Preparation and application of seven-membered N,O heterocyclic compounds

Abstract

The invention discloses the preparation and application of a seven-membered N,O heterocyclic compound. The dye uses 1-indanone and 2-formylpyrrole as raw materials, and undergoes a Knoevenagel condensation reaction under the action of a triethylamine catalyst to finally generate a seven-membered N,O fluoroboron fluorescent dye. The dye is combined with an acrylic resin on a film to form a film quickly, and clear fluorescence can be seen under an ultraviolet lamp. The fluorescent dye has a simple synthesis method, a short reaction time, a high yield, and a low manufacturing cost, and has great potential in the fields of fluorescent holographic anti-counterfeiting packaging films and OLEDs.

Description

Technical Field

[0001] The invention relates to a fluorescent dye, which is a novel BODIPY solid fluorescent dye showing different fluorescent brightness at different concentrations. The dye can be widely used in the fields of fluorescent holographic anti-counterfeiting films and fluorescent anti-counterfeiting packaging films. Background Art

[0002] Anti-counterfeiting technology is an interdisciplinary subject, involving optics, chemistry, computer technology, spectroscopy, printing technology, packaging technology and many other fields. There are many types of anti-counterfeiting technologies, mainly printing anti-counterfeiting technology, chemical material anti-counterfeiting technology, physical anti-counterfeiting technology, digital information anti-counterfeiting technology, etc. However, with the advancement of science and technology, the security function of traditional anti-counterfeiting technology is constantly decreasing. Therefore, it is very important to discover new anti-counterfeiting materials and create new anti-counterfeiting technologies.

[0003] Organic fluorescent materials are organic molecules that can emit fluorescence under the stimulation of light, electricity, etc. Organic fluorescent materials can be used as fluorescent coatings, fluorescent pigments, etc. and are widely used in traditional industries such as plastics, paper, and ink. Fluorescent anti-counterfeiting materials are made by dissolving dyes or pigments in resin binders. They can be divided into two categories: colorless transparent fluorescent and colored fluorescent, and show specific colors under ultraviolet light. At present, fluorescent holographic anti-counterfeiting dyes have problems such as low solid fluorescence yield, lack of hiding power, poor solubility in some resins, and poor weather resistance. Summary of the invention

[0004] The purpose of the present invention is to overcome the above technical difficulties and provide a new BODIPY solid fluorescent dye containing hydrogen, chlorine, alkoxy and hydroxyl. The dye can be combined with acrylic resin on a film to form a film quickly, and clear fluorescence can be seen under ultraviolet light. In addition, the fluorescent dye is simple and easy to obtain, has low manufacturing cost, and has a high solid fluorescence quantum yield. It has great potential in the field of fluorescent holographic anti-counterfeiting packaging film and OLED. The structural formula is as follows:

[0005] , wherein R1 is -H, -MeO, or -Cl; R2 is -H, -MeO; R3 is H, -OH.

[0006] The synthesis method of the present invention comprises the following synthesis path:

[0007]

[0008] Add 1-indanone derivative, ethanol, and 2-formylpyrrole to a reaction flask at room temperature and fully dissolve them, then add potassium hydroxide aqueous solution to obtain reaction solution 1. The structural formula of the 1-indanone derivative is , wherein R1 is -H, -MeO, or -Cl; R2 is -H, -MeO; R3 is H, -OH;

[0009] (2) adding water to the reaction solution 1 in step (1), filtering it with suction, and drying it to obtain a solid product;

[0010] (3) adding toluene, triethylamine and boron trifluoride ether to the solid product in step (2) respectively, and heating under reflux to obtain reaction solution 2;

[0011] (4) The reaction solution 2 in step (3) is washed with water, extracted, dried, rotary evaporated, and purified by column chromatography to obtain a solid product I.

[0012] In the step (1), the molar ratio of the 1-indanone derivative to 2-formylpyrrole and potassium hydroxide is 1:1-10:1-10.

[0013] The heating reflux temperature of step (1) is 50-100° C., and the heating time is 1-6 hours.

[0014] The order of feeding materials in step (3) is solid product 1, toluene, triethylamine, and boron trifluoride ether, and the feeding mass ratio is 1:30-40:2-4:5-8.

[0015] The heating reflux temperature of step (3) is 100-150° C., and the heating time is 0.5-2 hours.

