CN113694966B - Bimetallic MOF (metal oxide-organic framework) catalyst for synthesizing cyclic lactone by serially catalyzing cyclic alcohol as well as preparation method and application thereof - Google Patents

Bimetallic MOF (metal oxide-organic framework) catalyst for synthesizing cyclic lactone by serially catalyzing cyclic alcohol as well as preparation method and application thereof Download PDF

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CN113694966B
CN113694966B CN202010436514.7A CN202010436514A CN113694966B CN 113694966 B CN113694966 B CN 113694966B CN 202010436514 A CN202010436514 A CN 202010436514A CN 113694966 B CN113694966 B CN 113694966B
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CN113694966A (en
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薛光信
李国栋
唐智勇
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National Center for Nanosccience and Technology China
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Abstract

The invention relates to a bimetallic MOF catalyst for synthesizing cyclic lactone by serially catalyzing cyclic alcohol, a preparation method and application thereof, wherein bimetallic in the bimetallic MOF catalyst is selected from any two of Mg, mn, fe, co, ni, cu or Zn, and an organic ligand is selected from any one or a combination of at least two of 2-hydroxy terephthalic acid, 2, 5-dihydroxyterephthalic acid, 3-hydroxy-4, 4-dicarboxylic acid or 3, 3-dihydroxy-4, 4-dicarboxylic acid; the bimetallic MOF catalyst is used for preparing cyclic lactone by 'one-pot' series catalytic cyclic alcohol, and has the advantages of high reaction rate, mild reaction condition, high yield and selectivity of cyclic lactone and universality.

Description

Bimetallic MOF (metal oxide-organic framework) catalyst for synthesizing cyclic lactone by serially catalyzing cyclic alcohol as well as preparation method and application thereof
Technical Field
The invention belongs to the field of catalytic synthesis, and relates to a bimetallic MOF catalyst for synthesizing cyclic lactone by serially catalyzing cyclic alcohol, and a preparation method and application thereof.
Background
The preparation of cyclic lactones is an important reaction in organic synthesis and has a number of possible applications, for example, the synthesis of expensive intermediates or products such as antibiotics, steroids, pheromones, polymeric monomers and the like.
The most reliable reaction for preparing the cyclic lactone at present takes cyclic ketone as a raw material and synthesizes the corresponding cyclic lactone through a Bayer-Williger oxidation (Baeyer-Villiger Oxidation) process; however, this reaction typically requires the use of strong oxides such as hydrogen peroxide or peroxyacids (e.g., peroxyacetic acid, trifluoroperoxyacetic acid, and m-chloroperoxybenzoic acid) as oxidizing agents, which are dangerous to explosion and often very expensive (see R.A. Sheldon et al, the Baeyer-Villiger Reaction: new Developments toward Greener processes. Chem. Rev.,2004,104,4105-4123.); avelino Corma et al in dioxane solvent as H 2 O 2 (35%) is an oxidant, and the cyclohexanone is catalyzed and oxidized by using a Sn-beta molecular sieve as a catalyst, and the yield of the cyclohexanolactone reaches 52% after the reaction is carried out for 3 hours at 90 ℃ (see the literature: avelino Corma et al, "Sn-zeolite beta as a heterogeneous chemoselective catalyst for Baeyer-Villiger oxidation," Nature,2001,412 (6845), 423-425 "). The formation of cyclohexanol is generally unavoidable in the preparation of cyclic ketones, especially cyclohexanone, however, the synthesis of the corresponding cyclic lactones by heterogeneous catalytic oxidation processes using cyclic alcohols as starting materials has been reported only rarely.
Currently, the oxidation of cyclic alcohols usually requires noble metals such as gold (Au), palladium (Pd), rhodium (Rh) and the like as catalysts, and is carried out at higher temperatures, and the products are usually the corresponding ketones; kiyotomi Kaneda et al catalyzed oxidation of alcohols at 90℃with Hydroxyapatite-supported Pd nanoclusters as catalysts, after 24h, the conversion of cyclopentanol reached 91% and the yield of cyclopentanone was 84% (see, kiyotomi Kaneda et al. "Hydroxypatite-Supported Palladium Nanoclusters: A Highly Active Heterogeneous Catalyst for Selective Oxidation of Alcohols by Use of Molecular Oxygen." J.Am. Chem. Soc., "2004, 126 (34), 10657-10666.).
