Application of a decanuclear 3d-4f supramolecular nanocage material in catalyzing three-component strecker reaction
By using decanuclear 3d-4f supramolecular nanocage material catalysts, the problems of low efficiency and easy deactivation of heterogeneous Lewis acid catalysts in the Strecker reaction were solved, achieving efficient and stable catalytic effects suitable for industrial production.
Patent Information
- Application Number
- CN202311853095.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-12-29
- Publication Date
- 2026-01-27
- Estimated Expiration
- 2043-12-29
AI Technical Summary
Existing heterogeneous Lewis acid catalysts exhibit low catalytic efficiency, are prone to deactivation, have high loading of catalytic active components, and have long reaction times in the catalytic process of the Strecker reaction.
Using decanuclear 3d-4f supramolecular nanocages as catalysts, the reaction was carried out by mixing them with amino compounds, aldehyde compounds and trimethylsilyl cyanide in a solvent, and the reaction conditions were optimized to catalyze the three-component Strecker reaction.
The Strecker reaction, characterized by high catalytic activity, stability, and high yield, has been achieved, simplifying the operation steps, reducing reaction time, and making it suitable for industrial production.
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Figure CN117820165B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of homogeneous catalysis technology, and in particular to the application of a decanuclear 3d-4f supramolecular nanocage material in the catalytic three-component Strecker reaction. Background Technology
[0002] Among various Lewis acid-catalyzed organic transformations, the three-component Strecker reaction is an important CN-bond formation reaction, and its product, α-aminonitrile, is a valuable and widely used synthon in organic synthesis, serving as a superior scaffold in medicinal chemistry and pharmacology. Traditionally, heterogeneous Lewis acid catalysts have been used to catalyze the Strecker reaction, but they often face the key challenges of loss of activity and low efficiency. Metal-organic cages can form a special cavity that accelerates the Strecker reaction and produces unusual selectivity. Unfortunately, few have been reported to date, making the design and synthesis of metal-supramolecular nanocages of great significance, as they will significantly improve catalytic efficiency.
[0003] Therefore, how to develop a decanuclear 3d-4f supramolecular nanocage material with high catalytic activity as an artificial enzyme to promote multi-component catalytic activity has become an urgent problem to be solved by those skilled in the art. Summary of the Invention
[0004] The purpose of this invention is to provide an application of decanuclear 3d-4f supramolecular nanocage material in the catalytic three-component Strecker reaction, in order to solve the problems of low catalytic efficiency, long catalytic reaction time, high loading of catalytic active components, and easy deactivation during the catalytic process of existing heterogeneous Lewis acid catalysts used to catalyze the Strecker reaction.
[0005] To achieve the above objectives, the present invention adopts the following technical solution:
[0006] This invention provides an application of decanuclear 3d-4f supramolecular nanocage materials in catalyzing a three-component Strecker reaction, comprising the following steps:
[0007] The decanuclear 3d-4f supramolecular nanocage material, amino compound, aldehyde compound, trimethylsilyl cyanide and solvent are mixed and reacted to obtain the target product, thus completing the Strecker reaction.
[0008] Preferably, the amino compound includes one of aniline, p-chloroaniline, p-fluoroaniline, m-fluoroaniline, p-toluidine, p-tert-butylaniline, m-toluidine, p-aminophenethyl ether, m-tert-butylaniline, p-nitroaniline, and 1-naphthylamine.
[0009] Preferably, the aldehyde compound includes one of benzaldehyde, p-chlorobenzaldehyde, p-fluorobenzaldehyde, m-fluorobenzaldehyde, p-methylbenzaldehyde, p-tert-butylbenzaldehyde, m-methylbenzaldehyde, 4-ethoxybenzaldehyde, p-nitrobenzaldehyde, and 1-naphthaldehyde.
[0010] Preferably, the solvent includes methanol.
[0011] Preferably, the molar volume ratio of the amino compound, aldehyde compound, trimethylsilyl cyanide and solvent is 1 mmol: 1-1.2 mmol: 1-1.2 mmol: 4-6 mL.
[0012] Preferably, the amount of the decanuclear 3d-4f supramolecular nanocage material is 0.2 to 1 mol of the total amount of amino compound, aldehyde compound and trimethylsilyl cyanide.
[0013] Preferably, the reaction temperature is 20–30°C and the reaction time is 3–24 h.
