A compound, ultraviolet absorber and composition comprising the same, and use

Abstract

The present application relates to the technical field of ultraviolet absorption, in particular to a kind of compound, the ultraviolet absorber and composition comprising it and purposes.The present application provides a kind of compound of formula (I), has strong absorption effect to the ultraviolet in 260nm-380nm interval, absorption range covers UVA wave band and UVB wave band;And in UVB wave band absorption intensity is higher than UV-P, has better anti-ultraviolet performance than UV-P, can be applied more widely.The present application further provides an ultraviolet absorber comprising the compound of formula (I), composition and purposes thereof.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ultraviolet absorption, in particular to a compound, an ultraviolet absorber and a composition comprising the same and use. BACKGROUND

[0002] Ultraviolet light (also known as ultraviolet rays) is an electromagnetic wave with a wavelength of 0.1 μm-0.4 μm, accounting for 7% of the total solar radiation energy. The energy of ultraviolet light can break the chemical bonds of most materials, causing material failure, degradation or deterioration. Ultraviolet absorber is a kind of light stabilizer, which has strong absorption in the ultraviolet region and no obvious absorption in the visible light region, and can release the absorbed ultraviolet light in the form of other lower energy, such as longer wavelength light or heat, thereby protecting materials or dyes, etc. The ultraviolet absorber itself is not destroyed by ultraviolet light.

[0003] The ultraviolet absorber includes benzotriazole, benzophenone, triazine, etc. The benzotriazole ultraviolet absorber UV-P with good anti-ultraviolet effect is one of the best ultraviolet absorption products in BASF products, which shows high light stability under exposure. Its absorption range mainly concentrates in the interval of 260 nm-380 nm, which can absorb the interval of 260 nm-320 nm in the outdoor ultraviolet (UVB) band and the interval of 320 nm-380 nm in the long-wave black spot effect ultraviolet (UVA) band. However, the ultraviolet absorption intensity and anti-ultraviolet performance still need to be improved, and therefore, it is urgent to develop an ultraviolet absorber with better performance. SUMMARY

[0004] The purpose of the present application is to provide a compound to achieve strong absorption effect on ultraviolet light in the range of 260 nm-380 nm and improve the anti-ultraviolet performance.

[0005] The present application provides a compound in the first aspect, which has the structural formula shown in formula (I):

[0006]

[0007] (I)

[0008] wherein,

[0009] R is selected from hydrogen, hydroxyl, C1-C 12 alkyl, C1-C 12 alkoxy, amino;

[0010] R' is selected from hydrogen, C1-C8 alkyl, C1-C4 alkoxy, C2-C 10 alkenyl.

[0011] Further, R is selected from the following groups:

[0012] .

[0013] Further, R' is selected from the group consisting of:

[0014] .

[0015] Further, the compound is selected from the group consisting of compounds shown in B001-B048:

[0016]

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023] .

[0024] The second aspect of the present application provides an ultraviolet absorber comprising at least one of the compounds according to the first aspect of the present application.

[0025] The third aspect of the present application provides a composition comprising a component A and a component B, wherein the mass ratio of the component A to the component B is 100: (0.01-15).

[0026] The component A is an organic substance sensitive to light damage, oxygen damage and / or heat damage.

[0027] The component B is at least one of the compounds according to the first aspect of the present application or the ultraviolet absorber according to the second aspect of the present application.

[0028] Further, the component A comprises at least one of a thermoplastic polymer, a coating binder or a photosensitive material.

[0029] Further, the thermoplastic polymer is selected from at least one of polyethylene, polypropylene, polyvinyl chloride, vinyl chloride and vinyl acetate copolymer, polystyrene, styrene and acrylonitrile copolymer, polyamide, polyethylene terephthalate, the coating adhesive is selected from at least one of polyurethane, polyacrylate, natural rubber, silicone rubber, vinyl acetate, polyvinylidene chloride or polyvinyl alcohol, and the photosensitive material is selected from at least one of color-blind sheet, orthochromatic sheet, panchromatic sheet, infrared sheet or color sheet.

[0030] The fourth aspect of the present application provides a use of the compound provided by the first aspect of the present application or the ultraviolet absorber provided by the second aspect of the present application or the composition provided by the third aspect of the present application for preventing photodamage, oxygen damage and / or thermal damage in organic matter.

