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CN-122010965-A - Photochromic spiropyran derivative containing adamantyl group and preparation method and application thereof

CN122010965ACN 122010965 ACN122010965 ACN 122010965ACN-122010965-A

Abstract

The invention discloses an adamantane group-containing photochromic spiropyran derivative, a preparation method and application thereof, wherein the adamantane group-containing photochromic spiropyran derivative takes 4-dimethylaminopyridine and dicyclohexylcarbodiimide as catalysts, 2- (3 ',3' -dimethyl-6-nitrospiro [ chromene-2, 2 '-indoline ] -1' -yl) ethanol and adamantane carboxylic acid compounds are subjected to esterification reaction, adamantane acid ester series large steric hindrance groups are introduced on spiropyran molecules, a relatively loose stacking mode of the compounds is caused, and pi-pi stacking of spiropyran molecules is effectively prevented, so that the photochromic reaction of spiropyran in a solid state is realized.

Inventors

  • XIONG YUJIE
  • XIAO YANG
  • LI JIN

Assignees

  • 安徽师范大学

Dates

Publication Date
20260512
Application Date
20260127

Claims (10)

  1. 1. A photochromic spiropyran derivative containing adamantyl group, characterized in that, the structural formula of the photochromic spiropyran derivative containing adamantyl group is as follows: Wherein n=0 or 1, r is H or OH.
  2. 2. A process for the preparation of photochromic spiropyran derivatives containing adamantyl groups according to claim 1, characterised in that it comprises the steps of: Dissolving 2- (3 ',3' -dimethyl-6-nitrospiro [ chromene-2, 2 '-indoline ] -1' -yl) ethanol, adamantane carboxylic acid compounds and 4-dimethylaminopyridine in an organic solvent, cooling to-5 ℃, slowly dropwise adding dicyclohexylcarbodiimide solution under the protection of inert gas, stirring for reacting for 1-1.5 h, heating to normal temperature, continuing stirring for reacting for 40-46 h, and performing post-treatment to obtain the photochromic spiropyran derivative containing adamantane groups.
  3. 3. The method according to claim 2, wherein the adamantanecarboxylic acid compound is one of 1-adamantanecarboxylic acid, 1-adamantaneacetic acid, and 3-hydroxy-1-adamantaneacetic acid.
  4. 4. A process according to claim 2 or 3, wherein the molar ratio of 2- (3 ',3' -dimethyl-6-nitrospiro [ chromene-2, 2 '-indoline ] -1' -yl) ethanol to adamantane carboxylic acid is 1:1.
  5. 5. The method according to claim 2 or 3, wherein the molar ratio of the adamantanecarboxylic acid compound to the 4-dimethylaminopyridine to the dicyclohexylcarbodiimide is 1:0.1 to 0.12:1 to 1.1.
  6. 6. The process according to claim 2 or 3, wherein the organic solvent is methylene chloride and the dicyclohexylcarbodiimide solution is obtained by dissolving dicyclohexylcarbodiimide in methylene chloride.
  7. 7. The method according to claim 2 or 3, wherein the concentration of the adamantane carboxylic acid compound in the organic solvent is 0.02 to 0.05m.
  8. 8. The method of claim 2 or 3, wherein the post-treatment comprises concentrating the reaction solution under reduced pressure, purifying by column chromatography using a mixed solvent of petroleum ether and ethyl acetate as eluent, concentrating, and drying.
  9. 9. The preparation method of claim 8, wherein the volume ratio of petroleum ether to ethyl acetate is 3-5:1.
  10. 10. Use of a photochromic spiropyran derivative containing an adamantyl group according to claim 1 as a solid state photochromic material.

