N,O-heterocyclic compounds and their synthesis and application
By synthesizing a new N,O-heterocyclic compound, the problems of short wavelength and weak penetration of existing compounds are solved, and fluorescent dyes with good performance in the fields of fluorescent holographic anti-counterfeiting packaging films and OLEDs are realized.
Patent Information
- Application Number
- CN202211003121.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-08-19
- Publication Date
- 2025-03-28
- Estimated Expiration
- 2042-08-19
AI Technical Summary
The existing N,O-heterocyclic compounds have defects of short wavelengths and weak penetration, which are difficult to meet the needs of fluorescent holographic anti-counterfeiting packaging films and OLEDs.
A new N,O-heterocyclic compound with a molecular formula of C15H12BF2NO was designed to synthesize, and the fluorescent dye with long wavelengths and large Stokes displacement was obtained by specific synthetic methods, including reaction in ethanol, refrigerator placement, vacuum drying, water washing and column chromatography separation.
This compound has good penetration and high fluorescence quantum yield. It is suitable for fluorescent anti-counterfeiting films and OLEDs, especially in natural light, and shows clear fluorescence under ultraviolet lamps.
Smart Images
Figure CN115448936B_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the field of fluorescent dyes, and more specifically to a N,O-heterocyclic compound and its synthesis and application. The compound can be used as a seven-membered fluoroboron fluorescent dye and applied to a fluorescent anti-counterfeiting film. 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] Most existing N,O-heterocyclic compounds have the defects of short wavelength and weak penetration. The present invention designs and synthesizes a novel N,O heterocyclic fluorescent dye with a longer wavelength, a larger Stokes shift, and good penetration, and has great potential in the fields of fluorescent holographic anti-counterfeiting packaging films and OLEDs. Summary of the invention
[0004] The invention provides a N,O-heterocyclic compound and synthesis and application thereof. The compound can be used as a fluorescent dye and has broad application prospects.
[0005] The technical solution of the present invention is a N,O-heterocyclic compound, the molecular formula of which is C 15 H 12 BF2NO, the structural formula is as follows:
[0006]
[0007] Formula I.
[0008] The synthesis method of the N,O-heterocyclic compound has the following reaction path:
[0009] ;
[0010] The specific steps include:
[0011] (1) dissolving compound 1 1-tetralone and compound 2 2-formylpyrrole in ethanol, adding alkali to adjust the pH to 13-14, heating, stirring and refluxing to obtain reaction solution 1;
[0012] (2) adding water to the reaction solution 1, placing the mixture in a refrigerator at 4-6°C for more than 10 hours, and then filtering out the precipitated solid, which is compound 3. The solid is placed in a vacuum drying oven for drying and then dissolved in toluene, and heated and stirred to dissolve to obtain reaction solution 2;
[0013] (3) adding triethylamine and boron trifluoride etherate to the reaction solution 2 in sequence, stirring and refluxing to obtain the reaction solution 3;
[0014] (4) The reaction solution 3 is washed with water, extracted, dried, rotary evaporated, and separated and purified by column chromatography to obtain the compound of formula I.
[0015] Furthermore, in the step (1), the molar ratio of compound 11-tetralone, compound 22-formylpyrrole and potassium hydroxide is 1:1-10:1-10.
[0016] Furthermore, the heating reflux condition in step (1) is to raise the temperature to 70-80° C. and reflux for 2-5 hours.
[0017] Furthermore, the alkali in step (1) is an aqueous solution of potassium hydroxide.
[0018] In the step (3), the molar ratio of compound 3, triethylamine and boron trifluoride ether is 1:1-25:1-25.
[0019] Furthermore, in step (3), the reflux reaction temperature is 100-140° C. and the time is 30 minutes.
[0020] The present invention also relates to the application of the N,O-heterocyclic compound obtained by the synthesis method as a fluorescent dye in fluorescent anti-counterfeiting films, biological imaging fields and biosensors.
[0021] Furthermore, in specific applications, the N,O-heterocyclic compound is dissolved in a solvent to prepare a mother solution, and then acrylic resin or polyvinyl pyrrolidone is added to prepare a film-forming solution, and finally the film-forming solution is coated on the application target to form a film.
