CN114605392A - Compound, ultraviolet absorbent and application thereof - Google Patents

Compound, ultraviolet absorbent and application thereof Download PDF

Info

Publication number
CN114605392A
CN114605392A CN202210166201.3A CN202210166201A CN114605392A CN 114605392 A CN114605392 A CN 114605392A CN 202210166201 A CN202210166201 A CN 202210166201A CN 114605392 A CN114605392 A CN 114605392A
Authority
CN
China
Prior art keywords
compound
heteroaryl
hydrogen
independently
aryl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210166201.3A
Other languages
Chinese (zh)
Other versions
CN114605392B (en
Inventor
周英杰
张震
杨树斌
陈雪波
陈跃
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yantai Haisen Big Data Co ltd
Yantai Jingshi Materials Genomic Engineering Research Institute
Original Assignee
Yantai Haisen Big Data Co ltd
Yantai Jingshi Materials Genomic Engineering Research Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yantai Haisen Big Data Co ltd, Yantai Jingshi Materials Genomic Engineering Research Institute filed Critical Yantai Haisen Big Data Co ltd
Priority to CN202210166201.3A priority Critical patent/CN114605392B/en
Publication of CN114605392A publication Critical patent/CN114605392A/en
Application granted granted Critical
Publication of CN114605392B publication Critical patent/CN114605392B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat

Abstract

The application provides a compound of formula (I), which has a strong absorption effect on ultraviolet rays in a 280nm-380nm range, and the absorption range covers a 360nm-380nm range in a UVA wave band and a 280nm-315nm range in a UVB wave band; and the absorption intensity between 280nm-300nm and 340nm-380nm is higher than that of T1600, and the ultraviolet resistance is better than that of T1600, so that the ultraviolet-resistant coating has wider application field. The application also provides an ultraviolet absorber containing the compound of the formula (I) and application thereof.
Figure DDA0003516125360000011

