CN110483331B - Benzophenone Schiff base ultraviolet absorber and preparation method thereof - Google Patents
Benzophenone Schiff base ultraviolet absorber and preparation method thereof Download PDFInfo
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- CN110483331B CN110483331B CN201910822168.3A CN201910822168A CN110483331B CN 110483331 B CN110483331 B CN 110483331B CN 201910822168 A CN201910822168 A CN 201910822168A CN 110483331 B CN110483331 B CN 110483331B
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- -1 Benzophenone Schiff base Chemical class 0.000 title claims abstract description 94
- 239000012965 benzophenone Substances 0.000 title claims abstract description 31
- 239000002262 Schiff base Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000006097 ultraviolet radiation absorber Substances 0.000 title claims abstract description 9
- 239000002250 absorbent Substances 0.000 claims abstract description 34
- 230000002745 absorbent Effects 0.000 claims abstract description 34
- 238000010521 absorption reaction Methods 0.000 claims abstract description 17
- 238000006482 condensation reaction Methods 0.000 claims abstract description 17
- 239000006096 absorbing agent Substances 0.000 claims abstract description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 69
- 238000001035 drying Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 claims description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 claims description 8
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 7
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- VVAKEQGKZNKUSU-UHFFFAOYSA-N 2,3-dimethylaniline Chemical compound CC1=CC=CC(N)=C1C VVAKEQGKZNKUSU-UHFFFAOYSA-N 0.000 claims description 5
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 5
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 claims description 5
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 claims description 5
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 4
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 4
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 4
- MAVDRLHHHFGIOW-WSDLNYQXSA-N OC(C(/C=N/C(C=C1)=CC=C1Cl)=C1)=CC(O)=C1C(C1=CC=CC=C1)=O Chemical compound OC(C(/C=N/C(C=C1)=CC=C1Cl)=C1)=CC(O)=C1C(C1=CC=CC=C1)=O MAVDRLHHHFGIOW-WSDLNYQXSA-N 0.000 claims description 4
- RNDNCJKBEQGNJM-FYJGNVAPSA-N OC1=C(/C=N/C2=CC=CC=C2)C=C(C(C2=CC=CC=C2)=O)C(O)=C1 Chemical group OC1=C(/C=N/C2=CC=CC=C2)C=C(C(C2=CC=CC=C2)=O)C(O)=C1 RNDNCJKBEQGNJM-FYJGNVAPSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000012805 post-processing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 238000001228 spectrum Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000002994 raw material Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 8
- 238000012544 monitoring process Methods 0.000 description 8
- 210000003491 skin Anatomy 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 150000004982 aromatic amines Chemical class 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 208000000453 Skin Neoplasms Diseases 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 201000000849 skin cancer Diseases 0.000 description 3
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 208000024891 symptom Diseases 0.000 description 2
- 239000012801 ultraviolet ray absorbent Substances 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- 229920000832 Cutin Polymers 0.000 description 1
- 206010015150 Erythema Diseases 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 208000003251 Pruritus Diseases 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 108091092356 cellular DNA Proteins 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N cinnamic acid Chemical class OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical class C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000002615 epidermis Anatomy 0.000 description 1
- 231100000321 erythema Toxicity 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008832 photodamage Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 230000009759 skin aging Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Cosmetics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of ultraviolet absorbers, and provides a benzophenone Schiff base ultraviolet absorber and a preparation method thereof. The ultraviolet absorbent provided by the invention comprises unsaturated carbon-nitrogen double bonds, oxyhydrogen hydrogen bonds and conjugated structures of different substituted phenyl groups (R groups), mainly absorbs ultraviolet within the range of 250-400 nm, is a novel wide-spectrum ultraviolet absorbent, and has more excellent absorption capacity and stronger marketable potential compared with the existing ultraviolet absorbent. The preparation method provided by the invention can obtain the product only through one-step condensation reaction, has simple steps and low preparation cost, and is easy for industrial production.
