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CN-121990877-A - Preparation method and application of civet derivative and polymer thereof

CN121990877ACN 121990877 ACN121990877 ACN 121990877ACN-121990877-A

Abstract

The invention belongs to the technical field of compound preparation, and particularly relates to a preparation method and application of a civet derivative and a polymer thereof. The civet derivative takes civet as a core framework, and has good chemical stability and further participation in chemical reaction through controllable functionalization modification of a macrocyclic structure. The civet has unique macrocyclic configuration and modifiable site, and the derivative thereof can obtain new chemical properties and application potential on the basis of keeping the structural characteristics of a parent body. The preparation method of the civet derivative is simple and convenient to operate, mild in condition and capable of efficiently realizing regulation and functionalization of the civet structure. The prepared civet derivative can be applied to the preparation process of polymers, and a specific structural unit is introduced or the material performance is improved through the action of the civet derivative and the components related to a polymerization system, so that a new technical approach is provided for the construction of functionalized polymers.

Inventors

  • LIU YILIU
  • HAN QINGQING
  • Wu Cunluo
  • LI HAOXUAN

Assignees

  • 华南理工大学

Dates

Publication Date
20260508
Application Date
20251231

Claims (10)

  1. 1. A civet derivative based on civet, characterized in that the chemical structural formula of the civet derivative is as follows: In the structural formulas LMT-A to LMT-J, R 1 is a hydrogen atom, sulfonyl or substituted or unsubstituted C1-C50 alkyl or aryl, R 2 is a hydrogen atom, cyclopropene cation or substituted or unsubstituted C1-C50 alkyl or aryl, R 3 is a hydrogen atom, ketone group, aldehyde group, alkenyl ether, carboxyl, ester group, hydroxyalkyl or azide group, R 4 and R 5 are substituted or unsubstituted C1-C50 alkyl chains containing hetero atoms; Is a nitrogen-containing heterocycle.
  2. 2. The civet derivative according to claim 1, wherein the sulfonyl group in R 1 is an aliphatic sulfonyl group or an aromatic sulfonyl group, wherein when R 1 is a substituted C1-C50 alkyl group or aryl group, R 1 contains one or two or more of C, N, O, P, si, S atoms, wherein when R 2 is a substituted C1-C50 alkyl group or aryl group, R 2 contains one or two or more of C, N, O, P, si, S atoms, and wherein when R 4 and R 5 are a heteroatom-containing substituted or unsubstituted C1-C50 alkyl chain, R 4 and R 5 contain one or two or more of N, O, P, si, S atoms, wherein R 4 is covalently or non-cyclic with R 5 .
  3. 3. The civet derivative according to claim 1 or 2, characterized in that the substituent R 1 is selected from the structures shown below: wherein n and m are integers from 1 to 50; The substituent R 2 is selected from the structures shown below: Wherein n and m are integers of 1-50, X is a counter ion, specifically one or more than two of fluoride ion, chloride ion, bromide ion, iodide ion, tetrafluoroborate ion, hexafluorophosphate ion, carboxylate ion, lithium tetrakis (pentafluorophenyl) borate anion, nickel tetracarbonyl anion, carbonate ion, hypochlorite ion, phosphate ion and phenolate ion; The substituents R 4 and R 5 are selected from the structures shown below: wherein n is an integer of 1 to 50.
  4. 4. The civet derivative according to claim 1 or 2, characterized in that said Is a nitrogen-containing heterocycle, and is specifically selected from the following chemical structural formulas:
  5. 5. the derivative of civet according to claim 1 or 2, characterized in that it has the following structural formula:
  6. 6. The method for producing a civet derivative according to any one of claims 1 to 5, characterized by comprising the steps of synthesizing civet derivatives having chemical structures LMT-a to LMT-E as follows: (1) Dissolving the civet into an organic solvent, then adding sodium borohydride for reaction, and obtaining a civet derivative LMT-1 after the reaction is finished; (2) Dissolving a civet derivative LMT-1 in an organic solvent, adding alkali and 4-dimethylaminopyridine, then adding sulfonyl chloride for reaction, and obtaining a civet derivative LMT-2 after the reaction is finished; (3) Dissolving a civet derivative LMT-2 in an organic solvent, then adding sodium azide for reaction, and obtaining a civet derivative LMT-3 after the reaction is finished; Wherein the chemical structure of LMT-3 is (4) Dissolving a civet derivative LMT-3 in an organic solvent, then dropwise adding lithium aluminum hydride for reaction, and obtaining a civet derivative LMT-4 after the reaction is finished; Wherein the chemical structure of LMT-4 is (5) Dissolving a civet derivative LMT-4 in an organic solvent, then adding anhydride and alkali or halogenated cyclopropene cation and alkali to react, and obtaining the civet derivative after the reaction is finished; (6) Dissolving the civet into an organic solvent, then adding Pd/C, and obtaining a civet derivative LMT-0-R after the reaction is finished; Wherein the chemical structure of LMT-0-R is (7) Dissolving a civet derivative LMT-0-R in an organic solvent, then adding sodium borohydride for reaction, and obtaining the civet derivative LMT-1-R after the reaction is finished; wherein the chemical structure of LMT-1-R is (8) Dissolving a civet derivative LMT-1-R in an organic solvent, dropwise adding phosphorus oxychloride for reaction, and obtaining the civet derivative LMT-R after the reaction is finished; Wherein the LMT-R chemical structure is (9) Dissolving the civet in an organic solvent, dropwise adding binary (thio) alcohol or alkyl (thio) alcohol, then adding p-toluenesulfonic acid and triethyl orthoformate, and obtaining the civet derivative after the reaction is finished; (10) Dissolving the civet into an organic solvent, adding the organic solvent into a phosphorus ylide solution, and obtaining a civet derivative LMT-S-2 after the reaction is finished; Wherein the chemical structure of LMT-S-2 is (11) Dissolving a civet derivative LMT-S-2 in an organic solvent, dropwise adding a hydrochloric acid aqueous solution, and obtaining the civet derivative LMT-S-3 after the reaction is finished; Wherein the chemical structure of LMT-S-3 is
  7. 7. The method for producing a civet derivative according to claim 6, wherein the organic solvent is any one or a combination of two or more of N, N-dimethylformamide, tetrahydrofuran, acetonitrile, methanol, ethyl acetate, and methylene chloride, and the base is any one or a combination of two or more of triethylamine, potassium carbonate, N-diisopropylethylamine, sodium carbonate, and pyridine.
  8. 8. A civet derivative polymer, characterized in that the polymer is prepared by dissolving more than one civet derivative of civet LMT-0 or the civet derivative of any one of claims 1-5 in an organic solvent, adding Grubbs' S catalyst, and then carrying out polymerization reaction; the solvent Grubbs' S catalyst is any one or the combination of more than two of a first generation catalyst, a second generation catalyst and a third generation catalyst.
  9. 9. The civet derivative polymer of claim 8, wherein the civet derivative polymer structure is as follows:
  10. 10. Use of a civet derivative according to any one of claims 1 to 5 and a civet derivative polymer according to any one of claims 8 to 9, characterized in that said civet derivative and its polymer are used for supramolecular self-assembly, small molecule modification, polymer synthesis, hydrogel preparation, preparation of optoelectronic or mechanical materials.