In view of the above, the synthesis process of cyclic lactones (especially using cyclic alcohols as raw materials) still has many technical difficulties to be studied and solved, so developing a universal high-efficiency catalyst and catalytic system for one-pot serial conversion of cyclic alcohols into corresponding cyclic lactones has important significance.
Disclosure of Invention
The invention aims to provide a bimetallic MOF catalyst for synthesizing cyclic lactone by serially catalyzing cyclic alcohol, a preparation method and application thereof, wherein bimetallic in the bimetallic MOF catalyst is selected from any two of Mg, mn, fe, co, ni, cu or Zn, and an organic ligand is selected from any one or a combination of at least two of 2-hydroxy terephthalic acid, 2, 5-dihydroxyterephthalic acid, 3-hydroxy-4, 4-dicarboxylic acid and 3, 3-dihydroxy-4, 4-dicarboxylic acid; the bimetallic MOF catalyst is used for preparing cyclic lactone by 'one-pot' series catalytic cyclic alcohol, and has the advantages of high reaction rate, mild reaction condition, high yield and selectivity of cyclic lactone and universality.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a bimetallic MOF catalyst for tandem catalysis of cyclic alcohol to cyclic lactone, wherein the bimetallic in the bimetallic MOF catalyst is selected from any two of Mg, mn, fe, co, ni, cu or Zn, and the organic ligand of the bimetallic MOF catalyst is selected from any one or a combination of at least two of 2-hydroxyterephthalic acid, 2, 5-dihydroxyterephthalic acid, 3-hydroxy-4, 4-biphenyl dicarboxylic acid, or 3, 3-dihydroxy-4, 4-biphenyl dicarboxylic acid, and the combination comprises exemplified combinations of 2-hydroxyterephthalic acid and 2, 5-dihydroxyterephthalic acid, or combinations of 3-hydroxy-4, 4-biphenyl dicarboxylic acid and 3, 3-dihydroxy-4, 4-biphenyl dicarboxylic acid, and the like.
The bimetal is selected from any one of MgMn, mgFe, mgCo, mgNi, mgCu, mgZn, mnFe, mnCo, mnNi, mnCu, mnZn, feCo, feNi, feCu, feZn, coNi, coCu, coZn, niCu, niZn or CuZn.
The hydroxyl oxygen and carboxyl oxygen in the organic ligand adopted by the invention are mainly used for coordination with metal ions to form an unsaturated coordination center which is used as an active site for catalytic reaction.
The bimetallic MOF catalyst disclosed by the invention adopts the composition, can be used for preparing cyclic lactone through one-pot serial catalytic cyclic alcohol conversion, and has the advantages of high reaction rate, mild reaction condition, high cyclic lactone yield and selectivity and universality in the catalytic process; is hopefully applied to the industrial production of the cyclic lactone.
At present, noble metals such as gold (Au), palladium (Pd), rhodium (Rh) and the like are usually required as catalysts for the oxidation of cyclic alcohol, the oxidation is carried out at a higher temperature (more than 90 ℃), the products are usually corresponding ketones, and the synthesis of the cyclic lactone cannot be realized;
the bimetallic MOF catalyst is used for the reaction of synthesizing cyclic lactone by serially catalyzing cyclic alcohol, and the yield of the cyclic lactone can reach 99%.
The bimetallic MOF catalyst has the advantage of good stability, and the conversion rate and the selectivity are basically unchanged after the bimetallic MOF catalyst is recycled for a plurality of times.
As used herein, "tandem" in the tandem catalytic ring alcohol synthesis of cyclic lactones means a tandem reaction, which refers herein to: the cyclic alcohol is used as a raw material, the cyclic alcohol is firstly oxidized into cyclic ketone, and then the cyclic ketone is subjected to Bayer-Viiging oxidation reaction to produce the cyclic lactone.