[0031] The compound provided by the present application has strong absorption effect on ultraviolet rays in the range of 260nm-380nm, the absorption range covers the range of 320nm-380nm in the UVA band and the range of 260nm-320nm in the UVB band, and the absorption intensity in the range of 260nm-320nm is higher than that of UV-P, the anti-ultraviolet performance is better than that of UV-P, and the application field is wider. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 The ultraviolet-visible absorption spectrum diagram of the compound B040 corresponding to Example 3 and the comparative example UV-P is shown;

[0033] Figure 2 The standard curve diagram showing the relationship between the absorbance and the mass concentration of methyl orange is shown;

[0034] Figure 3 The mass concentration diagram of methyl orange corresponding to different time points in different reactors is shown. DETAILED DESCRIPTION

[0035] The following describes the embodiments of the present application by specific examples, and those skilled in the art can easily understand other advantages and effects of the present application from the content disclosed in the description. Although the description of the present application will be introduced in combination with the preferred embodiments, this does not mean that the features of the present application are limited to the embodiments. On the contrary, the purpose of introducing the application in combination with the embodiments is to cover other options or modifications that can be extended based on the claims of the present application. In order to provide a deep understanding of the present application, many specific details will be included in the following description. The present application can also be implemented without using these details. In addition, in order to avoid confusion or obscure the focus of the present application, some specific details will be omitted in the description. It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other without conflict.

[0036] The first aspect of the present application provides a compound having a structural formula shown in formula (I):

[0037]

[0038] (I)

[0039] wherein,

[0040] R is selected from hydrogen, hydroxyl, C1-C 12 alkyl, C1-C 12 alkoxy, amino;

[0041] R' is selected from hydrogen, C1-C8 alkyl, C1-C4 alkoxy, C2-C 10 alkenyl.

[0042] Optionally, R is selected from the following groups:

[0043] .

[0044] Optionally, R' is selected from the following groups:

[0045] .

[0046] The compound can be selected from the compounds shown in B001-B048, and the specific chemical structural formula of the compounds shown in B001-B048 is shown in the foregoing.

[0047] The compound of formula (I) provided by the present application has strong absorption effect on ultraviolet rays in the range of 260nm-380nm, the absorption range covers the range of 320nm-380nm in the UVA band and the range of 260nm-320nm in the UVB band; and the absorption intensity in the range of 260nm-320nm is higher than that of UV-P, has better anti-ultraviolet performance than UV-P, and can be applied in a wider field.

[0048] The second aspect of the present application provides an ultraviolet absorber comprising at least one of the compounds provided in the first aspect of the present application. The ultraviolet absorber provided in the present application can comprise other substances capable of absorbing ultraviolet rays and / or additives. The additives can be selected from at least one of an antioxidant, a metal deactivator, and a phosphite. The antioxidant can be selected from at least one of 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methoxyphenol, and N-isopropyl-N'-phenyl-p-phenylenediamine. The metal deactivator can be selected from at least one of N,N'-diphenylformamide and 3-salicylamin-1,2,4-triazole. The phosphite can be selected from at least one of triphenyl phosphite and tris(2,4-di-tert-butylphenyl) phosphite. The other substances capable of absorbing ultraviolet rays can be selected from at least one of a benzotriazole ultraviolet absorber, a benzophenone ultraviolet absorber, and a triazine ultraviolet absorber.

[0049] The present application does not limit the specific kind and amount of the other substances capable of absorbing ultraviolet rays and / or additives to be added, as long as the object of the present application can be achieved.

[0050] The third aspect of the present application provides a composition comprising Component A and Component B. Component A is an organic substance sensitive to light damage, oxygen damage, and / or heat damage. Component B is at least one of the compound provided in the first aspect of the present application or the ultraviolet absorber provided in the second aspect of the present application. The mass ratio of Component A to Component B is 100: (0.01-15).

[0051] The method for preparing the composition of the present application is not particularly limited, and any method known in the art can be used, for example, the components A and B can be directly mixed in a proportion to be uniform. The compound of formula (I) or the ultraviolet absorber provided in the present application is added to an organic substance sensitive to light damage, oxygen damage, and / or heat damage. The compound of formula (I) or the ultraviolet absorber can absorb ultraviolet rays in the range of 280 nm-380 nm, thereby avoiding the damage of the ultraviolet rays in the above range to the organic substance sensitive to light, oxygen, and / or heat, and achieving the effect of protecting the organic substance sensitive to light, oxygen, and / or heat.

[0052] In some embodiments of the present application, at least one of a thermoplastic polymer, a coating binder, or a photosensitive material is included as Component A.

