membered fluorine boron compound in fluorescent anti-counterfeiting film

Abstract

The invention discloses preparation of a nitrogen-containing seven-membered fluorine-boron compound and application of the nitrogen-containing seven-membered fluorine-boron compound to a fluorescent anti-counterfeiting film, the structure of the compound is as follows: # imgabs0, the dye takes 2, 3, 3-trimethylindole and dibromo-2-pyrrolecarboxaldehyde as raw materials, under the action of acetic acid, piperidine and methylbenzene, a Knoevenagel condensation reaction is carried out, and the dibromo seven-membered fluorine-boron fluorescent dye is generated. The dibromo seven-membered fluorine boron fluorescent dye respectively reacts with phenylboronic acid, 4-cyanophenylboronic acid, p-methoxyphenylboronic acid and triphenylamine phenylboronic acid to obtain a final compound. The compound can act with acrylic resin to form a film on a thin film, and can be colored under natural light, and clear fluorescence can be seen under an ultraviolet lamp (365nm). The fluorescent dye is simple, easy to obtain, low in manufacturing cost, high in film forming speed with acrylic resin or a polyvinyl alcohol solution on a thin film, high in anti-counterfeiting coefficient, large in counterfeiting difficulty and huge in potential in the aspects of fluorescent anti-counterfeiting packaging films, OLDE and the like.

Description

Technical Field

[0001] The present invention relates to the field of material technology, and more specifically, to the preparation of a nitrogen-containing seven-membered fluoroboron compound. The compound has high fluorescence intensity and can be widely used in the field of fluorescent anti-counterfeiting films. Background Art

[0002] Ultraviolet fluorescent ink is a relatively mature anti-counterfeiting ink in the current market. It is made by adding corresponding visible fluorescent compounds to the ink. Under ultraviolet light, the anti-counterfeiting logo can display or emit various colors of fluorescence or change color. This technology uses special fluorescent ink to combine with the label. The serial number, text or pattern cannot be found by naked eyes or touch. It must be illuminated by fluorescent light, that is, ultraviolet light, to see it, which has a good anti-counterfeiting effect.

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

[0004] The present invention provides a preparation method of a nitrogen-containing seven-membered fluorine-boron compound and research on its application in fluorescent anti-counterfeiting films. The compound is not only simple and easy to obtain, but also has low manufacturing cost, high fluorescence intensity and little environmental pollution.

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

[0006] The substituent R is any one selected from hydrogen, cyano, methoxy, and diphenylamino.

[0007] As a pre-selected solution, the chemical structural formula of the compound is:

[0008] Any one of .

[0009] A method for synthesizing the nitrogen-containing seven-membered fluorine boron compound, the method comprising the following synthesis path:

[0010] The method specifically comprises the following steps: (1) Add dibromo-7-membered fluoroborane compound 1 to a reaction flask at room temperature, then add compound 2, tetrakis(triphenylphosphine)palladium, and cesium carbonate in sequence, dissolve them in toluene and water, and heat to 120° C. under nitrogen protection to obtain a reaction solution; (2) The reaction solution in step (1) is extracted, dried, and rotary evaporated, and then separated by silica gel chromatography and rotary dried to obtain a solid product I.

[0011] Compound 1 is a dibromo-heptafluoroboric acid compound, and compound 2 is phenylboric acid containing different substituents, wherein the substituents include any one of hydrogen, cyano, methoxy, and diphenylamine. The feed ratio of compound 1 to compound 2 is 1:6-10, the feed ratio of compound 1 to tetrakis(triphenylphosphine)palladium is 1:0.05-0.1, and the feed ratio of compound 1 to cesium carbonate is 1:1-2.

[0012] The order of adding materials in step (1) is compound 1, compound 2, tetrakis(triphenylphosphine)palladium, cesium carbonate, which are dissolved with a small amount of water and finally dissolved with toluene.

[0013] The heating temperature of step (1) is 100-130° C. and the heating time is 15-17 hours to ensure that the reaction proceeds fully and reduce the generation of by-products.

[0014] Another technical solution of the present invention is to use the nitrogen-containing seven-membered fluorine boron compound as a fluorescent anti-counterfeiting film. The compound exhibits excellent fluorescent properties and chemical stability and is suitable for high-security anti-counterfeiting labels.