[0014] As can be seen from the above technical solution, compared with the prior art, the beneficial effects of the present invention are as follows:
[0015] (1) The decanuclear 3d-4f supramolecular nanocage material used in this invention has a well-defined geometric structure. The large window facilitates the entry and exit of substrate and product molecules, and the abundant Lewis acid sites accelerate substrate transfer and provide stability. Compared with other homogeneous catalysts, the preparation method of this decanuclear 3d-4f supramolecular nanocage material is simple, has a high yield, and can be industrialized. It is structurally stable in solution, exists in the form of molecular cages, and can realize homogeneous catalysis of the three-component Strecker reaction.
[0016] (2) The application of the decanuclear 3d-4f supramolecular nanocage material in the catalytic three-component Strecker reaction is simple in operation, has high catalytic activity, requires mild reaction conditions, and has a short total reaction time, which can realize the industrial production of the target product. Attached Figure Description
[0017] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.
[0018] Figure 1The image shows a ball-and-stick diagram of the decanuclear 3d-4f metal-supramolecular nanocage material described in this invention, wherein the cyan ball represents zinc, the purple ball represents rare earth elements, the red ball represents oxygen, the green ball represents chlorine, the blue ball represents nitrogen, and the gray ball represents carbon.
[0019] Figure 2 This is a diagram illustrating the catalytic mechanism of the decanuclear 3d-4f supramolecular nanocage material described in this invention in the catalytic three-component Strecker reaction.
[0020] Figure 3 The carbon spectrum of the target product obtained in Example 1;
[0021] Figure 4 The image shows the hydrogen spectrum of the target product obtained in Example 1. Detailed Implementation
[0022] This invention provides an application of decanuclear 3d-4f supramolecular nanocage materials in catalyzing a three-component Strecker reaction, comprising the following steps:
[0023] The decanuclear 3d-4f supramolecular nanocage material, amino compound, aldehyde compound, trimethylsilyl cyanide and solvent are mixed and reacted to obtain the target product, thus completing the Strecker reaction.
[0024] In this invention, the amino compound includes one of aniline, p-chloroaniline, p-fluoroaniline, m-fluoroaniline, p-toluidine, p-tert-butylaniline, m-toluidine, p-aminophenethyl ether, m-tert-butylaniline, p-nitroaniline, and 1-naphthylamine.
[0025] In this invention, the aldehyde compound includes one of benzaldehyde, p-chlorobenzaldehyde, p-fluorobenzaldehyde, m-fluorobenzaldehyde, p-methylbenzaldehyde, p-tert-butylbenzaldehyde, m-methylbenzaldehyde, 4-ethoxybenzaldehyde, p-nitrobenzaldehyde, and 1-naphthaldehyde.
[0026] In this invention, the solvent includes methanol.
[0027] In this invention, the preferred molar volume ratio of the amino compound, aldehyde compound, trimethylsilyl cyanide and solvent is 1 mmol: 1-1.2 mmol: 1-1.2 mmol: 4-6 mL, more preferably 1 mmol: 1.1 mmol: 1.1 mmol: 5-5.5 mL, and even more preferably 1 mmol: 1.1 mmol: 1.1 mmol: 5.2-5.4 mL.
[0028] In this invention, the amount of the decanuclear 3d-4f supramolecular nanocage material is preferably 0.2-1 mol of the total amount of amino compound, aldehyde compound, and trimethylsilyl cyanide, more preferably 0.3-0.5 mol, and even more preferably 0.4-0.45 mol.
[0029] In this invention, the reaction temperature is preferably 20-30°C, more preferably 22-28°C, and even more preferably 25-26°C; the reaction time is preferably 3-24 hours, more preferably 6-20 hours, and even more preferably 14-16 hours.
[0030] In this invention, the equation for the reaction is:
[0031]
[0032] Where R is R1 is Cl, F, -CH3, -C(CH3)3, -OC2H5, or -NO2; R' is... R2 can be Cl, F, -CH3, -C(CH3)3, -OC2H5, or -NO2.
[0033] In this invention, the yield of the target product is calculated using column chromatography yield; the target product is a bioactive drug prodrug.
[0034] The preparation of the decanuclear 3d-4f supramolecular nanocage material includes the following steps:
[0035] (1) The intermediate product a was obtained by reacting methyl 3-aminopropionate, triethylamine, dichloromethane, and monoethyl oxalyl chloride in a dichloromethane solution.