[0016] The order of feeding materials in step (3) is solid product 1, toluene, triethylamine, and boron trifluoride etherate.

[0017] The beneficial effects of the present invention are as follows:

[0018] The invention has simple synthesis steps, mild reaction conditions, simple purification, high yield, high solid fluorescence quantum yield and universal applicability.

[0019] (2) The seven-membered N,O fluoroboron dye and acrylic resin of the present invention have a fast film-forming speed on the film, and the fluorescence brightness varies greatly at different concentrations, and can be widely used in the fields of fluorescent holographic anti-counterfeiting films and fluorescent anti-counterfeiting packaging films. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is the TB-2 hydrogen spectrum of the compound obtained in Example 1.

[0021] Figure 2 This is the carbon spectrum of TB-2 of the compound obtained in Example 1.

[0022] Figure 3 This is the hydrogen spectrum of compound TB-1 obtained in Example 8.

[0023] Figure 4 This is the carbon spectrum of compound TB-1 obtained in Example 8.

[0024] Figure 5 It is the hydrogen spectrum of compound TB-3 obtained in Example 9.

[0025] Figure 6 This is the carbon spectrum of compound TB-3 obtained in Example 9.

[0026] Figure 7 This is the hydrogen spectrum of compound TB-4 obtained in Example 10.

[0027] Figure 8 It is the carbon spectrum of compound TB-4 obtained in Example 10.

[0028] Fig. 9 This is a clear fluorescence image obtained by taking a photo with an HONOR 20 mobile phone under a UV lamp of 365nm, in which compounds TB-1, TB-2, TB-3, and TB-4 obtained from top to bottom in Example 11 are respectively formed into films with acrylic resin on plastic wrap.

[0029] Fig.10 These are the clear fluorescence images obtained by taking photos with an HONOR 20 mobile phone under a UV lamp at 365nm when the concentrations from top to bottom are 1μL, 5μL, 10μL, and 15μL in Example 12.

[0030] Fig.11 In Example 12, clear natural light images were obtained by taking photos with an HONOR 20 mobile phone under natural light when the liquid concentrations were 1 μL, 5 μL, 10 μL, and 15 μL from top to bottom.

[0031] Fig.12 These are the ultraviolet absorption and fluorescence emission spectra of compounds TB-1, TB-2, TB-3, and TB-4 obtained in Example 13 in different solvents. DETAILED DESCRIPTION

[0032] 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.

[0033] Example 1

[0034] Weigh 5,6-dimethoxy-1-indanone (192 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. Monitor by TLC spot plate. After the reaction is complete, add 100 ml of water, place in the refrigerator overnight, then filter the precipitated solid, put the solid in a vacuum drying oven to dry, dissolve in 15 ml of toluene, heat and stir to dissolve. Then add triethylamine (1.5 ml, 10.8 mmol) and boron trifluoride ether (1.8 ml, 14.3 mmol) in sequence, heat to 120°C, stir and reflux for 0.5h. Monitor by TLC spot plate. After the reaction is complete, wash the product with water, extract, dry, rotary evaporate, and separate and purify by column chromatography to obtain a red solid product TB-2 with a yield of 46%. The molecular formula is C16H14BF2NO3, and the structural formula is .

[0035] Example 2

[0036] Weigh 5,6-dimethoxy-1-indanone (192 mg, 1.0 mmol) and 2-formylpyrrole (142.5 mg, 1.5mmol) 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 the refrigerator overnight, then filter the precipitated solid, put the solid in a vacuum drying oven to dry, dissolve in 15 ml of toluene, heat and stir to dissolve. Then add triethylamine (1.5 ml, 10.8 mmol) and boron trifluoride ether (1.8 ml, 14.3 mmol) in sequence, heat to 120℃, stir and reflux for 0.5h. Monitor by TLC spot plate. After the reaction is complete, wash the product with water, extract, dry, rotary evaporate, and separate and purify by column chromatography to obtain a red solid product TB-2 with a yield of 47.1%. The molecular formula is C16H14BF2NO3, and the structural formula is .

[0037] When the amount of 2-formylpyrrole was increased by 1.5 times relative to Example 1, the yield did not change significantly.

