An ultraviolet and blue light resistant compound, a preparation method and application thereof

Abstract

The application provides an ultraviolet and blue light preventing compound and a preparation method and application thereof, and relates to the technical field of organic compound synthesis. The ultraviolet and blue light preventing compound provided by the application is an UVA and blue light preventing compound with 1,3-diphenyl-1,3-propanedione as a molecular skeleton. The compound is simple to synthesize and low in cost, and has the potential for cheap mass production.

Description

Technical Field

[0001] This invention relates to the field of organic compound synthesis technology, and more specifically, to a compound that protects against ultraviolet and blue light, its preparation method, and its application. Background Technology

[0002] Ultraviolet (UV) radiation is a major cause of skin cancer, photoaging, and sunburn. According to the World Health Organization, approximately 2-3 million new cases of non-melanoma skin cancer are diagnosed globally each year, and sun protection measures can significantly reduce this risk. Solar ultraviolet radiation reaching Earth includes UVB (290-320nm), UVA2 (320-340nm), and UVA1 (340-400nm). UVB accounts for up to 5% of solar ultraviolet radiation and can induce potentially mutagenic DNA photoproducts, leading to erythema, skin pigmentation, photoimmunosuppression, and skin cancer. UVA1 accounts for 80% of the solar ultraviolet radiation received on Earth. While its energy is lower than UVB, it has higher penetrating power, reaching deep into the dermis. Currently, UV sunscreens lack sufficient absorption in the 340-400nm wavelength range.

[0003] Besides ultraviolet radiation, most LED lighting and display devices, sunlight, and its diffused light in daily life emit strong high-energy visible light (HEV, commonly known as blue light, 400-445nm). With the widespread use of electronic devices (mobile phones, computers, tablets, etc.) and LED light sources, the time humans spend exposed to high-energy visible light has increased significantly. Studies have shown that modern people spend an average of 6-8 hours a day in contact with electronic screens. Prolonged exposure to blue light can penetrate the epidermis and reach the dermis, inducing excessive production of reactive oxygen species (ROS), leading to collagen degradation, elastin damage, and lipid peroxidation, thus accelerating photoaging of the skin. In addition, blue light can also stimulate melanocyte activity, causing pigmentation.

[0004] Currently, some brands have achieved highly effective blocking of short-wavelength blue light through patented compounding technologies (such as synergistic effects of ingredients like ectoine, bisabolol, and hyaluronic acid). No compounds have been reported that can effectively block both UVA (320nm-400nm) and blue light (400-445nm) wavelengths. Developing sunscreen ingredients that protect against both UVA and blue light has significant market demand and importance in the skin protection field, providing consumers with a multi-dimensional protection system and a more comprehensive and efficient solution for UV and blue light protection. This also provides an extra protective barrier for sensitive skin and skin damaged after cosmetic procedures. Summary of the Invention

[0005] To address the aforementioned problems, the first aspect of this invention provides a compound that protects against ultraviolet (UV) radiation and blue light, the general structural formula of which is shown in Formula I.

[0006]

[0007] In Formula I, R1 is a nitrogen-containing electron-donating group, and R2 is a tert-butyl group.

[0008] Optionally, the nitrogen-containing electron-donating group is a nitrogen-containing hydrocarbon group.

[0009] Optionally, the number of carbon atoms in the hydrocarbon group of the nitrogen-containing hydrocarbon group is at least 1.

[0010] Optionally, the number of carbon atoms in the hydrocarbon group of the nitrogen-containing hydrocarbon group is 1-10. Optionally, the number of carbon atoms in the two hydrocarbon groups connected to the nitrogen atom in the nitrogen-containing hydrocarbon group can be any one or any combination of two of the following: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10.

[0011] Optionally, the hydrocarbon group can be any one or any combination of two of the following: alkyl, olefin, or alkyne groups.

[0012] Optionally, the hydrocarbon group is an alkyl group, which can be any one or a combination of two of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl or n-heptyl.

[0013] Optionally, R1 is independently selected from

[0014] One of them.