Description
Technical Field
The invention relates to the technical field of ultraviolet absorbers, in particular to a benzophenone Schiff base ultraviolet absorber and a preparation method thereof.
Background
In recent years, with the destruction of the atmospheric ozone layer, the amount of ultraviolet radiation has become one of the global environmental issues of greatest concern today. Ultraviolet rays in solar radiation cause obvious harm to human health, can cause phenomena of skin black spots, cutin growth, aging, relaxation and the like, and even can cause skin cancer, inhibit the immune system of an organism and the like. Ultraviolet rays are classified into UVA (wavelength of 320 to 400nm, long wave), UVB (wavelength of 280 to 320nm, medium wave) and UVC (wavelength of 100 to 280nm, short wave). UVC is absorbed by the ozone layer and cannot reach the earth's surface; UVB can reach the epidermis layer of the skin to generate strong photodamage, and the skin can have the symptoms of erythema, inflammation, aging and the like and even cause skin cancer; UVA penetrates the surface layer of the skin and then penetrates into dermal tissue, damaging cellular DNA, accelerating skin aging, and even causing skin cancer. Therefore, the overall defense against both UVA and UVB bands of ultraviolet light should be enhanced.
In order to reduce or prevent the harm of ultraviolet rays to human health, the addition of an ultraviolet ray absorbent is the most common and effective method, and is widely applied to the industries of textiles, high polymer materials and cosmetics. The ultraviolet absorbent selectively absorbs ultraviolet rays within the wavelength range of 290-400 nm, and converts the ultraviolet rays in an energy form to release absorbed energy as heat energy or harmless low-energy radiation, so that the skin is prevented from being damaged, and the high-molecular polymer is prevented from photo-physical and photochemical decomposition due to the absorption of the ultraviolet energy. The light energy absorption and conversion mechanism of the ultraviolet absorbent is mainly divided into two main categories of physical shielding and chemical absorption. The physical shielding mainly adopts titanium oxide and zinc oxide nano particles, the nano particles are uniformly coated on the surface, when ultraviolet rays are irradiated on the nano particles, the ultraviolet rays are scattered in all directions through the surface characteristics of the particles, and the ultraviolet ray blocking capacity is improved. Chemical absorption is primarily a protection by absorbing uv light, which is converted to other forms of energy, such as: thermal energy, visible light, etc. Taking 2-hydroxybenzophenone as an ultraviolet absorbent as an example, the action mechanism is shown as formula a:
the mechanism of action of the formula a 2-hydroxybenzophenone for absorbing ultraviolet radiation
The 2-hydroxybenzophenone contains hydroxyl hydrogen and carbonyl oxygen and can form stable intramolecular hydrogen bonds. When ultraviolet rays are irradiated, a large amount of heat is generated, so that the heat vibration of molecules is caused, hydrogen bonds are broken, and a chelate ring is opened. The structure is not stable, and when the structure is recovered to the original state, the redundant heat is released, so that the purpose of protecting ultraviolet rays is achieved. The chemical absorption type ultraviolet absorbent has the advantages of very obvious effect, extremely high transparency and relatively low price. But the disadvantages are obvious, part of the absorbent has certain irritation to the skin, and is easy to cause symptoms such as skin itch, allergy and the like, and the addition type and the amount of the chemical absorption type ultraviolet absorbent are strictly limited by the country. The chemical absorption type ultraviolet absorbers currently sold in the market mainly comprise nine types, namely, para-aminobenzoic acids, salicylates, cinnamates, benzophenones, camphor types, dibenzoylmethanes, benzotriazoles, triazines and acrylonitrile types, and specific molecular structural formulas, commercial varieties and absorption wave bands are shown in table 1.
TABLE 1 Classification of the chemical UV absorbers currently on the market
As can be seen from table 1, commercially available chemical absorption type ultraviolet absorbers are mainly concentrated on protection against the UVB band, while products for protection against the UVA band are relatively few; furthermore, there are fewer single products that can cover both the UVA and UVB bands.