Description

Compound, ultraviolet absorbent and application thereof
Technical Field
The application relates to the technical field of ultraviolet absorption, in particular to a compound, an ultraviolet absorbent and application thereof.
Background
Ultraviolet light (also called ultraviolet light) is electromagnetic waves with a wavelength of 0.1 μm to 0.4 μm, and accounts for 7% of the total energy of solar radiation. The energy of the ultraviolet light can break the chemical bonds of most materials, causing the materials to fail, degrade, or deteriorate. The ultraviolet absorbent is a light stabilizer, has strong absorption in an ultraviolet region, has no obvious absorption in a visible region, and can release the absorbed ultraviolet in other forms with lower energy, such as light with longer wavelength or heat, so as to protect materials or dyes and the like; and the ultraviolet absorber itself is not damaged by ultraviolet rays.
The ultraviolet absorbent comprises benzotriazoles, benzophenones, triazines and the like, wherein the triazine ultraviolet absorbent TINUVIN1600 (hereinafter referred to as T1600) with better ultraviolet resistance effect is one of the products with the best ultraviolet absorption effect in the sold products by BASF, the main ultraviolet absorption peak is 320nm, the absorption range is mainly concentrated in the interval of 290nm-360nm, the absorption range is weak in the interval of 280nm-300nm in the outdoor ultraviolet (hereinafter referred to as UVB) wave band, and the absorption range is weak in the interval of 360nm-380nm in the long-wave black spot effect ultraviolet (hereinafter referred to as UVA) wave band.
Disclosure of Invention
The application aims to provide a compound, which has a strong absorption effect on ultraviolet rays in the range of 280nm-380nm and improves the ultraviolet resistance.
The present application provides in a first aspect a compound of formula (I):
Figure BDA0003516125340000011
wherein L is1Selected from the group consisting of single bond, C6-C50Arylene radicals or C2-C50A heteroarylene group, wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Ra; the substituents Ra of each radical are each independently selected from C1-C12Alkyl, halogen, hydroxy, cyano, sulfonyl, sulfo, phenyl, biphenyl, terphenyl, naphthyl, nitro, carboxy, C1-C12Acyloxy or C1-C12An alkoxy group;
L2selected from hydrogen, C1-C12Alkyl radical, C2-C6Alkenyl radical, C1-C18Alkoxy radical, C5-C12Cycloalkoxy, C2-C18Alkenyloxy, cyano, C1-C4Haloalkyl, sulfo, hydroxy, C2-C18Amido, C1-C12Acyloxy, C6-C50Aryl or C2-C50Heteroaryl, the hydrogen atoms on the aryl and the heteroaryl each independently can be substituted with Rb; the substituents Rb of each group are each independently selected from C1-C12Alkyl, halogen, hydroxy, cyano, sulfonyl, sulfo, phenyl, biphenyl, terphenyl, naphthyl, nitro, carboxy, C1-C12Acyloxy or C1-C12An alkoxy group;
R1、R2、R3、R4each independently selected from hydrogen, hydroxy, C1-C20Alkyl radical, C6-C12Cycloalkyl radical, C1-C20Alkoxy radical, C6-C12Cycloalkoxy, allyl, amino, C6-C50Aryl or C2-C50A heteroaryl group; the hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Rc; the substituents Rc of each group are each independently selected from C1-C12Alkyl, halogen, hydroxy, cyano, sulfonyl, sulfo, phenyl, biphenyl, terphenyl, naphthyl, nitro, carboxyRadical or C1-C12An alkoxy group;
each heteroatom on the heteroaryl or the heteroarylene is independently selected from O, S or N;
R5、R6、R7、R8each independently selected from hydrogen or
Figure BDA0003516125340000021
And R is5、R6、R7、R8At least one of which is
Figure BDA0003516125340000022
In some embodiments, L1Selected from single bond, C6-C30Arylene radicals or C2-C30A heteroarylene group, wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Ra.
In some embodiments, L1Selected from the following groups:
Figure BDA0003516125340000023
in some embodiments, L2Selected from hydrogen, C1-C8Alkyl, allyl, C1-C4Alkoxy radical, C6-C30Aryl or C2-C30Heteroaryl, the hydrogen atoms on the aryl and the heteroaryl each independently can be substituted with Rb.
In some embodiments, L2Selected from the following groups:
Figure BDA0003516125340000031
x is selected from O, S, CR5R6Or NR7；R5、R6Each independently selected from C1-C10Alkyl radical, C6-C30Aryl or C3-C30Heteroaryl of the group R5And said R6Can be connected into a ring; r7Is selected from C6-C30Aryl or C3-C30A heteroaryl group; when R is7Is selected from C3-C30When heteroaryl, the heteroatom of the heteroaryl is selected from O or S.
In some embodiments, R1、R2、R3、R4Each independently selected from hydrogen, hydroxy, C1-C20Alkyl, cyclohexyl, C1-C20Alkoxy, cyclohexylalkoxy, allyl, amino, C6-C30Aryl or C2-C30Heteroaryl, the hydrogen atoms on the aryl and the heteroaryl each independently may be substituted with Rc.
In some embodiments, L1Selected from single bond, C6-C18Arylene radicals or C2-C18A heteroarylene group, wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Ra; the substituents Ra of each group are each independently selected from C1-C3Alkyl or hydroxy; l is2Selected from hydrogen, C6-C18Aryl or C2-C18Heteroaryl, the hydrogen atoms on the aryl and the heteroaryl each independently can be substituted with Rb; the substituents Rb of each group are each independently selected from C1-C3Alkyl or hydroxy;
R1、R2、R3、R4each independently selected from hydrogen and C6-C18Aryl or C2-C18A heteroaryl group; the hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Rc; the substituents Rc of each group are each independently selected from hydroxy;
each heteroatom on the heteroaryl or the heteroarylene is independently selected from N;
R5、R6、R8is selected from hydrogen and R7Is selected from
Figure BDA0003516125340000032
Or R5、R7、R8Is selected from hydrogen and R6Is selected from
Figure BDA0003516125340000033
In some embodiments, L1Selected from a single bond or
Figure BDA0003516125340000034
L2Selected from hydrogen,
Figure BDA0003516125340000035
Figure BDA0003516125340000036
R1、R2、R4Selected from hydrogen; r3Selected from hydrogen,
Figure BDA0003516125340000037
R5、R6、R8Is selected from hydrogen and R7Is selected from
Figure BDA0003516125340000041
Or R5、R7、R8Is selected from hydrogen and R6Is selected from
Figure BDA0003516125340000042
In some embodiments, the compound is selected from the group consisting of compounds represented by a1-a64 as follows:
Figure BDA0003516125340000043
Figure BDA0003516125340000051
Figure BDA0003516125340000061
Figure BDA0003516125340000071
Figure BDA0003516125340000081
Figure BDA0003516125340000091
in a second aspect, the present application provides an ultraviolet absorber comprising at least one of the compounds described in the first aspect of the present application.
A third aspect of the present application provides a composition comprising: A) organic substances that are sensitive to damage by light, oxygen and/or heat; and B) at least one of a compound provided in the first aspect of the present application or a UV absorber provided in the second aspect of the present application; wherein the mass ratio of the component A) to the component B) is 100: 0.01-15.
In some embodiments, at least one of a thermoplastic polymer, a coating binder, or a photosensitive material is included as component a).
In some embodiments, the thermoplastic polymer is selected from at least one of polyethylene, polypropylene, polyvinyl chloride, copolymers of vinyl chloride and vinyl acetate, polystyrene, copolymers of styrene and acrylonitrile, polyamide, polyethylene terephthalate, the coating binder is selected from at least one of polyurethane, polyacrylate, natural rubber, silicone rubber, vinyl acetate, polyvinylidene chloride, and polyvinyl alcohol, and the photosensitive material is selected from at least one of a color blind sheet, a positive color sheet, a full color sheet, an infrared sheet, and a color sheet.
A fourth aspect of the present application provides the use of a compound provided in the first aspect of the present application or a uv absorber provided in the second aspect of the present application or a composition provided in the third aspect of the present application to prevent damage by light, oxygen and/or heat in an organic substance.
The compound provided by the application has a strong absorption effect on ultraviolet rays within a 280nm-380nm range, and the absorption range covers a 360nm-380nm range in a UVA wave band and a 280nm-315nm range in a UVB wave band; and the absorption intensity between 280nm-300nm and 340nm-380nm is higher than that of T1600, and the ultraviolet resistance is better than that of T1600, so that the ultraviolet-resistant coating has wider application field.
Of course, not all advantages described above need to be achieved at the same time in the practice of any one product or method of the present application.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present application, and it is also obvious for a person skilled in the art to obtain other embodiments according to the drawings.
FIG. 1 is a graph showing the UV-VIS absorption spectra of a glass substrate + Rh101 fluorescent film, a glass substrate + Rh101 fluorescent film + UV protective film (containing Compound A9 of example 1), and a glass substrate + Rh101 fluorescent film + UV protective film (containing Compound T1600 of comparative example 1);
FIG. 2 is a graph showing ultraviolet absorption spectra of a glass substrate + Rh101 fluorescent layer + UV protective layer (containing the compound A9 of example 1), and a glass substrate + Rh101 fluorescent layer + UV protective layer (containing the compound T1600 of comparative example 1);
FIG. 3 is a graph showing the relationship between the absorbance at a wavelength of 580nm of a glass substrate + Rh101 fluorescent layer, a glass substrate + Rh101 fluorescent layer + UV protective layer (containing the compound A9 of example 1) and a glass substrate + Rh101 fluorescent layer + UV protective layer (containing the compound T1600 of comparative example 1) and the time of irradiation with ultraviolet light under a temperature condition of 25 ℃;
FIG. 4 is a standard graph of absorbance versus mass concentration for methyl orange;
fig. 5 is a graph of mass concentration of methyl orange at different time points in different reactors.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the description herein are intended to be within the scope of the present disclosure.
The present application provides in a first aspect a compound of formula (I):
Figure BDA0003516125340000101
wherein the content of the first and second substances,
L1selected from the group consisting of single bond, C6-C50Arylene radicals or C2-C50A heteroarylene group, wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Ra; the substituents Ra of each radical are each independently selected from C1-C12Alkyl, halogen, hydroxy, cyano, sulfonyl, sulfo, phenyl, biphenyl, terphenyl, naphthyl, nitro, carboxy, C1-C12Acyloxy or C1-C12An alkoxy group;