[0015] Optionally, R1 is independently selected from

[0016] This invention relates to UV- and blue-light-blocking compounds with 1,3-diphenyl-1,3-propanedione as the molecular backbone. Different donor and acceptor groups are selected to form different UVA and blue-light-blocking compounds. The absorption wavelength range of the compounds is precisely controlled by adjusting the strength of the electronic properties of the donor and acceptor groups. This type of structure achieves UV-blue light dual-region absorption through an intramolecular DA system (R1 → backbone). Specifically, the nitrogen-containing group (R1) is a strong electron-donating group, driving the absorption red-shift to the blue light band; the β-diketone backbone provides UVA and UVB absorption and acts as an electron acceptor.

[0017] To elaborate further, the core skeleton is 1,3-diphenyl-1,3-propanedione, a strong ultraviolet absorbing group that provides intrinsic absorption in the UVA region (315-400 nm), originating from the π→π* transition of the conjugated enol system. Simultaneously, the carbonyl carbon exhibits strong electronegativity, constituting an intramolecular electron acceptor.

[0018] In the R1 nitrogen-containing electron-donating group, the lone pair electrons of the nitrogen atom inject electrons into the benzene ring through p-π conjugation, significantly reducing the HOMO-LUMO band gap. Furthermore, the nitrogen atom has higher polarizability, enabling the formation of intramolecular hydrogen bonds (such as with adjacent carbonyl groups), further stabilizing the excited state and enhancing the redshift effect. This strong electron-donating property shifts the absorption band to the blue light region (400-450 nm), filling the blue light coverage blind spot of the β-diketone skeleton. In comparison, other groups include: alkoxy groups (-OR): weaker electron-donating ability (only σ-donates electrons), insufficient redshift effect; single alkyl groups (-R): weak hyperconjugation effect, unable to effectively regulate the band gap; halogen groups (-X): electron-withdrawing property leads to a blue shift, contrary to the target.

[0019] The large-volume R2-tert-butyl group, in synergy with other groups, can suppress intermolecular π-π stacking, preventing aggregation that leads to spectral broadening or quenching. Furthermore, the tert-butyl group can prevent reactions at the substitution sites in the excited state, thus improving the photostability of the molecule.

[0020] Optional, the UV-blocking and blue-light-blocking compounds have a light absorption range of 320-445nm and a maximum molar absorptivity of not less than 35000M. -1 cm -1 .

[0021] A second aspect of this invention provides a method for preparing a compound that blocks ultraviolet light and blue light, the method comprising the following steps:

[0022] A 4-nitrogen-containing electron-donating acetophenone, methyl 4-tert-butylbenzoate, a strong base, and a solvent are mixed at a certain temperature and then heated under reflux to obtain a compound that blocks ultraviolet and blue light.

[0023] Optionally, the strong base is one or more of sodium hydride, sodium ethoxide, sodium methoxide, or lithium diisopropylamino. Preferably, the strong base is sodium hydride, which has strong basicity, relatively weak nucleophilicity, good solubility in organic solvents, and is more likely to abstract the strongly acidic α-hydrogen from the ester molecule during the reaction to generate the enol anion of the ester.

[0024] Optionally, the solvent can be anhydrous alcohol or aprotic polar solvent. For example, anhydrous alcohol can be anhydrous ethanol. Aprotic polar solvent can be one or more of tetrahydrofuran, 1,4-dioxane, or N,N-dimethylformamide. However, the present invention is not limited thereto, and those skilled in the art can select a suitable solvent according to the reaction environment.

[0025] Optionally, the molar ratio of 4-nitrogen-containing electron-donating acetophenone to 4-tert-butylbenzoate is 1:(1.1-1.5).

[0026] Alternatively, the synthetic route for UV-protective and blue-light-protective compounds may be:

[0027]

[0028] Wherein, R is a nitrogen-containing electron-donating group, which is the same as the R1 group mentioned above.

[0029] Optionally, the temperature must not exceed 0℃.

[0030] Optionally, the heating reflux temperature shall not be lower than 70°C.

[0031] In an exemplary embodiment of the present invention, the method for preparing the UV-protective and blue-light-protective compound includes the following steps:

[0032] S1: Under an inert gas environment, 4-haloacetophenone is added to an anhydrous solvent, followed by a strong base. The mixture is then added at a temperature not higher than 0°C, and methyl 4-tert-butylbenzoate is added. The mixture is then refluxed at a temperature not lower than 70°C to obtain the intermediate.

[0033] Optionally, 4-haloacetophenone can be 4-chloroacetophenone or 4-bromoacetophenone.