Description

Photochromic spiropyran derivative containing adamantyl group and preparation method and application thereof Technical Field The invention belongs to the technical field of organic synthesis, and particularly relates to a photochromic spiropyran derivative containing adamantyl groups, and a preparation method and application thereof. Background The photochromic material is an intelligent material capable of generating reversible molecular structure transformation under the irradiation of a light source with specific wavelength and further accompanying remarkable color change, and has wide application prospect in the fields of information storage, photoelectric switch, intelligent anti-counterfeiting, environment sensing and the like due to unique light response characteristics. The spiropyran compound is used as a classical organic photochromic micromolecule material, and becomes one of research hot spots in the field of photochromic materials by virtue of the outstanding advantages of simple and convenient synthesis process, high color-changing contrast, high light response speed, excellent reversibility and the like. Although the spiropyran material has excellent photochromic intrinsic performance, a plurality of technical bottlenecks are still faced in practical application, and particularly, the problem of performance optimization under a solid state is needed to be solved. The solid spiropyran compound without matrix has compact molecular packing, lacking free space and difficult photochromic reaction, and this has limited practical application. Meanwhile, the traditional spiropyran compound has the defects of poor fat solubility, easiness in oxidative degradation and the like, wherein the problem of poor fat solubility can seriously influence the dissolution and dispersion properties of the spiropyran compound in an organic polymer matrix, so that the preparation difficulty of a solid block material is increased, a uniform and stable solid system is difficult to form, and even though the spiropyran compound is prepared in a marginal way, the problems of large local color change effect difference, poor light response consistency and the like can also occur due to uneven molecular distribution. Disclosure of Invention In order to solve the technical problems, the invention provides a photochromic spiropyran derivative containing adamantyl groups, a preparation method and application thereof, wherein the photochromic spiropyran derivative containing adamantyl groups has good fat solubility and has the characteristic of solid state photochromism. In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the invention provides a photochromic spiropyran derivative containing adamantyl groups, which has the structural formula: Wherein n=0 or 1, r is H or OH. The invention also provides a preparation method of the photochromic spiropyran derivative containing adamantyl groups, which comprises the following steps: Dissolving 2- (3 ',3' -dimethyl-6-nitrospiro [ chromene-2, 2 '-indoline ] -1' -yl) ethanol, adamantane carboxylic acid compounds and 4-dimethylaminopyridine in an organic solvent, cooling to-5 ℃, slowly dropwise adding dicyclohexylcarbodiimide solution under the protection of inert gas, stirring for reacting for 1-1.5 h, heating to normal temperature, continuing stirring for reacting for 40-46 h, and performing post-treatment to obtain the photochromic spiropyran derivative containing adamantane groups. Further, the adamantane carboxylic acid compound is one of 1-adamantane carboxylic acid, 1-adamantane acetic acid and 3-hydroxy-1-adamantane acetic acid. The molar ratio of the 2- (3 ',3' -dimethyl-6-nitrospiro [ chromene-2, 2 '-indoline ] -1' -yl) ethanol to the adamantane carboxylic acid compound is 1:1. The molar ratio of the adamantane carboxylic acid compound to the 4-dimethylaminopyridine to the dicyclohexylcarbodiimide is 1:0.1-0.12:1-1.1. The organic solvent is dichloromethane, the dicyclohexylcarbodiimide solution is obtained by dissolving dicyclohexylcarbodiimide in dichloromethane, and the concentration of the dicyclohexylcarbodiimide solution is 0.02-0.05M. The concentration of the adamantane carboxylic acid compound in the organic solvent is 0.01-0.05M. The post-treatment method comprises the steps of concentrating the reaction liquid under reduced pressure, then carrying out column chromatography purification by taking a mixed solvent consisting of petroleum ether and ethyl acetate as an eluent, and concentrating and drying the collected product. Further, the volume ratio of petroleum ether to ethyl acetate is 3-5:1. The invention also provides application of the photochromic spiropyran derivative containing adamantyl group as a solid state photochromic material. The photochromic spiropyran derivative containing adamantane groups provided by the invention introduces adamantane acid ester series large steric hindrance groups on spiropyran molecul