CN114276507A - Preparation method of HOFs material containing amino and imine bond - Google Patents
Preparation method of HOFs material containing amino and imine bond Download PDFInfo
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- CN114276507A CN114276507A CN202111635760.6A CN202111635760A CN114276507A CN 114276507 A CN114276507 A CN 114276507A CN 202111635760 A CN202111635760 A CN 202111635760A CN 114276507 A CN114276507 A CN 114276507A
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- 239000000463 material Substances 0.000 title claims abstract description 20
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 125000003277 amino group Chemical group 0.000 claims abstract description 3
- -1 aldehyde compound Chemical class 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims 2
- 239000003513 alkali Substances 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 11
- 150000001299 aldehydes Chemical class 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 abstract description 2
- 125000000879 imine group Chemical group 0.000 abstract description 2
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 239000013384 organic framework Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000013310 covalent-organic framework Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of HOFs material containing amino and imine bond, which provides a synthesis condition of ethanol/water/hydroxide, takes dialdehyde or multi-aldehyde compound containing 2, 6-dialdehyde phenol unit as raw material, and reacts with primary amine synthon under the reaction condition to prepare the HOFs material containing amino and imine bond simultaneously. The synthesis condition provided by the invention is green and simple, and the prepared HOFs product does not need to be further purified and has good crystallinity. The method is suitable for combination of various aldehydes and amine derivatives, has good synthesis condition universality, and can prepare the HOFs material simultaneously containing amine groups and imine groups.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of an HOFs material containing amino and imine bonds.
Background
The porous material has wide application in the fields of adsorption, separation, catalysis, loading, energy sources and the like. Various types of porous materials are being designed and synthesized from traditional molecular sieves, activated carbon to the later Metal Organic frameworks (Metal Organic frameworks), aromatic Organic frameworks (aromatic Organic frameworks), Covalent Organic frameworks (Covalent Organic frameworks), and the like. Especially in recent decades, the preparation of novel porous materials based on the principle of molecular design from bottom to top has become the mainstream. As organic framework materials emerging in recent years, Hydrogen-bonded organic frameworks (HOFs) have the common characteristics of large specific surface area, various structures, adjustable pore channel shapes and sizes, modifiable pore surface and the like. In addition, the method has the following unique advantages: i. the preparation condition is mild. The preparation of the HOFs generally only needs to be synthesized by natural volatilization of a solvent, diffusion of a poor solvent into a good solvent, or temperature reduction and precipitation of a saturated solution. HOFs have better solution processability. The HOFs are materials in which small molecules are connected into a three-dimensional framework through reversible forces such as hydrogen bonds and pi-pi interaction, so that the materials can be prepared into materials in a required form, such as films, blocks and the like, in an in-situ dissolution-precipitation growth mode. i i HOFs have better self-healing capability and self-repairing capability. Also due to the reversibility of connecting bonds, the structural damage caused by the HOFs after multiple uses can be recovered by self-repairing or dissolving recrystallization synthesis. Most of the HOFs do not contain metal ions, and the metal-free property endows the HOFs with better biocompatibility and lower cytotoxicity, so that the HOFs show huge application potential in the biological field.
Despite the numerous advantages of HOFs, HOFs have their own limitations in the synthetic preparation process. For example, the crystal structure of the HOFs greatly depends on the kind and proportion of the crystallization solvent, which results in the need to spend a lot of manpower and time in the synthesis process of the HOFs material to screen the optimal crystallization conditions; secondly, the number of types of building elements for synthesizing the HOFs is relatively small, and the functional groups commonly used for building the HOFs structure at present comprise a limited number of types such as carboxyl, amino, sulfonic acid, amide, imidazole, guanidino, ureido and the like. This greatly limits the range of applications for HOFs materials.
Therefore, developing a universal synthesis strategy compatible with multiple functional groups is of great significance for HOFs.
Disclosure of Invention
The invention provides a simple, convenient and green synthesis strategy aiming at the problem that the existing hydrogen bond organic framework material construction unit has a single structure, and particularly the construction unit containing a multifunctional functional group is more scarce, and the hydrogen bond organic framework material containing multiple functional groups can be rapidly and massively prepared in a one-pot boiling manner.
