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CN-121975141-A - Triamino cage type macromolecular hydrogen bond organic framework material and preparation method thereof

CN121975141ACN 121975141 ACN121975141 ACN 121975141ACN-121975141-A

Abstract

The invention discloses a triamino cage type macromolecular hydrogen bond organic framework material and a preparation method thereof, belonging to the technical field of organic synthetic chemistry. Aiming at the defects of complicated steps and low yield in the traditional method for preparing the trichloro cage type macromolecule through two steps of reactions (namely, synthesizing an intermediate and then closing a ring). Firstly, reacting 1,3, 5-tri (4-hydroxyphenyl) benzene with cyanuric chloride for 2-5 days by a one-pot method at room temperature under the catalysis of organic base to directly synthesize a trichloro cage type macromolecule, then, reacting the intermediate with ammonia water for 4 hours at 140 ℃, and washing and recrystallizing to obtain the target product of the triamino cage type macromolecule hydrogen bond organic framework material. The invention simplifies the traditional two-step synthesis of the trichloro cage type macromolecule into one step, omits the intermediate separation step, has simple process and mild condition, and has the total yield of 76.7 percent. The obtained material has definite structure and wide application prospect in the fields of molecular recognition, gas adsorption separation and the like.

Inventors

  • ZHANG SHENGLI
  • LI MING
  • TANG JINGYAN
  • LI RUIDAN
  • LI CHANGDA

Assignees

  • 洛阳理工学院

Dates

Publication Date
20260505
Application Date
20260316

Claims (10)

  1. 1. The preparation method of the triamino cage type macromolecular hydrogen bond organic framework material is characterized by comprising the following steps of: (1) Dissolving 1,3, 5-tris (4-hydroxyphenyl) benzene and cyanuric chloride in a molar ratio of 1:1.2-1:1.8 in tetrahydrofuran, adding organic base as a catalyst, sealing and stirring at room temperature for 2-5 days, and performing post-treatment purification to obtain a trichlorocage type macromolecule; (2) Mixing the trichloro cage type macromolecule obtained in the step (1) with a1, 4-dioxane solution, dropwise adding ammonia water under the ice water bath condition, carrying out ammoniation reaction for 4 hours at 140 ℃ in a closed reaction kettle under the protection of nitrogen, and washing and recrystallizing to obtain the triamino cage type macromolecule hydrogen bond organic framework material.
  2. 2. The process of claim 1, wherein in step (1), the molar ratio of 1,3, 5-tris (4-hydroxyphenyl) benzene to cyanuric chloride is 1:1.5.
  3. 3. The method according to claim 1, wherein in the step (1), the organic base is any one of N, N-diisopropylethylamine, triethylamine, or pyridine; the molar amount of the catalyst is 5-7 times of the molar amount of 1,3, 5-tris (4-hydroxyphenyl) benzene.
  4. 4. The process according to claim 3, wherein the organic base is N, N-diisopropylethylamine in a molar amount 5.7 times the molar amount of 1,3, 5-tris (4-hydroxyphenyl) benzene.
  5. 5. The process according to claim 1, wherein in the step (1), the reaction is carried out for 4 days at room temperature under sealed stirring.
  6. 6. The preparation method of claim 1, wherein in the step (1), the post-treatment purification comprises concentration, extraction, drying and column chromatography, and the developing agent adopted by the column chromatography is a mixed solvent of petroleum ether and ethyl acetate, and the volume ratio of the developing agent to the ethyl acetate is 2:1-4:1.
  7. 7. The method according to claim 6, wherein the volume ratio of petroleum ether to ethyl acetate is 3:1.
  8. 8. The preparation method of the 1,3, 5-tris (4-hydroxyphenyl) benzene according to claim 1, wherein in the step (1), the 1,3, 5-tris (4-hydroxyphenyl) benzene is prepared by dissolving p-hydroxyacetophenone in absolute ethanol, dropwise adding silicon tetrachloride at room temperature for reaction for 12 hours, and performing rotary evaporation concentration, dichloromethane dissolution and column chromatography purification to obtain 1,3, 5-tris (4-hydroxyphenyl) benzene.
  9. 9. The process of claim 8, wherein the molar ratio of p-hydroxyacetophenone to silicon tetrachloride is 1:3.
  10. 10. A triamino cage-type macromolecular hydrogen bond organic framework material, characterized in that it is prepared by the preparation method according to any one of claims 1 to 9.