[0036] (2) Intermediate product a, ethanol and hydrazine hydrate solution react to obtain intermediate product b;
[0037] (3) Intermediate b, 3,5-di-tert-butylsalicylaldehyde and ethanol react to obtain an asymmetric semi-rigid ligand;
[0038] (4) The decanuclear 3d-4f supramolecular nanocage material was obtained by reacting asymmetric semi-rigid ligands, zinc salts, rare earth salts, triethylamine and methanol.
[0039] In step (1) of the present invention, the molar ratio of methyl 3-aminopropionate, triethylamine and oxaloyl chloride monoethyl ester is preferably 1:1 to 5:0.9 to 6, more preferably 1:2 to 4:1.2 to 5.4, and even more preferably 1:3:2.6 to 3.2. The concentration of the dichloromethane solution of oxaloyl chloride monoethyl ester is preferably 0.8 to 6 mol / L, more preferably 1.2 to 4.7 mol / L, and even more preferably 2.6 to 3.3 mol / L. The volume ratio of dichloromethane to the dichloromethane solution of oxaloyl chloride monoethyl ester is preferably 4 to 6:1, more preferably 4.5 to 5.5:1, and even more preferably 5:1.
[0040] In step (1) of the present invention, the reaction is preferably carried out under a protective atmosphere, preferably argon, the reaction temperature is preferably 0-5°C, more preferably 1-4°C, more preferably 2-3°C, and the reaction time is preferably 12-24h, more preferably 16-22h, more preferably 18-20h.
[0041] In step (1) of the present invention, the product after reaction is preferably quenched, extracted, dried and purified in sequence; the quenching is preferably performed using sodium bicarbonate, the extraction is preferably performed using dichloromethane, and the drying is preferably performed using anhydrous calcium sulfate.
[0042] In step (2) of the present invention, the mass fraction of the hydrazine hydrate solution is preferably 75-85 wt%, more preferably 78-82 wt%, and even more preferably 80 wt%. The hydrazine hydrate solution is preferably an aqueous solution of hydrazine hydrate. The molar volume ratio of intermediate product a, ethanol and hydrazine hydrate is preferably 1 mol: 4.1-4.2 L: 2-6 mol, more preferably 1 mol: 4.1-4.2 L: 3-5 mol, and even more preferably 1 mol: 4.15 L: 4 mol.
[0043] In step (2) of the present invention, the reaction temperature is preferably 68-80°C, more preferably 70-78°C, and even more preferably 72-76°C. The reaction time is preferably 12-24h, more preferably 14-20h, and even more preferably 16-18h.
[0044] In step (2) of the present invention, the product after the reaction is preferably cooled, filtered, washed and dried in sequence; the cooling temperature is preferably 23-30°C, more preferably 25-28°C, and even more preferably 26-27°C; the washing is preferably done with ethanol, and the number of washings is preferably 3-6 times, more preferably 4-5 times; the drying is preferably done with anhydrous calcium sulfate.
[0045] In step (3) of the present invention, the molar volume ratio of intermediate product b, 3,5-di-tert-butylsalicylaldehyde and ethanol is preferably 1 mol: 2-6 mol: 4.8-5.2 L, more preferably 1 mol: 3-5 mol: 5 L, and even more preferably 1 mol: 4 mol: 5 L. The reaction is preferably a reflux reaction, the reflux reaction temperature is preferably 76-80°C, more preferably 77-79°C, and even more preferably 78°C. The reflux reaction time is preferably 10-14 h, more preferably 11-13 h, and even more preferably 12 h.
[0046] In step (3) of the present invention, the product after the reaction is preferably cooled, filtered, washed and dried in sequence; the cooling temperature is preferably 23-30°C, more preferably 25-28°C, and even more preferably 26-27°C; the washing is preferably done with ethanol, and the number of washings is preferably 3-6 times, more preferably 4-5 times; the drying is preferably done with anhydrous calcium sulfate.
[0047] In step (3) of this invention, the structural formula of the asymmetric semi-rigid ligand is as follows:
[0048]
[0049] In this invention, the reaction equation for the asymmetric semi-rigid ligand is as follows:
[0050]
[0051] In step (4) of the present invention, the preferred molar volume ratio of the asymmetric semi-rigid ligand, zinc salt, rare earth salt, triethylamine and methanol is 1 mmol: 1-2 mmol: 1-2 mmol: 2 mmol: 75-85 mL, more preferably 1 mmol: 1-2 mmol: 1-1.5 mmol: 2 mmol: 76-82 mL, and even more preferably 1 mmol: 1.5 mmol: 1-1.2 mmol: 2 mmol: 80 mL.