At present, the commercialized common practice is to reasonably compound the ultraviolet absorbers for protecting UVA and UVB, but the compound has the defects of poor product compatibility and stability, high formula process difficulty, high cost and the like. Therefore, it is important to develop a novel, composite type (capable of protecting against UVA and UVB), highly efficient, and inexpensive ultraviolet absorber.
Disclosure of Invention
The invention aims to provide a novel benzophenone Schiff base ultraviolet absorbent, the structure of the novel benzophenone Schiff base ultraviolet absorbent comprises unsaturated carbon-nitrogen double bonds, nitrogen-hydrogen-oxygen hydrogen bonds and a conjugated structure of an R group, the main ultraviolet absorption range of the novel benzophenone Schiff base ultraviolet absorbent is 250-400 nm, and the novel benzophenone Schiff base ultraviolet absorbent is a novel wide-spectrum ultraviolet absorbent.
In order to achieve the above object, the present invention provides the following technical solutions:
a benzophenone Schiff base ultraviolet absorbent has a structure shown in formula I:
in formula I: r comprises phenyl, p-chlorophenyl, 1-naphthyl, 2, 3-dimethylphenyl, p-methoxyphenyl, p-hydroxyphenyl, o-hydroxyphenyl, or p-methylphenyl.
Preferably, the benzophenone-based ultraviolet absorber includes (E) -2, 4-dihydroxy-5- ((phenylimino) methyl) benzophenone, (E) -2, 4-dihydroxy-5- ((4-chlorophenylimino) methyl) benzophenone, (E) -2, 4-dihydroxy-5- ((naphthalene-1-imino) methyl) benzophenone, (E) -2, 4-dihydroxy-5- (((2, 3-dimethylphenyl) imino) methyl) benzophenone, (E) -2, 4-dihydroxy-5- ((4-methoxyphenylimino) methyl) benzophenone, (E) -2, 4-dihydroxy-5- ((4-hydroxyphenylimino) methyl) benzophenone, and, (E) -2, 4-dihydroxy-5- ((2-hydroxyphenylimino) methyl) benzophenone or (E) -2, 4-dihydroxy-5- ((p-tolylimino) methyl) benzophenone.
Preferably, the ultraviolet ray absorption range of the benzophenone Schiff base ultraviolet ray absorbent is 250-400 nm.
The invention provides a preparation method of a benzophenone Schiff base ultraviolet absorbent in the scheme, which comprises the following steps:
carrying out condensation reaction on 2, 4-dihydroxy-5-formyl benzophenone and an arylamine compound to obtain a benzophenone Schiff base ultraviolet absorbent with a structure shown in a formula I;
wherein the arylamine compound comprises aniline, parachloroaniline, 1-naphthylamine, 2, 3-dimethylaniline, p-methoxyaniline, p-hydroxyphenylamine, o-hydroxyphenylamine or p-methylaniline.
Preferably, the molar ratio of the 2, 4-dihydroxy-5-formylbenzophenone to the arylamine compound is 1: 1-2.
Preferably, the condensation reaction is carried out at the temperature of 50-100 ℃ for 2-6 h.
Preferably, the solvent for the condensation reaction is one or more of methanol, ethanol, isopropanol, tert-butanol and tetrahydrofuran.
Preferably, after the condensation reaction is finished, the method further comprises the step of carrying out post-treatment on the obtained product liquid; the post-processing comprises: and (4) concentrating the product liquid under reduced pressure, and sequentially filtering and drying.
The invention provides a benzophenone Schiff base ultraviolet absorbent which has a structure shown in a formula I. The ultraviolet absorbent provided by the invention comprises unsaturated carbon-nitrogen double bonds, nitrogen-hydrogen-oxygen hydrogen bonds and a conjugated structure of an R group, mainly absorbs ultraviolet within the range of 250-400 nm, is a novel wide-spectrum ultraviolet absorbent, and has more excellent absorption capacity and stronger marketability compared with the existing ultraviolet absorbent.