[0022] Furthermore, the solvent is ethyl acetate.
[0023] The beneficial effects of the present invention are as follows:
[0024] (1) The N,O-heterocyclic compound synthesized by the present invention is a seven-membered fluoroboron compound, which has a simple synthesis process and low manufacturing cost, and the compound has a high fluorescence quantum yield in the film.
[0025] (2) The compound provided by the present invention is mixed with acrylic resin or polyvinyl pyrrolidone to form a film quickly on a thin film. It is red under natural light and has clear fluorescence under ultraviolet light. It is particularly suitable for fluorescent holographic anti-counterfeiting packaging film, or for OLED after being combined with anode, cathode and semiconductor materials. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Figure 1 It is the hydrogen spectrum of compound I obtained in Example 1.
[0027] Figure 2 The compound I in Example 7-1 and the acrylic resin formed a film on the plastic wrap. A photo was taken with an iPhone 12 under natural light to obtain a clear image.
[0028] Figure 3 Compound I in Examples 7-2, 7-3, and 7-4 was reacted with acrylic resin or polyvinyl pyrrolidone to form a film on plastic wrap, and a photo was taken with an iPhone 12 under ultraviolet light (365nm) to obtain a clear fluorescence image.
[0029] Figure 4 The compound I in Example 7-5 and polyvinyl pyrrolidone formed a film on the plastic wrap, and a clear picture was obtained by taking a photo with an iPhone 12 under natural light.
[0030] Figure 5 The absorption and emission spectra of the compound I obtained in Example 1 in different solvents. The absorption spectra are obtained from dichloromethane, toluene, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate, and acetonitrile from top to bottom. The emission spectra are obtained from toluene, ethyl acetate, dichloromethane, acetonitrile, dimethyl sulfoxide, and tetrahydrofuran from top to bottom. For example, in toluene, the ultraviolet absorption peak of compound I is detected at 529nm (the instrument is UV-1800 ultraviolet visible spectrophotometer), and the fluorescence emission peak is detected at 585nm (the instrument is RF-6000 fluorescence spectrophotometer), and the Stokes shift is 56nm. DETAILED DESCRIPTION
[0031] The embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only used to illustrate the present invention and should not be construed as limiting the scope of the present invention.
[0032] Example 1
[0033] Take 1-tetralone (146 mg, 1.0 mmol) and 2-formylpyrrole (95 mg, 1.0 mmol) and dissolve them in 10 ml of ethanol. After stirring and dissolving, add 1 ml of 1.0 mol / L potassium hydroxide aqueous solution, heat to 70℃, stir and reflux for 2h. Monitor by TLC spot plate. After the reaction is complete, add 100 ml of water, place in a refrigerator at 5℃ for 10 hours, and then filter out the precipitated green solid (134.9 mg, yield 60.5%). Put the green solid (133.8 mg, 0.6 mmol) in a vacuum drying oven and dry it, then dissolve it in 9 ml of toluene, heat and stir to dissolve. Then add triethylamine (0.42 ml, 3 mmol) and boron trifluoride etherate (0.37 ml, 3 mmol) in turn, heat to 120℃, stir and reflux for 0.5h. After the reaction was completed, the product was washed with water, extracted, dried, rotary evaporated, and purified by column chromatography to obtain a purple solid compound I (77.07 mg, yield 47.4%). Figure 1 .
[0034] The absorption and emission spectra of compound I obtained in this example in different solvents are shown in FIG. Figure 5 . The absorption spectra are obtained from top to bottom in dichloromethane, toluene, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate, and acetonitrile. The emission spectra are obtained from top to bottom in toluene, ethyl acetate, dichloromethane, acetonitrile, dimethyl sulfoxide, and tetrahydrofuran. For example, in toluene, the ultraviolet absorption peak of compound I is detected at 529nm (the instrument is UV-1800 ultraviolet visible spectrophotometer), the fluorescence emission peak is detected at 585nm (the instrument is RF-6000 fluorescence spectrophotometer), and the Stokes shift is 56nm.
