CN114149454B - 3d-4f bionic metal cage and preparation method and application thereof - Google Patents

3d-4f bionic metal cage and preparation method and application thereof Download PDF

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CN114149454B
CN114149454B CN202111605563.XA CN202111605563A CN114149454B CN 114149454 B CN114149454 B CN 114149454B CN 202111605563 A CN202111605563 A CN 202111605563A CN 114149454 B CN114149454 B CN 114149454B
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唐晓亮
周生斌
窦伟
刘伟生
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Xinyi Yilan Green Material Industry Research Institute Co ltd
Lanzhou University
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    • C—CHEMISTRY; METALLURGY
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    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/06—Zinc compounds
    • 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
    • B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
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    • C07D203/08—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring nitrogen atom
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    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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Abstract

The invention belongs to the technical field of homogeneous catalysis, and discloses a preparation method of a 3d-4f bionic metal cage, which comprises the following steps: (1) Will H 5 Mixing the L ligand, methanol and triethylamine, and reacting to obtain a suspension A; (2) ZnCl 2 Adding the mixture into the suspension A for mixing and reacting to obtain a suspension B; (3) Mixing rare earth nitrate, methanol and the suspension B for reaction to obtain the 3d-4f bionic metal cage. The method has simple operation steps, can realize industrialized preparation, and the prepared 3d-4f bionic metal cage has high catalytic activity in catalyzing three-component aza-Darzens reaction.

Description

3d-4f bionic metal cage and preparation method and application thereof
Technical Field
The invention relates to the technical field of homogeneous catalysis, in particular to a 3d-4f bionic metal cage, a preparation method and application thereof.
Background
As one of the Darzens reactions, the aza-Darzens reaction is widely used to synthesize various minimally saturated nitrogen heterocyclic compounds having biological activity, and is also a useful precursor for other nitrogen-containing compounds, which can be converted by nucleophilic ring opening reactions or other reactions. Although a variety of synthetic strategies are effective for preparing aziridine derivatives, most methods often suffer from the problems of expensive starting materials or cumbersome synthetic steps. At present, three-component aza-Darzens reaction is rarely studied, tetrahedral Ga (III) is used as a nano-reactor and Zr-MOF is used as a heterogeneous catalyst for the reaction, and the method is proved to be an effective method for synthesizing aziridine derivatives. However, these three groups based on different complex catalystsThe aza-Darzens reaction requires a longer reaction time, high catalyst loading or K 3 PO 4 As an additive.
Many highly nuclear coordination nanocages, such as the common tetrahedral and octahedral cages, have been modulated by using the same transition metal ions or lanthanide ions, but controlled self-assembly and application of 3d-4f metal cages remains one of the great challenges. The main influencing factors are uncontrollability of the polynuclear arrangement, the kind of metal ions and coordination number, mode and stereochemical differences. However, studies have shown that 3d-4f metal cages coated with some bridging ligands and two different metal ions as nanoscale reaction vessels can facilitate reactions of substrates in suitable cavities or on matched active sites, and can exhibit good solubility and high catalytic activity to accelerate the effective reaction rate, similar to enzymes.
Therefore, how to develop a 3d-4f metal cage with high catalytic activity is a problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a 3d-4f bionic metal cage and a preparation method and application thereof. The prepared 3d-4f bionic metal cage has high catalytic activity in catalyzing three-component aza-Darzens reaction. Effectively solves the technical problems of long reaction time, high catalyst load and the like of the existing different complex catalysts in the catalytic three-component aza-Darzens reaction.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a 3d-4f bionic metal cage, which comprises the following steps:
(1) Will H 5 Mixing the L ligand, methanol and triethylamine, and reacting to obtain a suspension A;
(2) ZnCl 2 Adding the mixture into the suspension A for mixing and reacting to obtain a suspension B;
(3) Mixing rare earth nitrate, methanol and the suspension B for reaction to obtain a 3d-4f bionic metal cage;
wherein H is 5 The structural formula of the L ligand is as follows：
Figure BDA0003433595010000031
The H is 5 The mass volume ratio of the L ligand, the methanol and the triethylamine is (20-25) mg: (3-6) mL: (15-20) mu L.
The reaction temperature in the step (1) is room temperature, and the reaction time is 8-15 min.
The step (2) is ZnCl 2 The addition amount of (2) and the step (1) H 5 The mass ratio of the L ligand is 1:2.5 to 4.
The reaction temperature in the step (2) is room temperature, and the reaction time is 8-15 min.