The invention also provides a preparation method of the benzophenone Schiff base ultraviolet absorbent in the scheme, the preparation method provided by the invention is simple in steps, the product can be obtained only through one-step condensation reaction, the preparation cost is low, and the industrial production is easy to carry out.
Drawings
FIG. 1 shows UV absorption spectra of benzophenone Schiff base UV absorbers obtained in examples 1 to 8.
Detailed Description
The invention provides a benzophenone Schiff base ultraviolet absorbent which has a structure shown in a formula I:
in formula I: r comprises phenyl, p-chlorophenyl, 1-naphthyl, 2, 3-dimethylphenyl, p-methoxyphenyl, p-hydroxyphenyl, o-hydroxyphenyl, or p-methylphenyl.
In the invention, when R is phenyl, p-chlorophenyl, 1-naphthyl, 2, 3-dimethylphenyl, p-methoxyphenyl, p-hydroxyphenyl, o-hydroxyphenyl, p-methylphenyl, the benzophenone Schiff base ultraviolet absorbent with the structure shown in formula I is specifically shown as follows: (E) -2, 4-dihydroxy-5- ((phenylimino) methyl) benzophenone, (E) -2, 4-dihydroxy-5- ((4-chlorophenylimino) methyl) benzophenone, (E) -2, 4-dihydroxy-5- ((naphthalene-1-imino) methyl) benzophenone, (E) -2, 4-dihydroxy-5- (((2, 3-dimethylphenyl) imino) methyl) benzophenone, (E) -2, 4-dihydroxy-5- ((4-methoxyphenylimino) methyl) benzophenone, (E) -2, 4-dihydroxy-5- ((4-hydroxyphenylimino) methyl) benzophenone, and (E) -2, 4-dihydroxy-5- ((4-hydroxyphenylimino) methyl) benzophenone, (E) -2, 4-dihydroxy-5- ((2-hydroxyphenylimino) methyl) benzophenone, (E) -2, 4-dihydroxy-5- ((p-tolylimino) methyl) benzophenone.
The ultraviolet absorbent structure provided by the invention comprises unsaturated carbon-nitrogen double bonds, oxygen-hydrogen-oxygen hydrogen bonds, nitrogen-hydrogen-oxygen hydrogen bonds and conjugated structures of different substituted phenyl groups (R groups), and a large amount of heat is generated when ultraviolet rays are irradiated, so that the molecular thermal vibration is caused, the hydrogen bonds are destroyed, and a chelate ring is opened. When the original structure is recovered, the redundant heat is released, thereby achieving the purpose of protecting ultraviolet rays. The specific principle is shown as formula II:
in the invention, the ultraviolet absorbent can strongly absorb ultraviolet rays, has the ultraviolet absorption range of 250-400 nm, can simultaneously absorb UVA and UVB, and is a wide-spectrum ultraviolet absorbent.
The invention also provides a preparation method of the benzophenone Schiff base ultraviolet absorbent in the scheme, which comprises the following steps:
carrying out condensation reaction on 2, 4-dihydroxy-5-formyl benzophenone and an arylamine compound to obtain a benzophenone Schiff base ultraviolet absorbent with a structure shown in a formula I;
in the invention, the arylamine compound comprises aniline, parachloroaniline, 1-naphthylamine, 2, 3-dimethylaniline, p-methoxyaniline, p-hydroxyaniline, o-hydroxyaniline or p-methylaniline.
In the invention, the molar ratio of the 2, 4-dihydroxy-5-formylbenzophenone to the arylamine compound is preferably 1: 1-2, and more preferably 1: 1.5; the temperature of the condensation reaction is preferably 50-100 ℃, more preferably 60-90 ℃, and the time of the condensation reaction is preferably 2-6 hours, more preferably 3-5 hours; in the specific embodiment of the present invention, it is preferable to monitor by TLC until the reaction of the raw materials is completed.