[0038] Example 3

[0039] Weigh 5,6-dimethoxy-1-indanone (192 mg, 1.0 mmol) and 2-formylpyrrole (190 mg, 2.0mmol) 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. Monitor by TLC spot plate. After the reaction is complete, add 100 ml of water, place in the refrigerator overnight, then filter the precipitated solid, put the solid in a vacuum drying oven to dry, dissolve in 15 ml of toluene, heat and stir to dissolve. Then add triethylamine (1.5 ml, 10.8 mmol) and boron trifluoride ether (1.8 ml, 14.3 mmol) in sequence, heat to 120°C, stir and reflux for 0.5h. Monitor by TLC spot plate. After the reaction is complete, wash the product with water, extract, dry, rotary evaporate, and separate and purify by column chromatography to obtain a red solid product TB-2 with a yield of 47.5%. The molecular formula is C16H14BF2NO3, and the structural formula is .

[0040] When the amount of 2-formylpyrrole was increased by 2 times relative to Example 1, the yield did not change significantly.

[0041] Example 4

[0042] Weigh 5,6-dimethoxy-1-indanone (192 mg, 1.0 mmol) and 2-formylpyrrole (95 mg, 1.0mmol) 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 the refrigerator overnight, then filter the precipitated solid, put the solid in a vacuum drying oven to dry, dissolve in 15 ml of toluene, heat and stir to dissolve. Then add triethylamine (3 ml, 21.6 mmol) and boron trifluoride ether (3.6ml, 28.6mmol) in sequence, heat to 120℃, stir and reflux for 0.5h. Monitor by TLC spot plate. After the reaction is complete, wash the product with water, extract, dry, rotary evaporate, and separate and purify by column chromatography to obtain a red solid product TB-2 with a yield of 46.5%. The molecular formula is C16H14BF2NO3, and the structural formula is

[0043] .

[0044] When the amount of triethylamine and boron trifluoride etherate was increased by 2 times relative to Example 1, the yield did not change significantly.

[0045] Example 5

[0046] Weigh 5,6-dimethoxy-1-indanone (192 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. Monitor by TLC spot plate. After the reaction is complete, add 100 ml of water, place in the refrigerator overnight, then filter the precipitated solid, put the solid in a vacuum drying oven to dry, dissolve in 15 ml of toluene, heat and stir to dissolve. Then add boron trifluoride ether (1.8 ml, 14.3 mmol) and triethylamine (1.5 ml, 10.8 mmol) in turn, heat to 120°C, stir and reflux for 0.5h. Monitor by TLC spot plate. After the reaction is complete, wash the product with water, extract, dry, rotary evaporate, and separate and purify by column chromatography to obtain a red solid product TB-2 with a yield of 17%. The molecular formula is C16H14BF2NO3, and the structural formula is

[0047] .

[0048] When the order of adding triethylamine and boron trifluoride ether solution was changed relative to Example 1, the yield decreased by 29%.

[0049] Example 6

[0050] Weigh 5,6-dimethoxy-1-indanone (192 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 90°C, stir and reflux for 2h. Monitor by TLC spot plate. After the reaction is complete, add 100 ml of water, place in the refrigerator overnight, then filter the precipitated solid, put the solid in a vacuum drying oven to dry, dissolve in 15 ml of toluene, heat and stir to dissolve. Then add triethylamine (1.5 ml, 10.8 mmol) and boron trifluoride ether (1.8 ml, 14.3 mmol) in sequence, heat to 120°C, stir and reflux for 0.5h. Monitor by TLC spot plate. After the reaction is complete, wash the product with water, extract, dry, rotary evaporate, and separate and purify by column chromatography to obtain a red solid product TB-2 with a yield of 35%. The molecular formula is C16H14BF2NO3, and the structural formula is

[0051] .

[0052] When the reaction temperature was increased by 20°C relative to Example 1, the yield decreased by 11%.

[0053] Example 7

[0054] Weigh 5,6-dimethoxy-1-indanone (192 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 50°C, stir and reflux for 2h. Monitor by TLC spot plate. After the reaction is complete, add 100 ml of water, place in the refrigerator overnight, then filter the precipitated solid, put the solid in a vacuum drying oven to dry, dissolve in 15 ml of toluene, heat and stir to dissolve. Then add triethylamine (1.5 ml, 10.8 mmol) and boron trifluoride ether (1.8 ml, 14.3 mmol) in sequence, heat to 120°C, stir and reflux for 0.5h. Monitor by TLC spot plate. After the reaction is complete, wash the product with water, extract, dry, rotary evaporate, and separate and purify by column chromatography to obtain a red solid product TB-2 with a yield of 31%. The molecular formula is C16H14BF2NO3, and the structural formula is

[0055] .

