Tb-naphthalimide derivative organic purple light absorbing material and preparation and application thereof

Abstract

The application provides a kind of preparation and application of TB-naphthalimide derivative-based organic purple light absorbing material and application, mainly in the application of shielding ultraviolet light. With p-bromoaniline, 4-bromo-3-methoxy aniline, paraformaldehyde, n-butyllithium, 1,8-naphthalimide, n-butylamine, lawson reagent and the like as raw materials, through a plurality of steps: the product has stable light absorption and emission in solid state, has a wide pH application range, and can be applied to human physiological environment. The results of photodynamic (PDT) experiment show that the dark toxicity and phototoxicity of the product to human liver immortal (THLE-2) cells are very low, and the product has the potential to be developed into photocatalyst, human sunscreen product and sunscreen product for glass, textile and the like.

Description

Technical Field

[0001] This invention belongs to the field of chemical synthesis, specifically involving Synthesis of base (TB)-naphthalimide derivatives; doping Preparation of PVA films based on naphthalimide derivatives and their applications in ultraviolet light blocking and visible light transmission. Background Technology

[0002] Ultraviolet (UV) radiation is divided into three bands: UVA (320-400nm), UVB (320-280nm), and UVC (280-100nm). Since UVC radiation, with its shorter wavelength, accounts for only 5% of ultraviolet radiation and is mostly absorbed by the ozone layer and atmosphere, its impact on the Earth and atmospheric environment is usually ignored.

[0003] UVB photons have high energy and bioactivity. They can penetrate the superficial layers of the skin and reach the deepest layer of the epidermis—the basal layer. Harmful reactive oxygen species and reactive nitrogen species (ROS and RNS) produced during the process of absorbing UVB and releasing energy by chromophores (such as melanin) in the skin can accelerate skin aging, cause inflammation, and even sunburn. If the high-energy photons of UVB are directly absorbed by the bases of cellular DNA, they will form cyclobutanepyrimidine dimers (CPD) and 6-4 photoproducts (6-4PPs). CPD will prevent DNA replication and transcription, leading to cell death or mutation; while 6-4PPs will change the DNA structure, causing sunburn and triggering melanin production, which is the main cause of melanoma in humans. Melanoma is a highly malignant tumor that originates from melanocytes, and its incidence is increasing at an alarming rate of 4-5% per year [8]. Even more alarming is that the proportion of melanoma in the 15-29 age group has risen sharply, becoming the third most common cancer, accounting for 11% of all new cancer cases each year. UVA radiation has lower energy than UVB, but higher concentrations and stronger penetrating power, reaching deep into the skin and the dermis. Melanin, flavin mononucleotide (FMN), and flavin adenine dinucleotide (FAD) are the main compounds that absorb UVA energy. Recent studies have shown that UVA also produces reactive oxygen species (ROS) and reactive oxygen species (RNS), leading to changes in DNA, lipids, and proteins in the body. The resulting oxidative damage significantly promotes premature skin aging and wrinkle formation, and indirectly increases the risk of cancer by oxidizing DNA bases (mainly 2-amino-6,8-dihydroxypurine).

[0004] In summary, ultraviolet (UV) light causes significant damage to the human body through a series of photochemical reactions. Reducing or even avoiding direct exposure to UV light is particularly important for key populations and workers in specialized industries. Furthermore, UV light also has negative effects on artwork, wood, polymers, plastics, and fabrics. The photon energy of UV light is sufficient to break the chemical bonds in polymers, wood, paper, and other organic materials, leading to photodegradation through rapid photolysis and photooxidation reactions. Artwork such as paintings and photographs exposed to natural and artificial lighting for extended periods will gradually fade and eventually lose their color due to severe photodegradation. UV radiation is particularly damaging to library archival materials, as it weakens and embrittles fibers, causing paper to bleach, yellow, or darken depending on its specific composition.

[0005] Therefore, the development of highly efficient UV protection materials is of great significance.

[0006] Currently, common UV absorbers are divided into inorganic and organic UV absorbers. Inorganic UV absorbers include ferric oxide, nano-silica, titanium dioxide, nano-zinc oxide, and cerium dioxide, which have advantages such as high specific surface energy and strong polarity. However, their compatibility with polymers is relatively poor, affecting the physical properties of polymers, such as mechanical properties and product color, thus impacting practical applications and limiting their application areas. Therefore, current research focuses on organic UV absorbers. Commonly used organic UV absorbers include benzotriazole, triazine, and benzophenone, most of which have long conjugated structures and multiple transition modes. However, traditional organic UV absorbers such as 2,4-dihydroxybenzophenone have relatively small molecular weights, and long-term use can lead to migration or precipitation. Therefore, it is necessary to develop new organic UV absorbing materials that are simple, low-cost, and stable to reduce the harm of UV radiation to the human body.

[0007] TB and its derivatives have a unique V-shaped framework and a long conjugated structure. Under photon excitation, they exhibit multiple transition modes (π-π*, n-π*, and spatial transitions), and theoretically have a large molar absorption coefficient, making them an excellent basic framework for ultraviolet light absorption materials.

[0008] 1,8-Naphthalenedicarboximide (NI) possesses unique photophysical properties and diverse biological activities, is easily derivatized, and is one of the most widely studied skeletal structures. Compared to NI, thio-NI exhibits a larger Stokes shift, stronger DNA photocleavage ability, and broader-spectrum, more efficient antitumor activity. Introducing an electron-donating group at the 4-position of 1,8-naphthalenedicarboximide causes a redshift in the maximum absorption wavelength, while the lipophilic side chain can adjust the molecule's lipid-water partition coefficient. Although the sulfur atom is less electronegative than oxygen, it is isoelectronic with the thiocarbonyl group and possesses an empty d orbital, thus exhibiting a stronger electron-withdrawing ability compared to the carbonyl group. Its unique structure and photophysical properties, such as a significant absorption redshift, low fluorescence quantum yield, and higher intersystem crossing (ISC) efficiency, make thio-NI a promising candidate for applications in phototherapy and sensing. The oxygen atom in the methoxy group contains two lone pairs of electrons, which can increase the molecular electron cloud density and affect the spectral properties of the molecule.