In the invention, the solvent of the condensation reaction is preferably one or more of methanol, ethanol, isopropanol, tert-butanol and tetrahydrofuran, and more preferably ethanol; the invention preferably dissolves 2, 4-dihydroxy-5-formyl benzophenone and arylamine compounds in ethanol respectively to obtain dihydroxy-5-formyl benzophenone ethanol solution and arylamine compound ethanol solution, and then dropwise adds the arylamine compound ethanol solution into the dihydroxy-5-formyl benzophenone ethanol solution for reaction; in the invention, the concentration of the dihydroxy-5-formyl benzophenone ethanol solution is preferably 0.2-0.3 mmol/mL, more preferably 0.25mmol/mL, and the concentration of the arylamine compound ethanol solution is preferably 0.6-0.7 mmol/mL, more preferably 0.65 mmol/mL; the condensation reaction time of the invention is calculated from the time when the arylamine compound ethanol solution is dripped.
In the present invention, the formula of the condensation reaction is shown in formula III, wherein the type of R group is consistent with the above scheme:
in the invention, after the condensation reaction is completed, the method preferably further comprises the step of carrying out post-treatment on the obtained product liquid; the post-treatment preferably comprises: and (4) concentrating the product liquid under reduced pressure, and sequentially filtering and drying. The invention preferably concentrates the product feed liquid to 1/3 of the original volume, and the filtration is preferably suction filtration; the drying temperature is preferably 50 ℃ and the drying time is preferably 16 h. The product obtained after drying is yellow solid, namely the benzophenone Schiff base ultraviolet absorbent.
The embodiments of the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Firing into 100mL round bottomA bottle was charged with 1.21g (5.0mmol) of an ethanol (20mL) solution of 2, 4-dihydroxy-5-formylbenzophenone, and 0.74g (6.0mmol) of an ethanol (10mL) solution of p-anisidine was added dropwise thereto at a molar ratio of 2, 4-dihydroxy-5-formylbenzophenone to p-anisidine of 1: 1.2. The reaction temperature is controlled to be 75 ℃, and the reaction is carried out for 4 hours. After TLC monitoring of the complete reaction of the raw materials, decompressing and distilling 20mL of ethanol solvent, filtering, drying to obtain 1.51g of yellow solid, namely the corresponding product (E) -2, 4-dihydroxy-5- ((4-methoxyphenyl imino) methyl) benzophenone. Yield 87.0%, m.p.129-131 ℃, TLC (PE: EA ═ 5:1, R)f＝0.24),FT-IR(KBr)(cm-1):3416m,3058m,2990m,2834m,1750m,1624s,1560s,1504s,1448s,1030s,876m,826s,780m,704m.1H NMR(CDCl3,400MHz),δ:14.75(s,1H),12.77(s,1H),8.42(s,1H),7.69-7.49(m,6H),7.25-7.19(m,2H),6.93-6.88(m,2H),6.56(s,1H),2.74(s,3H).
Example 2
A100 mL round bottom flask was charged with 1.21g (5.0mmol) of an ethanol (20mL) solution of 2, 4-dihydroxy-5-formylbenzophenone, and a 0.79g (6.5mmol) of an ethanol (10mL) solution of 2, 3-dimethylaniline was added dropwise thereto, so that the molar ratio of 2, 4-dihydroxy-5-formylbenzophenone to 2, 3-dimethylaniline was 1: 1.3. The reaction temperature is controlled at 85 ℃ and the reaction lasts for 3.5 h. After TLC monitoring the raw material complete reaction, decompressing and distilling 20mL ethanol solvent, filtering, drying to obtain 1.46g yellow solid, namely the corresponding product (E) -2, 4-dihydroxy-5- (((2, 3-dimethylphenyl) imino) methyl) benzophenone. Yield 84.7%, m.p.126-127 ℃, TLC (PE: EA ═ 5:1, R)f＝0.73),FTIR(KBr)(cm-1):3428m,3054m,2966m,2918m,2860m,1622s,1588s,1562s,1474s,1354s,1310s,850m,776m,704m.1H NMR(CDCl3,400MHz),δ:14.84(s,1H),12.78(s,1H),8.36(s,1H),7.68-7.49(m,6H),7.14-7.07(m,2H),6.91-6.88(m,1H),6.58(s,1H),2.33(s,3H),2.29(s,3H).