[0035] Example 2
[0036] Take 1-tetralone (146 mg, 1.0 mmol) and 2-formylpyrrole (95 mg, 1.0 mmol) and dissolve them in 10 ml of ethanol. After stirring and dissolving, add 2 ml of 1.0 mol / L potassium hydroxide aqueous solution, heat to 70°C, stir and reflux for 2h. TLC spot plate monitoring, after the reaction is complete, add 100 ml of water, place in a 5°C refrigerator for 10 hours, and then filter the precipitated green solid (154.1 mg, yield 69.1%). When the amount of potassium hydroxide is increased by 1 times (relative to Example 1), the yield of compound 3 increases by 8.6%. Put the green solid (133.8 mg, 0.6 mmol) in a vacuum drying oven and dry it, then dissolve it in 9 ml of toluene, heat and stir to dissolve. Then add triethylamine (0.84 ml, 6 mmol) and boron trifluoride etherate (0.74 ml, 6 mmol) in turn, heat to 120°C, stir and reflux for 0.5h. After the reaction was completed, the product was washed with water, extracted, dried, rotary evaporated, and purified by column chromatography to obtain a purple solid product I (114.0 mg, yield 70.1%). When the amount of triethylamine and boron trifluoride ether was increased by 1 times (relative to Example 1), the yield of compound I increased by 22.7%.
[0037] Example 3
[0038] Take 1-tetralone (146 mg, 1.0 mmol) and 2-formylpyrrole (95 mg, 1.0 mmol) and dissolve them in 10 ml of ethanol. After stirring and dissolving, add 2 ml of 1.0 mol / L potassium hydroxide aqueous solution, heat to 80°C, stir and reflux for 1.5h. TLC spot plate monitoring, after the reaction is complete, add 100 ml of water, place in a 5°C refrigerator for 10 hours, and then filter the precipitated green solid (168.1 mg, yield 75.4%). When the reaction temperature increases by 10 degrees Celsius (relative to Example 2), the yield of compound 3 increases by 6.3%, and the reaction time is shortened by 0.5 hours (relative to Example 2). The green solid (133.8 mg, 0.6 mmol) is placed in a vacuum drying oven and dried, then dissolved in 9 ml of toluene, heated and stirred to dissolve. Then triethylamine (0.84 ml, 6 mmol) and boron trifluoride etherate (0.74 ml, 6 mmol) were added in sequence, and the temperature was raised to 140°C, stirred and refluxed for 0.5 h. After the reaction was completed, the product was washed with water, extracted, dried, rotary evaporated, and purified by column chromatography to obtain a purple solid product I (66.5 mg, yield 40.9%). When the temperature increased by 20°C (relative to Example 2), the yield of compound I decreased by 29.2%.
[0039] Example 4
[0040] Take 1-tetralone (146 mg, 1.0 mmol) and 2-formylpyrrole (190 mg, 2.0 mmol) and dissolve them in 10 ml of ethanol. After stirring and dissolving, add 2 ml of 1.0 mol / L potassium hydroxide aqueous solution, heat to 70°C, stir and reflux for 2 hours. TLC spot plate monitoring, after the reaction is complete, add 100 ml of water, place in a 5°C refrigerator for 10 hours, and then filter the precipitated green solid (197.1 mg, yield 88.4%). When the amount of 2-formylpyrrole is increased by 1 times (relative to Example 2), the yield of compound 3 increases by 19.3%. Put the green solid (133.8 mg, 0.6 mmol) in a vacuum drying oven to dry, then dissolve in 18 ml of toluene, heat and stir to dissolve. Then triethylamine (0.42 ml, 3 mmol) and boron trifluoride etherate (0.37 ml, 3 mmol) were added in sequence, and the temperature was raised to 120°C, stirred and refluxed for 0.5 h. After the reaction was completed, the product was washed with water, extracted, dried, rotary evaporated, and purified by column chromatography to obtain a purple solid product I (118.0 mg, yield 72.6%). When the volume of toluene was increased by 1 times (relative to Example 2), the yield of compound I did not change significantly.