The adding amount of the rare earth nitrate in the step (3) and the adding amount of the rare earth nitrate in the step (1) H 5 The mass ratio of the L ligand is 1:1-2, and the volume ratio of the addition amount of the methanol to the methanol in the step (1) is 1:1-2.
The reaction temperature in the step (3) is room temperature, and the reaction time is 30-50 min.
The rare earth nitrate is one of lanthanum nitrate, cerium nitrate, praseodymium nitrate, neodymium nitrate, samarium nitrate, europium nitrate, gadolinium nitrate, terbium nitrate, dysprosium nitrate, holmium nitrate, erbium nitrate, yttrium nitrate and lutetium nitrate.
The invention provides the 3d-4f bionic metal cage prepared by the preparation method.
The invention also provides application of the 3d-4f bionic metal cage in catalyzing three-component aza-Darzens reaction.
Compared with the prior art, the invention has the following beneficial effects:
h used in the present invention 5 The L ligand has a multidentate coordination mode with bridged 3d and 4f metal ions, thereby forming a heteropolynuclear molecular cage. Four multidentate acylhydrazone bridging ligands can be assembled with two Zn (II) ions and four rare earth ions to obtain the hexanuclear 3d-4f bionic metal cage with an open cavity. Compared with other homogeneous catalysts, the preparation method of the hexanuclear 3d-4f bionic metal cage is simple, has high yield, and can realize industrialized preparation; in solution inThe structure is stable, and the molecular cage exists; can realize homogeneous catalysis of three-component aza-Darzens reaction, has simple operation steps, high catalytic activity, mild reaction conditions and short total reaction time, and can realize industrial production.
Detailed Description
The invention provides a preparation method of a 3d-4f bionic metal cage, which comprises the following steps:
(1) Will H 5 Mixing the L ligand, methanol and triethylamine, and reacting to obtain a suspension A;
(2) ZnCl 2 Adding the mixture into the suspension A for mixing and reacting to obtain a suspension B;
(3) Mixing rare earth nitrate, methanol and the suspension B for reaction to obtain a 3d-4f bionic metal cage;
wherein H is 5 The structural formula of the L ligand is as follows:
Figure BDA0003433595010000041
preferably, the H 5 The preparation method of the L ligand comprises the following steps:
s1, under protective gas, mixing glycine ethyl ester hydrochloride, triethylamine, anhydrous methylene dichloride and oxalyl chloride monoethyl ester solution, and reacting to obtain 3- ((2-ethoxy-2-oxyethyl) amino) -3-oxo-propionic acid ethyl ester;
s2, mixing 3- ((2-ethoxy-2-oxyethyl) amino) -3-oxo-propionic acid ethyl ester, hydrazine hydrate and ethanol for reaction to obtain 2-hydrazino-N- (2-hydrazino-2-oxo-ethyl) -2-oxo-acetamide;
s3, mixing 2-hydrazino-N- (2-hydrazino-2-oxo-ethyl) -2-oxo-acetamide, 3-ethoxy-2-hydroxybenzaldehyde and ethanol for reaction to obtain H 5 An L ligand;
in step S1, the shielding gas is one of nitrogen, argon, helium, neon and carbon dioxide;
the concentration of the oxalyl chloride monoethyl ester solution is 0.5-2 mmol/mL;
the mass volume ratio of the glycine ethyl ester hydrochloride to the triethylamine to the anhydrous methylene dichloride to the oxalyl chloride monoethyl ester solution is (2.5-3.5) g: (7-10) mL: (90-110) mL: (15-30) mL;
the reaction temperature in the step S1 is-5-2 ℃ and the reaction time is 8-15 h;
in the step S2, the mass volume ratio of the 3- ((2-ethoxy-2-oxyethyl) amino) -3-oxo-propionic acid ethyl ester, the hydrazine hydrate and the ethanol is (1.5-3) g: (2-4) g: (30-60) mL;
the reaction temperature in the step S2 is 70-90 ℃ and the reaction time is 8-15 h;
in the step S3, the mass-volume ratio of the 2-hydrazino-N- (2-hydrazino-2-oxo-ethyl) -2-oxo-acetamide, the 3-ethoxy-2-hydroxybenzaldehyde and the ethanol is (0.5 to 2) g: (1.5-3) g: (30-60) mL;
the reaction temperature in the step S3 is 70-90 ℃ and the reaction time is 6-12 h.
Preferably, the H 5 The mass volume ratio of the L ligand, the methanol and the triethylamine is (23-24) mg: (4-5) mL: (16-18) mu L.
Preferably, the reaction time in the step (1) is 10 to 12 minutes.