Description

Triamino cage type macromolecular hydrogen bond organic framework material and preparation method thereof Technical Field The invention belongs to the technical field of organic synthetic chemistry, and particularly relates to a preparation method of a triamino cage type macromolecular hydrogen bond organic framework material and the triamino cage type macromolecular hydrogen bond organic framework material prepared by the method. The material has the dual properties of macromolecules and hydrogen bond organic frameworks, and has wide application prospects in the fields of molecular recognition, catalysis, gas adsorption separation, drug delivery and the like. Background The triamino Cage type macromolecular hydrogen bond organic framework material (Cage-HOF) is a novel crystalline porous material formed by self-assembling organic macromolecules with specific three-dimensional Cage structures through intermolecular hydrogen bonding. The method is characterized in that the method has the main body recognition capability of a small molecular cage and the permanent porosity of an expanded framework structure. The material has the outstanding characteristics that firstly, the inherent three-dimensional cavity can realize high-selectivity identification and inclusion of guest molecules with specific size, shape or property, so that the material has great potential in the aspects of molecular identification, enantiomer separation, drug targeted delivery and the like, secondly, the steric hindrance effect of the rigid cage-shaped framework can effectively stabilize the molecular configuration, the stability of the material in thermal and chemical environments is improved, the possibility is provided for the application of the material under severe conditions, and in addition, the structural designability is extremely strong, and the polarity, the size and the host-guest interaction of the cavity can be finely regulated and controlled by carrying out precise modification on the cage wall (especially introducing functional groups such as amino groups) so as to adapt to different application scenes such as catalysis, sensing, gas storage and separation. In particular, the introduction of amino groups not only provides hydrogen bond donor/acceptor sites for the material to construct a stable HOF structure, but also provides reactive sites for subsequent functional modification of the material. Therefore, developing a high-efficiency and simple synthesis method to obtain a high-purity and well-defined triamino cage-type macromolecule and further constructing a hydrogen bond organic framework material is one of the research hot spots of the current supermolecular chemistry and material chemistry. In the prior art, construction of such tri-amino containing cage macromolecules generally relies on synthesis of a key intermediate, the trichloro cage macromolecule. The traditional trichloro cage type macromolecule synthesis strategy adopts a two-step method. The method takes 1,3, 5-tri (4-hydroxyphenyl) benzene and cyanuric chloride as starting materials, the first step needs to strictly control the reaction condition at low temperature, so that one chlorine atom on cyanuric chloride and one phenolic hydroxyl group on 1,3, 5-tri (4-hydroxyphenyl) benzene undergo nucleophilic substitution reaction to obtain a partially substituted linear or dendritic intermediate, and the step is often accompanied with various side reactions, and the intermediate needs to be separated and purified by column chromatography. And secondly, carrying out intramolecular cyclization or reaction with another molecular raw material on the purified intermediate under proper conditions, and carrying out complex operations such as column chromatography and the like again to finally obtain the target trichlorocage type macromolecule. As shown in FIG. 1, the conventional two-step method has a plurality of inherent defects that (1) two independent chemical reactions are involved, and at least two column chromatography purification are carried out, so that the whole experiment period is long, and the operation complexity is high. (2) The multi-step reaction implies more raw material, solvent and reagent consumption, and more energy consumption. The separation and purification process of the intermediate is time-consuming, and a large amount of waste liquid is generated, so that the method does not accord with the concept of green chemistry. (3) The yield loss exists in each chemical reaction, and the transfer and purification process of the intermediate also causes unavoidable material loss, so that the final total yield is usually low, and the large-scale preparation and subsequent application research of the intermediate are severely limited. Therefore, a method capable of directly and efficiently constructing the trichloro cage type macromolecule and further conveniently preparing the triamino cage type macromolecule hydrogen bond organic framework materi