In order to solve the technical problems, the invention adopts a technical scheme that:
an HOFs material containing amino and imine bond has a structure shown in formula (1):
wherein G is1Can be a structure containing aromatic rings and similar aromatic structures, as shown in formula (2):
G2can be an aromatic ring-containing structure or a hydrazine hydrate structure, and is shown as a formula (3):
a preparation method of the HOFs material containing the amino and the imine bond comprises the following steps:
dissolving 0.1-20 mmols of aldehyde compound (A) and 1-10 mmols of strong base compound (B) in a mixed solution of deionized water and ethanol, and refluxing and stirring at 70-95 ℃ for 12-24 hours;
weighing 1-10 mmols of primary amine compound (C) and dissolving in 10-200 mL of ethanol until the mixture is dissolved and clarified, adding into the mixture, continuing to perform reflux reaction for 12-24 h, closing the reaction, and cooling to room temperature;
directly filtering to obtain a target product (D) under the condition that powder is precipitated;
in the case of no powder precipitation, the clear solution is left for several days, and crystals, namely the target product (D), are precipitated after the solution is volatilized.
The process for preparing and synthesizing the HOFs material containing the amino and the imine bond by the method is as follows:
further, the aldehyde compound has a number of phenol groups ≧ 1.
Further, the aldehyde compound is a compound containing 2, 6-dialdehyde phenol unit and derivatives thereof.
Further, the strong base compound is L iOH, NaOH, or KOH.
Further, the primary amine compound is an aromatic amine compound or hydrazo hydrate
Further, the mixing volume ratio of the deionized water to the ethanol is 1: 1-1: 10.
Further, the volumes of the deionized water and the ethanol are both 10-200 mL.
The invention has the beneficial effects that: the method is suitable for combination of various aldehydes and amine derivatives, has good synthesis condition universality, and can prepare the HOFs material simultaneously containing amine groups and imine groups.
Drawings
FIG. 1 is a schematic diagram of the synthesis of HOFs of the present invention;
FIG. 2 is a schematic diagram of the synthesis of HOF-1 in example 1;
FIG. 3 is a hydrogen spectrum of HOF-1 in example 1 (400MHz, DMSO-d)6)；
FIG. 4 is a powder Scanning Electron Micrograph (SEM) of HOF-1 of example 1;
FIG. 5 is a schematic diagram of the synthesis of HOF-2 in example 2;
FIG. 6 is a hydrogen spectrum (400MHz, DMSO-d) of HOF-2 in example 26)；
FIG. 7 is a powder Scanning Electron Micrograph (SEM) of HOF-2 from example 2.
Detailed Description
The following detailed description of the preferred embodiments of the present invention, taken in conjunction with the accompanying drawings, will make the advantages and features of the invention easier to understand by those skilled in the art, and thus will clearly and clearly define the scope of the invention.
Example 1
As shown in FIG. 2, HOF-1 was synthesized as follows: tetraldehyde 1(596mg,2mmo l) and KOH (224mg,8mmo l) were dissolved in a mixed solvent of water and ethanol (5 mL of water, 20mL of ethanol), and reacted at 80 ℃ under reflux for 12 hours. P-phenylenediamine (216mg,2 mmol) was weighed out and dissolved in 20mL of ethanol, added to the above mixture, and allowed to react for 12 hours, then the reaction was stopped, and cooled to room temperature. Filtering and washing with water to obtain HOF-1 microcrystalline powder.
The nuclear magnetic hydrogen spectrum of HOF-1 is shown in FIG. 3, and the SEM image of HOF-1 is shown in FIG. 4.
Example 2
As shown in FIG. 5, HOF-2 was synthesized as follows: tetraldehyde 1(596mg,2mmo l) and KOH (224mg,8mmo l) were dissolved in a mixed solvent of water and ethanol (10 mL of water and 30mL of ethanol), and reacted at 80 ℃ under reflux for 12 hours. Hydrazine hydrate (1000mg,20 mmol) is weighed and dissolved in 20mL ethanol, added into the mixture to continue reacting for 12h, then the reaction is stopped, cooled to room temperature, placed for 24h, and filtered to separate out transparent crystals, thus obtaining HOF-2.
