CN114561022B - Chiral Cd-MOFs material and preparation method thereof - Google Patents
Chiral Cd-MOFs material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of chiral metal-organic framework materials, and discloses a chiral Cd-MOFs material and a preparation method thereof. Mixing 1, 2-cyclohexane diamine, triethylamine and anhydrous dichloromethane, adding an anhydrous dichloromethane solution of oxalyl chloride monoethyl ester for reaction, and performing alkaline hydrolysis on the prepared intermediate product to obtain a chiral carboxylic acid ligand; dissolving chiral carboxylic acid ligand and 4,4' -bipyridine in N, N-dimethylformamide, adding cadmium nitrate tetrahydrate and water, and heating to react to obtain the chiral Cd-MOFs material. The chiral Cd-MOFs material has permanent porosity, large specific surface area and uniform chiral space, and has good stability in common organic solvents.
Description
Technical Field
The invention relates to the technical field of chiral metal-organic framework materials, in particular to a chiral Cd-MOFs material and a preparation method thereof.
Background
Chiral metal-organic frameworks (MOFs) are a major component of chiral hybrid inorganic-organic materials, which have attracted considerable attention by researchers at this stage. In particular, in recent years, these chiral porous materials can be synthesized by various methods and used for various asymmetric applications such as catalysis, separation, luminescence recognition, and the like. MOFs with homogeneous chiral elements, permanent porosity and diversified structures with chiral resolution capability are very suitable as Chiral Stationary Phases (CSP) in chiral resolution. In recent studies, the great potential of some MOFs as CSPs in the resolution of enantiomers by gas phase (GC), capillary Electrophoresis (CE) and High Performance Liquid Chromatography (HPLC) has been reported, and for example, the yuanmin university topic group at yunnan university, the treigy topic group at shanghai transportation university, the zhonghong talent topic group at texas university in the united states, and the like all make important contributions in the research and application of chiral metal-organic frameworks.
However, the existing synthesis method of chiral MOFs is complex, the prepared chiral MOFs particles are irregular in shape and wide in size distribution, and the existing chiral MOFs lack of a proper chiral ligand, so that the separation efficiency is low when the chiral MOFs is used for CSP, and the wide application of the chiral MOFs material is limited.
Therefore, how to provide a chiral MOFs material with a stable structure and excellent separation performance has important significance.
Disclosure of Invention
The invention aims to provide a chiral Cd-MOFs material and a preparation method thereof, and solves the problem that the preparation process of the chiral MOFs material provided by the prior art is complex.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a chiral Cd-MOFs material, which comprises the following steps:
(1) Preparation of intermediate product: mixing 1, 2-cyclohexanediamine, triethylamine and anhydrous dichloromethane, then adding an anhydrous dichloromethane solution of oxalyl chloride monoethyl ester for reaction, and after the reaction is finished, extracting, drying and purifying a product to obtain an intermediate product;
(2) Preparation of chiral carboxylic acid ligand: dissolving the intermediate product in a mixed solution of ethanol and water, adding sodium hydroxide for reaction, adjusting the pH value to be less than or equal to 1 after the reaction is finished, carrying out reduced pressure rotary evaporation to obtain a product, and filtering, washing and drying the product to obtain a chiral carboxylic acid ligand;
(3) Preparing a chiral Cd-MOFs material: dissolving chiral carboxylic acid ligand and 4,4' -bipyridine in N, N-dimethylformamide, and then adding cadmium nitrate tetrahydrate and water for reaction to obtain the chiral Cd-MOFs material.
Preferably, in the above method for preparing chiral Cd-MOFs material, the 1, 2-cyclohexanediamine in the step (1) is (1R, 2R) -cyclohexane-1, 2-diamine or (1S, 2S) -cyclohexane-1, 2-diamine.
Preferably, in the above preparation method of chiral Cd-MOFs materials, the molar ratio of 1, 2-cyclohexanediamine, triethylamine and oxalyl chloride monoethyl ester in step (1) is 1:1 to 5:1 to 6; the volume ratio of the anhydrous dichloromethane solution of the anhydrous dichloromethane and the oxalyl chloride monoethyl ester is 4-6: 1.
preferably, in the above preparation method of chiral Cd-MOFs, the protective gas reacted in step (1) is argon; the reaction temperature is 0-5 ℃; the reaction time is 6-12 h.