[0034] Optionally, the anhydrous solvent may be one or more of anhydrous tetrahydrofuran, anhydrous ethanol, 1,4-dioxane, or N,N-dimethylformamide. However, the present invention is not limited thereto, and those skilled in the art can select a suitable anhydrous solvent according to the reaction environment.

[0035] Optionally, the strong base may be one or more of sodium hydride, sodium ethoxide, sodium methoxide, or lithium diisopropylamide. Preferably, the strong base is sodium hydride.

[0036] Optionally, the molar ratio of 4-haloacetophenone to methyl 4-tert-butylbenzoate is 1:(1.1-1.5).

[0037] S2: Add intermediates, nitrogen-containing electron-donating amines, catalysts, catalyst ligands, and strong bases to an anhydrous solvent and reflux at a temperature not lower than 110°C to obtain compounds that protect against ultraviolet and blue light.

[0038] Optionally, the nitrogen-containing electron-donating amine can be a nitrogen-containing hydrocarbon amine, which contains two hydrocarbon groups, and the hydrocarbon groups in the nitrogen-containing hydrocarbon amine have at least 1 carbon atom. Further, the hydrocarbon groups have 1-10 carbon atoms.

[0039] Optionally, the nitrogen-containing electron-donating amine can be one of dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, or di-n-decylamine.

[0040] Optionally, the catalyst may be tris(dibenzylindeneacetone)dipalladium (Pd2dba3), however, the present invention is not limited thereto, and those skilled in the art may select the type of catalyst according to the reaction environment.

[0041] Optionally, the catalyst ligand may be 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (Sphos).

[0042] Optionally, in step S2, the strong base can be a tert-butoxide salt. For example, the tert-butoxide salt can be potassium tert-butoxide or sodium tert-butoxide.

[0043] Optionally, in step S2, the anhydrous solvent can be anhydrous toluene.

[0044] A third aspect of the present invention provides the application of an anti-ultraviolet and anti-blue light compound in optical films, optical lenses, goggles, skin care products, cosmetics, coatings, light stabilizers or panels.

[0045] Compared with the prior art, the present invention achieves at least one of the following beneficial effects:

[0046] (1) The UV-protecting and blue light-protecting compounds of the present invention are UVA and blue light-protecting compounds with 1,3-diphenyl-1,3-propanedione as the molecular skeleton. These compounds are simple to synthesize, low in cost, and have the potential for cheap and large-scale manufacturing.

[0047] (2) The UV-protective and blue-light-protective compounds of this invention have strong UV absorption capacity in the 320nm-400nm UVA band and strong blue light absorption capacity in the 400-445nm band, with a maximum molar absorptivity of not less than 35000M. -1 cm -1 The molar absorptivity is even as high as 4.2 x 10⁻⁶. 4 M -1 cm -1 Meanwhile, absorption is very weak in the wavelength range after 445nm.

[0048] (3) The UV-protective and blue-light-protective compounds of this invention have excellent photostability, and can withstand strong blue light (intensity 5 mW / cm²) at 405 nm that matches their absorption peak. 2 No photodecomposition occurred after 4 hours of irradiation. After 6 hours of sunlight irradiation, the decomposition rate was no higher than 70%, while the decomposition rate of avobenzylhydrazone under the same conditions was close to 100%. The stability is significantly improved compared to structurally similar avobenzylhydrazone. Excellent UVA and blue light absorption, photostability, and visible light transmittance make this compound a promising candidate for market applications. Attached Figure Description

[0049] The accompanying drawings, which are included to provide a further understanding of the invention and form part of this invention, illustrate exemplary embodiments of the invention and are used to explain the invention, but do not constitute an undue limitation of the invention. In the drawings:

[0050] Figure 1 An exemplary embodiment of the 1H NMR spectrum of the UV-protective and blue-light-protective compound B1 of the present invention is shown;

[0051] Figure 2 An exemplary embodiment of the carbon NMR spectrum of the UV-protective and blue-light-protective compound B1 of the present invention is shown;

[0052] Figure 3 An exemplary embodiment of a high-resolution mass spectrum of compound B1, which provides protection against ultraviolet and blue light, is shown.

[0053] Figure 4 An exemplary embodiment of the 1H NMR spectrum of 1-(4-bromophenyl)-3-(4-(tert-butyl)phenyl)propane-1,3-dione is shown;

[0054] Figure 5 An exemplary embodiment of the proton NMR spectrum of compound B2, which provides protection against ultraviolet and blue light, is shown.