Description

Preparation method and application of civet derivative and polymer thereof Technical Field The invention belongs to the technical field of compound preparation, and particularly relates to a series of civet derivatives and a preparation method and application of a polymer thereof. Background The polymer material is widely applied to the fields of coating, adhesives, elastomers, medical materials, fine chemicals and the like. With the development of novel functional materials, higher requirements are put on the properties and structure of polymers, especially in terms of precise regulation of molecular structure, introduction of specific structural units and controllability of polymerization process. In recent years, organic small molecule derivatives with designable molecular structures are becoming important tools for realizing the regulation of polymer structures, and materials with specific reactivity or functional properties can be obtained by modifying the structures of the organic small molecule derivatives. The civet is a natural product with a unique macrocyclic skeleton structure, contains a plurality of modifiable sites in the molecule, and has good chemical reactivity and functionalization potential (Russ. Chem. Rev.,2020,89,469-490). The civet derivative can remarkably expand the chemical property and application range by introducing different functional groups, and has potential value in the fields of pharmaceutical chemistry, material science, fine chemistry and the like (Angew.chem.int.ed.2021, 133, 19837-19842). However, the existing preparation method of the civet derivative is relatively limited, and part of the route has complicated steps, insufficient selectivity or difficult realization of structural diversification, so that the further development and application of the civet derivative in the field of high polymer materials are limited. With the increasing demand for green, efficient, structurally controllable polymerization processes, it is of particular importance to develop novel organic molecules which can be used as building blocks or regulatory elements in the polymerization system. If the civet derivative can be introduced into a polymer structure, the civet derivative is expected to endow the material with new physicochemical properties, and a new way is provided for designing a functionalized polymer (adv. Synth. Catalyst. 2002,344, 507-510). However, the presently disclosed technology lacks a system capable of efficiently preparing a civet derivative, and does not see an effective application technical scheme in polymer synthesis. Therefore, there is a need to provide a controllable preparation method of a civirudin derivative, and further explore the application of the civirudin derivative in polymer synthesis, so as to expand the utilization mode of the civirudin structure and meet the requirements of the field of high polymer materials on novel structural units and functionalization strategies. Disclosure of Invention In order to solve the problems of limited structural modification, complex preparation steps, insufficient application in the field of polymer materials and the like of the civet derivative in the prior art, the primary aim of the invention is to provide a civet derivative with a controllable structure. The civet molecule has a unique macrocyclic skeleton structure and contains a plurality of reaction sites capable of being chemically modified, and the molecule design space and chemical application potential can be remarkably expanded by reasonably introducing functional groups, so that a foundation is laid for constructing a novel functional material. Another object of the present invention is to provide a process for preparing the above-mentioned civet derivative. The method can realize the efficient and controllable functionalization of the civet structure, and the obtained derivative has good chemical stability and further reactive characteristic groups, so that the problems of complicated steps, limited product types and insufficient selectivity in the traditional preparation method are effectively solved. It is a further object of the present invention to provide the use of the above-mentioned civet derivatives. The civet derivative can be applied to polymer synthesis, and can be used as a structural unit or a functional group to participate in a polymerization process by introducing the civet derivative into a polymer system, so that the composition, structure or property of the polymer can be regulated and controlled, and specific functional performance is given to the material. The civet derivative and the application system thereof expand the application way of the natural product structure in the polymer field, and provide a new technical direction for designing and preparing functionalized high-performance polymer materials. The invention also provides a civet derivative polymer. In order to achieve the above purpose, the present invention adopts