Preferably, in the above preparation method of chiral Cd-MOFs materials, the molar ratio of the intermediate product to the sodium hydroxide in step (2) is 1:1 to 5; the reaction temperature is 85-95 ℃; the reaction time is 10-14 h.
Preferably, in the above preparation method of chiral Cd-MOFs materials, the molar ratio of the chiral carboxylic acid ligand, 4' -bipyridine and cadmium nitrate tetrahydrate in step (3) is 1:0.5 to 2:0.5 to 4.
Preferably, in the preparation method of the chiral Cd-MOFs material, the reaction temperature in the step (3) is 80-120 ℃; the reaction time is 1 to 5 days.
The invention also provides a chiral Cd-MOFs material prepared by the preparation method.
In the invention, cadmium ions in the chiral Cd-MOFs material are heptadentate, and comprise six oxygen atoms from different ligands and a nitrogen atom of a 4,4 '-bipyridyl auxiliary ligand, the cadmium ions are connected into a one-dimensional chain through a chiral carboxylic acid main ligand, and then are connected into a two-dimensional reticular metal framework organic material through the 4,4' -bipyridyl.
Through the technical scheme, compared with the prior art, the invention has the following beneficial effects:
the chiral Cd-MOFs material has permanent porosity, large specific surface area and uniform chiral space, and has good stability in common organic solvents; the material can be used as chiral filler after simple mechanical treatment, is used for chiral resolution, and has wide application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a diagram of an asymmetric unit of the chiral Cd-RMOFs material of example 1;
FIG. 2 is a three-dimensional structure diagram of the chiral Cd-RMOFs material of example 1;
FIG. 3 is a thermogram of the chiral Cd-RMOFs material of example 1;
FIG. 4 is a graph of nitrogen adsorption desorption of the chiral Cd-RMOFs material of example 1;
FIG. 5 is an XRD pattern of chiral Cd-RMOFs material of example 1 after soaking in different solvents for 7 days.
Detailed Description
The invention provides a preparation method of a chiral Cd-MOFs material, which comprises the following steps:
(1) Preparation of intermediate product: mixing 1, 2-cyclohexanediamine, triethylamine and anhydrous dichloromethane, then adding an anhydrous dichloromethane solution of oxalyl chloride monoethyl ester for reaction, and after the reaction is finished, extracting, drying and purifying a product to obtain an intermediate product;
(2) Preparation of chiral carboxylic acid ligand: dissolving the intermediate product in a mixed solution of ethanol and water, adding sodium hydroxide, heating for reaction, adjusting the pH to be less than or equal to 1 after the reaction is finished, carrying out reduced pressure rotary evaporation to obtain a product, filtering, washing and drying the product to obtain a chiral carboxylic acid ligand;
(3) Preparing a chiral Cd-MOFs material: dissolving chiral carboxylic acid ligand and 4,4' -bipyridine in N, N-dimethylformamide, adding cadmium nitrate tetrahydrate and water for reaction, and filtering, washing and drying a product after the reaction is finished to obtain the chiral Cd-MOFs material.
In the present invention, the 1, 2-cyclohexanediamine in the step (1) is preferably (1R, 2R) -cyclohexane-1, 2-diamine or (1S, 2S) -cyclohexane-1, 2-diamine, and more preferably (1R, 2R) -cyclohexane-1, 2-diamine.
In the present invention, the molar ratio of 1, 2-cyclohexanediamine, triethylamine and oxalyl chloride monoethyl ester in step (1) is preferably 1:1 to 5:1 to 6, more preferably 1:1.3 to 4.6:2 to 5, more preferably 1:2.7:3.
in the present invention, the volume ratio of the anhydrous dichloromethane solution of anhydrous dichloromethane and oxalyl chloride monoethyl ester in the step (1) is preferably 4 to 6:1, more preferably 4.3 to 5.7:1, more preferably 4.9:1.
in the present invention, the concentration of the oxalyl chloride monoethyl ester in anhydrous dichloromethane in the step (1) is preferably 5 to 7mol/L, more preferably 5.1 to 6.8mol/L, and still more preferably 5.9mol/L.