Example 3
A100 mL round bottom flask was charged with 1.21g (5.0mmol) of an ethanol (20mL) solution of 2, 4-dihydroxy-5-formylbenzophenone, and a 0.75g (7.0mmol) ethanol (10mL) solution of p-methylaniline was added dropwise thereto at a molar ratio of 2, 4-dihydroxy-5-formylbenzophenone to methylaniline of 1:1.4. The reaction temperature is controlled to be 80 ℃, and the reaction is carried out for 4 hours. After TLC monitoring of the complete reaction of the raw materials, decompressing and distilling 20mL of ethanol solvent, filtering, drying to obtain 1.56g of yellow solid, namely the corresponding product (E) -2, 4-dihydroxy-5- ((p-tolylimino) methyl) benzophenone. Yield 91.2%, m.p.108-109 ℃, TLC (PE: EA ═ 5:1, R)f＝0.71),FTIR(KBr)(cm-1):3430m,3026m,2918m,2862m,1626s,1584s,1510s,1454m,1354s,1306s,1176s,816s,752m,700m.1H NMR(DMSO-D6,400MHz),δ:12.30(s,1H),10.01(s,1H),8.94(s,1H),7.81-7.53(m,6H),7.33-7.23(m,2H),6.82-6.79(m,1H),6.50-6.38(m,1H),2.50(m,3H).
Example 4
A100 mL round bottom flask was charged with 1.21g (5.0mmol) of an ethanol (20mL) solution of 2, 4-dihydroxy-5-formylbenzophenone and a 0.70g (7.5mmol) ethanol (10mL) solution of aniline was added dropwise at a 1:1.5 molar ratio of 2, 4-dihydroxy-5-formylbenzophenone to aniline. The reaction temperature is controlled at 60 ℃ and the reaction lasts for 3 hours. After TLC monitoring of the complete reaction of the raw materials, decompressing and distilling 20mL of ethanol solvent, filtering, drying to obtain 1.05g of yellow solid, namely the corresponding product (E) -2, 4-dihydroxy-5- ((phenylimino) methyl) benzophenone. Yield 66.5%, m.p.93-95 ℃, TLC (PE: EA ═ 5:1, R)f＝0.77),FTIR(KBr)(cm-1):3410s,3048m,2968m,2852m,1622s,1594s,1512s,1440s,1376s,1322s,1232s,752m,698m.1H NMR(CDCl3,400MHz),δ:14.54(s,1H),12.78(s,1H),8.46(s,1H),7.72-7.41(m,10H),7.32-7.28(m,1H),6.59(s,1H).
Example 5
A100 mL round bottom flask was charged with 1.21g (5.0mmol) of an ethanol (20mL) solution of 2, 4-dihydroxy-5-formylbenzophenone, and a 0.95g (7.5mmol) ethanol (10mL) solution of p-chloroaniline was added dropwise thereto at a molar ratio of 2, 4-dihydroxy-5-formylbenzophenone to p-chloroaniline of 1: 1.5. The reaction temperature is controlled at 60 ℃ and the reaction lasts for 3 hours. After TLC monitoring of the complete reaction of the raw materials, decompressing and distilling 20mL of ethanol solvent, filtering, drying to obtain 1.26g of yellow solid, namely the corresponding product (E) -2, 4-dihydroxy-5- ((4-chlorphenyl imino) methyl) benzophenone. Yield 71.8%, m.p.136-138 ℃, TLC (PE: EA ═ 5:1, R)f＝0.76),FTIR(KBr)(cm-1):3420m,3058m,2970m,2898m,1622s,1538s,1488s,1446m,1364s,1304s,1234s,832s,758m,700m,622m.1H NMR(DMSO-D6,400MHz),δ:12.11(s,1H),10.02(s,1H),8.92(s,1H),7.80-7.51(m,8H),7.02-7.97(m,2H),6.48(s,1H).