[0052] In step (4) of the present invention, the zinc salt is preferably zinc perchlorate or zinc chloride, and the rare earth salt is preferably lanthanum chloride, cerium chloride, praseodymium chloride, neodymium chloride, samarium chloride, europium chloride, gadolinium chloride, terbium chloride, dysprosium chloride, holmium chloride, erbium chloride, yttrium chloride, lutetium chloride, or erbium perchlorate.
[0053] In step (4) of the present invention, the reaction temperature is preferably 23-35°C, more preferably 26-32°C, and even more preferably 28-30°C. The reaction time is preferably 1-5 days, more preferably 2-4 days, and even more preferably 3 days.
[0054] In step (4) of the present invention, after the reaction, it is preferable to filter, wash and dry in sequence; the washing is preferably done with ether, and the number of washings is preferably 3 to 6 times, more preferably 4 to 5 times; the drying is preferably done using vacuum drying.
[0055] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.
[0056] The preparation of the decanuclear 3d-4f supramolecular nanocage material used in the following examples and the asymmetric semi-rigid ligand used in the comparative examples includes the following steps:
[0057] 0.022 mol of methyl 3-aminopropionate, 0.065 mol of triethylamine, and 100 mL of dichloromethane were mixed to obtain a colorless and transparent mixed solution. 20 mL of a 1 mol / L dichloromethane solution of oxaloyl chloride was added dropwise to the mixed solution at a rate of 30 drops / min. After the addition was complete, the mixture was stirred at 0 °C for 13 h to obtain a pale yellow solution. The reaction was quenched with 150 mL of saturated sodium bicarbonate solution, and the solution was extracted with dichloromethane to obtain a yellow organic phase. The organic phase was dried with anhydrous calcium sulfate to obtain intermediate product a.
[0058] Take 0.012 mol of intermediate product a, 3.75 mL of 80 wt% aqueous solution of hydrazine hydrate and 50 mL of ethanol, heat to 78 °C and react for 13 h, then cool to 25 °C, filter the cooled product, wash it 5 times with ethanol solution, and dry it with anhydrous calcium sulfate to obtain intermediate product b.
[0059] 0.01 mol of intermediate product b, 0.05 mol of 3,5-di-tert-butylsalicylaldehyde and 50 mL of ethanol were mixed, heated to 78 °C and reacted for 13 h, then cooled to 25 °C. The cooled product was filtered and washed 5 times with ethanol solution. After drying with anhydrous calcium sulfate, the asymmetric semi-rigid ligand was obtained.
[0060] 0.05 mmol of an asymmetric semi-rigid ligand, 0.05 mmol of zinc perchlorate, 0.05 mmol of erbium chloride, and 0.1 mmol of triethylamine were mixed with 4 mL of methanol and stirred at 25 °C for 36 h. After the reaction was complete, the product was filtered, evaporated to crystallize, and the crystals were washed five times with diethyl ether. The washed product was then vacuum dried to obtain decanuclear 3d-4f supramolecular nanocage materials. Calculations showed that the yield of the obtained decanuclear 3d-4f supramolecular nanocage materials was 45%.
[0061] Example 1
[0062] Preparation of the target product:
[0063] A three-component Strecker reaction was performed using 0.5 mmol aniline, 0.5 mmol benzaldehyde, and 0.5 mmol trimethylsilylcyanine (TMSCN) as model substrates. 6 mL of methanol was added as the reaction solvent, followed by the addition of 0.5 mol% of decanuclear 3d-4f supramolecular nanocage material as a catalyst, based on the total amount of aniline, benzaldehyde, and TMSCN. The reaction was carried out at 25 °C for 3 h to obtain the target product.
[0064] The structural formula of the obtained target product is: The yield of the target product was 98%.
[0065] Example 2
[0066] Preparation of the target product:
[0067] A three-component Strecker reaction was performed using 0.5 mmol p-chloroaniline, 0.5 mmol benzaldehyde, and 0.5 mmol trimethylsilylcyanine (TMSCN) as model substrates. 5 mL of methanol was added as the reaction solvent, followed by the addition of 0.5 mol% of decanuclear 3d-4f supramolecular nanocage material as a catalyst, based on the total amount of aniline, benzaldehyde, and TMSCN. The reaction was carried out at 25 °C for 10 h to obtain the target product.