[0041] Example 5
[0042] Take 1-tetralone (146 mg, 1.0 mmol) and 2-formylpyrrole (95 mg, 1.0 mmol) and dissolve them in 20 ml of ethanol. After stirring and dissolving, add 2 ml of 1.0 mol / L potassium hydroxide aqueous solution, heat to 80°C, stir and reflux for 1.5h. TLC spot plate monitoring, after the reaction is complete, add 100 ml of water, place in a 5°C refrigerator for 10 hours, and then filter the precipitated green solid (172.6 mg, yield 77.4%). When the amount of ethanol is increased by 1 times (relative to Example 3), the yield of compound 3 does not change significantly. Put the green solid (113.8 mg, 0.6 mmol) in a vacuum drying oven and dry it, then dissolve it in 9 ml of toluene, heat and stir to dissolve. Then add triethylamine (0.84 ml, 6 mmol) and boron trifluoride etherate (0.74 ml, 6 mmol) in turn, heat to 100°C, stir and reflux for 0.5h. After the reaction was completed, the product was washed with water, extracted, dried, rotary evaporated, and purified by column chromatography to obtain a purple solid product I (74.1 mg, 45.6% yield). When the temperature was reduced by 20 degrees Celsius (relative to Example 2), the yield of compound I was reduced by 24.5%.
[0043] Example 6
[0044] Take 1-tetralone (146 mg, 1.0 mmol) and 2-formylpyrrole (95 mg, 1.0 mmol) and dissolve them in 10 ml of ethanol. After stirring and dissolving, add 1 ml of 1.0 mol / L potassium hydroxide aqueous solution, heat to 70°C, stir and reflux for 2h. TLC spot plate monitoring, after the reaction is complete, add 50 ml of water, place in a 5°C refrigerator for 10 hours, and then filter the precipitated green solid (101.9 mg, yield 45.7%). When the volume of water is reduced to half of the original (relative to Example 1), the yield of compound 3 is reduced by 14.8%. Put the green solid (89.2 mg, 0.4 mmol) in a vacuum drying oven and dry it, then dissolve it in 6 ml of toluene, heat and stir to dissolve. Then add triethylamine (0.14 ml, 1 mmol) and boron trifluoride etherate (0.12 ml, 1 mmol) in turn, heat to 120°C, stir and reflux for 0.5h. After the reaction was completed, the product was washed with water, extracted, dried, rotary evaporated, and purified by column chromatography to obtain a purple solid product I (32.1 mg, yield 29.6%). When the amount of triethylamine and boron trifluoride ether was reduced by 1 times (relative to Example 1), the yield of compound I was reduced by 17.8%.
[0045] Example 7 Preparation of anti-counterfeiting film
[0046] Example 7-1
[0047] Weigh compound I (2.71 mg, 0.01 mmol) prepared in Example 1, take 1 mL of ethyl acetate to dissolve it into a 0.01 mol / L mother liquor, then take 5 μL of the mother liquor and dissolve it in 10 μL of acrylic resin, and evenly apply it on the plastic wrap, dry it at 30°C, place the plastic wrap under natural light, and take a photo with an iPhone 12 to obtain a clear picture, as shown below. Figure 2 It can be observed that the surface of the anti-counterfeiting film is uneven. Since the film formed by the mother liquid and the 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.
[0048] Example 7-2
[0049] Weigh compound I (2.71 mg, 0.01 mmol) in Example 1, take 1 mL of ethyl acetate to dissolve it into a 0.01 mol / L mother liquor, then take 5 μL of the mother liquor and dissolve it in 10 μL of acrylic resin, and evenly apply it on the plastic wrap, let it air-dry naturally at room temperature (25°C), put the plastic wrap under a (365 nm) ultraviolet lamp, and take a photo with an iPhone 12 to obtain a clear fluorescence image, as shown below. Figure 3 As shown in Figure 1. It can be observed that the surface of the anti-counterfeiting film is smooth, which is conducive to the preparation of the anti-counterfeiting film.
[0050] Example 7-3
[0051] Weigh compound I (2.71 mg, 0.01 mmol) in Example 1, take 1 mL of ethyl acetate to dissolve it into a 0.01 mol / L mother liquor, then take 5 μL of the mother liquor and dissolve it in 5 μL of acrylic resin, and evenly apply it on the plastic wrap, let it dry naturally at room temperature (25°C), put the plastic wrap under a (365nm) ultraviolet lamp, and take a photo with an iPhone 12 to obtain a clear fluorescence image, as shown below. Figure 3 As shown in Figure 2. It can be observed that when the volume ratio of the mother solution to the acrylic resin is 1:1, the fluorescence intensity is found to be enhanced compared with Example 7-2.