[0009] Therefore, introducing naphthalimide, sulfur atoms, and methoxy groups into the TB backbone can adjust the electron cloud density and charge distribution of the molecule, and increase the probability of electron transitions, thereby increasing its light absorption intensity and efficiency. In this invention, naphthalimide, sulfur atoms, and methoxy groups were sequentially introduced into the TB backbone to synthesize three TB-naphthalimide derivatives and two TB-thio-naphthalimide derivatives. Their ultraviolet light absorption properties were investigated, showing broad prospects for the development and utilization of novel organic ultraviolet light absorbing materials. Summary of the Invention

[0010] Technical Problem: The purpose of this invention is to provide a class of organic ultraviolet light absorbing materials based on TB-naphthalimide derivatives, their preparation and application. Using p-bromoaniline, 4-bromo-3-methoxyaniline, paraformaldehyde, n-butyllithium, 1,8-naphthalimide, n-butylamine, Lawson's reagent, etc., as raw materials, five [materials / materials] were obtained through a multi-step reaction. Base-naphthaleneimide derivatives were doped into PVA to prepare novel, highly efficient PVA-

[0011] Base-naphthalimide organic ultraviolet absorbing films, and their application

[0012] Used for blocking ultraviolet light and allowing visible light to pass through.

[0013] Technical solution: The present invention provides a class of TB-naphthalimide derivatives with the following structures: first derivative 11, second derivative 12, third derivative 13, fourth derivative 14, and fifth derivative 15.

[0014]

[0015] A method for preparing a type of TB-naphthalimide derivative according to the present invention includes the following steps:

[0016] Step 1: 4-Bromoaniline 1 and 2-methoxy-4-bromoaniline 4 react with paraformaldehyde 2 to obtain the first intermediate 3 and the second intermediate 5, respectively, as shown in the following reaction formula:

[0017]

[0018] Step 2: The first intermediate 3 and the second intermediate 5 react with butyllithium-boron trimethyl ester to obtain the third intermediate 6 and the fourth intermediate 7, respectively, as shown in the following reaction formulas:

[0019]

[0020] Step 3: n-Butylamine 8 reacts with 4-bromo-1,8-naphthalenedicarboxylic anhydride 9 to give the fifth intermediate 10, as shown in the following reaction formula:

[0021]

[0022] Step 4: The third intermediate 6 reacts with the fourth intermediate 10 in a one-step reaction, yielding two products: a first derivative 11 with unilateral substitution and a second derivative 12 with bilateral substitution.

[0023] The fourth intermediate 7 reacts with the fourth intermediate 10 to give the third derivative 13;

[0024] The reaction formula is as follows:

[0025]

[0026] Step 5: The first derivative 11 and the third derivative 13 react with Lawson's reagent to obtain the fourth derivative 14 and the fifth derivative 15, respectively, as shown in the following reaction formulas:

[0027]

[0028] The present invention discloses a method for preparing organic ultraviolet light absorbing materials based on TB-naphthalimide derivatives, wherein a first derivative 11, a second derivative 12, a third derivative 13, a fourth derivative 14, and a fifth derivative 15 are respectively doped into polyvinyl alcohol (PVA) to prepare corresponding PVA films PVA-11, PVA-12, PVA-13, PVA-14, and PVA-15.

[0029] The PVA films are described as follows: PVA-11 consists of three types of films with masses of 0.1 wt%, 0.5 wt%, and 1.0 wt% in the PVA film composition; PVA-12 consists of three types of films with masses of 0.1 wt%, 0.5 wt%, and 1.0 wt% in the PVA film composition; PVA-13 consists of three types of films with masses of 0.1 wt%, 0.5 wt%, and 1.0 wt% in the PVA film composition; PVA-14 consists of three types of films with masses of 0.1 wt%, 0.5 wt%, and 1.0 wt% in the PVA film composition; and PVA-15 consists of three types of films with masses of 0.1 wt%, 0.5 wt%, and 1.0 wt% in the PVA film composition.

[0030] The polyvinyl alcohol (PVA) has a relative molecular mass MW = 3000 g / mol.

[0031] The present invention describes an application based on TB-naphthalimide derivatives, specifically the first derivative 11, the second derivative 12, the third derivative 13, the fourth derivative 14, and the fifth derivative 15, which exhibit dark toxicity and phototoxicity to human liver immortalized cells THLE-2.

[0032] The application of the organic ultraviolet light absorbing material based on TB-naphthalimide derivative obtained by the preparation method of the present invention, and the application of the PVA films PVA-11, PVA-12, PVA-13, PVA-14 and PVA-15 in shielding ultraviolet light.

[0033] The application of the organic violet light absorbing material based on TB-naphthalimide derivatives obtained by the preparation method of the present invention, and the application of the PVA films PVA-11, PVA-12, PVA-13, PVA-14 and PVA-15 in blocking Rhodamine B fluorescence.

[0034] The application of the organic violet light absorbing material based on TB-naphthalimide derivative obtained by the preparation method of the present invention, and the application of the PVA films PVA-11, PVA-12, PVA-13, PVA-14 and PVA-15 in visible light transmission.

[0035] Beneficial effects:

[0036] 1. First synthesis Base-naphthalimide-based ultraviolet light absorbing materials have simple synthesis methods and convenient post-processing.

[0037] 2. The product has a wide pH range and can be used in human physiological environments.

[0038] 3. The product exhibits very low dark toxicity and phototoxicity to normal human liver immortalized cells (THLE-2).

[0039] 4. The prepared anti-UV film is a pure organic small molecule film, which can avoid the disadvantages of inorganic materials such as non-renewable, non-modifiable, and non-foldable. Moreover, it is easier to control the designability and adjustability of the molecular structure.