L2selected from hydrogen, C1-C12Alkyl radical, C2-C6Alkenyl radical, C1-C18Alkoxy radical, C5-C12Cycloalkoxy, C2-C18Alkenyloxy, cyano, C1-C4Haloalkyl, sulfo, hydroxy, C2-C18Amido, C1-C12Acyloxy, C6-C50Aryl or C2-C50Heteroaryl, the hydrogen atoms on the aryl and the heteroaryl each independently can be substituted with Rb; the substituents Rb of each group are each independently selected from C1-C12Alkyl, halogen, hydroxy, cyano, sulfonyl, sulfo, phenyl, biphenyl, terphenyl, naphthyl, nitro, carboxy, C1-C12Acyloxy or C1-C12An alkoxy group;
R1、R2、R3、R4each independently selected from hydrogen, hydroxy, C1-C20Alkyl radical, C6-C12Cycloalkyl radical, C1-C20Alkoxy radical, C6-C12Cycloalkoxy, allyl, amino, C6-C50Aryl or C2-C50A heteroaryl group; the hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Rc; the substituents Rc of each group are each independently selected from C1-C12Alkyl, halogen, hydroxy, cyano, sulfonyl, sulfo, phenyl, biphenyl, terphenyl, naphthyl, nitro, carboxy or C1-C12An alkoxy group;
each heteroatom on the heteroaryl or the heteroarylene is independently selected from O, S or N;
R5、R6、R7、R8each independently selected from hydrogen or
Figure BDA0003516125340000111
And R is5、R6、R7、R8At least one of which is
Figure BDA0003516125340000112
In some embodiments of the present application, L1Selected from single bond, C6-C30Arylene radicals or C2-C30A heteroarylene group, wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Ra.
In some embodiments of the present application, L1Selected from the following groups:
Figure BDA0003516125340000113
in some embodiments of the present application, L2Selected from hydrogen, C1-C8Alkyl, allyl, C1-C4Alkoxy radical, C6-C30Aryl or C2-C30Heteroaryl group, aThe hydrogen atoms on the aryl and the heteroaryl groups each independently may be substituted with Rb.
In some embodiments of the present application, L2Selected from the following groups:
Figure BDA0003516125340000121
x is selected from O, S, CR5R6Or NR7；
R5、R6Each independently selected from C1-C10Alkyl radical, C6-C30Aryl or C3-C30Heteroaryl of said R5And said R6Can be connected into a ring;
R7is selected from C6-C30Aryl or C3-C30A heteroaryl group; when R is7Is selected from C3-C30In the case of heteroaryl, the heteroatom of the heteroaryl is selected from O or S.
In some embodiments of the present application, R1、R2、R3、R4Each independently selected from hydrogen, hydroxy, C1-C20Alkyl, cyclohexyl, C1-C20Alkoxy, cyclohexylalkoxy, allyl, amino, C6-C30Aryl or C2-C30Heteroaryl, the hydrogen atoms on the aryl and the heteroaryl each independently may be substituted with Rc.
In some embodiments of the present application, L1Selected from single bond, C6-C18Arylene radicals or C2-C18A heteroarylene group, wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Ra; the substituents Ra of each group are each independently selected from C1-C3Alkyl or hydroxy;
L2selected from hydrogen, C6-C18Aryl or C2-C18Heteroaryl, the hydrogen atoms on the aryl and the heteroaryl each independently can be substituted with Rb; substituents Rb of each radical eachIs independently selected from C1-C3Alkyl or hydroxy;
R1、R2、R3、R4each independently selected from hydrogen and C6-C18Aryl or C2-C18A heteroaryl group; the hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Rc; the substituents Rc of each group are each independently selected from hydroxy;
each heteroatom on the heteroaryl or the heteroarylene is independently selected from N;
R5、R6、R8is selected from hydrogen and R7Is selected from
Figure BDA0003516125340000122
Or R5、R7、R8Is selected from hydrogen and R6Is selected from
Figure BDA0003516125340000123
In some embodiments of the present application, L1Selected from a single bond or
Figure BDA0003516125340000124
L2Selected from hydrogen,
Figure BDA0003516125340000131
R1、R2、R4Selected from hydrogen; r3Selected from hydrogen,
Figure BDA0003516125340000132
R5、R6、R8Is selected from hydrogen and R7Is selected from
Figure BDA0003516125340000133
Or R5、R7、R8Is selected from hydrogen and R6Is selected from
Figure BDA0003516125340000134
For example, the compound of formula (I) can be selected from compounds represented by A1-A64, and specific chemical structural formulas of the compounds represented by A1-A64 are detailed in the foregoing.
The compound of the formula (I) has a strong absorption effect on ultraviolet rays within a 280nm-380nm range, and the absorption range covers a 360nm-380nm range in a UVA wave band and a 280nm-315nm range in a UVB wave band; and the absorption intensity in the interval of 280nm-300nm and 340nm-380nm is higher than that of T1600, and the ultraviolet resistance is better than that of T1600, so that the ultraviolet-resistant UV-resistant coating has a wider application field.
In a second aspect, 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 by the application can comprise other substances and/or additives capable of absorbing ultraviolet rays, and the additives can be selected from at least one of antioxidants, metal deactivators and phosphites. Wherein the antioxidant can be at least one selected from 2, 6-di-tert-butyl-4-methylphenol, 2, 6-di-tert-butyl-4-methoxyphenol and N-isopropyl-N' -phenyl p-phenylenediamine; the metal passivator can be at least one selected from N, N' -diphenylformamide and 3-salicylamido-1, 2, 4-triazole; the phosphite ester may be at least one selected from triphenyl phosphite and tris (2, 4-di-t-butylphenyl) phosphite. The other ultraviolet-absorbing substance may be at least one selected from benzotriazole ultraviolet-absorbing agents, benzophenone ultraviolet-absorbing agents, and triazine ultraviolet-absorbing agents.
The specific type and amount of the other ultraviolet-absorbing substances and/or additives added in the present application are not limited as long as the object of the present application can be achieved.
A third aspect of the present application provides a composition comprising: A) organic substances that are sensitive to damage by light, oxygen and/or heat; and B) at least one of a compound provided in the first aspect of the present application or a UV absorber provided in the second aspect of the present application; wherein the mass ratio of the component A) to the component B) is 100: 0.01-15.
The method for preparing the composition of the present application is not particularly limited, and any method known in the art may be employed, for example, directly mixing the component a) and the component B) in proportion to be uniform. The compound of the formula (I) or the ultraviolet absorbent provided by the application is added into an organic substance sensitive to light, oxygen and/or heat damage, and the compound of the formula (I) or the ultraviolet absorbent can absorb ultraviolet rays within the range of 280nm-380nm, so that the organic substance sensitive to light, oxygen and/or heat damage is prevented from being damaged by the ultraviolet rays within the range, and the effect of protecting the organic substance sensitive to light, oxygen and/or heat damage is achieved.
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).
In some embodiments of the present application, the thermoplastic polymer is selected from at least one of polyethylene, polypropylene, polyvinyl chloride, copolymers of vinyl chloride and vinyl acetate, polystyrene, copolymers of styrene and acrylonitrile, polyamide, polyethylene terephthalate, the coating binder is selected from at least one of polyurethane, polyacrylate, natural rubber, silicone rubber, vinyl acetate, polyvinylidene chloride, and polyvinyl alcohol, and the photosensitive material is selected from at least one of a color blind sheet, a positive color sheet, a full color sheet, an infrared sheet, and a color sheet.
A fourth aspect of the present application provides the use of a compound provided in the first aspect of the present application or a uv absorber provided in the second aspect of the present application or a composition provided in the third aspect of the present application to prevent damage by light, oxygen and/or heat in an organic substance.
The method for synthesizing the compound of the present application is not particularly limited, and the synthesis can be carried out by any method known to those skilled in the art. The following illustrates the synthesis of the compounds of the present application.
The silica gel column used in the following examples was a silica gel column of type coarse pore (zcx-II) available from Qingdao Specification separation materials Co., Ltd; the yields in the following examples are mass of actual synthesis product/mass of theoretical synthesis product x 100%.
Example 1: synthesis of Compound A9
Figure BDA0003516125340000141
1-3 preparation: adding compound 1-1(925mg, 4mmol), compound 1-2(1.4g, 4.4mmol), tetrakistriphenylphosphine palladium (231mg, 0.2mmol), potassium carbonate (2.2g, 16mmol), 35mL anhydrous THF (tetrahydrofuran) and 15mL deionized water into a reaction bottle, refluxing at 80 ℃ for 14h under nitrogen atmosphere, concentrating the reaction system after the reaction is completed, and performing silica gel column chromatography (eluent is petroleum ether: ethyl acetate ═ 10: 1, v/v) to obtain product 1-3, wherein the yield is 80%.
1-4 preparation: compound 1-3(1.3g, 3mmol) and 10mL of anhydrous DCM (dichloromethane) were added to a 50mL reaction flask, then a dichloromethane solution of NBS (N-bromosuccinimide) (570mg, 3.2mmol NBS in 14mL dichloromethane) was added dropwise to the reaction flask in ice bath, and the reaction was returned to room temperature for 12h, after completion of the reaction, the reaction system was concentrated and subjected to silica gel column chromatography (eluent petroleum ether: dichloromethane ═ 5: 1, v/v) to give product 1-4 in 77% yield.
1-5 preparation: compound 1-4(1.1g, 2mmol), pinacol diboron (533mg, 2.1mmol), potassium acetate (490mg, 5mmol), and 20mL anhydrous DMF (N, N-dimethylformamide) were added to a 50mL reaction flask, followed by PdCl2(dppf) (73mg, 0.1mmol) was reacted at 85 ℃ for 15 hours, after completion of the reaction, 50mL of water was added to the system, extracted with ethyl acetate (3 × 50mL), the organic phases were combined, dried over anhydrous sodium sulfate, the organic phase was concentrated, and chromatography was performed by silica gel column chromatography (eluent petroleum ether: ethyl acetate: 30: 1, v/v) to obtain 1 to 5% of a product, with a yield of 60%.