The universality referred to herein means that the bimetallic MOF catalysts of the present invention are applicable to a wide variety of cyclic alcohols containing substituents, such as 4-methylcyclohexanol, p-ethylcycloheptanol, and the like.
The bimetallic MOF catalyst is used for the reaction of synthesizing the cyclic lactone by catalyzing the cyclic alcohol in series, and the reaction has the advantages of easiness in operation, simplicity in equipment requirement, easiness in realization and high efficiency, and does not cause obvious increase of production cost.
Preferably, the ratio of the molar amount of metal element to the molar amount of organic ligand in the bimetallic MOF catalyst is 2-4, such as 2.5, 3 or 3.5, etc.
Preferably, the bimetal is selected from any two of Mn, fe, co, ni or Cu.
Preferably, the organic ligand is selected from the group consisting of a mixture of 2, 5-dihydroxyterephthalic acid and 3, 3-dihydroxy-4, 4-diphthalic acid, a mixture of 2-hydroxyterephthalic acid and 2, 5-dihydroxyterephthalic acid, and a mixture of 3-hydroxy-4, 4-diphthalic acid and 3, 3-dihydroxy-4, 4-diphthalic acid.
In a second aspect, the present invention provides a method of preparing a bimetallic MOF catalyst as set forth in the first aspect, the method comprising: dissolving a bimetallic salt and an organic ligand in a solvent to obtain a reaction solution, and then carrying out solvothermal reaction to obtain the bimetallic MOF catalyst.
According to the preparation method of the bimetallic MOF catalyst, bimetallic salt and organic ligand are mixed in a solvent, and then solvothermal reaction is carried out, so that the bimetallic MOF catalyst is obtained, the MOF materials with different structures can be prepared by changing the components of the bimetallic salt and the organic ligand in the preparation process, the obtained bimetallic MOF catalyst has higher structural stability, and the conversion rate of the catalyst and the selectivity to the cyclic lactone are basically unchanged after the bimetallic MOF catalyst is used in the process of synthesizing the cyclic lactone by serially catalyzing cyclic alcohol.
Preferably, the bimetallic salt is selected from divalent metal salts.
The bimetallic salt is a divalent metal salt, and divalent metal ions can be freely combined or mutually substituted to form the MOF material with the same crystal form.
Preferably, the anion of the divalent metal salt is selected from at least one of nitrate, sulfate, acetate and chloride.
Preferably, the solvent is selected from the group consisting of N, N-dimethylformamide, ethanol and water.
Preferably, the volume ratio of N, N-dimethylformamide, ethanol and water in the mixed solvent is (5-15): 1-5, e.g. 5:5:5, 6:4:5, 6:5:4, 7:4:4, 8:4:3, 8:3:4, 9:3:3, 10:1.5:3.5, 10:3.5:1.5, 11:3:1, 12:2:1 or 13:1:1, etc.
The solvent in the preparation method is selected from mixed solvents of N, N-dimethylformamide, ethanol and water, wherein the N, N-dimethylformamide is used for dissolving a ligand, the ethanol is used for promoting crystallization, and the water is used for facilitating the dissolution of metal salt and further facilitating the formation of a bimetallic MOF catalyst structure, so that the bimetallic MOF material keeps good stability and excellent catalytic activity.
Preferably, the ratio of the molar amount of metal ions in the reaction solution to the molar amount of the organic ligand is 2 to 4, for example 2.5, 3 or 3.5, etc.
In the preparation method, the molar ratio of the metal ions to the organic ligands in the reaction liquid is controlled within the range, so that the bimetallic MOF catalyst with stable structure and excellent activity is formed, and when the molar ratio is less than 2 or more than 4, part of raw materials cannot be converted into MOF materials, so that waste is caused.
Preferably, the molar concentration of the metal ions in the reaction liquid is 0.02 to 0.04mmol/mL, for example, 0.025mmol/mL, 0.03mmol/mL, 0.035mmol/mL, etc., preferably 0.03 to 0.035mmol/mL.