[0040] 5. The prepared anti-UV film has a high UV blocking rate. PVA-11, PVA-12 and PVA-13 (1.0wt%) have blocking rates of 88.55%, 91.01% and 97.64% for 300-400nm UV light, respectively. Compared with the literature value (40wt% carbon dot film has a UV blocking rate of 90%), the content is lower and the blocking rate is higher.

[0041] 6. The obtained UV-resistant film has high visible light transmittance. When the content is 1.0wt%, the transmittance of PVA-11, PVA-12 and PVA-13 in the 500-800nm ​​visible light region reaches 85.95%, 80.64% and 86.14%, respectively.

[0042] 7. Compared with commercially available UV protection films, the prepared UV protection film has a lower cost. Attached Figure Description

[0043] Figure 1 The following are the UV absorption and fluorescence emission spectra of the first derivative 11 in different solvents in the examples: (a) UV absorption and (b) fluorescence emission spectra of the second derivative 12 in different solvents; (c) UV absorption and (d) fluorescence emission spectra of the third derivative 13 in different solvents; (e) UV absorption and (f) fluorescence emission spectra of the fourth derivative 14 in different solvents; (g) UV absorption and (h) fluorescence emission spectra of the fifth derivative 15 in different solvents;

[0044] Figure 2 These are the solid-state fluorescence emission spectra of the first derivative 11, the second derivative 12, the third derivative 13, the fourth derivative 14, and the fifth derivative 15 in the embodiments;

[0045] Figure 3 The fluorescence emission spectra and line graphs (a)-(e) of the first derivative 11, the second derivative 12, the third derivative 13, the fourth derivative 14, and the fifth derivative 15 at different pH values ​​are shown in the examples.

[0046] Figure 4 These are photographs of films (a) PVA-11, (b) PVA-12, (c) PVA-13, (d) PVA-14, and (e) PVA-15 prepared in the examples with different contents (from left to right: 0.0 wt%, 0.1 wt%, 0.5 wt%, and 1.0 wt%).

[0047] Figure 5These are photographs of films prepared in the examples with different contents (from left to right: 0.1wt%, 0.5wt%, 1.0wt%), including (a) PVA-11, (b) PVA-12, (c) PVA-13, (d) PVA-14, and (e) PVA-15, covered with the word "JSNU".

[0048] Figure 6 The transmission spectra of films with different contents (a) PVA-11, (b) PVA-12, (c) PVA-13, (d) PVA-14, and (e) PVA-15 prepared in the examples are shown.

[0049] Figure 7 This is the transmission spectrum of a commercially available anti-UV film;

[0050] Figure 8 The following are the fluorescence emission spectra and line graphs of the films (a) PVA-11, (b) PVA-12, (c) PVA-13, (d) PVA-14, and (e) PVA-15 prepared in the examples with a content of 1.0 wt% at different pH values.

[0051] Figure 9 The fluorescence emission spectra and line graphs of the films (a) PVA-11, (b) PVA-12, (c) PVA-13, (d) PVA-14, and (e) PVA-15 prepared in the examples with a content of 1.0 wt% in different solvents are shown.

[0052] Figure 10 These are fluorescence images of Rhodamine B after the prepared films (a) blank, (b) PVA-11, (c) PVA-12, (d) PVA-13, (e) PVA-14, and (f) PVA-15 (1.0 wt%) were used to block a 310 nm UV lamp in the examples.

[0053] Figure 11 The survival rate of THLE-2 cells after incubation with different concentrations of compounds 11-15 ((a)-(e)) in the examples under dark conditions or light for 48 hours is shown.

[0054] Figure 12 It is the first derivative 11 in the embodiment. 1 H NMR spectrum;

[0055] Figure 13 It is the first derivative 11 in the embodiment. 13 C NMR spectrum;

[0056] Figure 14 This is the HRMS spectrum of the first derivative 11 in the embodiment;

[0057] Figure 15It is the second derivative 12 in the embodiment. 1 H NMR spectrum;

[0058] Figure 16 It is the second derivative 12 in the embodiment. 13 C NMR spectrum;

[0059] Figure 17 This is the HRMS spectrum of the second derivative 12 in the embodiment;

[0060] Figure 18 It is the third derivative 13 in the embodiment. 1 H NMR spectrum;

[0061] Figure 19 It is the third derivative 13 in the embodiment. 13 C NMR spectrum;

[0062] Figure 20 This is the HRMS spectrum of the third derivative 13 in the embodiment;

[0063] Figure 21 It is the fourth derivative 14 in the embodiment. 1 H NMR spectrum;

[0064] Figure 22 It is the fourth derivative 14 in the embodiment. 13 C NMR spectrum;

[0065] Figure 23 This is the HRMS spectrum of the fourth derivative 14 in the examples;

[0066] Figure 24 It is the fifth derivative 15 in the embodiment. 1 H NMR spectrum;

[0067] Figure 25 It is the fifth derivative 15 in the embodiment. 13 C NMR spectrum;

[0068] Figure 26 This is the HRMS spectrum of the fifth derivative 15 in the embodiment. Detailed Implementation

[0069] The embodiments of the present invention are described in detail below. The embodiments described below are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention. Those skilled in the art will understand that various changes and modifications can be made to the present invention without departing from the spirit and scope thereof.

[0070] Example 1: Synthesis of first derivative 11, second derivative 12, third derivative 13, fourth derivative 14, and fifth derivative 15

[0071] This invention provides the above-mentioned novel Methods for preparing base-triphenylamine derivatives include:

[0072] In this embodiment, a class of materials was synthesized through a multi-step reaction process using p-bromoaniline, 4-bromo-3-methoxyaniline, paraformaldehyde, n-butyllithium, 1,8-naphthalimide, n-butylamine, Lawson's reagent, etc. The base-naphthalimide derivatives are the first derivative 11, the second derivative 12, the third derivative 13, the fourth derivative 14, and the fifth derivative 15, as shown in the following steps:

[0073] 1. Synthesis of the first intermediate 3

[0074] Weigh p-bromoaniline (10.32 g, 60 mmol) and paraformaldehyde (4.5 g, 150 mmol) into a 250 mL round-bottom flask, cool to -15 °C, and slowly add 120 mL of trifluoroacetic acid dropwise through a constant-pressure dropping funnel. After the addition is complete, move the reaction system to room temperature and react for seven days. Quench with ice water, adjust the pH to neutral with ammonia, extract with ethyl acetate, extract the organic phase again with saturated brine, dry with anhydrous sodium sulfate, and purify by column chromatography (V... 石油醚 :V 乙酸乙酯 =2:1), and finally recrystallized with acetone, dried, weighed, and collected to obtain the first intermediate 3.