Preferably, the step (2) is ZnCl 2 The addition amount of (2) and the step (1) H 5 The mass ratio of the L ligand is 1:3 to 3.5.
Preferably, the reaction time in the step (2) is 10 to 12 minutes.
Preferably, the addition amount of the rare earth nitrate in the step (3) is equal to that in the step (1) H 5 The mass ratio of the L ligand is 1:1.2-1.6, and the volume ratio of the addition amount of the methanol to the methanol in the step (1) is 1:1.2-1.5.
Preferably, the reaction time of the step (3) is 35 to 40 minutes.
Preferably, after the reaction in the step (3) is finished, washing with cold methanol for three times, and drying in air to obtain the 3d-4f bionic metal cage.
Preferably, the rare earth nitrate is lanthanum nitrate or samarium nitrate or erbium nitrate.
The invention provides the 3d-4f bionic metal cage prepared by the preparation method.
The invention also provides application of the 3d-4f bionic metal cage in catalyzing three-component aza-Darzens reaction.
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
H 5 Preparation of L ligands
S1, to a 250mL three-necked flask equipped with a stirring bar and an addition funnel, 3.071g of glycine ethyl ester hydrochloride, 9.0mL of triethylamine and 100mL of anhydrous dichloromethane were added. To this mixture system, 20mL of an anhydrous methylene chloride solution containing 2.73g (0.02 mol) of oxalyl chloride monoethyl ester was added dropwise under the protection of argon (Ar) in an ice-water bath, and the dropping rate was controlled to about half an hour. The resulting solution was stirred at 0 ℃ for 10h and the reaction quenched by the addition of 50mL of distilled water. The mixture is washed by saturated sodium bicarbonate aqueous solution, and simultaneously, a proper amount of distilled water is added for liquid separation extraction, the organic layer is dried by anhydrous sodium sulfate and concentrated by a rotary evaporator, thus obtaining the intermediate 3- (2-ethoxy-2-oxyethyl) amino) -3-oxo-propionic acid ethyl ester.
S2, placing 2.03g of 3- ((2-ethoxy-2-oxoethyl) amino) -3-oxopropanoic acid ethyl ester, 3.0g of hydrazine hydrate with the mass fraction of 80% and 40mL of ethanol solution into a 100mL round bottom flask. The mixture solution was stirred under reflux at 80 ℃. The reaction was allowed to react for 12 hours and then cooled to room temperature. The crude product was isolated by filtration and washed three times with cold ethanol to give 2-hydrazino-N- (2-hydrazino-2-oxoethyl) -2-oxoacetamide as a white solid.
S3, 1.994g of 3-ethoxy-2-hydroxybenzaldehyde and 40mL of ethanol are added to a 100mL round bottom flask, 0.876g of 2-hydrazino-N- (2-hydrazino-2-oxoethyl) -2-oxoacetamide are added, and the mixture system is refluxed at 78℃for 8 hours. After the reaction is finishedCooling to room temperature, filtering to obtain white solid, washing with cold methanol for 3 times, and air drying to obtain H 5 An L ligand.
H prepared by the method 5 The L ligands were used in examples 1-3 below.
Example 1
Will be 23.6mg H 5 L ligand, 4mL methanol and 16. Mu.L triethylamine were placed in a 25mL round bottom flask and stirred at room temperature for 10 min to give pale yellow suspension A; then 6.8mg ZnCl 2 Adding the mixture into the suspension A, and stirring the mixture at room temperature for 10 minutes to obtain yellow suspension B; 22.2mg of lanthanum nitrate was added to suspension B, and after stirring at room temperature for 5 minutes, 3mL of methanol was added, stirring was continued for 30 minutes, filtration was continued, and volatilization was performed at room temperature. After two weeks, pale yellow blocky crystals suitable for crystal analysis are obtained, washed three times with cold methanol and dried in air, and the 3d-4f bionic metal cage is obtained. The yield of the 3d-4f biomimetic metal cage of this example was calculated to be 56.8%.
Example 2
21.8mg of H 5 L ligand, 4mL of methanol and 17. Mu.L of triethylamine were placed in a 25mL round bottom flask and stirred at room temperature for 8 min to give pale yellow suspension A; 7.3mg ZnCl 2 Adding the mixture into the suspension A, and stirring the mixture at room temperature for 8 minutes to obtain yellow suspension B; 20.9mg of samarium nitrate was added to suspension B, and after stirring at room temperature for 5 minutes, 4mL of methanol was added, stirring was continued for 35 minutes, filtration was continued, and volatilization was performed at room temperature. After two weeks, pale yellow blocky crystals suitable for crystal analysis are obtained, washed three times with cold methanol and dried in air, and the 3d-4f bionic metal cage is obtained. The yield of the 3d-4f biomimetic metal cage of this example was calculated to be 54.6%.