[0052] Example 7-4
[0053] Weigh compound I (2.71 mg, 0.01 mmol) in Example 1, dissolve in 1 mL of ethyl acetate to prepare a 0.01 mol / L mother liquor, then dissolve 5 μL of the mother liquor in 5 μL of polyvinyl pyrrolidone, and evenly apply it on the plastic wrap, dry it naturally at room temperature (25°C), put the plastic wrap under a (365 nm) ultraviolet lamp, and take a photo with an iPhone 12. Figure 3 As shown in Figure 3. It can be observed that when the acrylic resin is replaced with polyvinyl pyrrolidone (relative to Example 7-3), the fluorescence intensity is further enhanced.
[0054] Example 7-5
[0055] Weigh compound I (2.71 mg, 0.01 mmol) in Example 1, take 1 mL of ethyl acetate to dissolve it into a 0.01 mol / L mother liquor, then take 5 μL of the mother liquor and dissolve it in 1 μL of polyvinyl pyrrolidone, and evenly apply it on the plastic wrap, let it air-dry naturally at room temperature (25°C), put the plastic wrap under a (365 nm) ultraviolet lamp, and take a photo with an iPhone 12 to obtain a clear fluorescence image, as shown below. Figure 4 It can be observed that when the volume ratio of the mother liquid to polyvinyl pyrrolidone is 5:1 (relative to Example 7-4), the film-forming speed on the cling film is slow. When Example 7-4 forms a film, Example 7-5 is still in liquid form on the cling film. Figure 4 shown.
[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 N,O-heterocyclic compound, characterized in that: The molecular formula of this compound is C 15 H 12 BF2NO, the structural formula is as follows: ； Formula I.
2. The method for synthesizing the N,O-heterocyclic compound according to claim 1, characterized in that: The reaction path is as follows: ； The specific steps include: (1) dissolving 1-tetralone and 2-formylpyrrole in ethanol, adding potassium hydroxide aqueous solution to adjust the pH to 13-14, heating, stirring and refluxing to obtain a reaction solution 1; (2) adding water to the reaction solution 1, placing the mixture in a refrigerator at 4-6°C for more than 10 hours, and then filtering out the precipitated solid, which is compound 3. The solid is placed in a vacuum drying oven for drying and then dissolved in toluene, and heated and stirred to dissolve to obtain reaction solution 2; (3) adding triethylamine and boron trifluoride etherate to the reaction solution 2 in sequence, stirring and refluxing to obtain the reaction solution 3; (4) The reaction solution 3 is washed with water, extracted, dried, rotary evaporated, and separated and purified by column chromatography to obtain the compound of formula I.
3. The method for synthesizing the N,O-heterocyclic compound according to claim 2, characterized in that: In the step (1), the molar ratio of 1-tetralone, 2-formylpyrrole and potassium hydroxide is 1:1-10:1-10.
4. The method for synthesizing the N,O-heterocyclic compound according to claim 2, characterized in that: The heating reflux condition in step (1) is to raise the temperature to 70-80° C. and reflux for 2-5 hours.
5. The method for synthesizing a N,O-heterocyclic compound according to claim 2, characterized in that: In the step (3), the molar ratio of compound 3, triethylamine and boron trifluoride ether is 1:1-25:1-25.
6. The method for synthesizing N,O-heterocyclic compounds according to claim 2, characterized in that: The reflux reaction temperature in step (3) is 100-140° C. and the reaction time is 30 minutes.
7. Use of the N,O-heterocyclic compound according to claim 1 as a fluorescent dye in a fluorescent anti-counterfeiting film.
8. The use according to claim 7, characterized in that: In specific application, the N,O-heterocyclic compound is dissolved in a solvent to prepare a mother solution, and then acrylic resin or polyvinyl pyrrolidone is added to prepare a film-forming solution, and finally the film-forming solution is coated on the application target to form a film.
9. The use according to claim 8, characterized in that: The solvent is ethyl acetate.