[0053] In some embodiments of the present application, the thermoplastic polymer is selected from at least one of polyethylene, polypropylene, polyvinyl chloride, vinyl chloride and vinyl acetate copolymer, polystyrene, styrene and acrylonitrile copolymer, polyamide, polyethylene terephthalate, the coating adhesive is selected from at least one of polyurethane, polyacrylate, natural rubber, silicone rubber, vinyl acetate, polyvinylidene chloride or polyvinyl alcohol, and the photosensitive material is selected from at least one of color-blind sheet, orthochromatic sheet, panchromatic sheet, infrared sheet or color sheet.

[0054] The fourth aspect of the present application provides a use of the compound provided in the first aspect of the present application or the ultraviolet absorber provided in the second aspect of the present application or the composition provided in the third aspect of the present application for preventing photodamage, oxygen damage and / or thermal damage in organic matter.

[0055] The method for synthesizing the compound of the present application is not particularly limited, and any method known to those skilled in the art can be used for synthesis. The following illustrates the synthesis process of the compound of the present application.

[0056] The silica gel chromatographic column used in the following examples is a silica gel chromatographic column with coarse pores (zcx-Ⅱ) purchased from Qingdao Suike Separation Material Co., Ltd.; the yield in the following examples = actual synthesis product mass / theoretical synthesis product mass x 100%.

[0057] Example 1: Synthesis of compound B048

[0058]

[0059] Step A:

[0060]

[0061] Specific steps: in a 250 mL eggplant flask with a magnet, compound 1a (2.48 g, 18 mmol), 2a (4.27 g, 15 mmol), potassium carbonate (3.10 g, 22.5 mmol), deoxygenated toluene (105 mL), ethanol (63 mL), water (21 mL), Pd(PPh3)4(521.2 mg, 0.71 mmol) were sequentially added, the condenser was installed and replaced with nitrogen three times, and the system was placed in an 85°C environment for reflux heating reaction for 24 h. After TLC detection of the complete reaction, the system was reduced pressure filtration, the filter cake was washed with DCM, the filtrate was rotary evaporated, extracted with DCM and water, the organic phase was combined, and anhydrous sodium sulfate was dried. The organic phase was rotary evaporated, dried and loaded, and column chromatography separation (PE:DCM=5:1 / 3:1) was performed to obtain white solid product 2.92 g, with a yield of 78%.

[0062] Step B:

[0063]

[0064] Specific steps: In a 100 mL round bottom flask with a magnetic bar, add compound 4a (4.46 g, 20 mmol), n-bromobutane (3.28 g, 24 mmol), potassium carbonate (3.31 g, 24 mmol), DMF (30 mL) in sequence, and react at 80°C for 5 h. After TLC detection of complete reaction, pour the system into 150 mL of water, extract with DCM (3 x 50 mL), combine the organic phases, dry with anhydrous sodium sulfate, spin dry the organic phase, and purify by column chromatography (PE:EA=100:1) to obtain 4.96 g of product, with a yield of 89%.

[0065] Step C:

[0066]

[0067] Specific steps: In a 250 mL round bottom flask with a magnetic bar, add compound 5a (3.01 g, 10.8 mmol), bis(pinacolato)diboron (4.11 g), potassium acetate (3.18 g, 32.4 mmol), PdCl2(dppf) (397.2 mg, 0.54 mmol), and add 75 mL of 1,4-dioxane without oxygen, and react by refluxing at 90°C. After TLC detection of complete reaction, the system is first filtered, the filter cake is washed with DCM, the filtrate is spin dried, and purified by column chromatography (PE:EA=30:1) to obtain 2.78 g of product, with a yield of 79%.

[0068] Step D:

[0069]

[0070] Specific steps: In a 500 mL round bottom flask with a magnetic bar, add compound 3a (2.01 g, 8 mmol), 6a (3.13 g, 9.60 mmol), potassium carbonate (3.31 g, 24.00 mmol), deoxygenated toluene (80 mL), ethanol (40 mL), water (13 mL), Pd(PPh3)4(463.9 mg, 0.40 mmol), install a condenser and replace nitrogen three times, and place in an 85 o C environment to heat and reflux the reaction. After TLC detection of complete reaction, the system is filtered under reduced pressure, the filter cake is washed with DCM, the filtrate is spin dried as much as possible, extracted with H2O and DCM, the organic phases are combined and dried with anhydrous sodium sulfate, spin dried, and purified by column chromatography (PE:DCM=3:1 / 2:1) to obtain 2.28 g of product 7a (compound B048) as a light yellow solid, with a yield of 77%.

[0071] NMR data of the target compounds: 1 H NMR (500 MHz, Chloroform- d ) δ 12.50 (s, 1H), δ 9.17 (m, 2H), 7.92 – 7.85 (s, 1H), 7.83 (s, 1H), 7.80 – 7.74 (s, 1H), 7.55 – 7.38 (m, 2H), 7.33 – 7.24 (m, 2H), 7.12 – 7.01 (m, 2H), 6.85 (s, 1H), 4.15 (t, J = 6.9 Hz, 2H), 1.79 – 1.69 (m, 2H), 1.57 – 1.39 (m, 2H), 1.38 (t, J = 7.3 Hz, 3H). 13 C NMR (125 MHz, Chloroform- d ) δ 165.7, 158.8, 155.2, 153.1, 135.7, 133.9, 132.2, 131.8, 130.5, 128.1, 126.8, 126.1, 125.2, 124.9, 124.0, 122.7, 113.8, 113.1, 112.9, 64.3, 33.7, 18.4, 15.2.

[0072] Example 2: Synthesis of compound B047

[0073]

[0074] Step A:

[0075]

[0076] Specific procedure: In a 250 mL flask with a magnetic bar, compound 1a (2.48 g, 18 mmol), 2a (4.27 g, 15 mmol), potassium carbonate (3.10 g, 22.5 mmol), deoxygenated toluene (105 mL), ethanol (63 mL), water (21 mL), Pd(PPh3)4(521.2 mg, 0.71 mmol) were added in sequence, the condenser was installed and the system was purged with nitrogen three times, then the system was heated at 85 °C for 24 h. After TLC detection of the reaction completion, the system was filtered under reduced pressure, the filter cake was washed with DCM, the filtrate was rotary evaporated, extracted with DCM and water, the organic phase was combined and dried over anhydrous sodium sulfate. The organic phase was rotary evaporated, dried and loaded onto the column, and column chromatography was performed (PE : DCM=5:1 / 3:1) to obtain the white solid product 2.92 g, with a yield of 78%.

[0077] Step B:

[0078]

[0079] Specific procedure: In a 100 mL flask with a magnetic bar, compound 4b (4.46 g, 20 mmol), n-bromobutane (3.28 g, 24 mmol), potassium carbonate (3.31 g, 24 mmol), DMF (30 mL) were added in sequence, and the system was heated at 80 °C for 5 h. After TLC detection of the reaction completion, the system was poured into 150 mL water, extracted with DCM (3 x 50 mL), the organic phase was combined and dried over anhydrous sodium sulfate, the organic phase was rotary evaporated, and column chromatography was performed (PE : EA=150:1) to obtain the product 5.18 g, with a yield of 93%.

[0080] Step C:

[0081]

[0082] Specific procedure: In a 250 mL flask with a magnetic bar, compound 5b (3.01 g, 10.8 mmol), bis(pinacolato)diboron (4.11 g), potassium acetate (3.18 g, 32.4 mmol), PdCl2(dppf) (397.2 mg, 0.54 mmol) were added in sequence, and 1,4-dioxane 75 mL without oxygen was added, and the system was heated at 90 °C for 5 h. After TLC detection of the reaction completion, the system was filtered under reduced pressure, the filter cake was washed with DCM, the filtrate was rotary evaporated, and column chromatography was performed (PE : EA=50:1) to obtain the product 2.39 g, with a yield of 68%.

[0083] Step D:

[0084]

[0085] Procedure: In a 500 mL round bottom flask equipped with a magnetic bar, compound 3a (2.02 g, 8 mmol), 6b (3.14 g, 9.60 mmol), potassium carbonate (3.31 g, 24.00 mmol), deoxygenated toluene (80 mL), ethanol (40 mL), water (13 mL), Pd(PPh3)4(463.9 mg, 0.40 mmol) were sequentially added, the condenser was installed and the system was purged with nitrogen three times, it was placed in a 85 o C environment and heated to reflux. After TLC control of the reaction completion, the system was filtered under reduced pressure, the filter cake was washed with DCM, the filtrate was spun as much as possible, it was extracted with H2O and DCM, the organic phases were combined and dried with anhydrous sodium sulfate, spun and column chromatographed (PE : DCM = 3: 1 / 2: 1), obtaining the product 7b (compound B047) as a yellowish solid 2.13 g, 72% yield

[0086] Product NMR data: 1 H NMR (500 MHz, Chloroform- d ) δ 12.51 (s, 1H), δ 9.37(m, 2H), 8.32 (s, 1H), 7.88 – 7.71 (m, 2H), 7.59 (s, 1H), 7.49 – 7.39 (m,2H), 7.24 – 7.09 (m, 2H), 7.01 – 6.82 (m, 2H), 4.33 (t, J = 7.9 Hz, 2H), 1.78 –1.70 (m, 2H), 1.58 – 1.39 (m, 2H), 1.21 (t, J = 8.9 Hz, 3H). 13 C NMR (125 MHz, Chloroform- d ) δ 168.5, 156.4, 155.7, 152.9, 134.8, 133.6, 130.8, 128.5,128.1, 127.2, 126.5, 126.0, 125.2, 123.9, 120.0, 115.7, 111.5, 70.2, 33.8,18.7, 12.4.

[0087] Example 3: Synthesis of compound B040

[0088]

[0089] Step A:

[0090]

[0091] Specific procedure: In a 250 mL round bottom flask with a magnetic bar, compound 1a (2.48 g, 18 mmol), 2a (4.27 g, 15 mmol), potassium carbonate (3.10 g, 22.5 mmol), deoxygenated toluene (105 mL), ethanol (63 mL), water (21 mL), Pd(PPh3)4(521.2 mg, 0.71 mmol) were sequentially added, the condenser was installed and the system was purged with nitrogen three times, then the system was heated at 85 °C for 24 h. After TLC detection of the complete reaction, the system was filtered under reduced pressure, the filter cake was washed with DCM, the filtrate was rotary evaporated, extracted with DCM and water, the organic phases were combined and dried over anhydrous sodium sulfate. The organic phase was rotary evaporated, dry loaded and column chromatography was performed (PE : DCM = 5:1 / 3:1) to obtain the white solid product 2.92 g, yield 78%.

[0092] Step D:

[0093]

[0094] Specific procedure: In a 500 mL round bottom flask with a magnetic bar, compound 3a (2.01 g, 8 mmol), 6c (1.73 g, 10.0 mmol), potassium carbonate (3.31 g, 24.00 mmol), deoxygenated toluene (80 mL), ethanol (40 mL), water (13 mL), Pd(PPh3)4(463.9 mg, 0.40 mmol) were sequentially added, the condenser was installed and the system was purged with nitrogen three times, then the system was heated at 85 °C for 24 h. After TLC detection of the complete reaction, the system was filtered under reduced pressure, the filter cake was washed with DCM, the filtrate was rotary evaporated, extracted with H2O and DCM, the organic phases were combined and dried over anhydrous sodium sulfate, rotary evaporated and column chromatography was performed (PE : DCM = 3:1 / 2:1) to obtain the yellow solid product 7c (compound B040) 2.11 g, yield 87% o

[0095] Product NMR data: 1 H NMR (500 MHz, Chloroform- d ​) δ 12.54 (s, 1H), δ 9.93(s, 1H), 9.38 (m, 2H), 8.06 – 7.91 (s, 1H), 7.88 – 7.79 (m, 3H), 7.73 (s,1H), 7.58 – 7.43 (m, 3H), 7.31 – 7.26 (s, 1H), 7.12 – 6.99 (m, 2H). 13 C NMR (125 MHz, Chloroform- d ) δ 163.8, 158.1, 155.7, 144.9, 134.7, 132.5, 130.9,129.1, 128.5, 127.0, 126.5, 126.0, 125.8, 125.3, 122.4, 120.7, 115.9.

[0096] Example 4: Synthesis of compound B046

[0097]

[0098] Step A:

[0099]

[0100] Specific procedure: In a 250 mL flask with a magnetic bar, compound 1a (2.48 g, 18 mmol), 2a (4.27 g, 15 mmol), potassium carbonate (3.10 g, 22.5 mmol), deoxygenated toluene (105 mL), ethanol (63 mL), water (21 mL), Pd(PPh3)4(521.2 mg, 0.71 mmol) were added in sequence, the condenser was installed and the system was replaced with nitrogen three times, then the reaction was heated at 85 °C for 24 h. After TLC detection of the complete reaction, the system was filtered under reduced pressure, the filter cake was washed with DCM, the filtrate was rotary evaporated, extracted with DCM and water, the organic phase was combined and dried over anhydrous sodium sulfate. The organic phase was rotary evaporated and dry loaded, column chromatography separation (PE : DCM=5:1 / 3:1) to obtain white solid product 2.92 g, yield 78%.

[0101] Step B:

[0102]

[0103] Specific steps: In a 100 mL round bottom flask with a magnetic bar, compound 4d (4.46 g, 20 mmol), methacryloyl chloride (2.50 g, 24 mmol), triethylamine (2.83 g, 28 mmol), DCM (50 mL) were added in sequence, and the reaction was carried out at room temperature for 10 h. After TLC detection of complete reaction, the system was filtered, the filtrate was collected and rotary evaporated, and column chromatography was used for separation and purification (PE:EA=20:1) to obtain 5.35 g of product with a yield of 92%.

[0104] Step C:

[0105]

[0106] Specific steps: In a 250 mL round bottom flask with a magnetic bar, compound 5d (3.14 g, 10.8 mmol), bis(pinacolato)diboron (4.11 g), potassium acetate (3.18 g, 32.4 mmol), PdCl2(dppf) (397.2 mg, 0.54 mmol) were added in sequence, and 1,4-dioxane 75 mL without oxygen was added, and the reaction was carried out at 90°C under reflux. After TLC detection of complete reaction, the system was first filtered, the filter cake was washed with DCM, the filtrate was rotary evaporated, and column chromatography was used for separation and purification (PE:EA=30:1) to obtain 2.74 g of product with a yield of 75%.

[0107] Step D:

[0108]

[0109] Specific steps: In a 500 mL round bottom flask with a magnetic bar, compound 3a (2.01 g, 8 mmol), 6d (3.24 g, 9.6 mmol), potassium carbonate (3.31 g, 24.00 mmol), deoxygenated toluene (80 mL), ethanol (40 mL), water (13 mL), Pd(PPh3)4(463.9 mg, 0.40 mmol) were added in sequence, a condenser was installed and nitrogen was replaced three times, and the system was heated to reflux in an 85 o C environment. After TLC detection of complete reaction, the system was filtered under reduced pressure, the filter cake was washed with DCM, the filtrate was rotary evaporated as much as possible, extracted with H2O and DCM, the organic phases were combined and dried with anhydrous sodium sulfate, rotary evaporated, and column chromatography was used (PE:DCM=3:1 / 2:1) to obtain 2.33 g of product 7d (compound B046) as a light yellow solid with a yield of 76%

[0110] Product NMR data: 1 H NMR (500 MHz, Chloroform- d) δ 12.52 (s, 1H), δ 9.33(m, 2H), 7.92 (dd, J = 7.9, 2.0 Hz, 2H), 7.83 – 7.59 (m, 3H), 7.47 – 7.29 (s,1H), 7.24 – 7.19 (m, 2H), 7.02 – 6.85 (m, 2H), 6.05 (s, 1H), 5.77 (s, 1H),2.25 (t, J = 1.7 Hz, 3H). 13 C NMR (125 MHz, Common NMR Solvents) δ 167.1, 162.4,157.1, 155.2, 147.3, 137.1, 135.8, 133.1, 132.7, 132.1, 130.6, 129.8, 128.3,127.2, 126.9, 125.8, 125.1, 123.9, 122.1, 115.6, 111.8, 21.3.

[0111] Example 5: Synthesis of compound B042

[0112]

[0113] Step A:

[0114]

[0115] Specific procedure: In a 250 mL of eggplant flask with a magnetic bar, compound 2e (3.49 g, 18 mmol), 1a (4.27 g, 15 mmol), potassium carbonate (3.10 g, 22.5 mmol), deoxygenated toluene (105 mL), ethanol (63 mL), water (21 mL), Pd(PPh3)4(521.2 mg, 0.71 mmol) were added in sequence, the condenser was installed and replaced with nitrogen three times, and the reaction was heated at 90 °C for 24 h. After TLC detection, the system was filtered under reduced pressure, the filter cake was washed with DCM, the filtrate was rotary evaporated, extracted with DCM and water, the organic phase was combined and dried over anhydrous sodium sulfate. The organic phase was rotary evaporated and dry loaded, and column chromatography separation (PE : DCM=7:1 / 4:1) was carried out to obtain white solid product 7e (compound B040) 3.36 g, yield 73%.

[0116] Step C:

[0117]

[0118] Specific procedure: In a 250 mL round bottom flask with a magnetic bar, compound 5e (3.00 g, 10.8 mmol), bis(pinacolato)diboron (4.11 g), potassium acetate (3.18 g, 32.4 mmol), PdCl2(dppf) (397.2 mg, 0.54 mmol) were added sequentially, and 1,4-dioxane 75 mL without oxygen was added, and the reaction was refluxed at 90 °C. After TLC detection of the complete reaction, the system was first filtered, the filter cake was washed with DCM, the filtrate was rotary evaporated, and column chromatography was used for separation and purification (PE : EA=30:1) to obtain the product 2.87 g, yield 82%.