[0068] The structural formula of the obtained target product is: The yield of the target product was 92%.
[0069] Example 3
[0070] Preparation of the target product:
[0071] A three-component Strecker reaction was performed using 0.5 mmol of p-fluoroaniline, 0.5 mmol of benzaldehyde, and 0.5 mmol of trimethylsilylcyanine (TMSCN) as model substrates. 5 mL of methanol was added as the reaction solvent, followed by the addition of 0.5 mol% of decanuclear 3d-4f supramolecular nanocage material as a catalyst, based on the total amount of aniline, benzaldehyde, and TMSCN. The reaction was carried out at 25 °C for 10 h to obtain the target product.
[0072] The structural formula of the obtained target product is: The yield of the target product was 96%.
[0073] Example 4
[0074] Preparation of the target product:
[0075] A three-component Strecker reaction was performed using 0.5 mmol m-fluoroaniline, 0.5 mmol benzaldehyde, and 0.5 mmol trimethylsilylcyanine (TMSCN) as model substrates. 5 mL of methanol was added as the reaction solvent, followed by the addition of 0.5 mol% of decanuclear 3d-4f supramolecular nanocage material as a catalyst, based on the total amount of aniline, benzaldehyde, and TMSCN. The reaction was carried out at 25 °C for 14 h to obtain the target product.
[0076] The structural formula of the obtained target product is: The yield of the target product was 62%.
[0077] Example 5
[0078] Preparation of the target product:
[0079] A three-component Strecker reaction was performed using 0.5 mmol p-toluidine, 0.5 mmol benzaldehyde, and 0.5 mmol trimethylsilylcyanine (TMSCN) as model substrates. 5 mL of methanol was added as the reaction solvent, followed by the addition of 0.5 mol% of decanuclear 3d-4f supramolecular nanocage material as a catalyst, based on the total amount of aniline, benzaldehyde, and TMSCN. The reaction was carried out at 28 °C for 14 h to obtain the target product.
[0080] The structural formula of the obtained target product is: The yield of the target product was 81%.
[0081] Example 6
[0082] Preparation of the target product:
[0083] A three-component Strecker reaction was performed using 0.5 mmol of p-tert-butylaniline, 0.5 mmol of benzaldehyde, and 0.5 mmol of trimethylsilylcyanine (TMSCN) as model substrates. 5 mL of methanol was added as the reaction solvent, followed by the addition of 0.5 mol% of decanuclear 3d-4f supramolecular nanocage material as a catalyst, based on the total amount of aniline, benzaldehyde, and TMSCN. The reaction was carried out at 25 °C for 10 h to obtain the target product.
[0084] The structural formula of the obtained target product is: The yield of the target product was 76%.
[0085] Example 7
[0086] Preparation of the target product:
[0087] A three-component Strecker reaction was performed using 0.5 mmol m-toluidine, 0.5 mmol benzaldehyde, and 0.5 mmol trimethylsilylcyanine (TMSCN) as model substrates. 5 mL of methanol was added as the reaction solvent, followed by the addition of 0.5 mol% of decanuclear 3d-4f supramolecular nanocage material as a catalyst, based on the total amount of aniline, benzaldehyde, and TMSCN. The reaction was carried out at 25 °C for 10 h to obtain the target product.
[0088] The structural formula of the obtained target product is: The yield of the target product was 68%.
[0089] Example 8
[0090] Preparation of the target product:
[0091] A three-component Strecker reaction was performed using 0.5 mmol p-aminophenethyl ether, 0.5 mmol benzaldehyde, and 0.5 mmol trimethylsilyl cyanide (TMSCN) as model substrates. 5 mL of methanol was added as the reaction solvent, followed by the addition of 0.5 mol% of decanuclear 3d-4f supramolecular nanocage material as a catalyst, based on the total amount of aniline, benzaldehyde, and TMSCN. The reaction was carried out at 25 °C for 16 h to obtain the target product.
[0092] The structural formula of the obtained target product is: The yield of the target product was 91%.