1-8 preparation: adding the compounds 1-7(685mg and 5mmol), the compounds 1-6(1.4g and 5mmol), potassium carbonate (1.0g and 7.5mmol), 40mL of toluene, 16mL of absolute ethanol and 8mL of deionized water into a 250mL reaction bottle, adding tetratriphenylphosphine palladium (289mg and 0.25mmol), reacting at 85 ℃ for 20h, concentrating the reaction system after the reaction is completed, and performing silica gel chromatography (an eluent is petroleum ether: ethyl acetate: 15: 1, v/v) to obtain the products 1-8, wherein the yield is 78%.
Preparation of a 9: adding the compounds 1-5(561mg, 1mmol), the compounds 1-8(276mg, 1.1mmol), potassium carbonate (196mg, 2mmol), toluene 10mL, absolute ethyl alcohol 6mL and 2mL of water into a 50mL reaction bottle, adding tetratriphenylphosphine palladium (57mg, 0.05mmol), reacting at 85 ℃ in an oil bath for 9h, concentrating the reaction system after the reaction is completed, and performing silica gel chromatography (an eluent is petroleum ether: ethyl acetate: 15: 1, v/v) to obtain the product A9 with the yield of 65%.
Of Compound A91H NMR results:1H NMR(400MHz,Chloroform-d)δ13.14(d,J＝16.1Hz,1H),9.12(d,J＝9.1Hz,2H),8.55(dd,J＝8.0,1.7Hz,1H),8.40(d,J＝1.3Hz,1H),8.37–8.33(m,1H),8.24(d,J＝7.8Hz,1H),7.93(d,J＝8.4Hz,2H),7.86(d,J＝7.8Hz,1H),7.81–7.75(m,2H),7.73–7.63(m,5H),7.62–7.56(m,1H),7.54–7.48(m,2H),7.44–7.35(m,4H),7.08(d,J＝8.2Hz,1H),7.01(t,J＝7.5Hz,1H),1.60(s,6H).
example 2: synthesis of Compound A26
Figure BDA0003516125340000161
2-2 preparation: compound 2-1(2.0g, 5mmol), pinacol diboron (3.1g, 12mmol), potassium acetate (2.0g, 20mmol) and 50mL of anhydrous DMF were charged into a 250mL reaction flask, nitrogen was bubbled for 30min, and PdCl was added2(dppf) (290mg, 0.4mmol) was reacted at 85 ℃ for 25 hours, after completion of the reaction, 400mL of water was added to the system, extracted with ethyl acetate (3 × 200mL), the organic phases were combined, dried over anhydrous sodium sulfate, the organic phase was concentrated, and chromatography was performed by silica gel column chromatography (eluent petroleum ether: ethyl acetate: 15: 1, v/v) to obtain 2-2, a yield of 71%.
1-8 preparation: adding the compounds 1-7(685mg and 5mmol), the compounds 1-6(1.4g and 5mmol), potassium carbonate (1.0g and 7.5mmol), 40mL of toluene, 16mL of absolute ethanol and 8mL of deionized water into a 250mL reaction bottle, adding tetratriphenylphosphine palladium (289mg and 0.25mmol), reacting at 85 ℃ for 20h, concentrating the reaction system after the reaction is completed, and performing silica gel chromatography (an eluent is petroleum ether: ethyl acetate: 15: 1, v/v) to obtain the products 1-8, wherein the yield is 78%.
Preparation of a 26: putting compound 2-2(990mg, 2mmol), compound 1-8(1.1g, 4.2mmol), potassium carbonate (1.1g, 8mmol), toluene 20mL, absolute ethanol 10mL and 6mL deionized water into a 100mL reaction flask, adding tetratriphenylphosphine palladium (288mg, 0.25mmol), reacting at 85 ℃ in oil bath for 9h, concentrating the reaction system after the reaction is completed, and performing silica gel column chromatography (eluent is petroleum ether: ethyl acetate: 5: 1, v/v) to obtain product A26 with the yield of 63%.
Of Compound A261H NMR results:1H NMR(400MHz,Chloroform-d)δ9.62(s,2H),9.24(s,4H),8.31(dd,J＝7.2,1.6Hz,1H),8.13(d,J＝7.2Hz,1H),7.99(dd,J＝7.0,1.5Hz,1H),7.89(d,J＝8.1Hz,2H),7.76(d,J＝8.1Hz,1H),7.70–7.59(m,5H),7.52–7.49(m,2H),7.34–7.28(m,2H),7.13–7.02(m,4H).
example 3: synthesis of Compound A44
Figure BDA0003516125340000171
4-3 preparation: compound 4-2(1.2g, 5mmol), pinacol diboron (3.0g, 12mmol), potassium acetate (1.9g, 20mmol) and 50mL of anhydrous DMF were charged to a 250mL reaction flask, followed by PdCl2(dppf) (183mg, 0.25mmol) was reacted at 85 ℃ for 25 hours, after completion of the reaction, 50mL of water was added to the system, extracted with ethyl acetate (3 × 50mL), the organic phases were combined, dried over anhydrous sodium sulfate, the organic phase was concentrated, and chromatography was performed on silica gel column (eluent: petroleum ether: ethyl acetate ═ 10: 1, v/v) to obtain 4 to 3% of a product, with a yield of 79%.
1-8 preparation: adding the compounds 1-7(685mg and 5mmol), the compounds 1-6(1.4g and 5mmol), potassium carbonate (1.0g and 7.5mmol), 40mL of toluene, 16mL of absolute ethanol and 8mL of deionized water into a 250mL reaction bottle, adding tetratriphenylphosphine palladium (289mg and 0.25mmol), reacting at 85 ℃ for 20h, concentrating the reaction system after the reaction is completed, and performing silica gel chromatography (an eluent is petroleum ether: ethyl acetate: 15: 1, v/v) to obtain the products 1-8, wherein the yield is 78%.
4-5 preparation: adding 4-3(879mg, 3mmol), 1-8(800mg, 3.2mmol), potassium carbonate (589mg, 6mmol), toluene 30mL, absolute ethyl alcohol 15mL and 8mL of water into a 100mL reaction flask, adding tetratriphenylphosphine palladium (173mg, 0.15mmol), reacting at 85 ℃ in an oil bath for 9h, concentrating the reaction system after the reaction is completed, and performing silica gel column chromatography (eluent is petroleum ether: ethyl acetate: 3: 1, v/v) to obtain 4-5, wherein the yield is 68%.
4-6 preparation: mixing compound 4-5(674mg, 2mmol), p-bromophenylboronic acid (480mg, 2.4mmol) and Pd2(dba)3(46mg，0.05mmol)、P(t-Bu)3(tri-tert-butylphosphine, 24mg, 0.12mmol), sodium tert-butoxide (576mg, 6mmol) and 30mL of toluene were added to a 250mL reaction flask, and after completion of the reaction at 110 ℃ under a nitrogen atmosphere, 50mL of water was added to the system, and extraction was performed with ethyl acetate (3X 50mL), the organic phases were combined, dried over anhydrous sodium sulfate, the organic phase was concentrated, and chromatography was performed by silica gel column chromatography (eluent: petroleum ether: ethyl acetate: 3: 1, v/v) to obtain 4-6% of a product with a yield of 71%.
Preparation of a 44: adding the compound 4-6(457mg, 1mmol), the compound 1-8(300mg, 1.2mmol), potassium carbonate (200mg, 1.5mmol), 10mL of toluene, 4mL of absolute ethanol and 2mL of deionized water into a 250mL reaction bottle, adding tetratriphenylphosphine palladium (58mg, 0.05mmol), reacting at 85 ℃ for 20h, concentrating the reaction system after the reaction is completed, and performing silica gel chromatography (an eluent is petroleum ether: ethyl acetate ═ 10: 1, v/v) to obtain a product A44 with the yield of 74%.
Of Compound A441H NMR results:1H NMR(400MHz,Chloroform-d)δ9.61(s,1H),9.60(s,1H),9.25(s,2H),9.23(s,2H),8.62(d,J＝7.6Hz,1H),8.25–8.13(m,2H),7.93–7.90(m,4H),7.74(d,J＝1.8Hz,1H),7.61–7.55(m,3H),7.52–7.49(m,1H),7.34–7.29(m,2H),7.22–7.19(m,1H),7.10–6.93(m,4H)。
example 4: synthesis of Compound A58
Figure BDA0003516125340000181
2-2 preparation: compound 2-1(1.6g, 5mmol), pinacol diboron (1.55g, 6mmol), potassium acetate (2.0g, 10mmol) and 40mL of anhydrous DMF were charged into a 100mL reaction flask, nitrogen was bubbled for 30min, and PdCl was added2(dppf) (182mg, 0.25mmol) was reacted at 85 ℃ for 25 hours, after completion of the reaction, 30mL of water was added to the system, extracted with ethyl acetate (3 × 30mL), the organic phases were combined, dried over anhydrous sodium sulfate, the organic phase was concentrated, and chromatography was performed by silica gel column chromatography (eluent petroleum ether: ethyl acetate: 30: 1, v/v) to obtain 2-2, a yield of 79%.
1-8 preparation: adding the compounds 1-7(685mg and 5mmol), the compounds 1-6(1.4g and 5mmol), potassium carbonate (1.0g and 7.5mmol), 40mL of toluene, 16mL of absolute ethanol and 8mL of deionized water into a 250mL reaction bottle, adding tetratriphenylphosphine palladium (289mg and 0.25mmol), reacting at 85 ℃ for 20h, concentrating the reaction system after the reaction is completed, and performing silica gel chromatography (an eluent is petroleum ether: ethyl acetate: 15: 1, v/v) to obtain the products 1-8, wherein the yield is 75%.
2-3 preparation: adding the compound 2-2(1.1g and 3mmol), the compound 1-8(838g and 3.2mmol), potassium carbonate (690mg and 5mmol), toluene 20mL, absolute ethyl alcohol 10mL and deionized water 6mL into a 100mL reaction bottle, adding tetratriphenylphosphine palladium (272mg and 0.15mmol), reacting at 85 ℃ in an oil bath for 9h, concentrating the reaction system after the reaction is completed, and performing silica gel chromatography (an eluent is petroleum ether: ethyl acetate: 10: 1, v/v) to obtain a product 2-3, wherein the yield is 71%.
2-4 preparation: adding the compound 2-3(826mg and 2mmol) and 10mL of anhydrous DCM into a 50mL reaction bottle, dropwise adding a DCM solution of NBS (310mg and 2.1mmol of NBS dissolved in 6mL of DCM) under the ice-bath condition, returning to room temperature after dropwise adding, continuing to react for 12h, concentrating the reaction system after the reaction is completed, and performing silica gel column chromatography (an eluent is petroleum ether, and ethyl acetate is 20: 1, v/v) to obtain a product 2-4 with the yield of 78%.
2-5 preparation: adding compound 2-4(539mg, 1mmol), pinacol diboron (310mg, 1.2mmol), potassium acetate (400mg, 2mmol) and 8mL anhydrous DMF into a reaction flask, bubbling nitrogen for 30min, and adding PdCl2(dppf) (37mg, 0.05mmol) was reacted at 85 ℃ for 25 hours, after completion of the reaction, 6mL of water was added to the system,extraction was performed with ethyl acetate (3 × 8mL), the organic phases were combined, dried over anhydrous sodium sulfate, the organic phase was concentrated, and chromatography was performed by silica gel column chromatography (eluent petroleum ether: ethyl acetate ═ 10: 1, v/v) to give 2-5, 77% yield.
Preparation of a 58: adding the compound 2-5(491mg, 0.5mmol), the compound 1-8(129mg, 0.65mmol), potassium carbonate (134mg, 1mmol), 5mL of toluene, 2mL of absolute ethyl alcohol and 1mL of deionized water into a 250mL reaction bottle, then adding tetratriphenylphosphine palladium (29mg, 0.025mmol), reacting at 85 ℃ for 16h, concentrating the reaction system after the reaction is completed, and performing silica gel chromatography (an eluent is petroleum ether: ethyl acetate ═ 10: 1, v/v) to obtain a product A58 with the yield of 75%.
Of Compound A581H NMR results:1H NMR(400MHz,Chloroform-d)δ9.63(s,1H),9.62(s,1H),9.28(s,4H),8.62(d,J＝7.1Hz,1H),8.22(dd,J＝7.4,1.7Hz,1H),7.98(dd,J＝7.5,1.6Hz,1H),7.88(d,J＝1.7Hz,1H),7.80–7.71(m,2H),7.69–7.54(m,5H),7.52–7.45(m,2H),7.39–7.26(m,2H),7.13–6.93(m,4H)
example 5: synthesis of Compound A60
Figure BDA0003516125340000201
2-2 preparation: the compound 2-1(1.6g, 5mmol), pinacol diboron (1.55g, 6mmol), potassium acetate (2.0g, 10mmol) and 40mL of anhydrous DMF were put in a 100mL reaction flask, nitrogen was bubbled for 30min, and PdCl was added2(dppf) (182mg, 0.25mmol) was reacted at 85 ℃ for 25 hours, after completion of the reaction, 30mL of water was added to the system, extracted with ethyl acetate (3 × 30mL), the organic phases were combined, dried over anhydrous sodium sulfate, the organic phase was concentrated, and chromatography was performed by silica gel column chromatography (eluent petroleum ether: ethyl acetate: 30: 1, v/v) to obtain 2-2, a yield of 79%.