[0055] Figure 6 An exemplary embodiment of the absorption spectrum of the UV- and blue light-blocking compound B1 is shown;

[0056] Figure 7 An exemplary embodiment is shown, illustrating the change of the absorption spectrum of the UV- and blue-light-blocking compound B1 over time.

[0057] Figure 8 An exemplary embodiment is shown, illustrating the light transmittance of the UV-protective and blue-light-protective compound B1. Detailed Implementation

[0058] To more clearly illustrate the overall concept of the present invention, a detailed description will be provided below with reference to the accompanying drawings and examples.

[0059] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and therefore the scope of protection of the invention is not limited to the specific embodiments disclosed below.

[0060] Example 1

[0061] In an exemplary embodiment of the present invention, the method for preparing the UV-blocking and blue light-blocking compounds includes the following steps:

[0062] In an air-conditioned environment, 10 g of 4-dimethylaminoacetophenone was added to a two-necked round-bottom flask, followed by 100 mL of anhydrous tetrahydrofuran. Then, 4.9 g of sodium hydride was slowly added, and the mixture was stirred at 0°C for 5 minutes. Subsequently, 14.1 g of methyl p-tert-butylbenzoate was weighed, dissolved in 100 mL of anhydrous tetrahydrofuran, and slowly added dropwise to the system. After the addition was complete, the temperature was raised to reflux at 70°C and stirred for 15 hours. After the reaction was complete, the reaction system was quenched with water, and the pH was adjusted to 2 with 6 M HCl. The organic solvent was removed by rotary evaporation, and the crude product was obtained by filtration. After washing with water multiple times, the product was recrystallized from n-hexane to give a yellow crystalline compound B1 (16.27 g, yield: 82.1%). The synthetic route of the UV-protective and blue-light-protective compound B1 is shown in the figure below.

[0063]

[0064] Reference: 1H NMR spectrum (CDCl3) of compound B1, which protects against UV and blue light. Figure 1 As shown, 1 H NMR (500MHz, CDCl3): δ=7.91 (t, J=9.2Hz, 4H, Ar), 7.49 (d, J=8.4Hz, 2H, Ar), 6.7 5(s,1H,CH),6.71(d,J=9.0Hz,2H,Ar),3.07(s,6H,N-CH3),1.36(s,9H,CH3)ppm.

[0065] Reference: Carbon NMR spectrum (CDCl3) of compound B1, which protects against ultraviolet and blue light. Figure 2 As shown, 13 C{ 1 H}NMR (125MHz, CDCl3): δ=186.70,182.56,155.50,153.39,133.28,131.39,129.36,12 9.12,126.83,125.75,125.65,123.00,111.19,91.62,40.21,35.15,31.32ppm.HRMSm / z calcdfor(C 21 H 25 NO2)[M+H] + :324.1959, found:324.1962, |Δ|=1.0ppm.

[0066] High-resolution mass spectrum reference of compound B1, which protects against ultraviolet and blue light. Figure 3 As shown.

[0067] Example 2

[0068] In an exemplary embodiment of the present invention, the method for preparing the UV-blocking and blue light-blocking compounds includes the following steps:

[0069] S1: Under nitrogen atmosphere, 10 g of 4-bromoacetophenone and 100 mL of anhydrous tetrahydrofuran were added to a two-necked round-bottom flask. 4.9 g of sodium hydride was slowly added, and the mixture was stirred at 0°C for 5 minutes. Then, 12.2 g of methyl 4-tert-butylbenzoate was weighed, dissolved in 100 mL of anhydrous tetrahydrofuran, and slowly added dropwise to the system. After the addition was complete, the temperature was raised to reflux at 70°C and stirred for 15 hours. After the reaction was complete, the reaction system was quenched with water, and the pH was adjusted to 3 with 6 M HCl. The organic solvent was removed by rotary evaporation, and the crude product was obtained by filtration and washed repeatedly with water. Recrystallization from n-hexane yielded 11.3 g of pure product 1-(4-bromophenyl)-3-(4-(tert-butyl)phenyl)propane-1,3-dione (pale yellow solid, yield: 62.5%).