[0093] Example 9
[0094] Preparation of the target product:
[0095] A three-component Strecker reaction was performed using 0.5 mmol m-tert-butylaniline, 0.5 mmol benzaldehyde, and 0.5 mmol trimethylsilylcyanine (TMSCN) as model substrates. 5 mL of methanol was added as the reaction solvent, followed by the addition of 0.5 mol% of decanuclear 3d-4f supramolecular nanocage material as a catalyst, based on the total amount of aniline, benzaldehyde, and TMSCN. The reaction was carried out at 25 °C for 10 h to obtain the target product.
[0096] The structural formula of the obtained target product is: The yield of the target product was 67%.
[0097] Example 10
[0098] Preparation of the target product:
[0099] A three-component Strecker reaction was performed using 0.5 mmol p-nitroaniline, 0.5 mmol benzaldehyde, and 0.5 mmol trimethylsilylcyanine (TMSCN) as model substrates. 5 mL of methanol was added as the reaction solvent, followed by the addition of 0.5 mol% of decanuclear 3d-4f supramolecular nanocage material as a catalyst, based on the total amount of aniline, benzaldehyde, and TMSCN. The reaction was carried out at 22 °C for 10 h to obtain the target product.
[0100] The structural formula of the obtained target product is: The yield of the target product was 34%.
[0101] Example 11
[0102] Preparation of the target product:
[0103] A three-component Strecker reaction was performed using 0.5 mmol 1-naphthylamine, 0.5 mmol benzaldehyde, and 0.5 mmol trimethylsilylcyanine (TMSCN) as model substrates. 5 mL of methanol was added as the reaction solvent, followed by the addition of 0.5 mol% of decanuclear 3d-4f supramolecular nanocage material as a catalyst, based on the total amount of aniline, benzaldehyde, and TMSCN. The reaction was carried out at 22 °C for 10 h to obtain the target product.
[0104] The structural formula of the obtained target product is: The yield of the target product was 25%.
[0105] Example 12
[0106] Preparation of the target product:
[0107] A three-component Strecker reaction was performed using 0.5 mmol aniline, 0.5 mmol p-chlorobenzaldehyde, and 0.5 mmol trimethylsilylcyanine (TMSCN) as model substrates. 5 mL of methanol was added as the reaction solvent, followed by the addition of 0.5 mol% of decanuclear 3d-4f supramolecular nanocage material as a catalyst, based on the total amount of aniline, benzaldehyde, and TMSCN. The reaction was carried out at 22 °C for 10 h to obtain the target product.
[0108] The structural formula of the obtained target product is: The yield of the target product was 99%.
[0109] Example 13
[0110] Preparation of the target product:
[0111] A three-component Strecker reaction was performed using 0.5 mmol aniline, 0.5 mmol p-fluorobenzaldehyde, and 0.5 mmol trimethylsilylcyanine (TMSCN) as model substrates. 5 mL of methanol was added as the reaction solvent, followed by the addition of 0.5 mol% of decanuclear 3d-4f supramolecular nanocage material as a catalyst, based on the total amount of aniline, benzaldehyde, and TMSCN. The reaction was carried out at 25 °C for 10 h to obtain the target product.
[0112] The structural formula of the obtained target product is: The yield of the target product was 97%.
[0113] Example 14
[0114] Preparation of the target product:
[0115] A three-component Strecker reaction was performed using 0.5 mmol aniline, 0.5 mmol m-fluorobenzaldehyde, and 0.5 mmol trimethylsilylcyanine (TMSCN) as model substrates. 5 mL of methanol was added as the reaction solvent, followed by the addition of 0.5 mol% of decanuclear 3d-4f supramolecular nanocage material as a catalyst, based on the total amount of aniline, benzaldehyde, and TMSCN. The reaction was carried out at 25 °C for 10 h to obtain the target product.
[0116] The structural formula of the obtained target product is: The yield of the target product was 62%.
[0117] Example 15
[0118] Preparation of the target product:
[0119] A three-component Strecker reaction was performed using 0.5 mmol aniline, 0.5 mmol p-methylbenzaldehyde, and 0.5 mmol trimethylsilylcyanine (TMSCN) as model substrates. 5 mL of methanol was added as the reaction solvent, followed by the addition of 0.5 mol% of decanuclear 3d-4f supramolecular nanocage material as a catalyst, based on the total amount of aniline, benzaldehyde, and TMSCN. The reaction was carried out at 25 °C for 10 h to obtain the target product.
[0120] The structural formula of the obtained target product is: The yield of the target product was 88%.
