Preparation of a phosphorus-containing seven-membered fluorine-boron compound and its application in fluorescent ink

Abstract

The invention discloses a preparation of a phosphorus-containing seven-membered fluorine-boron compound and its application in fluorescent ink. The compound structure is as shown in the figure below: the dye uses 2,3,3-trimethylindole and 2-pyrrolecarboxaldehyde as raw materials. Under the action of acetic acid, piperidine and toluene, through Knoevenagel condensation reaction, a seven-membered fluorine-boron fluorescent dye is generated. This seven-membered fluorine-boron fluorescent dye is reacted with dimethyl phosphite, diphenylphosphine oxide, diisopropyl phosphite, diisobutyl phosphite and diethyl phosphite to obtain the final compound. The compound has a high fluorescence quantum yield in some solutions. The compound is dissolved in a n-butanol solution of acrylic resin and can be used as a fluorescent ink. It acts on materials such as sulfuric acid paper and glass plates and has high concealment and is simple and easy to obtain.

Description

Technical Field

[0001] The present invention relates to the field of material technology, and more specifically, to the preparation of a novel phosphorus-containing seven-membered fluoroboron compound. The compound has a high fluorescence quantum yield and can be widely used in the field of fluorescent ink. Background Art

[0002] Fluorescent ink is a special type of ink that fluoresces brightly under ultraviolet light (365nm). This ink is commonly used to enhance the security of documents or products, such as currency, passports, tickets, and other items requiring anti-counterfeiting measures. Fluorescent ink comes in a variety of colors, with common ones including yellow-green, orange-red, and blue-green. These colors are nearly invisible under normal light but fluoresce brightly under ultraviolet light.

[0003] Fluorescent inks are not limited to security applications; they are also widely used in artwork, glow-in-the-dark products, advertising signs, and apparel printing to attract visual attention. When using fluorescent inks, special attention should be paid to their compatibility with the print media or coating to ensure optimal fluorescent effect and longevity. Summary of the Invention

[0004] The present invention provides a preparation method of a phosphorus-containing seven-membered fluoroboron compound and research on its application in fluorescent ink. The compound is not only simple and easy to obtain, but also has low manufacturing cost, high fluorescence quantum yield, and little environmental pollution.

[0005] A phosphorus-containing seven-membered fluorine-boron compound and its application in fluorescent ink, wherein the chemical structural formula of the compound is:

[0006]

[0007] The substituent R is any one selected from methoxy, phenyl, isopropoxy, isobutoxy, and ethoxy. As a preliminary solution, the chemical structure of the compound is:

[0008]

[0009] Any one of .

[0010] The method for synthesizing the phosphorus-containing seven-membered fluoroboron compound comprises the following synthesis path:

[0011]

[0012] The method specifically comprises the following steps:

[0013] (1) Add the seven-membered fluoroborane compound 1 to a reaction flask at room temperature, dissolve it in acetonitrile, then add the compound 2 and silver nitrate, and heat to 80°C under nitrogen protection to obtain a reaction solution;

[0014] (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.

[0015] Compound 1 is a seven-membered fluorine-boron compound, and compound 2 is a phosphorus-containing compound; the feed ratio of compound 1 to compound 2 is 1:1-2, and the feed ratio of compound 1 to silver nitrate is 1:1-2.

[0016] The order of adding materials in step (1) is compound 1, acetonitrile, compound 2, and silver nitrate as the oxidant should be added last.

[0017] The heating temperature of step (1) is 60-100° C., and the heating time is 1.5-5 hours.

[0018] The beneficial effects of the present invention are as follows:

[0019] (1) The phosphorus-containing seven-membered fluoroboron compound synthesized by the present invention has high fluorescence quantum yield, is simple and easy to obtain, has low manufacturing cost, and is low in pollution.

[0020] (2) The phosphorus-containing seven-membered fluoroboron compound of the present invention has great potential in the field of fluorescent ink, and the effect is best when the mass proportion of the fluorescent powder is 1.0%~1.5%. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

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

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

[0025] Figure 5 This is the hydrogen spectrum of compound I-5 obtained in Example 11.

[0026] Figure 6 The fluorescent ink prepared with compound Ⅰ-1 in Example 12-8 was applied to sulfuric acid paper, and then photographed with a VIVO S1 mobile phone under natural light and under ultraviolet light (365nm), to obtain clear fluorescent images.