[0070] S2: Under nitrogen atmosphere, 1-(4-bromophenyl)-3-(4-(tert-butyl)phenyl)propane-1,3-dione (300 mg), diethylamine (90 mg), tris(dibenzylindeneacetone)dipalladium (15 mg), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (15 mg), sodium tert-butoxide (240 mg), and 10 mL of anhydrous toluene were added to a 50 mL Young's tube. The mixture was then refluxed at 110 °C with stirring for 12 hours. After the reaction was complete, the mixture was cooled to room temperature and extracted with dichloromethane. The extract was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation. Column chromatography yielded 153 mg of compound B2 (yellow solid, yield: 52.3%).

[0071] The synthetic route of compound B2, which protects against ultraviolet and blue light, is shown in the figure below:

[0072]

[0073] 1H NMR spectrum (CDCl3) of 1-(4-bromophenyl)-3-(4-(tert-butyl)phenyl)propane-1,3-dione (reference) Figure 4 As shown. 1 H NMR (500MHz, CDCl3) δ = 7.92 (d, J = 8.5Hz, 2H), 7.85 (d, J = 8.5Hz, 2H), 7.63 (d, J = 8.5Hz, 2H), 7.51 (d, J = 8.4Hz, 2H), 6.79 (s, 1H), 1.36 (s, 9H) ppm.

[0074] Reference: 1H NMR spectrum (CDCl3) of compound B2, which protects against UV and blue light. Figure 5 As shown. 1H NMR (500MHz, CDCl3): δ=7.90 (dd, J=8.8, 2.0Hz, 4H), 7.48 (d, J=8.5Hz, 2H), 6.73 (s, 1H ), 6.68 (d, J = 9.0Hz, 2H), 3.44 (q, J = 7.0Hz, 4H), 1.36 (s, 9H), 1.22 (t, J = 7.1Hz, 6H) ppm.

[0075] Example 3

[0076] In an exemplary embodiment of the present invention, the method for preparing the UV-blocking and blue light-blocking compounds includes the following steps:

[0077] S1: Under nitrogen atmosphere, 10 g of 4-bromoacetophenone was added to 100 mL of anhydrous ethanol, followed by the slow addition of 4.9 g of sodium ethoxide. The mixture was stirred at 0°C for 5 minutes. Then, 13.5 g of methyl 4-tert-butylbenzoate was weighed, dissolved in 100 mL of anhydrous tetrahydrofuran, and slowly added dropwise to the system. After the addition was complete, the temperature was raised to reflux at 80°C and stirred for 15 hours. After the reaction was complete, the reaction system was quenched with water, and the pH was adjusted to 3 with 6 M HCl. The organic solvent was removed by rotary evaporation, and the crude product was obtained by filtration and washed repeatedly with water. Recrystallization from n-hexane yielded the intermediate.

[0078] S2: Under nitrogen atmosphere, the intermediate (300 mg), di-n-propylamine (90 mg), tris(dibenzylindeneacetone)dipalladium (15 mg), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (15 mg), and sodium tert-butoxide (240 mg) were added to a 50 mL Young's tube. 10 mL of anhydrous toluene was added, and the mixture was refluxed at 120°C with stirring for 12 hours. After the reaction was complete, the mixture was cooled to room temperature and extracted with dichloromethane. The extract was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation. Column chromatography was then used to obtain B3.

[0079] The 1H NMR spectrum of compound B3, which protects against ultraviolet and blue light. 1 H NMR (500MHz, CDCl3): δ=7.89 (dd, J=8.7, 2.0Hz, 4H), 7.46 (d, J=8.7Hz, 2H), 6.73 (s, 1H), 6 .68(d,J=8.8Hz,2H),3.42(q,J=7.1Hz,4H),1.39-1.28(m,13H),0.88(t,J=7.1Hz,6H)ppm.

[0080] Example 4

[0081] In an exemplary embodiment of the present invention, the synthesis of the UV-protective and blue-light-protective compound B4 is carried out using the same method as that for B2, the main difference being that di-n-butylamine is used instead of diethylamine in the synthesis process. The other steps are the same as for B2.

[0082] The 1H NMR spectrum of compound B4, which protects against ultraviolet and blue light. 1 H NMR (500MHz, CDCl3): δ=7.88 (dd, J=8.8, 2.0Hz, 4H), 7.45 (d, J=8.7Hz, 2H), 6.73 (s, 1H), 6 .68(d,J=8.8Hz,2H),3.42(q,J=7.0Hz,4H),1.81-1.12(m,17H),0.82(t,J=7.1Hz,6H)ppm.