1-8 preparation: adding the compounds 1-7(685mg and 5mmol), the compounds 1-6(1.4g and 5mmol), potassium carbonate (1.0g and 7.5mmol), 40mL of toluene, 16mL of absolute ethanol and 8mL of deionized water into a 250mL reaction bottle, adding tetratriphenylphosphine palladium (289mg and 0.25mmol), reacting at 85 ℃ for 20h, concentrating the reaction system after the reaction is completed, and performing silica gel chromatography (an eluent is petroleum ether: ethyl acetate: 15: 1, v/v) to obtain the products 1-8, wherein the yield is 75%.
2-3 preparation: adding the compound 2-2(1.1g and 3mmol), the compound 1-8(838g and 3.2mmol), potassium carbonate (690mg and 5mmol), toluene 20mL, absolute ethyl alcohol 10mL and deionized water 6mL into a 100mL reaction bottle, adding tetratriphenylphosphine palladium (272mg and 0.15mmol), reacting at 85 ℃ in an oil bath for 9h, concentrating the reaction system after the reaction is completed, and performing silica gel chromatography (an eluent is petroleum ether: ethyl acetate: 10: 1, v/v) to obtain a product 2-3, wherein the yield is 71%.
2-4 preparation: adding the compound 2-3(826mg and 2mmol) and 10mL of anhydrous DCM into a 50mL reaction bottle, dropwise adding a DCM solution of NBS (310mg and 2.1mmol of NBS dissolved in 6mL of DCM) under the ice-bath condition, returning to room temperature after dropwise adding, continuing to react for 12h, concentrating the reaction system after the reaction is completed, and performing silica gel column chromatography (an eluent is petroleum ether, and ethyl acetate is 20: 1, v/v) to obtain a product 2-4 with the yield of 78%.
Preparation of a 60: adding the compound 2-4(491mg, 1mmol), the compound 2-5(257mg, 1.3mmol), potassium carbonate (200mg, 1.5mmol), 8mL of toluene, 4mL of absolute ethyl alcohol and 2mL of deionized water into a 250mL reaction bottle, then adding tetratriphenylphosphine palladium (58mg, 0.05mmol), reacting for 20h at 85 ℃, concentrating the reaction system after the reaction is completed, and performing silica gel chromatography (an eluent is petroleum ether: ethyl acetate ═ 10: 1, v/v) to obtain a product A60 with the yield of 69%.
Of Compound A601H NMR results:1H NMR(400MHz,Chloroform-d)δ9.63(s,1H),9.26(s,2H),8.62(d,J＝7.4Hz,1H),8.22(dd,J＝7.2,1.6Hz,1H),7.95(dd,J＝7.3,1.8Hz,1H),7.89(d,J＝1.8Hz,1H),7.77–7.74(m,4H),7.62–7.58(m,4H),7.50–7.43(m,4H),7.41–7.25(m,6H),7.12–6.98(m,2H).
other compounds of the present application can be synthesized by selecting suitable raw materials according to the above-mentioned idea of synthesizing compounds a9, a26, a44, a58, or a60, and can also be synthesized by selecting any other suitable methods and raw materials.
Comparative example 1
T1600, having the formula (II):
Figure BDA0003516125340000221
the following performance measurements were performed on the compounds synthesized in the above examples and T1600 of comparative example 1.
1. Ultraviolet protection coating Performance testing
0.7mol of tetraethoxysilane (TEOS for short), 0.3mol of phenyltriethoxysilane (PhTES for short) and 1mol of ethanol are mixed, then 1.4mol of water and 0.003L of nitric acid with the molar concentration of 14mol/L are added, and the mixture is stirred and hydrolyzed for 24 hours at room temperature to obtain an alkoxide solution. 1mL of an ethanol solution containing 0.001mol of rhodamine 101 dye was added to the above alkoxide solution to obtain a mixed solution. And (2) spin-coating the mixed solution on a glass substrate at the rotating speed of 2000rpm by adopting a spin-coating method, drying the glass substrate at room temperature for 2 days, and then drying the glass substrate at 50 ℃ for 24 hours to obtain the glass substrate (hereinafter referred to as glass substrate + Rh101 fluorescent film) covered with the rhodamine 101 dye-doped organic modified silicate gel glass coating, wherein the thickness of the Rh101 fluorescent film is 0.8 mu m.
Mixing 1mol TEOS and 1mol PhTES, adding the mixture into 100mL ethanol, fully dissolving, adding 2mol water and 6mL nitric acid with the molar concentration of 14mol/L, and stirring and hydrolyzing for 24h at room temperature; 0.4mol of each of the compounds of examples and comparative examples was added; and then spin-coating the glass substrate and the Rh101 fluorescent film on the glass substrate at a rotating speed of 2000rpm, drying the glass substrate at room temperature for 2 days, and then drying the glass substrate at 50 ℃ for 2 hours to obtain the glass substrate (hereinafter, referred to as glass substrate, Rh101 fluorescent film and UV protective film) sequentially covered with the rhodamine 101 dye-doped organic modified silicate gel glass coating and the ultraviolet light absorption layer, wherein the thicknesses of the two layers of films are respectively 0.8 mu m.
(1) Ultraviolet visible absorption Spectroscopy testing
The test method comprises the following steps: the ultraviolet-visible absorption spectra of the glass substrate + Rh101 fluorescent layer, the glass substrate + Rh101 fluorescent layer + UV protective layer (containing compound a9 of example 1), and the glass substrate + Rh101 fluorescent layer + UV protective layer (containing T1600 of comparative example 1) were measured in a range of 300nm to 700nm using an ultraviolet-visible spectrophotometer, using a glass substrate + Rh101 fluorescent layer, and the glass substrate + Rh101 fluorescent layer + UV protective layer as samples to be measured.
And (3) testing results: the ultraviolet-visible absorption spectra of the glass substrate + Rh101 fluorescent film, the glass substrate + Rh101 fluorescent film + UV protective film (containing compound a9 of example 1), and the glass substrate + Rh101 fluorescent film + UV protective film (containing compound T1600 of comparative example 1) are shown in fig. 1, in which: rh101 corresponds to a glass substrate + Rh101 fluorescent layer, T1600 corresponds to a glass substrate + Rh101 fluorescent layer + UV protective layer (T1600 as an ultraviolet absorber), and a9 corresponds to a glass substrate + Rh101 fluorescent layer + UV protective layer (a9 as an ultraviolet absorber). As can be seen from fig. 1: in the range of 300nm-400nm, the absorbance of the glass substrate + Rh101 fluorescent film + UV protective film (A9) and the absorbance of the glass substrate + Rh101 fluorescent film + UV protective film (T1600) are far greater than that of the glass substrate + Rh101 fluorescent film (Rh 101); in the range of 400nm-650nm, the difference between the absorbance of the glass substrate + Rh101 fluorescent film + UV protective film (A9) and the absorbance of the glass substrate + Rh101 fluorescent film (Rh101) is small. Without being bound to any theory, the inventors believe that the absorption peak occurring in the interval 400nm-650nm is mainly due to the absorption effect of Rh101 on visible light.
The above results show that the compounds A9 and T1600 have no significant absorption in the visible (400nm-650nm) and strong absorption in the ultraviolet (300nm-400 nm). Therefore, covering the surface of the Rh101 fluorescent film with the UV protective film containing the compounds a9 and T1600 of example 1 can significantly reduce the ultraviolet rays reaching the Rh101 fluorescent film, thereby reducing the degree of degradation of the Rh101 fluorescent film by ultraviolet rays.
(2) Ultraviolet absorption Spectroscopy testing
The ultraviolet absorption spectra of the glass substrate + Rh101 fluorescent film + UV protective film (containing compound a9 of example 1) and the glass substrate + Rh101 fluorescent film + UV protective film (containing compound T1600 of comparative example 1) were measured in the range of 280nm to 400nm using an ultraviolet-visible spectrophotometer.
And (3) testing results: the ultraviolet absorption spectra of the glass substrate + Rh101 fluorescent layer + UV protective layer (containing compound a9 of example 1), the glass substrate + Rh101 fluorescent layer + UV protective layer (containing compound T1600 of comparative example 1) are shown in fig. 2, wherein: a9 corresponds to glass substrate + Rh101 phosphor layer + UV protection film (containing compound A9 from example 1), and T1600 corresponds to glass substrate + Rh101 phosphor layer + UV protection film (containing compound T1600 from comparative example 1). As can be seen from fig. 2: the absorption range of the glass substrate + Rh101 fluorescent film + UV protective film (A9) is wider than that of the glass substrate + Rh101 fluorescent film + UV protective film (T1600), and the absorbance of the glass substrate + Rh101 fluorescent film + UV protective film (A9) is greater than that of the glass substrate + Rh101 fluorescent film + UV protective film (T1600) in the interval of 280nm-300nm and 340nm-380 nm.
The results show that the compound A9 in the UV protective film has strong absorption effect on ultraviolet rays in the range of 280nm-380nm, and has higher absorption intensity than T1600 in the ranges of 280nm-300nm and 340nm-380nm, and better ultraviolet resistance than T1600.
(3) Photodegradation rate test
The test method comprises the following steps: respectively placing the glass substrate + Rh101 fluorescent film, the glass substrate + Rh101 fluorescent film + UV protective film (respectively containing the compounds of each example and comparative example) as samples to be tested in a QUV-Spray ultraviolet aging oven at the temperature of 25 ℃, wherein the UVA wave band light power is 0.4 W.m-2。
And (3) measuring the change of the absorbance of each sample to be measured along with the irradiation time of the ultraviolet light at the maximum absorption wavelength (580nm) of the Rh101 fluorescent dye by using an ultraviolet-visible spectrophotometer.
And (3) testing results: the absorbance at a wavelength of 580nm of the glass substrate + Rh101 fluorescent layer, the glass substrate + Rh101 fluorescent layer + UV protective layer (containing the compound a9 of example 1), and the glass substrate + Rh101 fluorescent layer + UV protective layer (containing the compound T1600 of comparative example 1) at a temperature of 25 ℃ as a function of the irradiation time of ultraviolet light is shown in fig. 3, in which: a9 corresponds to the glass substrate + Rh101 phosphor layer + UV protective film (containing compound a9 of example 1), T1600 corresponds to the glass substrate + Rh101 phosphor layer + UV protective film (containing compound T1600 of comparative example 1), and the blank corresponds to the glass substrate + Rh101 phosphor layer. As can be seen in fig. 3: as the ultraviolet light irradiation time was prolonged, the rate of decrease in absorbance of the glass substrate + Rh101 fluorescent film + UV protective film (a9) was much smaller than the rate of decrease in absorbance of the glass substrate + Rh101 fluorescent film (blank), and slightly smaller than the decrease in absorbance of the glass substrate + Rh101 fluorescent film + UV protective film (containing the compound T1600 in the comparative example). The above results show that A9 has better UV resistance than T1600.