Example 3
24.2mg of H 5 L ligand, 5mL of methanol and 18. Mu.L of triethylamine were placed in a 25mL round bottom flask and stirred at room temperature for 12min to give pale yellow suspension A; then 8.3mg ZnCl 2 Adding the mixture into the suspension A, and stirring the mixture at room temperature for 12 minutes to obtain yellow suspension B; 23.4mg of erbium nitrate was added to suspension B, and after stirring at room temperature for 6 minutes, 4mL of methanol was added, followed byAfter stirring for 40min, filtration and evaporation at room temperature were carried out. After two weeks, pale yellow blocky crystals suitable for crystal analysis are obtained, washed three times with cold methanol and dried in air, and the 3d-4f bionic metal cage is obtained. The yield of the 3d-4f biomimetic metal cage of this example was calculated to be 55.2%.
The embodiment 1-3 shows that the preparation method of the 3d-4f bionic metal cage is simple and has higher yield.
Application example 1
The three components aza-Darzens with 0.2mmol of aniline, 0.04mmol of formaldehyde and 0.04mmol of ethyl diazoacetate as model substrates react, and under the room temperature condition, the 3d-4f bionic metal cage (0.8 mol%) prepared in the embodiment 1 of the invention is used as a catalyst, and methanol is used as a reaction solvent. The reaction was carried out for 3 hours to give the objective product, and the yield was 83%.
Application example 2
The reaction time was prolonged to 4 hours in this example, and the other conditions were the same as in example 1. The yield was 84%.
Application example 3
In this application example, 0.8mol% H 5 The L ligand was used as a catalyst, and the other conditions were the same as in application example 1. The reaction is carried out for more than 3 hours, and the target product is not obtained.
Application example 4
In this application example, 0.8mol% ZnCl 2 As the catalyst, other conditions were the same as in application example 1. The reaction is carried out for more than 3 hours, and the target product is not obtained.
Application example 5
In this example, 0.8mol% Er (NO 3 ) 3 ·5H 2 O was used as a catalyst, and the other conditions were the same as in application example 1. The reaction was carried out for 3 hours to give the objective product in 7% yield.
Application example 6
In this example, 0.8mol% Er (NO 3 ) 3 ·5H 2 O+0.8mol％ZnCl 2 As the mixed catalyst, other conditions were the same as in application example 1. The reaction was carried out for 3 hours to give the objective product in 9% yield.
The reaction procedure for application examples 1-6 is as follows:
Figure BDA0003433595010000101
as can be seen from application examples 1-6, the 3d-4f bionic metal cage prepared by the method has higher catalytic activity compared with other homogeneous catalysts.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (3)

1. The preparation method of the 3d-4f bionic metal cage is characterized by comprising the following steps of:
(1) Will H 5 Mixing the L ligand, methanol and triethylamine, and reacting to obtain a suspension A;
(2) ZnCl 2 Adding the mixture into the suspension A for mixing and reacting to obtain a suspension B;
(3) Mixing rare earth nitrate, methanol and the suspension B for reaction to obtain a 3d-4f bionic metal cage;
wherein H is 5 The structural formula of the L ligand is as follows:
Figure QLYQS_1
H 5 L ；
the H is 5 The mass volume ratio of the L ligand, the methanol and the triethylamine is as follows（20~25）mg：（3~6）mL：（15~20）μL；
The reaction temperature in the step (1) is room temperature, and the reaction time is 8-15 min;
the step (2) is ZnCl 2 The addition amount of (2) and the step (1) H 5 The mass ratio of the L ligand is 1: 2.5-4;
the reaction temperature in the step (2) is room temperature, and the reaction time is 8-15 min;
the adding amount of the rare earth nitrate in the step (3) and the adding amount of the rare earth nitrate in the step (1) H 5 The mass ratio of the L ligand is 1:1-2, and the volume ratio of the addition amount of the methanol to the methanol in the step (1) is 1:1-2;
the reaction temperature in the step (3) is room temperature, and the reaction time is 30-50 min;
the rare earth nitrate is lanthanum nitrate.
2. The 3d-4f biomimetic metal cage prepared by the method for preparing the 3d-4f biomimetic metal cage of claim 1.
3. Use of the 3d-4f biomimetic metal cage according to claim 2 for catalyzing three-component aza-Darzens reactions, characterized in that the reaction process is as follows:
Figure QLYQS_2
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