Preferably, the solvothermal reaction is at a temperature of 80-160 ℃, e.g., 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃ or the like, and the reaction time is 18-72 hours, e.g., 20 hours, 24 hours, 28 hours, 32 hours, 36 hours, 40 hours, 44 hours, 48 hours, 52 hours, 56 hours, 60 hours, 64 hours, 68 hours, or the like.
Preferably, the solvothermal reaction is further followed by solid-liquid separation, washing and vacuum drying.
Preferably, the solid-liquid separation method comprises centrifugation.
Preferably, the washed detergent comprises N, N-dimethylformamide and/or methanol.
Preferably, the temperature of the vacuum drying is 80-250 ℃, such as 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ or the like, for a period of 6-24 hours, such as 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours or the like.
According to the preparation method, vacuum drying is carried out at the temperature, so that the bimetallic MOF catalyst with a stable structure is formed, the stability of the catalyst in the use process is improved, and the catalyst with high activity is obtained.
As a preferred technical scheme of the invention, the preparation method of the bimetallic MOF catalyst comprises the following steps:
(a) Dissolving a bimetallic salt and an organic ligand in a mixed solvent of N, N-dimethylformamide, ethanol and water to obtain a reaction solution, wherein the ratio of the molar quantity of metal ions to the molar quantity of the organic ligand in the reaction solution is 2-4;
(b) And (c) placing the reaction liquid in the step (a) in a reaction kettle, performing solvothermal reaction for 18-72h at the temperature of 80-160 ℃, centrifugally separating, washing the solid with N, N-dimethylformamide and methanol, and then drying in vacuum for 6-24h at the temperature of 80-250 ℃ to obtain the bimetallic MOF catalyst.
In a third aspect, the invention provides a method for the tandem catalysis of a cyclic alcohol to a cyclic lactone, the method comprising in a catalytic system a bimetallic MOF catalyst as described in the first aspect, a solvent, an aldehyde, oxygen, and a cyclic alcohol.
The synthesis method adopts the catalytic system, and can take cyclic alcohol as a raw material to synthesize cyclic lactone through catalysis, the reaction rate in the synthesis process is high, the conversion rate of the cyclic alcohol is high, and the cyclic lactone has high selectivity to the product cyclic lactone; the catalytic reaction can be stably carried out; the catalytic system has universality and can be used for catalyzing and synthesizing corresponding cyclic lactone by various cyclic alcohols containing substituent groups; wherein, the reaction mechanism of the catalytic system is as follows: firstly, benzaldehyde is oxidized into peroxy acid by oxygen under the catalysis of a metal active center; the generated peroxyacid is used as an oxidant, and the cyclic alcohol is oxidized into cyclic ketone under the catalysis of the metal active center; finally, the cyclic ketone is oxidized into cyclic lactone by peroxy acid through Bayer-Viigt oxidation reaction.
The method adopts the bimetallic MOF catalyst to catalyze the cyclic alcohol to synthesize the cyclic lactone, so that the problem that the conventional synthesis method needs to adopt cyclic ketone as a raw material to introduce an oxidant (hydrogen peroxide or peroxyacid) with explosion hazard and high price is solved; the catalyst system provided by the invention has the advantages of mild operation conditions, higher safety, lower cost and high yield of the cyclic lactone.
Preferably, the solvent is at least one selected from toluene, ethanol, ethyl acetate, N-dimethylformamide, tetrahydrofuran, dichloroethane, and dioxane.
Preferably, the aldehyde is selected from at least one of trifluoroacetaldehyde, isovaleraldehyde, benzaldehyde, m-chlorobenzaldehyde and p-nitrobenzaldehyde.
Preferably, the cyclic alcohol includes at least one of cyclic butanol, cyclopentanol, cyclohexanol, and cycloheptanol having a substituent R.
The cyclic alcohol in the present invention includes cyclic alcohols having a substituent and/or cyclic alcohols containing no substituent; preferably, the cyclic alcohol containing no substituent is selected from at least one of cyclobutylalcohol, cyclopentanol, cyclohexanol or cycloheptanol.
Preferably, the substituent R is selected from the group consisting of-CH 3 、-CH 2 CH 3 、-OCH 3 At least one of, -Br and-I.