[0075]

[0076] 2. Synthesis of the second intermediate 5

[0077] Weigh 11.16 g (60 mmol) of 4-bromo-3-methoxyaniline and 4.5 g (150 mmol) of paraformaldehyde into a 250 mL round-bottom flask and cool to -15 °C. Slowly add 120 mL of trifluoroacetic acid through a constant-pressure dropping funnel. After the addition is complete, move the reaction system to room temperature and react for seven days. Quench with ice water and adjust the pH to neutral with ammonia. A large amount of precipitate is produced. Filter, dry, weigh, and collect to obtain the second intermediate 5.

[0078]

[0079] 3. Synthesis of the third intermediate 6

[0080] Weigh 1 mmol of the first intermediate 3 into a 100 mL round-bottom flask, use 50 mL of anhydrous tetrahydrofuran as solvent, place the flask in a -78 °C cryogenic bath under anhydrous and oxygen-free conditions, slowly add 9.6 mL of n-butyllithium, and after 2 h, quickly add 6.6 mL of trimethyl borate. After 1 h, quench with 100 mL of ice water, extract with DCM, acidify the aqueous layer with HCl, filter, and obtain the third intermediate 6.

[0081]

[0082] 4. Synthesis of the fourth intermediate 7

[0083] Weigh 1 mmol of the second intermediate 5 into a 100 mL round-bottom flask, use 50 mL of anhydrous tetrahydrofuran as solvent, place it in a -78 °C cryogenic bath under anhydrous and oxygen-free conditions, slowly add 5 mL of n-butyllithium, after 2 h, quickly add 5 mL of trimethyl borate, after 1 h, quench with 100 mL of ice water, extract with DCM, acidify the aqueous layer with HCl, filter, and obtain the fourth intermediate 7.

[0084]

[0085] 5. Synthesis of the fifth intermediate 10

[0086] Weigh out n-butylamine (1 mmol) and 4-bromo-1,8-naphthalenedicarboxylic anhydride (1 mmol) and place them in a 50 mL round-bottom flask. Use water as solvent and reflux in an oil bath at 60 °C for 12 h. After the reaction is complete (monitored by TLC), cool to room temperature. A large amount of precipitate will precipitate. Filter and dry to obtain powdered solid fifth intermediate 10.

[0087]

[0088] 6. Synthesis of Derivative 11 and Derivative 12

[0089] Weigh 6 (3 mmol), 10 (8 mmol), tetra(triphenylphosphine)palladium (0.3 mmol), and potassium carbonate (1.38 g) into a 100 mL round-bottom flask. Using toluene (15 mL) as solvent, reflux at 90 °C in an oil bath for 24 h. After the reaction is complete (monitored by TLC), extract with ethyl acetate, remove the solvent under vacuum, and purify by column chromatography (V). 石油醚 :V 乙酸乙酯 =3:1), yielding first derivative 11 (yield 43%) and second derivative 12 (yield 54%):

[0090]

[0091] The molecular formula of the first derivative 11 is: C 31 H 28BN3O4

[0092] The Chinese name is:

[0093] (8-(2-Butyl-1,3-dioxo-2,3-dihydro-1H-benzo[de]isoquinoline-6-yl)-6H,12H-5,11-methyldibenzo[b,f][1,5]diazin-2-yl)boronic acid

[0094] The English name is:

[0095] (8-(2-butyl-1,3-dioxo-2,3-dihydro-1H-benzo[de]isoquinolin-6-yl)-6H,12H-5,11-methanodibenzo[b,f][1,5]diazocin-2-yl)boronic acid

[0096] Appearance: Yellow solid

[0097] Melting point: 115.1-115.7℃

[0098] 1H NMR spectrum: 1 H NMR (400MHz, CDCl3) δ8.65 (d, J = 8.3Hz, 1H), 8.27 (s, 1H), 7.73-7.64 (m, 1H), 7.58 (s ,1H),7.37(dd,J=30.1,7.0Hz,3H),7.13(dd,J=29.5,7.4Hz,2H),7.05(s,1H),4.93 (d,J=15.8Hz,1H),4.58(s,1H),4.39-4.25(m,2H),4.21(d,J=22.6Hz,1H),1.80-1. 63(m,2H),1.46(dd,J=26.2,19.3Hz,2H),1.32(d,J=12.0Hz,4H),1.05-0.91(m,2H).

[0099] Carbon NMR spectrum: 13 C NMR (100MHz, CDCl3): δ164.38,164.18,132.69,131.17,130.81,129.98,129.10,128.72,128.45,127.77,127.62,12 7.10,126.78,125.28,123.01,121.74,66.82,58.74,58.65,40.30,31.48,30.26,29.70,24.81,22.74,20.44,13.91.

[0100] Mass spectrometry: HRMS(ESI) m / z calcd for C 31 H 28 BN3O4[M+H] + :517.2179; found,517.2008.