Example 6
A100 mL round bottom flask was charged with 1.21g (5.0mmol) of an ethanol (20mL) solution of 2, 4-dihydroxy-5-formylbenzophenone, and a 1.15g (8.0mmol) of an ethanol (10mL) solution of 1-naphthylamine was added dropwise thereto, at a molar ratio of 2, 4-dihydroxy-5-formylbenzophenone to 1-naphthylamine of 1: 1.6. The reaction temperature was controlled at 70 ℃ for 3.5 h. After TLC monitoring of the complete reaction of the raw materials, decompressing and distilling 20mL of ethanol solvent, filtering, drying to obtain 0.97g of yellow solid, namely the corresponding product (E) -2, 4-dihydroxy-5- ((naphthalene-1-imino) methyl) benzophenone. Yield 52.9%, m.p.97-99 ℃, TLC (PE: EA ═ 5:1, R)f＝0.70),FTIR(KBr)(cm-1):3430m,3058m,2966m,2728m,1630s,1594s,1568s,1508m,1444m,1372s,1304s,854m.1H NMR(DMSO-D6,400MHz),δ:12.31(s,1H),10.01(s,1H),9.00(s,1H),8.03-7.96(m,1H),7.82-7.61(m,6H),7.60-7.52(m,3H),7.45-7.30(m,2H),7.22-7.16(m,1H),7.09-7.06(m,1H).
Example 7
A100 mL round-bottomed flask was charged with 1.21g (5.0mmol) of an ethanol (20mL) solution of 2, 4-dihydroxy-5-formylbenzophenone, and a 0.82g (7.5mmol) of an ethanol (10mL) solution of p-hydroxyaniline was added dropwise thereto at a molar ratio of 2, 4-dihydroxy-5-formylbenzophenone to p-hydroxyaniline of 1: 1.5. The reaction temperature was controlled at 70 ℃ and the reaction was carried out for 4 hours. After TLC monitoring of the complete reaction of the raw materials, decompressing and distilling 20mL of ethanol solvent, filtering, drying to obtain 1.33g of yellow solid, namely the corresponding product (E) -2, 4-dihydroxy-5- ((4-hydroxyphenylimino) methyl) benzophenone. Yield 79.6%, m.p.157-160 ℃, TLC (PE: EA ═ 5:1, R)f＝0.53),FTIR(KBr)(cm-1):3402m,3058m,2924m,2816m,2680m,1634s,1514s,1478s,1364s,1308s,1284s,828s,746m,698m.1H NMR(DMSO-D6,400MHz),δ:12.10(s,1H),10.00(s,1H),9.90(s,1H),8.87(s,1H),7.80-7.52(m,6H),7.31-7.28(m,2H),6.83-6.79(m,2H),6.36(s,1H).
Example 8
A100 mL round bottom flask was charged with 1.21g (5.0mmol) of an ethanol (20mL) solution of 2, 4-dihydroxy-5-formylbenzophenone, and a 0.82g (7.5mmol) of an ethanol (10mL) solution of o-hydroxyaniline was added dropwise thereto, so that the molar ratio of 2, 4-dihydroxy-5-formylbenzophenone to o-hydroxyaniline was 1: 1.5. The reaction temperature was controlled at 70 ℃ and the reaction was carried out for 4 hours. After TLC monitoring of the complete reaction of the raw materials, decompressing and distilling 20mL of ethanol solvent, filtering, drying to obtain 1.60g of yellow solid, namely the corresponding product (E) -2, 4-dihydroxy-5- ((2-hydroxyphenylimino) methyl) benzophenone. Yield 95.8%, m.p.263-265 ℃, TLC (PE: EA ═ 5:1, R)f＝0.17),FTIR(KBr)(cm-1):3430m,3056m,2918m,2848m,1628s,1592s,1508s,1462s,1374s,1336s,1220s,850s,746m,710m.1H NMR(DMSO-D6,400MHz),δ:12.12(s,1H),10.31(s,1H),9.97(s,1H),8.84(s,1H),7.77-7.52(m,6H),7.21-7.17(m,2H),6.62-6.59(m,2H),6.28(s,1H).