[0056] When the reaction temperature was reduced by 20°C relative to Example 1, the yield decreased by 15%.

[0057] Example 8

[0058] Weigh 1-indanone (132 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. Monitor by TLC spot plate. After the reaction is complete, add 100 ml of water and place in the refrigerator overnight. Then filter the precipitated solid, dry the solid in a vacuum drying oven, and dissolve it in 15 ml of toluene. Heat and stir to dissolve. Then add triethylamine (1.5 ml, 10.8 mmol) and boron trifluoride ether (1.8 ml, 14.3 mmol) in turn, heat to 120°C, stir and reflux for 0.5h. Monitor by TLC spot plate. After the reaction is complete, wash the product with water, extract, dry, rotary evaporate, and purify by column chromatography to obtain an orange-yellow solid product TB-1 with a yield of 41%. The molecular formula is C14H10BF2N, and the structural formula is

[0059] .

[0060] Example 9

[0061] Weigh 5-chloro-1-indanone (167 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 2 h. Monitor by TLC spot plate. After the reaction is complete, add 100 ml of water and place in the refrigerator overnight. Then filter the precipitated solid, dry the solid in a vacuum drying oven, and dissolve it in 15 ml of toluene. Heat and stir to dissolve. Then add triethylamine (1.5 ml, 10.8 mmol) and boron trifluoride ether (1.8 ml, 14.3 mmol) in sequence, heat to 120 °C, stir and reflux for 0.5 h. Monitor by TLC spot plate. After the reaction is complete, wash the product with water, extract, dry, rotary evaporate, and separate and purify by column chromatography to obtain an orange-yellow solid product TB-3 with a yield of 39%. The molecular formula is C14H9BF2ClNO, and the structural formula is

[0062] .

[0063] Example 10

[0064] Weigh 4-hydroxy-1-indanone (148 mg, 1.0 mmol) and 2-formylpyrrole (95 mg, 1.0 mmol) and dissolve in 15 ml of toluene, heat and stir to dissolve. Add triethylamine (1.5 ml, 10.8 mmol) and boron trifluoride etherate (1.8 ml, 14.3 mmol), reflux at 120°C, and stir for 4 hours. Monitor by TLC spot plate. After the reaction is completed, wash the product with water, extract, dry, and rotary evaporate. Separate and purify by column chromatography to obtain an orange solid product TB-4 with a yield of 25%. The molecular formula is C14H10BF2NO2, and the structural formula is

[0065] .

[0066] Embodiment 11

[0067] Weigh the compounds TB-1 (3.17 mg, 0.01 mmol), TB-2 (3.77 mg, 0.01 mmol), TB-3 (2.9 mg, 0.01 mmol), and TB-4 (3.33 mg, 0.01 mmol), respectively, dissolve the above four compounds in 1 mL of ethyl acetate to prepare 0.01 mol / L mother solution, then take 5 μL of each mother solution and dissolve it in 20 μL of acrylic resin, and evenly apply it on the plastic wrap, dry it at 36°C, and then put the plastic wrap under a (365 nm) ultraviolet light, take a photo with an HONOR 20 mobile phone, and get a clear fluorescence image. Fig. 9It can be observed that the solid fluorescence intensity of compound TB-2 is the strongest, therefore, compound TB-2 is selected as the solid fluorescent dye for subsequent applications.

[0068] Example 12

[0069] Weigh compound TB-2 (3.77 mg, 0.01 mmol), dissolve it in 1 mL of ethyl acetate to prepare a 0.01 mol / L mother solution, take 1 μL, 5 μL, 10 μL, and 15 μL of the mother solution respectively and dissolve them in 20 μL of acrylic resin, and evenly apply them on the plastic wrap, dry them at 36°C, and then put the plastic wrap under a (365 nm) ultraviolet light, take a photo with an HONOR 20 mobile phone, and get a clear fluorescence image. Fig.10 It can be observed that with the increase of the amount of mother solution, the fluorescence intensity changes from weak to strong and then becomes weaker, and the fluorescence intensity of the mother solution of 5 μL is the brightest. This concentration is most suitable for the preparation of anti-counterfeiting film. Fig.10 The compound TB-2 obtained in Example 12 was first dissolved in ethyl acetate to prepare a mother liquor, and then 1 μL, 5 μL, 10 μL, and 15 μL of the mother liquor were dissolved in 20 μL of acrylic resin and formed into a film on plastic wrap. Under ultraviolet light (365 nm), photos were taken with an HONOR 20 mobile phone to obtain clear fluorescence images. Fig.11 The compound TB-2 obtained in Example 12 was first dissolved in ethyl acetate to prepare a mother solution, and then 1 μL, 5 μL, 10 μL, and 15 μL of the mother solution were dissolved in 20 μL of acrylic resin and formed into a film on a plastic wrap. Under natural light, a photo was taken with an HONOR 20 mobile phone to obtain a clear natural light image. It can be seen from the figure that the natural light intensity is best when the mother solution is 5 μL, which is conducive to the preparation of the anti-counterfeiting film.