In the present invention, the protective gas for the reaction in step (1) is preferably argon; the reaction temperature is preferably 0 to 5 ℃, more preferably 1 to 4 ℃, and even more preferably 2 ℃; the reaction time is preferably 6 to 12 hours, more preferably 7 to 10 hours, and still more preferably 8 hours.
In the present invention, the extractant extracted in step (1) is preferably dichloromethane; the drying is preferably performed using anhydrous magnesium sulfate.
In the present invention, the purification of step (1) is preferably silica gel column purification; the purified eluent is preferably petroleum ether and ethyl acetate; the volume ratio of petroleum ether to ethyl acetate is preferably 3:1.
in the present invention, the volume ratio of ethanol to water in step (2) is preferably 1:1.
in the present invention, the mass-to-volume ratio of the intermediate product to the mixed solution in the step (2) is preferably 3 to 10g:50 to 80mL, more preferably 4 to 9g:55 to 76mL, more preferably 6g:60mL.
In the present invention, the molar ratio of the intermediate product to sodium hydroxide in the step (2) is preferably 1:1 to 5, more preferably 1:2 to 4, more preferably 1:2.5.
in the present invention, the temperature of the reaction in step (2) is preferably 85 to 95 ℃, more preferably 87 to 93 ℃, and still more preferably 89 ℃; the reaction time is preferably 10 to 14 hours, more preferably 11 to 13 hours, and still more preferably 12 hours.
In the present invention, the structural formula of the chiral carboxylic acid ligand in step (2) is one of the following structural formulas:
in the present invention, the molar ratio of the chiral carboxylic acid ligand, 4' -bipyridine and cadmium nitrate tetrahydrate in step (3) is preferably 1:0.5 to 2:0.5 to 4, more preferably 1:0.7 to 1.6:1.1 to 3.2, more preferably 1:1.2:2.5.
in the present invention, the molar volume ratio of the chiral carboxylic acid ligand, N-dimethylformamide and water in step (3) is preferably 1 to 3mmol:100mL of: 400 to 500mL, more preferably 1.2 to 2.6mmol:100mL of: 420 to 490mL, more preferably 2.3mmol:100mL of: 470mL.
In the present invention, the temperature of the reaction in step (3) is preferably 80 to 120 ℃, more preferably 87 to 114 ℃, and still more preferably 96 ℃; the reaction time is preferably 1 to 5 days, more preferably 1.2 to 4.5 days, and still more preferably 3 days.
The invention also provides a chiral Cd-MOFs material prepared by the preparation method.
The invention also provides application of the chiral Cd-MOFs material in the resolution of dihydropyrimidinone derivatives in high performance liquid chromatography. The principle of chiral separation of the chiral Cd-MOFs material on the dihydropyrimidinone derivatives is to realize the separation of the dihydropyrimidinone enantiomers by constructing the combination effect of strong hydrogen bonds between the chiral material and a stationary phase-split object and utilizing the high specific surface area of the chiral material structure and the stereoselectivity of the material.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a chiral R-Cd-MOFs material, and a preparation method thereof comprises the following steps:
(1) Chiral carboxylic acid ligands R-H 2 L was prepared as follows:
under the protection of argon, (1R, 2R) -cyclohexane-1, 2-diamine (5.709g, 0.05mol) and triethylamine (21mL, 0.15mol) are dissolved into a colorless and transparent mixed solution by using 100mL of anhydrous dichloromethane; then, 20mL of an anhydrous dichloromethane solution containing oxalyl chloride monoethyl ester (14.336g, 0.105mol) was added dropwise; stirring and reacting for 8 hours at 0 ℃ after the dropwise adding is finished to obtain a light yellow solid-liquid mixture; with 150mL saturated NaHCO 3 After quenching the solution, the yellow organic phase is isolated by extraction with dichloromethane and over anhydrous MgSO 4 The organic phase is dried and then spin-dried over silica gel, and the crude product obtained is purified over a silica gel column (eluent is PE and EA in a volume ratio of 3;