The ultraviolet absorption spectrum of the ultraviolet absorbers obtained in examples 1 to 8 was measured, and 2, 4-dihydroxybenzophenone (BP-1) was used as a control, and the results are shown in FIG. 1. As can be seen from FIG. 1, the ultraviolet absorbent provided by the invention has excellent absorption performance in the wavelength range of 250-400 nm, which shows that the ultraviolet absorbent provided by the invention can absorb UVA and UVB at the same time, while BP-1 has good absorption performance only in the range of 280-330 nm (UVB), and cannot absorb UVA.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A benzophenone Schiff base ultraviolet absorbent is characterized by having a structure shown in formula I:
in formula I: r is phenyl, p-chlorophenyl, 1-naphthyl, 2, 3-dimethylphenyl, p-methoxyphenyl, p-hydroxyphenyl, o-hydroxyphenyl or p-methylphenyl.
2. The benzophenone-Schiff base ultraviolet absorber according to claim 1, wherein the benzophenone-Schiff base ultraviolet absorber is (E) -2, 4-dihydroxy-5- ((phenylimino) methyl) benzophenone, (E) -2, 4-dihydroxy-5- ((4-chlorophenylimino) methyl) benzophenone, (E) -2, 4-dihydroxy-5- ((naphthalene-1-imino) methyl) benzophenone, (E) -2, 4-dihydroxy-5- (((2, 3-dimethylphenyl) imino) methyl) benzophenone, (E) -2, 4-dihydroxy-5- ((4-methoxyphenylimino) methyl) benzophenone, or a mixture thereof, (E) -2, 4-dihydroxy-5- ((4-hydroxyphenylimino) methyl) benzophenone, (E) -2, 4-dihydroxy-5- ((2-hydroxyphenylimino) methyl) benzophenone or (E) -2, 4-dihydroxy-5- ((p-tolylimino) methyl) benzophenone.
3. The benzophenone-based uv absorber of claim 1, wherein the uv absorber of benzophenone-based uv absorber has a uv absorption range of 250 to 400 nm.
4. The method for preparing the benzophenone schiff base ultraviolet absorber of any one of claims 1 to 3, comprising the following steps:
carrying out condensation reaction on 2, 4-dihydroxy-5-formyl benzophenone and an arylamine compound to obtain a benzophenone Schiff base ultraviolet absorbent with a structure shown in a formula I;
wherein the arylamine compound is aniline, parachloroaniline, 1-naphthylamine, 2, 3-dimethylaniline, p-methoxyaniline, p-hydroxyphenylamine, o-hydroxyphenylamine or p-methylaniline.
5. The preparation method according to claim 4, wherein the molar ratio of the 2, 4-dihydroxy-5-formylbenzophenone to the arylamine compound is 1: 1-2.
6. The preparation method according to claim 4, wherein the condensation reaction is carried out at a temperature of 50-100 ℃ for 2-6 hours.
7. The method according to claim 4, wherein the solvent for the condensation reaction is one or more selected from methanol, ethanol, isopropanol, tert-butanol and tetrahydrofuran.
8. The preparation method according to claim 4, further comprising post-treating the obtained product liquid after the condensation reaction is completed; the post-processing comprises: and (4) concentrating the product liquid under reduced pressure, and sequentially filtering and drying.
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