[0101] The molecular formula of the second derivative 12 is: C 47 H 40 N4O4

[0102] The Chinese name is:

[0103] 6,6'-(6H,12H-5,11-methyldibenzo[b,f][1,5]diazoazine-2,8-diyl)bis(2-butyl-1H-benzo[de]isoquinoline-1,3(2H)-dione)

[0104] The English name is:

[0105] 6,6'-(6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine-2,8-diyl)bis(2-butyl-1H-benzo[de]isoquinoline-1,3(2H)-dione)

[0106] Appearance: Yellow solid

[0107] Melting point: 105.6-106.2℃

[0108] 1H NMR spectrum: 1 H NMR (400MHz, CDCl3) δ8.66 (q, J=7.4Hz, 4H), 8.31 (dd, J=27.8, 8.5Hz, 2H), 7.75 (t,J=8.0Hz,2H),7.69(d,J=7.5Hz,2H),7.47-7.34(m,4H),7.18(d,J=27.2Hz,2 H),4.96(d,J=16.8Hz,2H),4.62-4.37(m,4H),4.27(dd,J=16.5,9.0Hz,4H),1. 78(dd,J=14.9,7.7Hz,4H), 1.51(dd,J=15.1,7.6Hz,4H), 1.04(t,J=7.3Hz,6H).

[0109] Carbon NMR spectrum: 13C NMR (100MHz, CDCl3) δ164.28,164.08,148.54,146.20,134.66,132.49,131.16,130.76,129.91,129.22,12 8.72,128.50,128.28,127.76,126.80,125.42,122.98,121.67,66.89,58.73,40.28,30.23,20.41,13.88.

[0110] Mass spectrometry: HRMS(ESI) m / z calcd for C 47 H 40 N4O4[M+H] + :725.3122; found,725.3127.

[0111] 7. Synthesis of the third derivative 13

[0112] Weigh 7 (3 mmol), 10 (8 mmol), tetra(triphenylphosphine)palladium (0.3 mmol), and potassium carbonate (1.38 g) into a 100 mL round-bottom flask. Using toluene (15 mL) as solvent, reflux in an oil bath at 110 °C for 24 h. After the reaction is complete (monitored by TLC), extract with ethyl acetate, remove the solvent under vacuum, and purify by column chromatography (V). 石油醚 :V 乙酸乙酯 =2:1), yielding the third derivative 13 (yield 64%):

[0113]

[0114] The molecular formula of the third derivative 13 is: C 33 H 32 BN3O6

[0115] The Chinese name is:

[0116] (8-(2-Butyl-1,3-dioxo-2,3-dihydro-1H-benzo[de]isoquinoline-6-yl)-3,9-dimethoxy-6H,12H-5,11-ethylenedibenzo[b,f][1,5]diazozinin-2-yl)boronic acid

[0117] The English name is:

[0118] (8-(2-butyl-1,3-dioxo-2,3-dihydro-1H-benzo[de]isoquinolin-6-yl)-3,9-dimethoxy-6H,12H-5,11-methanodibenzo[b,f][1,5]diazocin-2-yl)boronic acid

[0119] Appearance: Yellow solid

[0120] Melting point: 101.7-103.4℃

[0121] 1H NMR spectrum: 1 H NMR(400MHz, CDCl3)δ8.68-8.60(m,2H),7.97(dd,J=32.3,8.4Hz,1H),7.75-7.70(m,2H) ,7.63-7.58(m,2H),7.52(t,J=6.3Hz,2H),6.90(s,1H),6.75(d,J=7.9Hz,1H),4.83(t,J =15.5Hz,2H),4.48(d,J=10.6Hz,2H),4.25(t,J=7.4Hz,2H),3.85(s,3H),3.73(s,3H),1 .79-1.74(m,2H),1.51(dd,J=15.0,7.4Hz,2H),1.39-1.30(m,2H),1.03(t,J=7.3Hz,3H).

[0122] Carbon NMR spectrum: 13 C NMR (100MHz, CDCl3) δ164.51,164.31,159.18,159.14,156.26,156.16,133.15,132.23,132.13,132.03,132.00,131.07,130.84,130.5 7,129.77,129.63,128.64,128.52,127.82,126.50,126.37,122.86,122.82,121.91,121.85,66.88,66.79,55.66,55.37,40.25,30.31.

[0123] Mass spectrometry: HRMS(ESI) m / z calcd for C 33 H 32 BN3O6[M+H] + :578.2462; found,579.1557.

[0124] 8. Synthesis of the fourth derivative 14

[0125] Weigh 2 mmol of the first derivative 11 and 5 mmol of Lawesson's reagent into a 10 mL Schlenk tube. Using toluene (5 mL) as solvent, heat the mixture in an oil bath at 130 °C for 12 h. Cool to room temperature, remove the solvent under reduced pressure, and purify the residue by column chromatography (V). 石油醚 :V 乙酸乙酯 =1:1), respectively yielding the fourth derivative 14 (46%):

[0126]

[0127] The molecular formula of the fourth derivative 14 is: C 31 H 28 BN3O2S2

[0128] The Chinese name is:

[0129] (8-(2-Butyl-1,3-dithiooxy-2,3-dihydro-1H-benzo[de]isoquinoline-6-yl)-6H,12H-5,11-methylethylenedibenzo[b,f][1,5]diazin-2-yl)boronic acid

[0130] The English name is:

[0131] (8-(2-butyl-1,3-dithioxo-2,3-dihydro-1H-benzo[de]isoquinolin-6-yl)-6H,12H-5,11-methanodibenzo[b,f][1,5]diazocin-2-yl)boronic acid

[0132] Appearance: Red solid

[0133] Melting point: >300℃

[0134] 1H NMR spectrum: 1HNMR(400MHz,DMSO-d6)δ8.75(dd,J=7.5,1.2Hz,1H),8.57(d,J=7.4Hz,1H),8.37(dd,J=7 .5,1.3Hz,1H),7.82-7.73(m,2H),7.61-7.52(m,2H),7.46(dd,J=7.5,1.9Hz,1H),7.16-7 .07(m,2H),6.79(d,J=7.5Hz,1H),5.41(s,2H),4.65(d,J=3.3Hz,2H),4.64(d,J=0.6Hz,4 H), 3.13 (t, J = 5.1Hz, 2H), 1.54 (p, J = 5.2Hz, 2H), 1.35-1.25 (m, 2H), 0.90 (t, J = 7.9Hz, 3H).

[0135] Carbon NMR spectrum: 13 C NMR (100MHz, CDCl3): δ191.18,190.81,138.14,137.65,132.24,129.81,128.69,128.52,12 8.38,127.84,125.34,127.21,125.38,125.31,124.11,66.89,58.68,58.59,55.00,53.52.