[0083] Example 5

[0084] In an exemplary embodiment of the present invention, the synthesis of the UV-protective and blue-light-protective compound B5 is carried out using the same method as that for B2, the main difference being that di-n-pentylamine is used instead of diethylamine in the synthesis process.

[0085] The 1H NMR spectrum of compound B5, which protects against ultraviolet and blue light. 1 H NMR (500MHz, CDCl3): δ=7.87 (dd, J=8.7, 2.0Hz, 4H), 7.42 (d, J=8.7Hz, 2H), 6.73 (s, 1H), 6 .67(d,J=8.8Hz,2H),3.41(q,J=7.1Hz,4H),1.81-1.01(m,21H),0.81(t,J=7.1Hz,6H)ppm.

[0086] Example 6

[0087] In an exemplary embodiment of the present invention, the synthesis of the UV-blocking and blue-light-blocking compound B6 is based on the synthesis method of B2, the main difference being that dihexylamine is used instead of diethylamine in the synthesis process.

[0088] The 1H NMR spectrum of compound B6, which provides UV and blue light protection. 1 H NMR (500MHz, CDCl3): δ=7.87 (dd, J=8.8, 2.1Hz, 4H), 7.45 (d, J=8.6Hz, 2H), 6.73 (s, 1H), 6 .67(d,J=8.8Hz,2H),3.39(q,J=6.9Hz,4H),1.81-1.01(m,25H),0.81(t,J=7.1Hz,6H)ppm.

[0089] Example 7

[0090] In an exemplary embodiment of the present invention, the synthesis of the UV-blocking and blue-light-blocking compound B7 is based on the synthesis method of B2, the main difference being that di-n-heptylamine is used instead of diethylamine in the synthesis process.

[0091] The 1H NMR spectrum of compound B7, which protects against ultraviolet and blue light. 1 H NMR (500MHz, CDCl3): δ=7.86 (dd, J=8.7, 2.1Hz, 4H), 7.46 (d, J=8.7Hz, 2H), 6.73 (s, 1H), 6 .68(d,J=8.8Hz,2H),3.39(q,J=7.0Hz,4H),1.81-1.01(m,29H),0.81(t,J=7.1Hz,6H)ppm.

[0092] Example 8

[0093] In an exemplary embodiment of the present invention, the synthesis of the UV-blocking and blue-light-blocking compound B8 is carried out using the same method as that of B2, the main difference being that dioctylamine is used instead of diethylamine in the synthesis process.

[0094] The 1H NMR spectrum of compound B8, which provides UV and blue light protection. 1 H NMR (500MHz, CDCl3): δ=7.86 (dd, J=8.8, 2.1Hz, 4H), 7.46 (d, J=8.6Hz, 2H), 6.73 (s, 1H), 6 .68(d,J=8.8Hz,2H),3.42(q,J=6.8Hz,4H),1.81-1.00(m,33H),0.80(t,J=7.0Hz,6H)ppm.

[0095] Example 9

[0096] In an exemplary embodiment of the present invention, the synthesis of the UV-protective and blue-light-protective compound B9 is carried out using the same method as that for B2, the main difference being that di-n-nonylamine is used instead of diethylamine in the synthesis process.

[0097] The 1H NMR spectrum of compound B9, which provides UV and blue light protection. 1 H NMR (500MHz, CDCl3): δ=7.85 (dd, J=8.7, 2.0Hz, 4H), 7.46 (d, J=8.8Hz, 2H), 6.73 (s, 1H), 6 .67(d,J=8.6Hz,2H),3.42(q,J=7.1Hz,4H),1.81-1.00(m,37H),0.80(t,J=6.8Hz,6H)ppm.

[0098] Example 10

[0099] In an exemplary embodiment of the present invention, the synthesis of the UV-protective and blue-light-protective compound B10 is based on the synthesis method of B2, the main difference being that di-n-decylamine is used instead of diethylamine in the synthesis process.

[0100] The 1H NMR spectrum of compound B10, which protects against ultraviolet and blue light. 1 H NMR (500MHz, CDCl3): δ=7.89 (dd, J=8.7, 2.0Hz, 4H), 7.46 (d, J=8.7Hz, 2H), 6.73 (s, 1H), 6 .68(d,J=8.8Hz,2H),3.42(q,J=7.0Hz,4H),1.81-1.00(m,41H),0.80(t,J=7.0Hz,6H)ppm.