[0015] The present invention also provides a fluorescent anti-counterfeiting film, comprising the nitrogen-containing seven-membered fluorine-boron compound.

[0016] The preparation of fluorescent anti-counterfeiting film is to dissolve the compound in a solvent to prepare a mother solution, then add acrylic resin to prepare a film-forming solution, and finally apply the film-forming solution on the anti-counterfeiting object to form a film to achieve the fluorescent anti-counterfeiting effect. By adjusting the concentration of the mother solution 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.

[0017] The solvent includes ethyl acetate, dichloromethane, dimethyl sulfoxide, acetonitrile, toluene and the like.

[0018] The beneficial effects of the present invention are as follows: (1) The nitrogen-containing seven-membered fluoroboron compound synthesized by the present invention has high fluorescence intensity, is easy to obtain, has low manufacturing cost and low pollution.

[0019] (2) The compound provided by the present invention is mixed with acrylic resin or polyvinyl alcohol solution, and a film can be quickly formed on a glass plate, showing color under natural light and clear fluorescence under ultraviolet light. The best effect is achieved when the volume ratio of the mother solution to the acrylic resin is 1:1 to 1.5. It is particularly suitable for fluorescent anti-counterfeiting packaging film, or for OLDE after being combined with anodes, cathodes and semiconductor materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1This is the hydrogen spectrum of compound Ⅰ-1 obtained in Example 1.

[0021] Figure 2 This is the hydrogen spectrum of compound Ⅰ-2 obtained in Example 8.

[0022] Figure 3 This is the hydrogen spectrum of compound Ⅰ-3 obtained in Example 9.

[0023] Figure 4 This is the hydrogen spectrum of compound Ⅰ-4 obtained in Example 10.

[0024] Figure 5 The compound I-1 in Example 11-1 and the polyvinyl alcohol solution were film-formed on a glass plate, and a photo was taken with a VIVO S1 mobile phone under ultraviolet light (365nm) to obtain a clear fluorescence image.

[0025] Figure 6 , Figure 7 , Figure 8 Compound I-1 in Examples 11-2, 11-3, and 11-4 was reacted with acrylic resin to form a film on a glass plate, and a clear fluorescence image was obtained by taking a photo with a VIVO S1 mobile phone under ultraviolet light (365 nm).

[0026] Fig. 9 Compound I-2 in Example 11-4 and acrylic resin were film-formed on a glass plate, and a photo was taken with a VIVO S1 mobile phone under ultraviolet light (365nm) to obtain a clear fluorescence image.

[0027] Fig.10 Compound I-3 in Example 11-6 and acrylic resin were film-formed on a glass plate, and a photo was taken with a VIVO S1 mobile phone under ultraviolet light (365nm) to obtain a clear fluorescence image.

[0028] Fig.11 Compound I-4 in Example 11-7 was filmed with acrylic resin on a glass plate, and a photo was taken with a VIVO S1 mobile phone under ultraviolet light (365 nm) to obtain a clear fluorescence image. DETAILED DESCRIPTION

[0029] 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.

[0030] Example 1 Weigh compound 1 dibromo-heptafluoroboron fluorescent dye (436.3 mg, 1 mmol), then add compound 2 p-cyanophenylboronic acid (1.17 g, 8 mmol), tetrakis(triphenylphosphine)palladium (57.8 mg, 0.05 mmol), cesium carbonate (325.8 mg, 1 mmol) in sequence, dissolve in a small amount of water, then add 15 mL of toluene to dissolve, protect with nitrogen, heat and stir at 120 ° C for 17 hours, and the reaction is complete. The reactant is extracted and rotary evaporated, and column chromatography is performed to obtain orange solid compound Ⅰ-1 with a yield of 56.8%.

[0031] .

[0032] Example 2 Weigh compound 1 dibromo-heptafluoroboron fluorescent dye (436.3 mg, 1 mmol), then add compound 2 p-cyanophenylboronic acid (1.17 g, 8 mmol), tetrakis(triphenylphosphine)palladium (57.8 mg, 0.05 mmol), cesium carbonate (325.8 mg, 1 mmol) in sequence, dissolve in a small amount of water, then add 15 mL of toluene to dissolve, protect with nitrogen, heat and stir at 100 ° C for 17 hours, compared with Example 1, the temperature is reduced by 20 ° C, and the raw material reaction is incomplete. The reactant is extracted and rotary evaporated, and after column chromatography, an orange solid compound I-1 is obtained with a yield of 40.6%.

[0033] .

[0034] Example 3 Weigh compound 1 dibromo-heptafluoroboron fluorescent dye (436.3 mg, 1 mmol), then add compound 2 p-cyanophenylboronic acid (1.17 g, 8 mmol), tetrakis(triphenylphosphine)palladium (57.8 mg, 0.05 mmol), cesium carbonate (325.8 mg, 1 mmol) in sequence, dissolve in a small amount of water, then add 15 mL of toluene to dissolve, protect with nitrogen, heat and stir at 130 ° C for 17 hours, compared with Example 1, the temperature is increased by 10 ° C, the reaction is complete, but there are more by-products. The reactant is extracted and then rotary evaporated, and the product is obtained after column chromatography, with a yield of 35.4% .

[0035] Example 4 Weigh compound 1 dibromo-heptafluoroboron fluorescent dye (436.3 mg, 1 mmol), then add compound 2 p-cyanophenylboronic acid (1.47 g, 10 mmol), tetrakis(triphenylphosphine)palladium (57.8 mg, 0.05 mmol), cesium carbonate (325.8 mg, 1 mmol) in sequence, dissolve in a small amount of water, then add 15 mL of toluene to dissolve, protect with nitrogen, heat and stir at 120 ° C for 17 hours, and the reaction is complete. Compared with Example 1, compound 2 is doubled in equivalent, and the yield is 69.1%.

[0036] .

[0037] Example 5 Weigh compound 1 dibromo-heptafluoroboron fluorescent dye (436.3 mg, 1 mmol), then add compound 2 p-cyanophenylboronic acid (881.6 mg, 6 mmol), tetrakis(triphenylphosphine)palladium (57.8 mg, 0.05 mmol), cesium carbonate (325.8 mg, 1 mmol) in sequence, dissolve in a small amount of water, then add 15 mL of toluene to dissolve, protect with nitrogen, heat and stir at 120 ° C for 17 hours, and the reaction is complete. Compared with Example 1, compound 2 is reduced by two times, and the raw material reaction is incomplete. The reactant is extracted and then rotary evaporated, and the orange solid compound I-1 is obtained after column chromatography with a yield of 31.1%.

[0038] .

[0039] Example 6 Weigh compound 1 dibromo-heptafluoroboron fluorescent dye (436.3 mg, 1 mmol), then add compound 2 p-cyanophenylboronic acid (1.47 g, 10 mmol), tetrakis(triphenylphosphine)palladium (57.8 mg, 0.05 mmol), cesium carbonate (651 mg, 2 mmol) in sequence, dissolve in a small amount of water, then add 15 mL of toluene to dissolve, protect with nitrogen, heat and stir at 120 ° C for 17 hours, and the reaction is complete. Compared with Example 4, cesium carbonate is increased by 1 times the equivalent, the reactant is extracted and then rotary evaporated, and column chromatography is performed to obtain orange solid compound Ⅰ-1, with a yield of 72.8%.

[0040] .

[0041] Example 7 Weigh compound 1 dibromo-heptafluoroboron fluorescent dye (436.3 mg, 1 mmol), then add compound 2 p-cyanophenylboronic acid (1.17 g, 10 mmol), tetrakis(triphenylphosphine)palladium (115.6 mg, 0.1 mmol), cesium carbonate (651 mg, 2 mmol) in sequence, dissolve in a small amount of water, then add 15 mL of toluene to dissolve, protect with nitrogen, heat and stir at 120 ° C for 15 hours, and the reaction is complete. Compared with Example 6, the catalyst tetrakis(triphenylphosphine)palladium is increased by 0.05 times the equivalent, the reaction time is shortened by 2 hours, the reactant is extracted and then rotary evaporated, and the orange solid compound I-1 is obtained after column chromatography with a yield of 72.8%.

[0042] .

[0043] Example 8 Weigh compound 1 dibromo-heptafluoroboron fluorescent dye (436.3 mg, 1 mmol), then add compound 2 phenylboric acid (1.2 g, 10 mmol), tetrakis(triphenylphosphine)palladium (57.8 mg, 0.05 mmol), cesium carbonate (651 mg, 2 mmol) in sequence, dissolve in a small amount of water, then add 15 mL of toluene to dissolve, protect with nitrogen, heat and stir at 120 ° C for 17 hours, and the reaction is complete. The reactant is extracted and rotary evaporated, and column chromatography is performed to obtain orange solid compound Ⅰ-1 with a yield of 52.9%.

[0044] .

[0045] Example 9 Weigh compound 1 dibromo-heptafluoroboron 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), cesium carbonate (651 mg, 2 mmol) in sequence, dissolve in a small amount of water, then add 15 mL of toluene to dissolve, protect with nitrogen, heat and stir at 120 ° C for 17 hours, and the reaction is complete. The reactant is extracted and rotary evaporated, and after column chromatography, an orange-red solid compound Ⅰ-1 is obtained with a yield of 67.6%.

[0046] .

[0047] Example 10 Weigh compound 1 dibromo-heptafluoroboron 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), cesium carbonate (651 mg, 2 mmol) in sequence, dissolve in a small amount of water, then add 15 mL of toluene to dissolve, protect with nitrogen, heat and stir at 120 ° C for 17 hours, and the reaction is complete. The reactant is extracted and rotary evaporated, and after column chromatography, a purple-red solid compound Ⅰ-1 is obtained with a yield of 61.8%.

[0048] .

[0049] Example 11 Preparation of fluorescent anti-counterfeiting film Example 11-1 Weigh the compound I (4.8 mg, 0.01 mmol) prepared in Example 1, dissolve it in 1 mL of ethyl acetate to prepare a 0.01 mol / L mother solution, then take 5 μL of the mother solution and dissolve it in 10 μL of polyvinyl alcohol solution, and evenly apply it to a glass plate, dry it at 30°C, place the glass plate under natural light, and take a photo with a VIVO S1 mobile phone to obtain a clear picture, as shown in the following figure. Figure 5 As shown. It can be observed that the surface of the anti-counterfeiting film is uneven, there are obvious bubbles, the film forming speed is slow and the fluorescence is weak. By adjusting the volume ratio of the mother solution to the polyvinyl alcohol solution to 1:1, the fluorescence intensity is further weakened, which is not conducive to the preparation of the anti-counterfeiting film.

[0050] Example 11-2 Weigh the compound I (4.8 mg, 0.01 mmol) prepared in Example 1, take 1 mL of ethyl acetate to dissolve it into a 0.01 mol / L mother solution, then take 5 μL of the mother solution and dissolve it in 10 μL of acrylic resin, and evenly apply it to a glass plate, dry it at 30°C, place the glass plate under natural light, and take a photo with a VIVO S1 mobile phone to obtain a clear picture, as shown in the following figure. Figure 6 As shown, it can be observed that the surface of the anti-counterfeiting film is uneven and has bubbles. Since the film formed by the mother liquid and the acrylic resin is relatively thin, it is easy to be heated unevenly in the oven, which is not conducive to the preparation of the anti-counterfeiting film.

[0051] Example 11-3 Weigh compound I (4.8 mg, 0.01 mmol) in Example 1, dissolve in 1 mL of ethyl acetate to prepare a 0.01 mol / L mother solution, then take 5 μL of the mother solution and dissolve in 10 μL of acrylic resin, and evenly apply it to a glass plate, air-dry naturally at room temperature (25°C), put the glass plate under a (365 nm) ultraviolet lamp, and take a photo with a VIVO S1 mobile phone to obtain a clear fluorescence image, as shown in FIG. Figure 7It can be observed that the surface of the anti-counterfeiting film is flat, which is conducive to the preparation of the anti-counterfeiting film.

[0052] Example 11-4 Weigh compound I (4.8 mg, 0.01 mmol) in Example 1, dissolve in 1 mL of ethyl acetate to prepare a 0.01 mol / L mother solution, then dissolve 5 μL of the mother solution in 5 μL of acrylic resin, and evenly apply it to a glass plate, air-dry naturally at room temperature (25°C), put the glass plate under a (365 nm) ultraviolet lamp, and take a photo with a VIVO S1 mobile phone to obtain a clear fluorescence image, as shown below: Figure 8 It can be observed that when the volume ratio of the mother solution to the acrylic resin is 1:1, the fluorescence intensity is enhanced compared with Example 12-2, and the film forming speed is faster.