[0027] Figure 7 The fluorescent ink prepared with compound Ⅰ-2 in Example 12-9 was applied to sulfuric acid paper, and clear fluorescent images were obtained by taking photos with a VIVO S1 mobile phone under natural light and under ultraviolet light (365nm).

[0028] Figure 8 The fluorescent ink prepared from compound I-3 in Example 12-10 was applied to sulfuric acid paper, and then photographed with a VIVO S1 mobile phone under natural light and under ultraviolet light (365nm), to obtain clear fluorescent images. DETAILED DESCRIPTION

[0029] The present invention is further described below with reference to the following examples. However, the scope of protection claimed in the present invention is not limited to the scope described in the examples.

[0030] Example 1

[0031] Compound 1 (7-membered fluoroboron fluorescent dye, 284 mg, 1 mmol) was dissolved in 20.00 mL of acetonitrile. Compound 2 (0.09 mL, 1 mmol) and silver nitrate (170 mg, 1 mmol) were then added sequentially. The mixture was stirred under nitrogen and heated at 80°C for 3 hours until the reaction was complete. The reactants were extracted, rotary evaporated, and purified by column chromatography to afford Compound I-1 as an orange solid in a 56.8% yield.

[0032] .

[0033] Example 2

[0034] Compound 1 heptafluoroboron fluorescent dye (284 mg, 1 mmol) was weighed and dissolved in 20.00 mL of acetonitrile. Compound 2 dimethyl phosphite (0.09 mL, 1 mmol) and silver nitrate (170 mg, 1 mmol) were added in sequence under nitrogen protection. Compared with Example 1, the temperature was reduced by 20 ° C, the reaction time was extended by 2 hours, the raw materials were not completely reacted, and the yield was reduced by 32.4%.

[0035] .

[0036] Example 3

[0037] Compound 1 (7-membered fluoroboron fluorescent dye, 284 mg, 1 mmol) was weighed and dissolved in 20.00 mL of acetonitrile. Compound 2 (0.09 mL, 1 mmol) and silver nitrate (170 mg, 1 mmol) were then added sequentially under nitrogen protection. Compared with Example 1, the temperature was increased by 20°C. The reaction was stirred at 100°C for 1.5 hours. The raw materials reacted completely and the reaction time was shortened, but more by-products were produced and the yield was reduced by 27.6%.

[0038] .

[0039] Example 4

[0040] Compound 1 (7-membered fluoroboron fluorescent dye, 284 mg, 1 mmol) was weighed and dissolved in 20.00 mL of acetonitrile. Compound 2 (dimethyl phosphite, 0.09 mL, 1 mmol) and silver nitrate (340 mg, 2 mmol) were then added sequentially under nitrogen atmosphere. The mixture was stirred and heated at 80°C for 2 hours. The reactants were extracted, rotary evaporated, and column chromatographed to obtain the product with a yield of 68.7%. Compared to Example 1, the oxidant silver nitrate was increased by 1 equivalent, the reaction time was shortened by 1 hour, and the yield was increased by 21.9%.

[0041] .

[0042] Example 5

[0043] Compound 1 heptafluoroboron fluorescent dye (284 mg, 1 mmol) was weighed and dissolved in 20.00 mL of acetonitrile. Compound 2 dimethyl phosphite (0.183 mL, 2 mmol) and silver nitrate (340 mg, 2 mmol) were added in sequence under nitrogen protection. The mixture was heated and stirred at 80 ° C for 1 hour. The reactants were post-treated to obtain the compound. Compared with Example 4, the amount of dimethyl phosphite was increased by 1 times, and the yield was increased by 8.7%.

[0044] .

[0045] Example 6

[0046] Compound 1 (7-membered fluoroboron fluorescent dye, 284 mg, 1 mmol) was weighed and dissolved in 25.00 mL of acetonitrile. Compound 2 (2, dimethyl phosphite, 0.183 mL, 2 mmol) and silver nitrate (340 mg, 2 mmol) were then added sequentially under nitrogen atmosphere. The mixture was stirred and heated at 80°C for 3.5 hours. The reaction was complete. The product was extracted, rotary evaporated, and column chromatographed to obtain the product with a yield of 80.8%. Compared to Example 5, the solvent was increased by 5 mL and the reaction time was increased by 0.5 h, resulting in a 6.6% decrease in yield.

[0047] .