[0136] Mass spectrometry: HRMS(ESI) m / z calcd for C 31 H 28 BN3O2S2[M+H] + :550.1794found,550.1786.

[0137] 9. Synthesis of Derivative 15 (Fifth Derivative)

[0138] Weigh 2 mmol of the third derivative 13 and 5 mmol of Lawesson's reagent into a 10 mL Schlenk tube. Using toluene (5 mL) as solvent, heat the mixture in an oil bath at 130 °C for 12 h. Cool to room temperature, remove the solvent under reduced pressure, and purify the residue by column chromatography (V). 石油醚 :V 乙酸乙酯 =1:1), yielding the fifth derivative 15 (53%):

[0139]

[0140] The molecular formula of the fifth derivative 15 is: C 33 H 32 BN3O4S2

[0141] The Chinese name is:

[0142] (8-(2-Butyl-1,3-dithiooxy-2,3-dihydro-1H-benzo[de]isoquinoline-6-yl)-3,9-dimethoxy-6H,12H-5,11-methyldibenzo[b,f][1,5]diazoazine-2-yl)boronic acid

[0143] The English name is:

[0144] (8-(2-butyl-1,3-dithioxo-2,3-dihydro-1H-benzo[de]isoquinolin-6-yl)-3,9-dimetho xy-6H,12H-5,11-methanodibenzo[b,f][1,5]diazocin-2-yl)boronic acid

[0145] Appearance: Red solid

[0146] Melting point: >300℃

[0147] 1H NMR spectrum: 1 H NMR (400MHz, CDCl3) δ8.64(ddd,J=11.2,7.2,4.1Hz,2H),7.97(dd,J=33.0,8.4Hz,1H),7.73( s,2H),7.60(s,2H),7.52(s,2H),6.89(s,1H),6.81(s,1H),4.80(dd,J=28.8,13.2Hz,2H),4.4 8(d,J=10.4Hz,2H),4.25(t,J=7.5Hz,2H),3.93-3.84(dd,J=32.6,4.8Hz,3H),3.73(s,3H),1 .80-1.73(m,2H),1.50(dd,J=15.0,7.5Hz,2H),1.32(d,J=11.9Hz,2H),1.03(t,J=7.3Hz,3H).

[0148] Carbon NMR spectrum: 13C NMR (100MHz, CDCl3): δ164.51,164.31,159.18,156.26,143.69,143.66,133.15,132.24,132.23,132.13,132.03,132.00,131.07,130. 84,129.77,129.63,128.64,128.52,127.82,111.59,109.59,109.53,107.60,107.38,55.66,55.41,40.25,30.31,20.48,14.28,13.94.

[0149] Mass spectrometry: HRMS(ESI) m / z calcd for C 33 H 32 BN3O4S2[M+Na] + :632.1826found,632.1889.

[0150] The physical properties (yield, melting point) of each compound are shown in Table 1 below:

[0151] Table 1. Yield and melting point of the product

[0152]

[0153] Example 2: Solvation effect of first derivative 11, second derivative 12, third derivative 13, fourth derivative 14, and fifth derivative 15

[0154] Derivative 11, derivative 12, derivative 13, derivative 14, and derivative 15 were respectively prepared into a concentration of 1×10⁻⁶ using 100 mL of N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), n-hexane, dichloromethane (CH₂Cl₂), toluene, tetrahydrofuran (THF), methanol, acetonitrile, and distilled water. -5 mol·L -1 The solution was analyzed, and its ultraviolet absorption and fluorescence emission spectra were measured. The optimal test solvent for subsequent experiments was selected by comprehensively considering factors such as solubility, absorbance, absorption wavelength, and luminescence properties. Figure 1 ).

[0155] The optical properties of the first derivative 11, the second derivative 12, the third derivative 13, the fourth derivative 14, and the fifth derivative 15 were tested using DMSO, which has high absorbance in the ultraviolet region and stable solution properties.

[0156] Example 3: Solid-state fluorescence spectra of first derivative 11, second derivative 12, third derivative 13, fourth derivative 14, and fifth derivative 15

[0157] Derivative 11, derivative 12, derivative 13, derivative 14, and derivative 15 were laid flat and pressed into tablets, and their solid-state fluorescence emission spectra were measured. Figure 2 ).Depend on Figure 2 It can be seen that the first derivative 11, the second derivative 12, the third derivative 13, the fourth derivative 14, and the fifth derivative 15 all have stable solid-state fluorescence emission, indicating that they can be doped into PVA films to determine their luminescence properties.

[0158] The spectral data of the products are shown in Table 2:

[0159] Table 2 Spectral data of the products

[0160]

[0161] a) Ultraviolet absorption wavelength in the solution; b) Molar extinction coefficient ε = A / bC, unit: L·mol⁻¹ -1 ·cm -1 c. Fluorescence emission wavelength in solution; d. Stokes shift in solution; e. Relative fluorescence quantum yield (reference: quinine sulfate); f. Fluorescence intensity FB = ε*Φ, unit: L·mol⁻¹ -1 ·cm -1 g is the solid-state excitation wavelength; h is the solid-state fluorescence emission wavelength; i is the solid-state Stokes shift; j is the lipid-water partition coefficient (ChemBioDraw Ultra simulation).

[0162] Depend on Figure 2 It can be seen that, similar to the fluorescence emission, the solid-state λ of derivatives 14 and 15... em Compared to derivative 11, derivative 13 shows a significant red shift. The solid-state fluorescence intensity of derivatives 11 and 13 is greater than that of derivatives 14 and 15. Figure 2 It can be seen that the first derivative 11, the second derivative 12, the third derivative 13, the fourth derivative 14, and the fifth derivative 15 all have stable solid-state fluorescence emission, indicating that they can be doped into PVA films to determine their luminescence properties.