[0121] Example 16
[0122] Preparation of the target product:
[0123] A three-component Strecker reaction was performed using 0.5 mmol aniline, 0.5 mmol p-tert-butylbenzaldehyde, and 0.5 mmol trimethylsilylcyanine (TMSCN) as model substrates. 5 mL of methanol was added as the reaction solvent, followed by the addition of 0.5 mol% of decanuclear 3d-4f supramolecular nanocage material as a catalyst, based on the total amount of aniline, benzaldehyde, and TMSCN. The reaction was carried out at 25 °C for 10 h to obtain the target product.
[0124] The structural formula of the obtained target product is: The yield of the target product was 86%.
[0125] Example 17
[0126] Preparation of the target product:
[0127] A three-component Strecker reaction was performed using 0.5 mmol aniline, 0.5 mmol m-methylbenzaldehyde, and 0.5 mmol trimethylsilylcyanine (TMSCN) as model substrates. 5 mL of methanol was added as the reaction solvent, followed by the addition of 0.5 mol% of decanuclear 3d-4f supramolecular nanocage material as a catalyst, based on the total amount of aniline, benzaldehyde, and TMSCN. The reaction was carried out at 25 °C for 10 h to obtain the target product.
[0128] The structural formula of the obtained target product is: The yield of the target product was 64%.
[0129] Example 18
[0130] Preparation of the target product:
[0131] A three-component Strecker reaction was performed using 0.5 mmol aniline, 0.5 mmol 4-ethoxybenzaldehyde, and 0.5 mmol trimethylsilylcyanine (TMSCN) as model substrates. 5 mL of methanol was added as the reaction solvent, followed by the addition of 0.5 mol% of decanuclear 3d-4f supramolecular nanocage material as a catalyst, based on the total amount of aniline, benzaldehyde, and TMSCN. The reaction was carried out at 25 °C for 10 h to obtain the target product.
[0132] The structural formula of the obtained target product is: The yield of the target product was 75%.
[0133] Example 19
[0134] Preparation of the target product:
[0135] A three-component Strecker reaction was performed using 0.5 mmol aniline, 0.5 mmol p-nitrobenzaldehyde, and 0.5 mmol trimethylsilylcyanine (TMSCN) as model substrates. 5 mL of methanol was added as the reaction solvent, followed by the addition of 0.5 mol% of decanuclear 3d-4f supramolecular nanocage material as a catalyst, based on the total amount of aniline, benzaldehyde, and TMSCN. The reaction was carried out at 25 °C for 10 h to obtain the target product.
[0136] The structural formula of the obtained target product is: The yield of the target product was 75%.
[0137] Example 20
[0138] Preparation of the target product:
[0139] A three-component Strecker reaction was performed using 0.5 mmol aniline, 0.5 mmol 1-naphthal, and 0.5 mmol trimethylsilylcyanine (TMSCN) as model substrates. 5 mL of methanol was added as the reaction solvent, followed by the addition of 0.5 mol% of decanuclear 3d-4f supramolecular nanocage material as a catalyst, based on the total amount of aniline, benzaldehyde, and TMSCN. The reaction was carried out at 25 °C for 10 h to obtain the target product.
[0140] The structural formula of the obtained target product is: The yield of the target product was 75%.
[0141] Example 21
[0142] The difference from Example 1 is that the reaction time was 24 hours, otherwise it was the same as Example 1. The yield of the target product was 88%.
[0143] Comparative Example 1
[0144] The decanuclear 3d-4f supramolecular nanocage material of Example 1 was replaced with an asymmetric semi-rigid ligand, otherwise the process remained the same as in Example 1. The target product was not obtained.
[0145] Comparative Example 2
[0146] The decanuclear 3d-4f supramolecular nanocage material of Example 1 was replaced with ZnCl2, otherwise the process remained the same as in Example 1. The yield of the target product was 19%.
[0147] Comparative Example 3
[0148] The decanuclear 3d-4f supramolecular nanocage material of Example 1 was replaced with Er(NO3)3·5H2O, otherwise the same as in Example 1. The yield of the target product was 27%.
[0149] Comparative Example 4
[0150] The "0.5 mol% of decanuclear 3d-4f supramolecular nanocage material (based on the total amount of aniline, benzaldehyde, and trimethylsilyl cyanide)" in Example 1 was replaced with "0.5 mol% of ZnCl2 and 0.5 mol% of Er(NO3)3·5H2O (based on the total amount of aniline, benzaldehyde, and trimethylsilyl cyanide)," while everything else remained the same as in Example 1. The yield of the target product was 30%.