The nuclear magnetic hydrogen spectrum of HOF-2 is shown in FIG. 6, and the SEM image of HOF-2 is shown in FIG. 7.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent structural changes made by using the contents of the present specification and the drawings, or applied directly or indirectly to other related technical fields, are included in the scope of the present invention.
Claims (8)
1. An HOFs material containing amino and imine bond has a structure shown in formula (1):
wherein G is1Can be a structure containing aromatic rings, as shown in formula (2):
G2can be an aromatic ring-containing structure or a hydrazine hydrate structure, and is shown as a formula (3):
2. a method for preparing the HOFs materials containing amine groups and imine bonds according to claim 1, characterized in that it comprises the following steps:
dissolving 0.1-20 mmol of aldehyde compound (A) and 1-10 mmol of strong base compound (B) in a mixed solution of deionized water and ethanol, and refluxing and stirring at 70-95 ℃ for 12-24 h;
weighing 1-10 mmol of primary amine compound (C), dissolving in 10-200 mL of ethanol until the solution is clear, adding into the mixture, continuing reflux reaction for 12-24 h, closing the reaction, and cooling to room temperature;
directly filtering to obtain a target product (D) under the condition that powder is precipitated;
in the case of no powder precipitation, the clear solution is left for several days, and crystals, namely the target product (D), are precipitated after the solution is volatilized.
3. The method according to claim 2, wherein said HOFs are selected from the group consisting of: the number of phenolic groups of the aldehyde compound is not less than 1.
4. The method according to claim 2, wherein said HOFs are selected from the group consisting of: the aldehyde compound is a phenol unit containing 2, 6-dialdehyde group and a derivative thereof.
5. The method according to claim 2, wherein said HOFs are selected from the group consisting of: the strong alkali compound is LiOH, NaOH or KOH.
6. The method according to claim 2, wherein said HOFs are selected from the group consisting of: the primary amine compound is an aromatic amine compound or hydrazine hydrate.
7. The method according to claim 2, wherein said HOFs are selected from the group consisting of: the mixing volume ratio of the deionized water to the ethanol is 1: 1-1: 10.
8. The method according to claim 2, wherein said HOFs are selected from the group consisting of: the volumes of the deionized water and the ethanol are 10-200 mL.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3946033A (en) * | 1972-11-24 | 1976-03-23 | Teijin Ltd. | Process for the preparation of hydantoin derivatives |
| CN109569026A (en) * | 2018-01-11 | 2019-04-05 | 南开大学 | It prepares the chromatographic stationary phases that porous framework material is matrix and is used for chiral separation |
| WO2020252536A1 (en) * | 2019-06-19 | 2020-12-24 | The University Of Adelaide | Hydrogen-bonded organic framework systems |
| CN112209849A (en) * | 2020-10-29 | 2021-01-12 | 西北师范大学 | Synthesis and application of fluorescent sensor capable of singly and selectively identifying methylbenzene |
-
2021
- 2021-12-29 CN CN202111635760.6A patent/CN114276507A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3946033A (en) * | 1972-11-24 | 1976-03-23 | Teijin Ltd. | Process for the preparation of hydantoin derivatives |
| CN109569026A (en) * | 2018-01-11 | 2019-04-05 | 南开大学 | It prepares the chromatographic stationary phases that porous framework material is matrix and is used for chiral separation |
| WO2020252536A1 (en) * | 2019-06-19 | 2020-12-24 | The University Of Adelaide | Hydrogen-bonded organic framework systems |
| CN112209849A (en) * | 2020-10-29 | 2021-01-12 | 西北师范大学 | Synthesis and application of fluorescent sensor capable of singly and selectively identifying methylbenzene |
Non-Patent Citations (3)
| Title |
|---|
| HOU, LX，等: "Highly Stable Single Crystals of Three-Dimensional Porous Oligomer Frameworks Synthesized under Kinetic Conditions", 《ANGEWANDTE CHEMIE-INTERNATIONAL EDITION》 * |
| LUO，J，等: "Hydrogen-bonded organic frameworks: design, structures and potential applications", 《CRYSTENGCOMM》 * |
| 甘世贤: "两种新型晶态有机多孔材料的构筑及其性质研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
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Application publication date: 20220405 |