Without being bound to any theory, the inventors believe that: since the ultraviolet light degrades the Rh101 fluorescence, the UV protective film covering the surface of the Rh101 fluorescent film contains the compound a9 of example 1, and the compound a9 can absorb the ultraviolet light, thereby reducing the ultraviolet light reaching the Rh101 fluorescent film, further reducing the degradation of the ultraviolet light to the Rh101 fluorescence, slowing down the rate of decrease in the absorbance of the Rh101 fluorescent dye, and finally making the rate of decrease in the absorbance of the glass substrate + Rh101 fluorescent film + UV protective film (containing the compound a9 of example 1) much smaller than the rate of decrease in the absorbance of the glass substrate + Rh101 fluorescent film. The ultraviolet absorber T1600 of comparative example 1 also has the same tendency that the rate of decrease in absorbance is much smaller than that of the glass substrate + Rh101 fluorescent film.
The photodegradation rate v of the Rh101 fluorescent dye in the glass substrate + Rh101 fluorescent film + UV protective film (containing the compounds of the examples and comparative examples respectively) was calculated according to the absorbance at 580nm of the glass substrate + Rh101 fluorescent film + UV protective film (containing the compounds of the examples and comparative examples respectively) and the absorbance at 580nm of the glass substrate + Rh101 fluorescent film under the temperature condition of 25 DEG C1Rate v of photodegradation of Rh101 fluorescent dye in glass substrate + Rh101 fluorescent film2(ii) a Rate of photodegradation v1And v2By the formula v ═ a0-a)/a0Is calculated to obtain wherein a0Represents the initial absorbance, and a represents the absorbance after aging for 12 hours; further, the ratio v of the photodegradation rate of Rh101 fluorescent dye in the glass substrate + Rh101 fluorescent film to the photodegradation rate of Rh101 fluorescent dye in the glass substrate + Rh101 fluorescent film + UV protective film (containing the compounds of each example and comparative example, respectively) was obtained2/v1The specific results are shown in table 1 below.
TABLE 1 photodegradation Rate test results
Figure BDA0003516125340000241
Figure BDA0003516125340000251
From the results shown in table 1, it is understood that the ratio v of the photodegradation rate of Rh101 fluorescent dye in the glass substrate + Rh101 fluorescent film to the photodegradation rate of Rh101 fluorescent dye in the glass substrate + Rh101 fluorescent film + UV protective film (each containing the compound of each example) under UV irradiation2/v1All of which were 5 or more, indicating that the compounds of each example included in the UV protective film covering the surface of the Rh101 fluorescent film were able to effectively absorb ultraviolet rays, thereby reducing the ultraviolet rays reaching the Rh101 fluorescent film and further reducing the degradation rate of the ultraviolet rays on the Rh101 fluorescence. And the ratio v of the photodegradation rate of Rh101 fluorescent dye in the glass substrate + Rh101 fluorescent film to the photodegradation rate of Rh101 fluorescent dye in the glass substrate + Rh101 fluorescent film + UV protective film (Compound T1600 of comparative example 1)2/v1Is 4.78, which shows that the compounds provided in the examples are better than the compounds provided in the comparative example T1600 in the light degradation rate ratio, thereby better protecting the product and reducing the light degradation rate of the product. The results show that the compound provided by the application can bear long-term solar radiation, can improve the durability of outdoor products when used for preparing the outdoor products, and has wide application prospects.
2. Photodegradation of methyl orange test
(1) Drawing of standard curve
Weighing 0.5g of methyl orange, dissolving in N-methylpyrrolidone (NMP) solvent, transferring to a 500mL volumetric flask, adding NMP to fix volume, and shaking up to obtain 1g/L methyl orange solution.
Weighing 20mL of the methyl orange solution with the concentration of 1g/L into a 1L volumetric flask, adding NMP to the volumetric flask to achieve constant volume, and shaking up to obtain the methyl orange solution with the concentration of 20 mg/L.
Taking 5 10mL colorimetric tubes, transferring 20mg/L methyl orange solution into the colorimetric tubes by a 10mL pipette respectively by 0mL, 2.5mL, 5mL, 7.5mL and 10mL, and adding NMP to respectively prepare the methyl orange standard solutions with the mass concentrations of 0mg/L, 5mg/L, 10mg/L, 15mg/L and 20 mg/L.
And measuring the absorbance of methyl orange in the methyl orange standard solution with different mass concentrations at the wavelength of 470nm by using an ultraviolet visible light spectrophotometer, and drawing a standard curve of the relation between the absorbance of the methyl orange and the mass concentration according to the measurement result. The results of absorbance of methyl orange in methyl orange standard solutions of different mass concentrations are shown in table 2 below.
TABLE 2 absorbance of methyl orange in methyl orange solutions of different mass concentrations
Mass concentration (mg/L) 0 5 10 15 20
Absorbance of the solution 0.000 0.371 0.692 1.029 1.350
According to the results in table 2, a standard curve of the relationship between the absorbance and the mass concentration of methyl orange is plotted, the obtained standard curve graph is shown in fig. 4, and the regression equation of the standard curve is that y is 0.0676x +0.0006, correlation coefficient R20.99858 where y is the absorbance and x is the methyl orange mass concentration.
(2) Photocatalytic degradation of methyl orange test
Respectively measuring 150mL of the 20mg/L methyl orange solution, and pouring the solution into reactors respectively added with 2mg of the compounds of each example and comparative example; in addition, 150mL of the 20mg/L methyl orange solution was directly poured into the reactor as a control group. Putting the reactor into a QUV-spray ultraviolet aging box, and setting the optical power of a UVA wave band to be 0.4 W.m-2To carry out photocatalysis on the methyl orange solution.
10mL of each of the reaction vessels corresponding to the control group, the reaction vessel to which 2mg of Compound A9 of example 1 was added, and the reaction vessel to which 2mg of Compound T1600 of comparative example 1 was added was sampled at 0h, 1h, 3h, 5h and 9h, respectively, and then the absorbance at a wavelength of 470nm was measured.
The absorbance of methyl orange measured at different time points is substituted into the regression equation Y of the standard curve of 0.0676X +0.0006, and the mass concentration of methyl orange at different time points is calculated, and the specific results are shown in table 3 and fig. 5 below.
TABLE 3 Mass concentration of methyl orange measured at various time points
Figure BDA0003516125340000261
Note: "blank" means no compound added
Fig. 5 is a graph of mass concentration of methyl orange at different time points in different reactors, wherein: a9 corresponds to the reactor to which 0.2g of Compound A9 from example 1 has been added, T1600 corresponds to the reactor to which 0.2g of Compound T1600 from comparative example 1 has been added, and a "blank" corresponds to the reactor of the control group. As can be seen from table 3 and fig. 5, as the uv irradiation time increases, the mass concentration of methyl orange in the three reaction vessels gradually decreases, but the mass concentration of methyl orange in the reaction vessel corresponding to the control group decreases at the fastest rate; the mass concentration of methyl orange in the reactor (a9) to which compound a9 of example 1 was added decreased the slowest and gradually flatter; the mass concentration of methyl orange in the reactor (T1600) to which compound T1600 of comparative example 1 was added decreased at a rate intermediate to the two. The above results show that: the compound A9 can absorb ultraviolet rays, so that the degradation of methyl orange is effectively inhibited; and compound a9 was more effective in absorbing ultraviolet rays than compound T1600.
Substituting the measured absorbance of the methyl orange into a regression equation Y of the standard curve which is 0.0676X +0.0006, and respectively calculating the mass concentration of the methyl orange in different reaction containers at different time points; then substituting η ═ C0-Ct)/C0(in the formula: C0Representing the initial mass concentration of the methyl orange solution; ctRepresenting the mass concentration of the methyl orange solution at the time of photocatalysis t), converting into percentage, and calculating to obtain the degradation rate eta of the methyl orange after 9 hours of light irradiation in each reactor, wherein the specific results are shown in the following table 4.
TABLE 4 results of measurements of methyl orange solutions in different reactors
Figure BDA0003516125340000271
Note: "-" represents no added compound
As can be seen from table 4, the degradation rate of methyl orange in the reactor added with the compound of each example of the present application is much lower than that of methyl orange in the reactor corresponding to the control group, and the above results show that the compound of each example of the present application can absorb ultraviolet rays, thereby effectively inhibiting the degradation of methyl orange. And the degradation rate of methyl orange in the reactor to which the compound T1600 of comparative example 1 was added was higher than that in the reactor to which the compound of the example of the present application was added, indicating that the compound of the example of the present application has a better effect of absorbing ultraviolet rays than the compound T1600.
All the embodiments in the present specification are described in a related manner, and the same and similar parts among the embodiments may be referred to each other, and each embodiment focuses on the differences from the other embodiments.
The above description is only for the preferred embodiment of the present application and is not intended to limit the scope of the present application. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application are included in the protection scope of the present application.