[0048] Example 7

[0049] Compound 1 (7-membered fluoroboron fluorescent dye, 284 mg, 1 mmol) was weighed and dissolved in 15.00 mL of acetonitrile. Compound 2 (0.183 mL, 2 mmol) and silver nitrate (340 mg, 2 mmol) were then added sequentially. The mixture was stirred under nitrogen and heated at 80°C for 3 hours. The reaction mixture was extracted, rotary evaporated, and column chromatographed to obtain the product with a yield of 94.1%. Compared to Example 5, the solvent was reduced by 5 mL, resulting in a 6.7% increase in yield.

[0050] .

[0051] Example 8

[0052] Compound 1 (284 mg, 1 mmol) was weighed and dissolved in 15.00 mL of acetonitrile. Compound 2 (404.4 mg, 2 mmol) and silver nitrate (340 mg, 2 mmol) were added in sequence under nitrogen protection. The mixture was heated and stirred at 80 ° C for 3 hours. The reactants were extracted, rotary evaporated, and column chromatography was performed to obtain a yellow product Ⅰ-2 with a yield of 58.6%.

[0053] .

[0054] Example 9

[0055] Compound 1 (284 mg, 1 mmol) was weighed and dissolved in 15.00 mL of acetonitrile. Compound 2 (0.333 mL, 2 mmol) and silver nitrate (340 mg, 2 mmol) were added in sequence under nitrogen protection. The mixture was heated and stirred at 80 ° C for 3 hours. The reactants were extracted, rotary evaporated, and column chromatography was performed to obtain a light yellow product Ⅰ-3 with a yield of 62.4%.

[0056] .

[0057] Example 10

[0058] Compound 1 (284 mg, 1 mmol) was weighed and dissolved in 15.00 mL of acetonitrile. Compound 2 (0.396 mL, 2 mmol) and silver nitrate (340 mg, 2 mmol) were added in sequence under nitrogen protection. The mixture was heated and stirred at 80 ° C for 3 hours. The reactants were extracted, rotary evaporated, and column chromatography was performed to obtain the orange product I-4 with a yield of 72.1%.

[0059] .

[0060] Example 11

[0061] Compound 1 (284 mg, 1 mmol) was weighed and dissolved in 15.00 mL of acetonitrile. Compound 2 (0.258 mL, 2 mmol) and silver nitrate (340 mg, 2 mmol) were added in sequence under nitrogen protection. The mixture was heated and stirred at 80 ° C for 3 hours. The reactants were extracted, rotary evaporated, and column chromatography was performed to obtain the orange product Ⅰ-5 with a yield of 68.9%.

[0062] .

[0063] Example 12 Preparation of fluorescent ink

[0064] Example 12-1

[0065] Acrylic resin (20 mg) was evenly dispersed in n-butanol (280 mg), stirred under magnetic stirring until completely dissolved, and allowed to stand for 10 minutes to form a uniformly dispersed carrier. Compound I-1 (4 mg) was then added, pre-dispersed on a magnetic electric stirrer for 30 minutes, and then stirred at high speed to obtain the desired color paste.

[0066] Example 12-2

[0067] Acrylic resin (20 mg) was evenly dispersed in n-butanol (280 mg), stirred under magnetic stirring until completely dissolved, and allowed to stand for 10 minutes to form a uniformly dispersed carrier. Compound I-1 (3 mg) was then added, pre-dispersed on a magnetic electric stirrer for 30 minutes, and then stirred at high speed to obtain the desired color paste.

[0068] Example 12-3

[0069] Acrylic resin (20 mg) was evenly dispersed in n-butanol (280 mg), stirred under magnetic stirring until completely dissolved, and allowed to stand for 10 minutes to form a uniformly dispersed carrier. Compound I-1 (5 mg) was then added, pre-dispersed on a magnetic stirrer for 30 minutes, and stirred at high speed to obtain the desired color paste.

[0070] Example 12-4

[0071] Acrylic resin (20 mg) was evenly dispersed in n-butanol (280 mg), stirred under magnetic stirring until completely dissolved, and allowed to stand for 10 minutes to form a uniformly dispersed carrier. Compound I-2 (4 mg) was then added, pre-dispersed on a magnetic stirrer for 30 minutes, and stirred at high speed to obtain the desired color paste.