[0151] As can be seen from Examples 1-17 and Comparative Examples 1-4, compared with other homogeneous catalysts, the decanuclear 3d-4f supramolecular nanocage material of the present invention has high catalytic activity, is not easily deactivated during catalysis, and has high catalytic efficiency.
[0152] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. The application of a decanuclear 3d-4f supramolecular nanocage material in the catalytic three-component Strecker reaction, characterized in that, Includes the following steps: The decanuclear 3d-4f supramolecular nanocage material, amino compound, aldehyde compound, trimethylsilyl cyanide and solvent were mixed and reacted to obtain the target product, that is, to complete the Strecker reaction. The amino compound is one of aniline, p-chloroaniline, p-fluoroaniline, m-fluoroaniline, p-toluidine, p-tert-butylaniline, m-toluidine, p-aminophenethyl ether, m-tert-butylaniline, p-nitroaniline, and 1-naphthylamine; The aldehyde compound is one of benzaldehyde, p-chlorobenzaldehyde, p-fluorobenzaldehyde, m-fluorobenzaldehyde, p-methylbenzaldehyde, p-tert-butylbenzaldehyde, m-methylbenzaldehyde, 4-ethoxybenzaldehyde, p-nitrobenzaldehyde, and 1-naphthaldehyde; The preparation of the decanuclear 3d-4f supramolecular nanocage material includes the following steps: 0.022 mol of methyl 3-aminopropionate, 0.065 mol of triethylamine, and 100 mL of dichloromethane were mixed to obtain a colorless and transparent mixed solution. 20 mL of a 1 mol / L dichloromethane solution of oxaloyl chloride was added dropwise to the mixed solution at a rate of 30 drops / min. After the addition was complete, the mixture was stirred at 0 °C for 13 h to obtain a pale yellow solution. The reaction was quenched with 150 mL of saturated sodium bicarbonate solution, and the solution was extracted with dichloromethane to obtain a yellow organic phase. The organic phase was dried with anhydrous calcium sulfate to obtain intermediate product a. Take 0.012 mol of intermediate product a, 3.75 mL of 80 wt% aqueous solution of hydrazine hydrate and 50 mL of ethanol, heat to 78 °C and react for 13 h, then cool to 25 °C, filter the cooled product, wash it 5 times with ethanol solution, and dry it with anhydrous calcium sulfate to obtain intermediate product b. 0.01 mol of intermediate product b, 0.05 mol of 3,5-di-tert-butylsalicylaldehyde and 50 mL of ethanol were mixed, heated to 78 °C and reacted for 13 h, then cooled to 25 °C. The cooled product was filtered and washed 5 times with ethanol solution. After drying with anhydrous calcium sulfate, the asymmetric semi-rigid ligand was obtained. 0.05 mmol of asymmetric semi-rigid ligand, 0.05 mmol of zinc perchlorate, 0.05 mmol of erbium chloride, 0.1 mmol of triethylamine and 4 mL of methanol were mixed and stirred at 25 °C for 36 h. After the reaction was completed, the product was filtered, evaporated and crystallized. The crystals were washed five times with diethyl ether. After washing, the product was dried under vacuum to obtain decanuclear 3d-4f supramolecular nanocage material.
2. The application of the decanuclear 3d-4f supramolecular nanocage material according to claim 1 in the catalytic three-component Strecker reaction, characterized in that, The solvent is methanol.
3. The application of the decanuclear 3d-4f supramolecular nanocage material according to claim 2 in the catalytic three-component Strecker reaction, characterized in that, The molar volume ratio of the amino compound, aldehyde compound, trimethylsilyl cyanide and solvent is 1 mmol: 1~1.2 mmol: 1~1.2 mmol: 4~6 mL.
4. The application of the decanuclear 3d-4f supramolecular nanocage material according to claim 3 in the catalytic three-component Strecker reaction, characterized in that, The amount of the decanuclear 3d-4f supramolecular nanocage material used is 0.2~1 mol of the total amount of amino compound, aldehyde compound and trimethylsilyl cyanide.
5. The application of the decanuclear 3d-4f supramolecular nanocage material according to claim 3 or 4 in the catalytic three-component Strecker reaction, characterized in that, The reaction temperature is 20~30℃, and the reaction time is 3~24h.