Claims (14)

1. A compound of formula (I):
Figure FDA0003516125330000011
wherein the content of the first and second substances,
L1selected from single bond, C6-C50Arylene radicals or C2-C50A heteroarylene group, wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Ra; the substituents Ra of each radical are each independently selected from C1-C12Alkyl, halogen, hydroxy, cyano, sulfonyl, sulfo, phenyl, biphenyl, terphenyl, naphthyl, nitro, carboxy, C1-C12Acyloxy or C1-C12An alkoxy group;
L2selected from hydrogen, C1-C12Alkyl radical, C2-C6Alkenyl radical, C1-C18Alkoxy radical, C5-C12Cycloalkoxy, C2-C18Alkenyloxy, cyano, C1-C4Haloalkyl, sulfo, hydroxy, C2-C18Amido, C1-C12Acyloxy, C6-C50Aryl or C2-C50Heteroaryl, the hydrogen atoms on the aryl and the heteroaryl each independently can be substituted with Rb; the substituents Rb of each group are each independently selected from C1-C12Alkyl, halogen, hydroxy, cyano, sulfonyl, sulfo, phenyl, biphenyl, terphenyl, naphthyl, nitro, carboxy, C1-C12Acyloxy or C1-C12An alkoxy group;
R1、R2、R3、R4each independently selected from hydrogen and hydroxyl、C1-C20Alkyl radical, C6-C12Cycloalkyl radical, C1-C20Alkoxy radical, C6-C12Cycloalkoxy, allyl, amino, C6-C50Aryl or C2-C50A heteroaryl group; the hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Rc; the substituents Rc of each group are each independently selected from C1-C12Alkyl, halogen, hydroxy, cyano, sulfonyl, sulfo, phenyl, biphenyl, terphenyl, naphthyl, nitro, carboxy or C1-C12An alkoxy group;
each heteroatom on the heteroaryl or the heteroarylene is independently selected from O, S or N;
R5、R6、R7、R8each independently selected from hydrogen or
Figure FDA0003516125330000012
And R is5、R6、R7、R8At least one of which is
Figure FDA0003516125330000013
2. The compound of claim 1, wherein L1Selected from single bond, C6-C30Arylene radicals or C2-C30A heteroarylene group, wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Ra.
3. The compound of claim 1, wherein L1Selected from the following groups:
Figure FDA0003516125330000021
4. the compound of claim 1, wherein L2Selected from hydrogen, C1-C8Alkyl, allyl, C1-C4Alkoxy radical, C6-C30Aryl or C2-C30Heteroaryl, the hydrogen atoms on the aryl and the heteroaryl each independently can be substituted with Rb.
5. The compound of claim 1, wherein L2Selected from the following groups:
Figure FDA0003516125330000022
x is selected from O, S, CR5R6Or NR7；
R5、R6Each independently selected from C1-C10Alkyl radical, C6-C30Aryl or C3-C30Heteroaryl of said R5And said R6Can be connected into a ring;
R7is selected from C6-C30Aryl or C3-C30A heteroaryl group; when R is7Is selected from C3-C30In the case of heteroaryl, the heteroatom of the heteroaryl is selected from O or S.
6. The compound of claim 1, wherein,
R1、R2、R3、R4each independently selected from hydrogen, hydroxy, C1-C20Alkyl, cyclohexyl, C1-C20Alkoxy, cyclohexylalkoxy, allyl, amino, C6-C30Aryl or C2-C30Heteroaryl, the hydrogen atoms on the aryl and the heteroaryl each independently may be substituted with Rc.
7. The compound according to claim 1, wherein,
L1selected from the group consisting of single bond, C6-C18Arylene radicals or C2-C18A heteroarylene group, wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Ra; the substituents Ra of each radical are each independently selected from C1-C3Alkyl or hydroxy;
L2selected from hydrogen, C6-C18Aryl or C2-C18Heteroaryl, the hydrogen atoms on the aryl and the heteroaryl each independently can be substituted with Rb; the substituents Rb of each group are each independently selected from C1-C3Alkyl or hydroxy;
R1、R2、R3、R4each independently selected from hydrogen and C6-C18Aryl or C2-C18A heteroaryl group; the hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Rc; the substituents Rc of each group are each independently selected from hydroxy;
each heteroatom on the heteroaryl or the heteroarylene is independently selected from N;
R5、R6、R8is selected from hydrogen and R7Is selected from
Figure FDA0003516125330000031
Or R5、R7、R8Is selected from hydrogen and R6Is selected from
Figure FDA0003516125330000032
8. The compound according to claim 1, wherein,
L1selected from a single bond or
Figure FDA0003516125330000033
L2Selected from hydrogen,
Figure FDA0003516125330000034
Or
Figure FDA0003516125330000035
R1、R2、R4Selected from hydrogen; r3Selected from hydrogen,
Figure FDA0003516125330000036
Or
Figure FDA0003516125330000037
R5、R6、R8Is selected from hydrogen and R7Is selected from
Figure FDA0003516125330000038
Or R5、R7、R8Is selected from hydrogen and R6Is selected from
Figure FDA0003516125330000039
9. The compound of claim 1, wherein the compound is selected from the compounds represented by a1-a 64:
Figure FDA0003516125330000041
Figure FDA0003516125330000051
Figure FDA0003516125330000061
Figure FDA0003516125330000071
Figure FDA0003516125330000081
10. an ultraviolet absorber comprising at least one of the compounds of any one of claims 1-9.
11. A composition, comprising:
A) organic substances that are sensitive to damage by light, oxygen and/or heat; and
B) at least one of the compound of any one of claims 1-9 or the ultraviolet absorber of claim 10;
wherein the mass ratio of the component A) to the component B) is 100: 0.01-15.
12. The composition of claim 11 comprising as component a) at least one of a thermoplastic polymer, a coating binder, or a photosensitive material.
13. The composition of claim 12, the thermoplastic polymer being selected from at least one of polyethylene, polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polystyrene, styrene-acrylonitrile copolymer, polyamide, polyethylene terephthalate, the coating binder being selected from at least one of polyurethane, polyacrylate, natural rubber, silicone rubber, vinyl acetate, polyvinylidene chloride, and polyvinyl alcohol, and the photosensitive material being selected from at least one of a color blind sheet, a positive color sheet, a full color sheet, an infrared sheet, and a color sheet.
14. Use of a compound according to any one of claims 1 to 9 or a uv absorber according to claim 10 or a composition according to any one of claims 11 to 13 for preventing damage by light, oxygen and/or heat in organic matter.
CN202210166201.3A 2022-02-23 2022-02-23 Compound and ultraviolet absorber and application thereof Active CN114605392B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210166201.3A CN114605392B (en) 2022-02-23 2022-02-23 Compound and ultraviolet absorber and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210166201.3A CN114605392B (en) 2022-02-23 2022-02-23 Compound and ultraviolet absorber and application thereof