[0119] Step D:

[0120]

[0121] Specific procedure: In a 500 mL round bottom flask with a magnetic bar, compound 3e (2.46 g, 8 mmol), 6e (3.15 g, 9.60 mmol), potassium carbonate (3.31 g, 24.00 mmol), deoxygenated toluene (80 mL), ethanol (40 mL), water (13 mL), Pd(PPh3)4(463.9 mg, 0.40 mmol) were added sequentially, the condenser was installed and replaced with nitrogen three times, and placed in an 85 °C environment to heat and reflux the reaction. After TLC detection of the complete reaction, the system was filtered under reduced pressure, the filter cake was washed with DCM, the filtrate was rotary evaporated, extracted with H2O and DCM, the organic phase was combined and dried with anhydrous sodium sulfate, rotary evaporated, and column chromatography (PE : DCM =4:1 / 2:1) was used for separation and purification to obtain the light yellow solid product 7e (compound B042) 4.20 g, yield 68%. o C environment to heat and reflux the reaction. After TLC detection of the complete reaction, the system was filtered under reduced pressure, the filter cake was washed with DCM, the filtrate was rotary evaporated, extracted with H2O and DCM, the organic phase was combined and dried with anhydrous sodium sulfate, rotary evaporated, and column chromatography (PE : DCM =4:1 / 2:1) was used for separation and purification to obtain the light yellow solid product 7e (compound B042) 4.20 g, yield 68%.

[0122] Product NMR data: 1 H NMR (500 MHz, Chloroform- d ) δ 12.57 (s, 1H), δ 9.35(m, 2H), 7.97 – 7.86 (m, 3H), 7.77 – 7.63 (m, 2H), 7.21 (s, 1H), 7.06 – 6.87(m, 3H), 4.26 (t, J = 7.9 Hz, 2H), 1.81 – 1.73 (m, 2H), 1.62 – 1.53 (s, 1H),1.46 – 1.39 (s, 1H), 1.45 (s, 7H), 1.13 (t, J = 7.6 Hz, 3H).13 C NMR (125 MHz, Chloroform- d ) δ 165.8, 158.3, 154.1, 151.7, 150.3, 137.2, 136.7, 132.2, 131.4, 129.8, 128.1, 127.9, 127.1, 125.2, 121.6, 115.7, 110.4, 109.3, 63.1, 38.2, 30.6, 28.9, 21.5, 18.3.

[0123] Other compounds of the present application can be synthesized according to the above-mentioned synthetic method of compound B040, B042, B046, B047 or B048 by selecting appropriate starting materials, or any other suitable method and starting materials.

[0124] Comparative Example 1

[0125] UV-P, whose structural formula is shown in formula (II):

[0126]

[0127] (II).

[0128] The following performance tests were conducted on the compounds synthesized in the above examples and UV-P of Comparative Example 1:

[0129] 1. Photodegradation of methyl orange test

[0130] (1) Drawing of standard curve

[0131] 0.5 g of methyl orange was weighed and dissolved in N-methyl pyrrolidone (NMP) solvent, transferred to a 500 mL volumetric flask, added with NMP to constant volume, shaken to obtain a 1 g / L methyl solution.

[0132] 20 mL of the above-mentioned 1 g / L methyl orange solution was measured in a 1 L volumetric flask, added with NMP to constant volume, shaken to obtain a 20 mg / L methyl orange solution.

[0133] 5 10 mL cuvettes were taken, 0 mL, 2.5 mL, 5 mL, 7.5 mL and 10 mL of 20 mg / L methyl orange solution were respectively taken with a 10 mL pipette and added with NMP to prepare methyl orange standard solutions with mass concentrations of 0 mg / L, 5 mg / L, 10 mg / L, 15 mg / L and 20 mg / L, respectively.

[0134] The absorbance of methyl orange in different mass concentrations of methyl orange standard solution was determined at 470 nm wavelength by UV-visible spectrophotometer. According to the determination results, the standard curve of the absorbance of methyl orange versus the mass concentration was drawn. The absorbance of methyl orange in different mass concentrations of methyl orange standard solution is shown in Table 1.

[0135] Table 1 The absorbance of methyl orange in different mass concentrations of methyl orange solution

[0136]

[0137] According to the results in Table 1, the standard curve of the absorbance of methyl orange versus the mass concentration was drawn, and the standard curve graph is shown in Figure 2 , the regression equation of the standard curve is y = 0.0676x + 0.0006, and the correlation coefficient R 2 = 0.99858, wherein y is the absorbance and x is the mass concentration of methyl orange.

[0138] (2) Photocatalytic degradation of methyl orange test

[0139] 150 mL of the above-mentioned 20 mg / L methyl orange solution was measured and poured into a reactor respectively added with 2 mg of the compound of each example and comparative example; in addition, 150 mL of the above-mentioned 20 mg / L methyl orange solution was measured and directly poured into a reactor as a control group. The above-mentioned reactors were placed in a QUV-spray ultraviolet aging box, and the UVB waveband irradiance was set to 0.2 W·m -2 ·nm, to irradiate the methyl orange solution.