[0101] Example 11

[0102] In an exemplary embodiment of the present invention, the method for preparing the UV-blocking and blue light-blocking compounds includes the following steps:

[0103] In an air-conditioned environment, 10 g of 4-diethylaminoacetophenone and 100 mL of anhydrous N,N-dimethylformamide were added to a two-necked round-bottom flask. 4.9 g of sodium methoxide was then slowly added, and the mixture was stirred at 0°C for 5 minutes. Subsequently, 14.1 g of methyl p-tert-butylbenzoate was weighed, dissolved in 100 mL of anhydrous tetrahydrofuran, and slowly added dropwise to the system. After the addition was complete, the temperature was raised to reflux at 75°C and stirred for 15 hours. After the reaction was complete, the reaction system was quenched with water, and the pH was adjusted to 2 with 6 M HCl. The organic solvent was removed by rotary evaporation, and the crude product was obtained by filtration. After washing with water several times, the product was recrystallized from n-hexane to obtain B11.

[0104] Comparative Example 1

[0105] The compound is avobenzylhydrazone, with the structural formula as follows:

[0106] Test case

[0107] Prepare a dilute solution of compound B1 (concentration 1 x 10⁻⁶). -5 The solvents were n-hexane, dichloromethane, and ethanol, respectively, and their absorption spectra were measured. The measurements were performed using a UV-Vis spectrophotometer (Hitachi UH5700 UV-Vis-NIR absorption spectrometer), with a scanning range of 300 nm to 500 nm.

[0108] Normalized absorption spectra of compound B1 in different solvents are as follows ( Figure 6As shown on the left, the maximum absorption peak of B1 in the nonpolar solvent n-hexane is 379 nm, and the absorption threshold is 422 nm. In the polar solvents ethanol and dichloromethane, the maximum absorption peak of B1 is 402 nm, and the absorption threshold reaches 450 nm. The molar absorptivity of B1 in ethanol is as high as 42000 MΩ. - 1 cm -1 ( Figure 6 (right), which ensures that only a small amount of the raw material needs to be added in the application, which can further reduce the product cost.

[0109] Compound B1 exhibits a molar absorptivity as high as 42000 M in both the blue light and ultraviolet (UVA) regions. -1 cm -1 In the UVB region (where the molar extinction coefficient reaches a maximum of 11000 M), -1 cm -1 It also has a strong light absorption capacity and can be used as a raw material for full-band ultraviolet protection and blue light protection.

[0110] Tests on the photostability of compound B1:

[0111] After continuous irradiation of a dilute ethanol solution of compound B1 under strong blue light at 405 nm, the absorption spectrum of the compound was measured over time using a UV-Vis spectrophotometer with a scanning range of 300 nm to 550 nm. The absorption spectrum of the same compound B1 solution was also measured over time after continuous irradiation under outdoor sunlight.

[0112] refer to Figure 7 It can be seen that after 4 hours of strong blue light irradiation, compound B1 in a dilute ethanol solution (concentration 1.8 x 10⁻⁶) showed... - 5 The absorption intensity of compound B1 in ethanol solution (concentration 1.9 x 10⁻⁶) remained unchanged under sunlight irradiation, indicating that compound B1 exhibits good blue light stability. -5 The absorption intensity in M ​​changed, indicating that compound B1 decomposed at a rate of approximately 60% after 6 hours of sunlight exposure. Figure 7 (right), while under the same conditions, the decomposition rate of avobenzimidone in Example 1 was close to 100%.

[0113] Blue light transmittance test of compound B1:

[0114] The analysis was performed using a Hitachi UH5700 UV-Vis-NIR absorption spectrometer. The sample was a dilute ethanol solution of compound B1 (absorbance 1, concentration 2.4 x 10⁻⁶). -5 Light transmittance reference (M) Figure 8As shown, the transmittance is less than 80% before 445nm, while the transmittance is greater than 80% after 445nm, which meets the requirements of GB / T 38120-2019.

[0115] The compounds prepared in the examples and comparative examples were subjected to dilute ethanol solution (concentration 1 x 10⁻⁶). -5 UV absorption spectroscopy, photostability, and blue light transmittance were performed on M), following the same testing methods as in B1. The results are shown in Table 1. It can be seen that the introduction of long alkyl chains has almost no effect on light absorption, photostability, or beneficial blue light transmittance. However, the introduction of long alkyl chains can improve the oil solubility of these compounds.