[0163] Table 2 shows that derivatives 11, 12, and 13 emit strong fluorescence, while derivatives 14 and 15 exhibit significantly reduced relative fluorescence intensity. This is because fluorescence emission and intersystem crossing (ISC) are in competition; the introduction of sulfur atoms promotes ISC from the singlet excited state to the triplet excited state, thus greatly reducing the probability of fluorescence emission from the products. The λ values ​​of derivatives 11, 12, 13, and 14 are also shown. abs It is located in the ultraviolet region (373-385nm).

[0164] Example 4: pH range of first derivative 11, second derivative 12, third derivative 13, fourth derivative 14, and fifth derivative 15

[0165] pH range is one of the key factors for the successful application of a compound in biological systems, so we explored the pH range of products 11-15.

[0166] Using DMSO as a solvent, the first derivative 11, the second derivative 12, the third derivative 13, the fourth derivative 14, and the fifth derivative 15 were prepared to a concentration of 1×10⁻⁶. -4 mol·L -1 For each working solution, measure 1.0 mL of the working solution into a 10 mL volumetric flask, then add 1.0 mL of buffer solution with a pH value of 2.2-10 (citric acid / disodium hydrogen phosphate system for pH 2.2-8, and sodium bicarbonate / sodium carbonate system for pH 9-10), and dilute to volume with DMSO to a concentration of 1×10⁻⁶. -5 mol·L -1 Measure its fluorescence emission spectrum ( Figure 3 ).

[0167] Depend on Figure 3 It can be seen that when the solution pH is 7-10, the fluorescence emission spectra of the first derivative 11, the second derivative 12, the third derivative 13, the fourth derivative 14, and the fifth derivative 15 do not change significantly, indicating that the first derivative 11, the second derivative 12, the third derivative 13, the fourth derivative 14, and the fifth derivative 15 have a wide pH range and can be used in human physiological environments.

[0168] Example 5: Properties of the PVA films of the present invention

[0169] 1.0 g of polyvinyl alcohol (PVA, MW = 3000 g / mol) powder was dissolved in 20 mL of deionized water and stirred vigorously at 90 °C until the solution became clear. The solution was then cooled to room temperature. Derivatives 11, 12, 13, 14, and 15 (0.1, 0.5, and 1.0 wt%) were added to the PVA solution, and the mixtures were stirred for 1 hour to obtain homogeneous solutions. The solutions were then transferred to petri dishes using pipettes and dried at 90 °C for 1 day. Different concentrations of PVA-11, PVA-12, PVA-13, PVA-14, and PVA-15 (0.1, 0.5, and 1.0 wt%) were obtained. Figure 4 ).

[0170] PVA-11, PVA-12, PVA-13, PVA-14, and PVA-15 are colorless under natural light. As the content of the first derivative 11, second derivative 12, third derivative 13, fourth derivative 14, and fifth derivative 15 increases, the color of the corresponding film deepens, while still maintaining high transparency. When observing the letters "JSNU" through PVA-11, PVA-12, PVA-13, PVA-14, and PVA-15, the color is not affected by the compounds themselves. Figure 5 ).

[0171] PVA films with different loadings all exhibit high transparency comparable to pure PVA films and can be used in subsequent experiments.

[0172] Example 6: Selection of PVA film loading in this invention

[0173] The transmittance of PVA-11, PVA-12, PVA-13, PVA-14, and PVA-15 was measured using a UV-Vis spectrophotometer. Figure 6 ).

[0174] Depend on Figure 6 It can be seen that PVA-11, PVA-12, and PVA-13 (0.1wt%, 0.5wt%, and 1.0wt%) exhibit reduced UV transmittance in the 300-400nm range, indicating their UV blocking capability. Furthermore, the UV transmittance decreases sharply with increasing content of the first derivative 11, the second derivative 12, and the third derivative 13. Calculations show that at a content of 1.0wt%, the UV blocking rates of the first derivative 11, the second derivative 12, and the third derivative 13 reach 88.55%, 91.01%, and 97.64%, respectively. Compared to literature values ​​(90% UV blocking rate for a 40wt% carbon dot film), PVA-11, PVA-12, and PVA-13 have lower contents but comparable or higher blocking rates.

[0175] The transmittance of PVA-11, PVA-12, and PVA-13 (0.1wt%, 0.5wt%, and 1.0wt%) in the visible light region of 500-800nm ​​decreases slightly with increasing content of the first derivative 11, the second derivative 12, and the third derivative 13. When the content of the first derivative 11, the second derivative 12, and the third derivative 13 is 1.0wt%, their transmittance to visible light is 85.95%, 80.64%, and 86.14%, respectively.

[0176] Therefore, taking into account both the blocking rate of ultraviolet light and the transmittance of visible light, 1.0 wt% was selected as the optimal loading of PVA-11, PVA-12, and PVA-13 films.

[0177] Depend on Figure 7 It can be seen that, compared with commercially available UV-resistant films, the UV-resistant film synthesized in this paper has a similar UV blocking rate. However, the film prepared in this paper is cheaper, and the light-absorbing compounds are all pure organic small molecules, which has many advantages and great development prospects.

[0178] Example 7: Stability of various PVA films of the present invention

[0179] PVA-11, PVA-12, and PVA-13 were soaked for 12 hours at pH values ​​ranging from 2.2 to 14.0, then air-dried. Acid and alkali resistance tests were then conducted, and their fluorescence emission spectra were measured. Figure 8 It can be seen that PVA-11, PVA-12, and PVA-13 can maintain their fluorescence intensity after being soaked for 12 hours under conditions of pH 2.2-14.0, indicating that PVA-11, PVA-12, and PVA-13 have high stability under both acidic and alkaline conditions.

[0180] PVA-11, PVA-12, and PVA-13 were immersed in different solvents for 24 hours, then dried, and solvent resistance tests were conducted to measure their fluorescence emission spectra. Figure 9 As shown, PVA-11, PVA-12, and PVA-13 can still maintain their fluorescence intensity after being immersed in different solvents for 24 hours, indicating that PVA-11, PVA-12, and PVA-13 have good solvent resistance.