[0140] At 0 h, 1 h, 3 h, 5 h and 9 h, 10 mL was taken from the control group, the reactor added with 2 mg of the compound B048 of Example 1, and the reactor added with 2 mg of the compound UV-P of Comparative Example 1, respectively, and then the absorbance at 470 nm wavelength was detected.

[0141] The absorbance of methyl orange determined at different time points was substituted into the regression equation Y = 0.0676X + 0.0006 of the above-mentioned standard curve, and the mass concentration of methyl orange at different time points was calculated, and the specific results are shown in Table 2 and Figure 3 .

[0142] Table 2 The mass concentration of methyl orange determined at different time points

[0143]

[0144] Note: "blank" represents no addition of compound

[0145] Figure 3The graph shows the mass concentration of methyl orange at different time points in different reactors. Here, B048 corresponds to the reactor with 0.2 g of compound B048 from Example 1 added, UV-P corresponds to the reactor with 0.2 g of compound UV-P from Comparative Example 1 added, and "blank" corresponds to the control group reactor. (From Table 2 and...) Figure 3 As can be seen, with the increase of ultraviolet irradiation time, the mass concentration of methyl orange in the three reaction vessels gradually decreased, but the rate of decrease was fastest in the reactor corresponding to the control group; the rate of decrease was slowest and gradually leveled off in the reactor (B048) containing compound B048 from Example 1; and the rate of decrease was between the two in the reactor (UV-P) containing compound UV-P from Comparative Example 1. These results indicate that compound B048 can absorb ultraviolet light, thereby effectively inhibiting the degradation of methyl orange; and compound B048 absorbs ultraviolet light more effectively than compound UV-P.

[0146] Substituting the measured absorbance of methyl orange into the regression equation Y = 0.0676X + 0.0006 of the standard curve above, the mass concentration of methyl orange in different reaction vessels at different time points was calculated; then, substituting... (Where: C0 represents the initial mass concentration of the methyl orange solution; C...) t The concentration of methyl orange solution at time t (representing the mass concentration of the methyl orange solution at photocatalysis time t) is converted to a percentage to obtain the degradation rate of methyl orange in each reactor after 9 hours of light irradiation. eta The specific results are shown in Table 3 below.

[0147] Table 3. Determination results of methyl orange solution in different reactors

[0148]

[0149] Note: "-" indicates that no compound is added.

[0150] As shown in Table 3, the degradation rate of methyl orange in reactors containing the compounds of the various embodiments of the present invention was significantly lower than that in reactors containing the control group. These results indicate that the compounds of the various embodiments of the present invention can absorb ultraviolet light, thereby effectively inhibiting the degradation of methyl orange. However, the degradation rate of methyl orange in reactors containing compound UV-P (Comparative Example 1) was higher than that in reactors containing the compounds of the embodiments of the present invention, indicating that the compounds of the embodiments of the present invention have a better ultraviolet light absorption effect than compound UV-P.

[0151] The various embodiments in this specification are described in a related manner. The same or similar parts between the various embodiments can be referred to each other. Each embodiment focuses on describing the differences from other embodiments.

[0152] The above description is only the preferred embodiment of the present application, and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A compound, characterized in that, The compound has the structural formula shown in formula (I): （I） in, R is selected from hydrogen, hydroxyl group, C1-C 12 Alkyl, C1-C 12 Alkoxy, amino; R' is selected from hydrogen, C1-C8 alkyl, C1-C4 alkoxy, C2-C 10 Alkenyloxy group.

2. The compound according to claim 1, characterized in that, R is selected from the following groups: 。 3. The compound according to claim 1, characterized in that, R' is selected from the following groups: 。 4. A compound, characterized in that, The compounds are selected from the compounds shown in B001-B048 below: 。 5. An ultraviolet absorber, characterized in that, It includes at least one of the compounds according to any one of claims 1-4.

6. A composition, characterized in that, The composition comprises component A and component B, wherein the mass ratio of component A to component B is 100:(0.01-15). Component A is an organic substance that is sensitive to light damage, oxygen damage, and / or heat damage; Component B is at least one of the compounds according to any one of claims 1-4 or the ultraviolet absorber according to claim 5.

7. The composition according to claim 6, characterized in that, Component A includes at least one of thermoplastic polymer, coating adhesive, or photosensitive material.

8. Use of the compound of any one of claims 1-4, the ultraviolet absorber of claim 5, or the composition of any one of claims 6-7 in an organic substance for preventing light damage, oxygen damage, and / or heat damage.

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