intermediate R-1 (6.283g, 0.02mol) was dissolved in 50mL of ethanol and water at a volume ratio of 1:1, adding sodium hydroxide (2g, 0.05mol), heating to 90 ℃ for reaction for 12H, adjusting the pH to be less than or equal to 1 by using hydrochloric acid after the reaction is finished, carrying out reduced pressure rotary evaporation to obtain a product, filtering the product, washing the product for 5 times by using water, and drying to obtain the chiral carboxylic acid ligand R-H 2 L (3.215 g, 63% yield);
(2) Preparing a chiral R-Cd-MOFs material: chiral carboxylic acid ligand R-H 2 L (25.8mg, 0.01mmol), 4' -bipyridine (15.6mg, 0.01mmol) are dissolved in 1mLN, N-dimethylformamide, then tetrahydrate of cadmium nitrate (30.8mg, 0.01mmol) and 5mL of water are added, the mixture is heated to 90 ℃ for reaction for 36h, and after the reaction is finished, a product is filtered, washed by ethanol for 5 times and dried to obtain the chiral R-Cd-MOFs material (the yield is 35%).
The crystal structure data of the chiral R-Cd-MOFs material is shown in Table 1.
TABLE 1 Crystal Structure data of chiral R-Cd-MOFs materials
The asymmetric unit diagrams and the three-dimensional structure diagrams of the chiral R-Cd-MOFs material are shown in FIGS. 1 and 2. As can be seen from FIGS. 1 and 2, the cadmium ions in the chiral R-Cd-MOFs material are heptadentate and comprise six oxygen atoms from the chiral carboxylic acid ligands and a nitrogen atom of a 4,4' -bipyridyl auxiliary ligand, wherein two oxygen atoms in one carboxylic acid terminal group in one chiral carboxylic acid ligand are coordinated with the same cadmium ion. The material of the invention connects cadmium ions into a one-dimensional chain through a chiral carboxylic acid main ligand, and then connects the one-dimensional chain into a two-dimensional reticular metal framework organic material through 4,4' -bipyridyl.
The chiral R-Cd-MOFs material is subjected to thermal analysis, nitrogen adsorption and desorption, and XRD test after being soaked in different solvents for 7 days, and the results are shown in figures 3-5. As shown in FIGS. 3 to 5, the chiral R-Cd-MOFs material has good stability at a temperature below 300 ℃ and good stability in different solvents due to the stacking of layer structures.
Example 2
This example provides a chiral R-Cd-MOFs material, and the preparation method is as in example 1, except that in step (2), a chiral carboxylic acid ligand R-H 2 L is 0.01mmol, 4' -bipyridine is 0.02mmol, and cadmium nitrate tetrahydrate is 0.03mmol.
Example 3
The embodiment provides a chiral R-Cd-MOFs material, and the preparation method is shown in the embodiment 2, except that the heating reaction in the step (2) is carried out at the temperature of 95 ℃ for 3 days.
Example 4
This example provides a chiral S-Cd-MOFs material, which was prepared as described in example 1, except that (1r, 2r) -cyclohexane-1, 2-diamine was replaced with (1s, 2s) -cyclohexane-1, 2-diamine in step (1).
The crystal structure data of the chiral S-Cd-MOFs material are as follows: triclinic system, chiral space group P1, and cell parameters of
α＝102.625(2)°,β＝109.1300(10)°,γ＝90.213(2)°,
Example 5
This example provides a chiral S-Cd-MOFs material, and the preparation method is as in example 4, except that in step (2), the chiral carboxylic acid ligand S-H 2 L is 0.01mmol, 4' -bipyridine is 0.015mmol, and cadmium nitrate tetrahydrate is 0.04mmol.
Example 6
The embodiment provides a chiral S-Cd-MOFs material, and the preparation method is shown in embodiment 5, except that the heating reaction in the step (2) is carried out at 85 ℃ for 2 days.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A preparation method of a chiral Cd-MOFs material is characterized by comprising the following steps:
(1) Preparation of intermediate product: mixing 1, 2-cyclohexanediamine, triethylamine and anhydrous dichloromethane, then adding an anhydrous dichloromethane solution of oxalyl chloride monoethyl ester for reaction, and after the reaction is finished, extracting, drying and purifying a product to obtain an intermediate product;
(2) Preparation of chiral carboxylic acid ligand: dissolving the intermediate product in a mixed solution of ethanol and water, adding sodium hydroxide for reaction, adjusting the pH value to be less than or equal to 1 after the reaction is finished, carrying out reduced pressure rotary evaporation to obtain a product, and filtering, washing and drying the product to obtain a chiral carboxylic acid ligand;
(3) Preparing a chiral Cd-MOFs material: dissolving chiral carboxylic acid ligand and 4,4' -bipyridine in N, N-dimethylformamide, and then adding cadmium nitrate tetrahydrate and water for reaction to obtain the chiral Cd-MOFs material.
2. The method for preparing chiral Cd-MOFs material according to claim 1, wherein the 1, 2-cyclohexanediamine in step (1) is (1R, 2R) -cyclohexane-1, 2-diamine or (1S, 2S) -cyclohexane-1, 2-diamine.
3. The method for preparing chiral Cd-MOFs materials according to claim 1 or 2, wherein the molar ratio of 1, 2-cyclohexanediamine, triethylamine and oxalyl chloride monoethyl ester in the step (1) is 1:1 to 5:1 to 6; the volume ratio of the anhydrous dichloromethane solution of the anhydrous dichloromethane and the oxalyl chloride monoethyl ester is (4-6): 1.
4. the method for preparing chiral Cd-MOFs materials according to claim 3, wherein the protective gas reacted in the step (1) is argon; the reaction temperature is 0-5 ℃; the reaction time is 6-12 h.
5. The method for preparing chiral Cd-MOFs materials according to claim 1 or 4, wherein the molar ratio of the intermediate product to the sodium hydroxide in the step (2) is 1:1 to 5; the reaction temperature is 85-95 ℃; the reaction time is 10-14 h.
6. The method for preparing chiral Cd-MOFs materials according to claim 1 or 2, wherein the molar ratio of the chiral carboxylic acid ligand, 4' -bipyridine and cadmium nitrate tetrahydrate in step (3) is 1:0.5 to 2:0.5 to 4.
7. The method for preparing the chiral Cd-MOFs material according to claim 6, wherein the reaction temperature in the step (3) is 80-120 ℃; the reaction time is 1 to 5 days.
8. A chiral Cd-MOFs material prepared by the preparation method of any one of claims 1 to 7.
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Citations (2)
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|---|---|---|---|---|
| CN106166482A (en) * | 2016-07-07 | 2016-11-30 | 安庆师范大学 | The preparation and application of novel chiral MOF skeleton chromatographic column |
| CN110862404A (en) * | 2019-04-02 | 2020-03-06 | 云南农业大学 | Metal organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106166482A (en) * | 2016-07-07 | 2016-11-30 | 安庆师范大学 | The preparation and application of novel chiral MOF skeleton chromatographic column |
| CN110862404A (en) * | 2019-04-02 | 2020-03-06 | 云南农业大学 | Metal organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl and preparation method thereof |
Non-Patent Citations (3)
| Title |
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| Chiral metal-organic framework as a platform for cooperative catalysis in asymmetric cyanosilylation of aldehydes;Chengfeng Zhu et al.;《ACS Catalysis》;20161002;第6卷(第11期);7590-7596 * |
| Supramolecular design of coordination complexes of silver(I) and cadmium(II) with chiral bidentate bridging ligands;Qi-Long Zhang et al.;《Polyhedron》;20131015;第68卷;40-45 * |
| Synthesis and Crystallographic Characterization of Chiral Bis-oxazoline-amides. Fine-Tunable Ligands for Pd-Catalyzed Asymmetric Alkylations;Vincenzo Giulio Albano et al.;《J. Org. Chem.》;20060726;第71卷;6451-6458 * |
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