[0072] Example 12-5

[0073] Acrylic resin (20 mg) was evenly dispersed in n-butanol (280 mg), stirred under magnetic stirring until completely dissolved, and allowed to stand for 10 minutes to form a uniformly dispersed carrier. Compound I-3 (4 mg) was then added, pre-dispersed on a magnetic stirrer for 30 minutes, and stirred at high speed to obtain the desired color paste.

[0074] Example 12-6

[0075] Acrylic resin (10 mg) and n-butanol (90 mg) were added to the color paste prepared in Example 12-1 and stirred to obtain fluorescent ink. The prepared fluorescent ink was applied to sulfuric acid paper and photographed using VIVO S1 under natural light and ultraviolet light (365 nm). Figure 6 It can be seen that there is no fluorescent effect under natural light, but under 365nm ultraviolet light, the fluorescent effect can be clearly seen.

[0076] Example 12-7

[0077] Acrylic resin (10 mg) and n-butanol (90 mg) were added to the color paste prepared in Example 12-2 and stirred to obtain fluorescent ink. The obtained fluorescent ink was applied to sulfuric acid paper.

[0078] Example 12-8

[0079] Acrylic resin (10 mg) and n-butanol (90 mg) were added to the color paste prepared in Example 12-3 and stirred to obtain a fluorescent ink. The obtained fluorescent ink was then applied to a paper substrate. A comparison of Examples 12-8, 12-9, and 12-10 revealed that the optimal effect was achieved when the phosphor content was between 1.0% and 1.5%.

[0080] Example 12-9

[0081] Acrylic resin (10 mg) and n-butanol (90 mg) were added to the color paste prepared in Example 12-4 and stirred to obtain fluorescent ink. The prepared fluorescent ink was applied to sulfuric acid paper and photographed using VIVO S1 under natural light and ultraviolet light (365 nm). Figure 7 It can be seen that there is no fluorescent effect under natural light, but under 365nm ultraviolet light, the fluorescent effect can be clearly seen.

[0082] Example 12-10

[0083] Acrylic resin (10 mg) and n-butanol (90 mg) were added to the color paste prepared in Example 12-5 and stirred to obtain fluorescent ink. The prepared fluorescent ink was applied to sulfuric acid paper and photographed using VIVO S1 under natural light and ultraviolet light (365 nm). Figure 8 As can be seen, there is no fluorescent effect under natural light, but under 365nm ultraviolet light, the fluorescent effect can be clearly seen. The five compounds described in this patent can all be used to obtain fluorescent inks using the above-mentioned embodiments. The fluorescent inks prepared in this patent can also be used on materials such as steel plates, wood, A4 paper, and glass.

[0084] The above embodiments are merely preferred technical solutions of the present invention and should not be construed as limiting the present invention. The embodiments and features in the embodiments of this application may be arbitrarily combined with each other unless they conflict. The scope of protection of the present invention shall be the technical solutions described in the claims, including equivalent alternatives to the technical features of the technical solutions described in the claims. Equivalent alternatives and improvements within this scope are also within the scope of protection of the present invention.

Claims

1. A phosphorus-containing seven-membered fluorine-boron compound, characterized in that: The structural formula of the compound is shown below: Ⅰ Wherein, the substituent R is any one selected from methoxy, phenyl, isopropoxy, isobutoxy, and ethoxy.

2. The method for synthesizing the phosphorus-containing seven-membered fluorine-boron compound according to claim 1, wherein: This is achieved by: Wherein, the substituent R is any one selected from methoxy, phenyl, isopropoxy, isobutoxy, and ethoxy; The method comprises the following steps: (1) Add compound 1, compound 2, silver nitrate, and acetonitrile to a reaction flask at room temperature, dissolve the mixture, and then heat the mixture under 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 solid product I, i.e., a seven-membered fluoroboron compound.

3. The method for synthesizing the phosphorus-containing seven-membered fluorine-boron compound according to claim 2, wherein: The molar ratio of compound 1 to compound 2 in step (1) is 1:1-2.

4. The method for synthesizing the phosphorus-containing seven-membered fluorine-boron compound according to claim 2, wherein: The heating temperature of step (1) is 60-100° C., and the heating time is 1.5-5 hours.

5. Use of the phosphorus-containing seven-membered fluorine-boron compound according to claim 1 in fluorescent ink.

6. A fluorescent ink material composition, characterized in that: The invention comprises the phosphorus-containing seven-membered fluoroboron compound according to claim 1.

Images