[0070] Embodiment 13

[0071] Weigh TB-1 (3.17 mg, 0.01 mmol), TB-2 (3.77 mg, 0.01 mmol), TB-3 (2.9 mg, 0.01 mmol), and TB-4 (3.33 mg, 0.01 mmol) compounds, add 1 mL of different solvents (Toluene, DCM, EA, MeCN, THF, DMSO) to prepare a dye mother solution with a concentration of 0.01 mol / L; take 3 μL of the solution from the mother solution, add 3 mL of the corresponding solvent to prepare a 1×10-5 mol / L test solution, and the obtained UV absorption and fluorescence emission spectra of compounds TB-1, TB-2, TB-3, and TB-4 in different solvents Fig.12 .from Fig.12It can be seen that for the unsubstituted compound TB-1, the UV absorption peak wavelength is 515 nm, the fluorescence emission peak wavelength is 540 nm, and its fluorescence quantum yield is 18%, which is higher than other solvents; for the hydroxyl substitution (TB-4), the position and luminescence intensity of UV and fluorescence are basically unchanged. When there is a weak electron-withdrawing group (TB-3, -Cl), the UV and fluorescence have a slight red shift, and the fluorescence quantum yield is also slightly improved; when there is a power-donating group (TB-2, -OCH3), not only the UV and fluorescence have a large red shift (529, 550 nm), but also the fluorescence quantum yield is significantly improved (30% in DMSO, >99% in other solvents). It can be concluded that different substituents on 1-indanone have a small effect on the position of the UV absorption peak and fluorescence emission peak, but it is closely related to the fluorescence quantum yield of the substance.

Claims

1. BODIPY solid fluorescent dye, characterized in that: The chemical structural formula of the fluorescent dye is: , wherein R1 is -H, -MeO, or -Cl; R2 is -H, -MeO; R3 is H, -OH.

2. The method for preparing the BODIPY solid fluorescent dye according to claim 1, characterized in that: The invention comprises the following preparation method: (1) Add 1-indanone derivative, ethanol and 2-formylpyrrole to a reaction flask at room temperature and fully dissolve them, then add potassium hydroxide aqueous solution to obtain reaction solution 1. The structural formula of the 1-indanone derivative is , wherein R1 is -H, -MeO, or -Cl; R2 is -H, -MeO; R3 is H, -OH; (2) adding water to the reaction solution 1 in step (1), filtering it with suction, and drying it to obtain a solid product; (3) adding toluene, triethylamine and boron trifluoride ether to the solid product in step (2) respectively, and heating under reflux to obtain reaction solution 2; (4) The reaction solution 2 in step (3) is washed with water, extracted, dried, rotary evaporated, and purified by column chromatography to obtain a solid product I.

3. The method according to claim 2, characterized in that In the step (1), the molar ratio of the 1-indanone derivative to 2-formylpyrrole and potassium hydroxide is 1:1-10:1-10.

4. The method according to claim 2, characterized in that: The step (1) is reacted under heating reflux, the reaction temperature is 50-100° C., and the heating time is 1-6 hours.

5. The method according to claim 2, characterized in that: The order of feeding in the step (3) is solid product, toluene, triethylamine, boron trifluoride ether, and the mass ratio of the feeding is 1:30-40:1-4:4-8.

6. The method according to claim 2, characterized in that The heating reflux temperature of step (3) is 100-150° C., and the heating time is 0.5-2 hours.

7. Use of the BODIPY solid fluorescent dye according to claim 1 in a fluorescent holographic anti-counterfeiting film.

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