Publications (2)

Publication Number Publication Date
CN114605392A true CN114605392A (en) 2022-06-10
CN114605392B CN114605392B (en) 2024-04-02

Family

ID=81859354

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210166201.3A Active CN114605392B (en) 2022-02-23 2022-02-23 Compound and ultraviolet absorber and application thereof

Country Status (1)

Country Link
CN (1) CN114605392B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115322161A (en) * 2022-06-27 2022-11-11 烟台京师材料基因组工程研究院 Compound, ultraviolet absorbent containing compound and application of ultraviolet absorbent

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103896924A (en) * 2012-12-27 2014-07-02 海洋王照明科技股份有限公司 Organic semiconductor material and preparation method thereof, and electroluminescent device
KR20160082067A (en) * 2014-12-30 2016-07-08 희성소재 (주) Compound and organic light emitting device using the same
CN110041268A (en) * 2019-05-17 2019-07-23 西安瑞联新材料股份有限公司 A kind of miazines bipolarity compound and its application in OLED device
CN111205272A (en) * 2020-02-20 2020-05-29 长春海谱润斯科技有限公司 Material for organic electroluminescent device and organic electroluminescent device thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103896924A (en) * 2012-12-27 2014-07-02 海洋王照明科技股份有限公司 Organic semiconductor material and preparation method thereof, and electroluminescent device
KR20160082067A (en) * 2014-12-30 2016-07-08 희성소재 (주) Compound and organic light emitting device using the same
CN110041268A (en) * 2019-05-17 2019-07-23 西安瑞联新材料股份有限公司 A kind of miazines bipolarity compound and its application in OLED device
CN111205272A (en) * 2020-02-20 2020-05-29 长春海谱润斯科技有限公司 Material for organic electroluminescent device and organic electroluminescent device thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115322161A (en) * 2022-06-27 2022-11-11 烟台京师材料基因组工程研究院 Compound, ultraviolet absorbent containing compound and application of ultraviolet absorbent
CN115322161B (en) * 2022-06-27 2024-02-09 烟台京师材料基因组工程研究院 Compound, ultraviolet absorber containing compound and application of ultraviolet absorber

Also Published As

Publication number Publication date
CN114605392B (en) 2024-04-02

Similar Documents

Publication Publication Date Title
Qu et al. Dendronized perylenetetracarboxdiimides with peripheral triphenylamines for intramolecular energy and electron transfer
Geervliet et al. Luminescent solar concentrators based on renewable polyester matrices
Qin et al. Ratiometric fluorescent monitoring of methanol in biodiesel by using an ESIPT-based flavonoid probe
CN114605392A (en) Compound, ultraviolet absorbent and application thereof
CN110546141A (en) Benzotriazole derivative compound
WO2015023574A1 (en) Luminescent solar concentrator utilizing organic photostable chromophore compounds
WO2015168439A1 (en) Inorganic oxide coated fluorescent chromophores for use in highly photostable wavelength conversion films
Sousa et al. Joining High Coloration and Fast Color Fading with Photochromic Fused‐Naphthopyrans
WO2016112200A1 (en) Thermal regulating wavelength conversion films incorporating phase change materials
CN111440193B (en) Indene-thick naphtho-spirooxazine photochromic compound and preparation method thereof
Franciscato Campo et al. New fluorescent monomers and polymers displaying an intramolecular proton‐transfer mechanism in the electronically excited state (ESIPT). IV. Synthesis of acryloylamide and diallylamino benzazole dyes and its copolymerization with MMA
Sali et al. A novel blue fluorescent chemosensor for metal cations and protons, based on 1, 8‐naphthalimide and its copolymer with styrene
Xu et al. Fluorescence fiber-optic turn-on detection of trace hydrazine vapor with dicyanovinyl-functionalized triazatruxene-based hyperbranched conjugated polymer nanoparticles
CN112552457A (en) Ultraviolet blue light absorbing composition, optical film comprising same and polarizing plate
Kulawardana et al. Dual responsive poly (N‐isopropylacrylamide) hydrogels having spironaphthoxazines as pendant groups
Miho et al. Fluorescent polymer films based on photo-induced electron transfer for visualizing water
CN115322161A (en) Compound, ultraviolet absorbent containing compound and application of ultraviolet absorbent
US6126869A (en) Solar blind optical filter
Marianetti et al. Solar collectors based on luminescent 2, 5-diarylimidazoles
Lee et al. Multiple switching behaviors of poly (N-isopropylacrylamide) hydrogel with spironaphthoxazine and D-π-A type dye
CN113307742B (en) Blue light absorption material, preparation method and application thereof, and blue light prevention lens
CN112662305A (en) Anti-ultraviolet and blue-light-absorbing composition, optical film comprising same and polarizing plate
CN117756710A (en) Compound, ultraviolet absorber containing compound, composition containing compound and application of ultraviolet absorber
CN116854639A (en) Compound, ultraviolet absorber containing compound, composition and application of ultraviolet absorber
CN101624519A (en) Preparation and application of pyrazolone-shrinking phenyl semicarbazide photochromic compounds

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant