CN112958160A - Rare earth metal-organic framework material catalyst and preparation and application thereof - Google Patents
Rare earth metal-organic framework material catalyst and preparation and application thereof Download PDFInfo
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- CN112958160A CN112958160A CN202110253274.1A CN202110253274A CN112958160A CN 112958160 A CN112958160 A CN 112958160A CN 202110253274 A CN202110253274 A CN 202110253274A CN 112958160 A CN112958160 A CN 112958160A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C253/00—Preparation of carboxylic acid nitriles
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- C07—ORGANIC CHEMISTRY
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- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/06—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups by reactions not involving the formation of carbamate groups
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/322—Hydrocyanation
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/38—Lanthanides other than lanthanum
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Abstract
The invention relates to a catalyst preparation technology, and aims to provide a rare earth metal-organic framework material catalyst, and preparation and application thereof. The structural formula of the catalyst is as follows: [ Ln2(HCOO)2(bct)2]·H2O (Ln = Tb (1), Eu (2), Gd (3)), wherein: bct is 3,5-bis (4' -carboxy-phenyl) -1,2, 4-triazole. The invention is catalyticThe active initiation center structure of the catalyst is an unsaturated coordinated Lewis acid metal site with high concentration on the inner surface, and can efficiently catalyze the strecker reaction of aldimine and trimethylsilanolate.
Description
Technical Field
The invention relates to a catalyst preparation technology, in particular to preparation of a novel rare earth metal-organic framework material catalyst and application thereof. In particular to a preparation technology and application of a rare earth metal-organic framework material catalyst with a catalytic activity center of coordination unsaturated rare earth metal sites (rare earth metals comprise Eu, Tb and Gd) and capable of catalyzing a series of aldimine to react with Trimethylsilylcyanide (TMSCN).
Background
Alpha-amino nitrile is an important intermediate for synthesizing various amino acids and is widely applied to the fields of biology, medicine and the like. The most common and used preparation method is the Strecker reaction between aldimine and Trimethylsilylcyanide (TMSCN). The Lewis acid is a catalyst commonly used in Strecker reaction, and can effectively improve the nucleophilic addition activity of trimethylsilylcyanide to imine and carbonyl double bonds. Conventional LouisThe silicic acid is AlCl3，BF3，TiCl4，SnCl4However, the defects of sensitivity to water, low catalytic efficiency and non-recyclability limit the wider application of the catalyst. Therefore, the development and development of a recyclable catalyst which is environmentally friendly and has a high catalytic yield under mild reaction conditions is imminent.
Rare earth Metal ions and organic ligands form a rare earth Metal-organic framework Material (MOFs) through coordination self-assembly, and because the rare earth Metal ions are not filled with 4f electrons, coordination unsaturated rare earth Metal sites can be used as potential Lewis acid sites; the adjustable pore size provides possibility for enriching substrates and improving product selectivity, so that the rare earth metal-organic framework material as a high-efficiency recyclable catalyst for catalyzing Strecker reaction becomes potential.
The invention reports a novel rare earth metal-organic framework material catalyst, wherein the inner surface of the catalyst is provided with high-concentration coordinated unsaturated rare earth metal as Lewis acid sites, so that Strecker reaction for efficiently catalyzing aldimine at room temperature can be realized.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a rare earth metal-organic framework material catalyst and preparation and application thereof.
In order to solve the technical problem, the solution of the invention is as follows:
the rare earth metal-organic framework material catalyst is provided, and the structural expression of the active component of the catalyst is as follows:
[Ln2(HCOO)2(bct)2]·H2O (Ln＝Tb(1),Eu(2),Gd(3)) (1)
in the formula: bct is 3,5-bis (4' -carboxy-phenyl) -1,2,4-triazole
In the invention, the rare earth metal-organic framework material catalyst is a compound 1-3([ Ln)2(HCOO)2(bct)2]·H2Single crystal X-ray diffraction analysis of O (Ln ═ Tb (1), Eu (2), Gd (3))) showed that they are isostructural, with their 3D backbone composed of dense, framework[Ln2(HCOO)2]∞2D layer passing bct2-Bridging ligands are linked. The crystal system of the compound 1 is an orthorhombic system, and the space group is Pnma. Compound 1 contains 1 Tb in the asymmetric unit3+1 bct2-Ligand, 1 formate anion and 1 lattice water molecule. Tb3+The ion center is eight coordinates, and adopts a slightly distorted double-cap triangular prism coordination geometrical configuration: in which 4 oxygen atoms are from 4 bct2-The anion, the other 4 oxygen atoms are from 2 formate anions. The formate anion adopts a chelating and bridging coordination mode, and bct2-The two carboxyl groups of the anion adopt a coordination mode of monoatomic chelation.
The invention further provides the rare earth metal-organic framework material catalyst, which comprises the following specific preparation steps:
0.067 mmol Ln (NO)3)3And 0.129 mmole of H2bct was added to a solution of 6 ml DMF and 4 ml H2In the inner lining of O polytetrafluoroethylene reaction kettle, 6 mol of HNO is used3The pH of the solution is adjusted to about 4, the solution is stirred for half an hour, the solution is filled into a reaction kettle and placed in an oven at 170 ℃ for 3 days. And carrying out suction filtration and washing to obtain a filter cake, and drying the filter cake in a vacuum oven to constant weight to obtain the active component of the catalyst.
Said H2The structural formula of bct is:
3,5-bis(4’-carboxy-phenyl)-1,2,4-triazole (2)
ln (NO) as described3)3＝Tb(NO3)3，Eu(NO3)3，Gd(NO3)3。
In the present invention, the pH range of the reaction solution is adjusted to 2 to 6.
The invention also provides a method for applying the rare earth metal-organic framework material catalyst, which is used as a catalyst for catalyzing Strecker reaction of aldimine and trimethylsilylcyanide.
In the invention, when the rare earth metal-organic framework material catalyst is used for catalyzing Strecker reaction, the reaction temperature is controlled to be about 25 ℃.
In the present invention, the aldimine is an aromatic aldimine (R) having different substituents1＝4-H,4-OMe,4-CH3,4-F,4-Cl,4-Br,4-NO2,2-NO2；R2＝Bn,Boc)。
Compared with the prior art, the invention has the following remarkable advantages and effects:
the invention provides a novel rare earth metal-organic framework material catalyst with rare earth metal Lewis acid as an active initiation center, wherein Lewis acid metal sites with high concentration on the inner surface provide possibility for efficiently catalyzing Strecker reaction of aldimine, and the rare earth metal-organic framework material catalyst is used as a heterogeneous catalyst, so that the problem of poor recoverability of the traditional homogeneous Lewis acid is solved.
Drawings
FIG. 1 is a structural formula of aldimine;
FIG. 2 is a schematic diagram of the coordination structure of Compound 1; FIG. 2(a) is Tb3+Ion coordination environment, Tb in FIG. 2(b)3+Ion center coordination geometry, FIG. 2(c) for formic acid and bct2-The coordination environment of the ligand.
FIG. 3 is a single crystal structural diagram of Compound 1; FIG. 3(a) is [ Tb ]2O2]SBU Structure diagram, FIG. 3(b) is [ Tb ]2(HCOO)2]An ∞ 2D layer structure, and FIG. 3(c) is a 3D structural diagram of Compound 1.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. 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:
0.067 millimole of Tb (NO)3)3And 0.129 mmole of H2bct was added to a solution of 6 ml DMF and 4 ml H2In the inner lining of O polytetrafluoroethylene reaction kettle, 6 mol of HNO is used3The solution was adjusted to pH 4, stirred for half an hour, charged to a reaction kettle, and placed in an oven at 170 ℃ for 3 days. And then filtering to obtain a filter cake, and drying to constant weight under a drying atmosphere to obtain the active component of the catalyst 1.
Example 2: strecker reaction of catalytic aldimine
0.125 mmol of trimethylsilylcyanide, 0.008 mmol of catalyst 1([ Tb ] was added in that order2(HCOO)2(bct)2]) And 0.05 mmol of aldimine were added in succession to a solution of 0.5 ml of CDCl3A standard 5 mm nmr tube. After that, the nuclear magnetic tube cap was covered and sealed with a teflon tape, and then inserted into a constant temperature water bath oscillator at room temperature. This reaction is carried out by1The H-NMR spectrum is monitored and the conversion of the product is determined from the ratio of the integral of the product signal to the sum of the integrals of all signals (aldimine and product).
The reaction results of catalyst 1 in example 2 are shown in Table 1.
Table 1: metal catalyst catalyzes strecker reaction of aldimine and trimethylsilylcyanide
a Reaction conditions:aldimine(0.05 mmol),TMSCN(0.125 mmol),catalyst 3(0.008 mmol),CDCl3(0.5mL)at room temperature.b％Yield calculatedby 1HNMR with aldimines.
Example 3:
0.067 mmol ofEu(NO3)3And 0.129 mmole of H2bct was added to a solution of 6 ml DMF and 4 ml H2In the inner lining of O polytetrafluoroethylene reaction kettle, 6 mol of HNO is used3The solution was adjusted to pH 4, stirred for half an hour, charged to a reaction kettle, and placed in an oven at 170 ℃ for 3 days. And then filtering to obtain a filter cake, and drying to constant weight under a drying atmosphere to obtain the active component of the catalyst 2.
Example 4:
0.067 mmol of Gd (NO)3)3And 0.129 mmole of H2bct was added to a solution of 6 ml DMF and 4 ml H2In the inner lining of O polytetrafluoroethylene reaction kettle, 6 mol of HNO is used3The solution was adjusted to pH 4, stirred for half an hour, charged to a reaction kettle, and placed in an oven at 170 ℃ for 3 days. And then filtering to obtain a filter cake, and drying to constant weight under a drying atmosphere to obtain the active component of the catalyst 3.
Claims (7)
1. A rare earth metal coordination polymer catalyst is characterized in that the structural formula of an active component of the catalyst is as follows:
[Ln2(HCOO)2(bct)2]·H2O (Ln =Tb(1), Eu(2), Gd(3)) （1）
in the formula: bct is 3,5-bis (4' -carboxy-phenyl) -1,2, 4-triazole.
2. The rare earth metal-organic framework material catalyst as claimed in claim 1, wherein the active component is a compound 1-3([ Ln ] Ln)2(HCOO)2(bct)2]·H2Single crystal X-ray diffraction analysis of O (Ln = Tb (1), Eu (2), Gd (3))) showed that they were isomorphic with a 3D backbone composed of dense [ Ln [2(HCOO)2]∞2D layer passing bct2-Bridged ligands are connected; the crystal system of the compound 1 is an orthorhombic system, and the space group isPnma; compound 1 contains 1 Tb in the asymmetric unit3+1 bct2-Ligand, 1 formate anion and 1 lattice water molecule; tb3+Ion center isEight coordinates, with a slightly distorted, double-capped triangular prism coordination geometry: in which 4 oxygen atoms are from 4 bct2-Anion, the other 4 oxygen atoms are from 2 formate anions; the formate anion adopts a chelating and bridging coordination mode, and bct2-The two carboxyl groups of the anion adopt a coordination mode of monoatomic chelation.
3. The rare earth metal-organic framework material catalyst according to claim 1, characterized by comprising the following specific steps: 0.067 mmol Ln (NO)3)3And 0.129 mmole of H2bct was added to a solution of 6 ml DMF and 4 ml H2In the inner lining of O polytetrafluoroethylene reaction kettle, 6 mol of HNO is used3Adjusting pH of the solution to 4, stirring for half an hour, placing into a reaction kettle, and stirring at 170 deg.CoC, placing the mixture in an oven for 3 days; then filtering to obtain a filter cake, and drying to constant weight under a drying atmosphere to obtain an active component of the catalyst;
said H2The structural formula of bct is:
3,5-bis(4’-carboxy-phenyl)-1,2,4-triazole （2）
ln (NO) as described3)3=Tb(NO3)3，Eu(NO3)3，Gd(NO3)3。
4. The method according to claim 3, wherein the pH of the reaction solution is adjusted to a pH in the range of 2 to 6.
5. The rare earth metal-organic framework material catalyst according to claim 1, wherein the catalyst is used for catalyzing Strecker reaction of aldimine and trimethylsilylcyanide.
6. The use of claim 5, wherein the rare earth metal-organic framework material catalyst is used for catalyzing a Strecker reaction, and the reaction temperature is controlled to be about 25 ℃.
7. Use according to claim 5, characterized in that said aldimine is an aromatic aldimine (R) containing different substituents1=4-H, 4- OMe, 4-CH3, 4-F, 4-Cl, 4-Br, 4-NO2, 2-NO2;R2=Bn, Boc）。
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757453A (en) * | 2012-07-16 | 2012-10-31 | 南开大学 | Multifunctional rare earth metal-organic framework and preparation method thereof |
| CN108722488A (en) * | 2018-05-04 | 2018-11-02 | 江苏师范大学 | A kind of bimetallic center metal-organic framework materials and preparation method thereof of enhancing lewis acidity |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757453A (en) * | 2012-07-16 | 2012-10-31 | 南开大学 | Multifunctional rare earth metal-organic framework and preparation method thereof |
| CN108722488A (en) * | 2018-05-04 | 2018-11-02 | 江苏师范大学 | A kind of bimetallic center metal-organic framework materials and preparation method thereof of enhancing lewis acidity |
Non-Patent Citations (1)
| Title |
|---|
| 王圣燕: ""稀土配位聚合物的合成、结构及荧光和催化性质研究"", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
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Application publication date: 20210615 |