[0053] Example 11-5 Weigh compound I (4.4 mg, 0.01 mmol) in Example 8, dissolve in 1 mL of ethyl acetate to prepare a 0.01 mol / L mother solution, then take 5 μL of the mother solution and dissolve in 5 μL of acrylic resin, and evenly apply it on a glass plate, dry it naturally at room temperature (25°C), and it will turn orange under natural light. Put the glass plate under a (365 nm) ultraviolet lamp, take a photo with a VIVO S1 mobile phone, and get a clear fluorescence image, as shown in the figure. Fig. 9 shown.

[0054] Example 11-6 Weigh compound I (4.9 mg, 0.01 mmol) in Example 9, dissolve in 1 mL of ethyl acetate to prepare a 0.01 mol / L mother solution, then take 5 μL of the mother solution and dissolve in 5 μL of acrylic resin, and evenly apply it on a glass plate, dry it naturally at room temperature (25°C), and it will be orange-red under natural light. Put the glass plate under a (365 nm) ultraviolet lamp, take a photo with a VIVO S1 mobile phone, and get a clear fluorescence image, as shown in the figure. Fig.10 shown.

[0055] Example 11-7 Weigh compound I (7.7 mg, 0.01 mmol) in Example 10, dissolve in 1 mL of ethyl acetate to prepare a 0.01 mol / L mother solution, then take 5 μL of the mother solution and dissolve in 5 μL of acrylic resin, and evenly apply it on a glass plate, dry it naturally at room temperature (25°C), and it will turn red under natural light. Put the glass plate under a (365 nm) ultraviolet lamp, take a photo with a VIVO S1 mobile phone, and get a clear fluorescence image, as shown in the figure. Fig.11 The anti-counterfeiting film described in this patent can also be used on materials such as cling film.

[0056] The above-mentioned embodiments are only preferred technical solutions of the present invention and should not be regarded as limitations of the present invention. The embodiments and features in the embodiments of the present application can be arbitrarily combined with each other without conflict. The protection scope of the present invention shall be the technical solutions recorded in the claims, including the equivalent replacement solutions of the technical features in the technical solutions recorded in the claims. That is, equivalent replacement improvements within this scope are also within the protection scope of the present invention.

Claims

1. A nitrogen-containing seven-membered fluorine-boron compound, characterized in that: The structural formula of the compound is shown below: Ⅰ The substituent R is any one selected from hydrogen, cyano, methoxy or diphenylamine.

2. The method for synthesizing the nitrogen-containing seven-membered fluorine boron compound according to claim 1, characterized in that: The method comprises the following steps: (1) Adding compound 1, compound 2, tetrakis(triphenylphosphine)palladium, cesium carbonate, toluene and water into a reaction bottle at room temperature, and heating the reaction under the protection of nitrogen to obtain a reaction solution; (2) The reaction solution in step (1) is extracted with dichloromethane and water, the extract is dried over anhydrous sodium sulfate and then rotary evaporated, and then separated by silica gel column chromatography to obtain a solid product I, i.e., a nitrogen-containing seven-membered fluoroboric compound; the reaction formula is as follows: ； The substituent R is any one selected from hydrogen, cyano, methoxy or diphenylamine.

3. The method for synthesizing the nitrogen-containing seven-membered fluorine boron compound according to claim 2, characterized in that: In the step (1), the molar ratio of compound 1 to compound 2 is 1:6-10.

4. The method for synthesizing the nitrogen-containing seven-membered fluorine boron compound according to claim 2, characterized in that: The heating temperature of step (1) is 100-130° C., and the heating time is 15-17 hours.

5. Use of the nitrogen-containing seven-membered fluorine boron compound according to claim 1 as a fluorescent anti-counterfeiting film.

6. A fluorescent anti-counterfeiting film, characterized in that: The invention comprises the nitrogen-containing seven-membered fluorine boron compound as claimed in claim 1.

7. The use according to claim 6, characterized in that: The compound is dissolved in a solvent to prepare a mother solution, and then an acrylic resin or polyvinyl alcohol solution is added to prepare a film-forming solution. Finally, the film-forming solution is coated on the anti-counterfeiting object to form a film to achieve a fluorescent anti-counterfeiting effect.

8. The use according to claim 7, characterized in that: The solvent includes ethyl acetate, dichloromethane, dimethyl sulfoxide, acetonitrile, or toluene.

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