CN-122010795-A - 4-Disubstituted aminobenzylidene camphorsulfonic acid and synthesis method and application thereof

Abstract

The invention relates to a water-soluble ultraviolet absorbent 4-disubstituted aminobenzylidene camphorsulfonic acid and a synthesis method and application thereof, wherein the synthesis method comprises the following steps of heating and refluxing camphorsulfonic acid and 2 equivalents of sodium methoxide in a toluene-methanol mixed solvent to react, slowly dripping corresponding 4-disubstituted aminobenzaldehyde solution with equal molar quantity of camphorsulfonic acid after enolization conversion is completed, continuously heating and stirring to react for 6-12 h, adding water to terminate the reaction, acidifying the reaction solution by using hydrochloric acid or sulfonic acid type cation exchange resin, separating and removing toluene, regulating pH value to about 6.5 by using water phase, decompressing, steaming and dehydrating, extracting crude products by a conventional method, purifying by column chromatography, and obtaining the target products.

Inventors

• LI YAN
• CHEN ZENAN
• YAO LIXIN
• XIE WENCHAO
• HU XINYUE
• REN JUN

Assignees

• 湖北大学

Dates

Publication Date

20260512

Application Date

20260108

Claims (7)

1. 1.4-Disubstituted aminobenzylidene camphorsulfonic acid, which is structurally characterized by the following: Wherein R 1 、R 2 is methyl, ethyl or phenyl.
2. 2. The method for synthesizing 4-disubstituted aminobenzylidene camphorsulfonic acid according to claim 1 comprises the steps of heating and refluxing camphorsulfonic acid and 2 equivalents of sodium methoxide in a toluene-methanol mixed solvent, slowly dropwise adding 4-disubstituted aminobenzaldehyde solution with equal molar weight of camphorsulfonic acid after enolization conversion is completed, continuously heating and stirring for reaction for 6-12 hours after the 4-disubstituted aminobenzaldehyde solution is added, adding water for terminating reaction, acidifying the reaction solution by using hydrochloric acid or sulfonic acid type cation exchange resin, separating and removing toluene, regulating the pH value of an aqueous phase to 6.5+/-0.5, and performing column chromatography purification after decompression, rotary evaporation and dehydration to obtain a target product.
3. 3. The method of claim 2, wherein the volume ratio of toluene to methanol is 9-10:1.
4. 4. The method of claim 2, wherein the heating and stirring reaction after the addition of the 4-disubstituted amino benzaldehyde solution is performed in an external bath heating mode, and the external bath temperature is 90-95 ℃.
5. 5. The method of claim 2, wherein the column chromatography is silica gel column chromatography using dichloromethane-methanol as eluent.
6. 6. Use of 4-disubstituted aminobenzylidene camphorsulfonic acid according to claim 1 as water-soluble uv absorber for the preparation of sunscreen products or cosmetics.
7. 7. Use of 4-disubstituted aminobenzylidene camphorsulfonic acid according to claim 1 as light fastness additive in the preparation of paints, varnishes, plastics, textiles or rubber.

Description

4-Disubstituted aminobenzylidene camphorsulfonic acid and synthesis method and application thereof Technical Field The invention belongs to the chemical synthesis technology of ultraviolet absorbent, and in particular relates to a water-soluble ultraviolet absorbent 4-disubstituted aminobenzylidene camphorsulfonic acid, and a synthesis method and application thereof. Background The ultraviolet rays of sunlight are divided into short-wave ultraviolet rays (UVC, 200-280 nm), medium-wave ultraviolet rays (UVB, 280-320 nm) and long-wave ultraviolet rays (UVA, 300-400 nm) according to the wavelength, any wave band ultraviolet rays possibly damage human skin, the UVC is absorbed by ozone in the atmosphere and is difficult to reach the surface of the earth, so people pay more attention to the protection of the ultraviolet rays UVA and the UVB, the ultraviolet rays UVB can generate strong photodamage to the surface layer of the skin, the irradiated part of the dermis is expanded, the symptoms such as redness, swelling and blisters are easily caused, the skin can be subjected to red spots, inflammation and skin aging for a long time, serious people can cause skin cancer, the ultraviolet rays UVA can reach deep and can act on melanin at the surface part of the skin, skin melanin pigmentation is caused, the skin is darkened, the ultraviolet rays UVA can not cause acute inflammation of the skin, the effect on the skin is slow, the skin can accumulate for a long time, and the side effect of the ultraviolet rays UVB can be enhanced, and the skin aging and the skin is one of the causes of serious skin aging and serious damage. In order to prevent skin from being damaged by sun or reduce skin injury caused by sun, various cosmetics containing sun screening agents are used for protecting ultraviolet rays, wherein the sun screening agents used for protecting ultraviolet rays mainly comprise two main types of physical ultraviolet screening agents and organic ultraviolet absorbing agents, the physical ultraviolet screening agents are commonly used for protecting the skin from being polluted by the sun, and the common physical ultraviolet screening agents comprise titanium dioxide, zinc oxide, kaolin, talcum powder, ferric oxide and the like, so that the problems of floating makeup, floating powder, slightly thick texture and the like are easy to occur when the sun screening cosmetics are used, and various organic ultraviolet absorbing agents are added into common sun screening cosmetics to achieve an ultraviolet protection function. Organic ultraviolet absorbers are organic compounds having a long conjugated chemical structure, and because the molecular structure of a single ultraviolet absorber is fixed, the molecular ultraviolet absorption peak thereof generally has only one main absorption peak in the UVA and UVB bands, so that a combination of two or more organic ultraviolet absorbers is generally contained in the formulation of sunscreen cosmetics for achieving a broad-spectrum UV protection effect. Meanwhile, the compound with long conjugated chemical structure fragments is usually hydrophobic, most organic ultraviolet absorbers are also hydrophobic, the problems of poor stability, easy precipitation and short storage period are easy to occur when the compound is used in sun-screening chemicals, the problems are more obvious when the compound is particularly used in aqueous cosmetics, the problems can be greatly improved when the compound is used in aqueous cosmetics, the development and application of the novel water-soluble ultraviolet absorbers are one of hot spots for the development of the organic ultraviolet absorbers, so that the novel water-soluble ultraviolet absorbers are developed, and the ultraviolet absorbers have the effects of protecting ultraviolet in UVA and UVB wave bands, and are very significant and can produce economic benefit research work. Disclosure of Invention The invention aims to provide 4-disubstituted aminobenzylidene camphorsulfonic acid, a synthesis method and application thereof, wherein the 4-disubstituted aminobenzylidene camphorsulfonic acid is used as a water-soluble ultraviolet absorber, and the ultraviolet absorber has the effect of absorbing ultraviolet rays in UVA and UVB wave bands. There are strict regulations for sunscreens used in cosmetics in countries around the world. According to the cosmetic safety technical Specification (2015 edition), 27 sun-screening agents (containing titanium dioxide and zinc oxide) are allowed to be used in China, wherein 25 chemical sun-screening agents comprise six types of organic ultraviolet absorbers of benzylidene camphor, 3-benzylidene camphor, 4-methylbenzylidene camphor, camphorbenzalkonium methyl sulfate, benzylidene camphor sulfonic acid and salts thereof, polyacrylamide methylbenzylidene camphor, terephthalylidene dicarbamate sulfonic acid and salts thereof. The benzylidene camphor organic ultraviolet absorbent containing the camphor ri