[0116] Table 1

[0117]

[0118] Referring to Table 1, it can be seen that the UV-protective and blue-light-protective compounds of this invention have strong UV absorption capabilities in the 320nm-400nm UVA band and strong blue light absorption capabilities in the 400-445nm band, with a maximum molar absorptivity of not less than 35000 MΩ. -1 cm -1 The molar absorptivity is even as high as 4.2 x 10⁻⁶. 4 M -1 cm -1 Meanwhile, absorption is very weak in the wavelength range after 445nm.

[0119] The UV-protective and blue-light-protective compounds of this invention exhibit good photostability, even under strong blue light (intensity 5 mW / cm²) at 405 nm, matching their absorption peaks. 2 No photodecomposition occurred after 4 hours of irradiation. After 6 hours of irradiation under sunlight, the decomposition rate was no higher than 70%, while the decomposition rate of avobenzimidone under the same conditions was close to 100%.

[0120] The UV-blocking and blue-light-blocking compounds of this invention have good transmittance of beneficial blue light, with a transmittance of not less than 75%, which to a certain extent proves that the UV-blocking and blue-light-blocking compounds of this application have good transmittance of beneficial blue light and good blocking properties of harmful blue light.

[0121] Compared to Comparative Example 1, avobenhydrazone, B1-B11 exhibits an absorption wavelength edge extension to 450 nm and an increased molar extinction coefficient to 42000 nm. -1 cm -1 This demonstrates that, in addition to being an anti-blue light compound, B1-B11 also exhibits a significantly increased ability to absorb ultraviolet light as a UVA absorbing material, proving the effectiveness of using small amounts of the compound and the resulting smaller environmental burden.

[0122] The above description is merely an embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principle of the present invention should be included within the scope of the claims of the present invention.

Claims

1. A compound that blocks ultraviolet and blue light, characterized in that, The general structural formula of the UV-protective and blue-light-protective compounds is shown in Formula I. Formula I, In Formula I, R1 is a nitrogen-containing electron-donating group, and R2 is a tert-butyl group; The nitrogen-containing electron-donating group is a nitrogen-containing hydrocarbon group, and the number of carbon atoms in the hydrocarbon group is at least 1. The number of carbon atoms in the two hydrocarbon groups connected to the nitrogen atom in the nitrogen-containing hydrocarbon group is selected from any one or any combination of two of the following: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10. The hydrocarbon group is any one or any combination of two of the following: alkyl, olefin, or alkyne groups.

2. The UV-protective and blue-light-protective compound according to claim 1, characterized in that, R1 is independently selected from , , , , , , , , , , , or One of them.

3. The UV-protective and blue-light-protective compound according to claim 2, characterized in that, R1 is independently selected from or .

4. The UV-protective and blue-light-protective compound according to claim 1, characterized in that, The light absorption range of the UV-protective and blue-light-protective compounds is 320-445nm, and the highest molar absorptivity is not less than 35000 M. -1 cm -1 .

5. A method for preparing a compound that blocks ultraviolet light and blue light as claimed in any one of claims 1-4, characterized in that, The preparation method includes the following steps: A 4-nitrogen-containing electron-donating acetophenone, methyl 4-tert-butylbenzoate, a strong base, and a solvent are mixed at a certain temperature and then heated under reflux to obtain a compound that blocks ultraviolet and blue light.

6. A method for preparing a compound that blocks ultraviolet light and blue light as claimed in any one of claims 1-4, characterized in that, The preparation method includes the following steps: S1: Under an inert gas environment, 4-haloacetophenone is added to an anhydrous solvent, then a strong base is added, and the mixture is mixed at a temperature not higher than 0°C. Then methyl 4-tert-butylbenzoate is added, and the mixture is refluxed at a temperature not lower than 70°C to obtain an intermediate. S2: Add intermediates, nitrogen-containing electron-donating amines, catalysts, catalyst ligands, and strong bases to an anhydrous solvent and reflux at a temperature not lower than 110°C to obtain compounds that protect against ultraviolet and blue light.

7. The application of a UV-blocking and blue-light-blocking compound as claimed in any one of claims 1-4 in optical films, optical lenses, goggles, skin care products, cosmetics, coatings, light stabilizers, or panels.

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