[0181] Example 8: Ultraviolet shielding capability of various PVA films produced according to the present invention

[0182] Rhodamine B emits bright orange fluorescence under ultraviolet light. PVA-11, PVA-12, and PVA-13 were placed between Rhodamine B molecules, and their fluorescence was compared with that of the unshielded molecules to test the UV shielding capabilities of PVA-11, PVA-12, and PVA-13. Figure 10When the light source was blocked by PVA-11, PVA-12, and PVA-13, the bright orange fluorescence of Rhodamine B disappeared significantly, proving that PVA-11, PVA-12, and PVA-13 have obvious ultraviolet shielding capabilities.

[0183] The anti-counterfeiting codes on banknotes fluoresce under ultraviolet light. To visually demonstrate the UV protection capabilities of PVA-11, PVA-12, and PVA-13, PVA film was placed between the banknote and the light source. The fluorescence brightness was compared with that of pure PVA film when it was blocked. Pictures were taken to test the UV shielding capabilities of PVA-11, PVA-12, and PVA-13.

[0184] Example 9: Dark toxicity and phototoxicity of first derivative 11, second derivative 12, third derivative 13, fourth derivative 14, and fifth derivative 15

[0185] Table 3 shows the half-maximal inhibitory rate (IC5) of derivatives 11, 12, 13, 14, and 15 on THLE-2 cells. 50 )

[0186]

[0187] The dark toxicity and phototoxicity of the compound on human liver immortalized cells (THLE-2) were detected by the MTT assay. After the test samples were prepared, THLE-2 cells were seeded into 96-well plates, and different concentrations of the compound were added. After incubation for 48 hours, the cells were irradiated with a photodynamic therapy device with a light source of 452 nm. The control group was not irradiated. Figure 11 As shown in Table 3, THLE-2 cells treated with the first derivative 11, the second derivative 12, the third derivative 13, the fourth derivative 14, and the fifth derivative 15 under both dark and light conditions exhibited high survival rates, indicating that the first derivative 11, the second derivative 12, the third derivative 13, the fourth derivative 14, and the fifth derivative 15 have negligible phototoxicity and dark toxicity, suggesting that they can be used as sunscreens in subsequent mouse experiments.

Claims

1. A class of derivatives based on TB-naphthalimide, characterized in that, The structures of the derivatives are shown in the following formulas: first derivative (11), second derivative (12), third derivative (13), fourth derivative (14), and fifth derivative (15).

2. A method for preparing a type of TB-naphthalimide derivative as described in claim 1, characterized in that... The preparation method of the TB-naphthalimide derivative includes the following steps: Step 1: 4-Bromoaniline (1) and 2-methoxy-4-bromoaniline (4) react with paraformaldehyde (2) to obtain the first intermediate (3) and the second intermediate (5), respectively, as shown in the following reaction formula: Step 2: The first intermediate (3) and the second intermediate (5) react with n-butyllithium-boronate trimethyl ester to obtain the third intermediate (6) and the fourth intermediate (7), respectively, as shown in the following reaction formula: Step 3: n-Butylamine (8) reacts with 4-bromo-1,8-naphthalenedicarboxylic anhydride (9) to give the fifth intermediate (10), as shown in the following reaction formula: Step 4: The third intermediate (6) reacts with the fifth intermediate (10) in a one-step reaction, yielding two products: a first derivative (11) with unilateral substitution and a second derivative (12) with bilateral substitution. The fourth intermediate (7) reacts with the fifth intermediate (10) to give the third derivative (13); The reaction formula is as follows: Step 5: The first derivative (11) and the third derivative (13) react with Lawson's reagent to obtain the fourth derivative (14) and the fifth derivative (15), respectively, as shown in the following reaction formulas: 。 3. A method for preparing an organic ultraviolet light absorbing material based on a TB-naphthalimide derivative as described in claim 1, characterized in that, The first derivative (11), the second derivative (12), the third derivative (13), the fourth derivative (14), and the fifth derivative (15) were respectively doped into polyvinyl alcohol (PVA) to prepare corresponding PVA films PVA-11, PVA-12, PVA-13, PVA-14, and PVA-15.

4. The method for preparing an organic ultraviolet light absorbing material based on a TB-naphthalimide derivative according to claim 3, characterized in that, The PVA films are described as follows: PVA-11 consists of three types of films with masses of 0.1 wt%, 0.5 wt%, and 1.0 wt% in the PVA film composition; PVA-12 consists of three types of films with masses of 0.1 wt%, 0.5 wt%, and 1.0 wt% in the PVA film composition; PVA-13 consists of three types of films with masses of 0.1 wt%, 0.5 wt%, and 1.0 wt% in the PVA film composition; PVA-14 consists of three types of films with masses of 0.1 wt%, 0.5 wt%, and 1.0 wt% in the PVA film composition; and PVA-15 consists of three types of films with masses of 0.1 wt%, 0.5 wt%, and 1.0 wt% in the PVA film composition.

5. The method for preparing an organic ultraviolet light absorbing material based on a TB-naphthalimide derivative according to claim 3, characterized in that, The polyvinyl alcohol (PVA) has a relative molecular mass MW = 3000 g / mol.

6. An application of an organic ultraviolet light absorbing material based on TB-naphthalimide derivatives obtained by the preparation method as described in claim 3, characterized in that, The PVA films PVA-11, PVA-12, PVA-13, PVA-14 and PVA-15 are used for shielding ultraviolet light.

7. An application of an organic ultraviolet light absorbing material based on TB-naphthalimide derivatives obtained by the preparation method as described in claim 3, characterized in that, The application of the PVA films PVA-11, PVA-12, PVA-13, PVA-14 and PVA-15 in blocking Rhodamine B fluorescence.

8. An application of an organic ultraviolet light absorbing material based on TB-naphthalimide derivatives obtained by the preparation method as described in claim 3, characterized in that, Applications of the PVA films PVA-11, PVA-12, PVA-13, PVA-14 and PVA-15 in terms of visible light transmission.

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