Preferably, the position of substituent R in the cyclic alcohol includes at least one of ortho, meta and para positions.
Preferably, the method comprises the steps of mixing a bimetallic MOF catalyst, a solvent and cyclic alcohol to obtain a mixed solution, introducing oxygen into the mixed solution, and carrying out a reaction, wherein aldehyde is added in the reaction process; obtaining the cyclic lactone.
Preferably, stirring is accompanied during the reaction.
Preferably, the temperature of the reaction is 40-70 ℃, e.g., 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, etc.
Preferably, the reaction time is 3-6 hours, such as 3.5 hours, 4 hours, 4.5 hours, 5 hours, or 5.5 hours, etc.
Preferably, the aldehyde is added dropwise.
Compared with the prior art, the invention has the following beneficial effects:
(1) The bimetallic MOF catalyst is used for series catalysis of cyclic alcohol to synthesize cyclic lactone, and the cyclic alcohol has high conversion rate and high selectivity to the cyclic lactone;
(2) The bimetallic MOF catalyst has high stability in the process of synthesizing cyclic lactone by catalyzing cyclic alcohol in series, and the conversion rate and the selectivity are basically unchanged after the bimetallic MOF catalyst is recycled for a plurality of times;
(3) The method for synthesizing the cyclic lactone by catalyzing the cyclic alcohol in series has the characteristics of easy operation, simple equipment, easy realization and lower cost;
(4) The method for synthesizing the cyclic lactone by catalyzing the cyclic alcohol in series is suitable for synthesizing the corresponding cyclic lactone by catalyzing various cyclic alcohols containing substituent groups in series in one pot.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The experimental methods in the following examples are all conventional methods unless otherwise specified; the experimental materials used, unless specified, are all purchased from conventional biochemical reagent manufacturers.
Example 1
The catalyst in this embodiment is MgMn-MOF catalyst, and the preparation method comprises the following steps:
(1) Magnesium nitrate hexahydrate (0.1 mmol), manganese nitrate (0.4 mmol) and 2-hydroxy terephthalic acid (0.25 mmol) are dissolved in a mixed solution composed of N, N-dimethylformamide (10 mL), ethanol (4 mL) and water (1 mL), and the precursor solution is prepared by stirring;
(2) Transferring the precursor solution in the step (1) into a reaction kettle, and reacting for 18 hours at 80 ℃;
(3) Centrifuging to prepare bimetallic MgMn-MOF, washing with DMF and methanol for several times, and vacuum drying at 80 ℃ for 6h to obtain the MgMn-MOF catalyst;
the method for synthesizing the cyclic lactone by catalyzing the cyclic alcohol in series comprises the following steps:
(a) Weighing MgMn-MOF catalyst (40 mg), placing in a three-neck flask with a condenser tube, adding toluene (10 mL), 1mmol of cyclobutanol, introducing oxygen at a flow rate of 40mL/min, stirring at 40 ℃ for 3h, and dropwise adding 1mmol of trifluoroacetaldehyde in the reaction process;
(b) After the reaction is finished, taking mesitylene as an internal standard, quantitatively analyzing each component in the catalytic system by using an Shimadzu gas chromatograph, and calculating the yield of the cyclic butyrolactone on the basis of the quantitative analysis.
Example 2
The catalyst in this embodiment is a MgFe-MOF catalyst, and the preparation method thereof comprises the following steps:
(1) Magnesium sulfate (0.2 mmol), ferrous nitrate (0.3 mmol) and 2, 5-dihydroxyterephthalic acid (0.24 mmol) are dissolved in a mixed solution composed of N, N-dimethylformamide (10 mL), ethanol (3 mL) and water (2 mL), and a precursor solution is prepared by stirring;
(2) Transferring the precursor solution in the step (1) into a reaction kettle, and reacting for 24 hours at 90 ℃;
(3) And (3) centrifugally separating the prepared bimetallic MgFe-MOF, washing with DMF and methanol for several times, and vacuum drying at 90 ℃ for 7 hours to obtain the MgFe-MOF catalyst.
The method for synthesizing the cyclic lactone by catalyzing the cyclic alcohol in series comprises the following steps:
(a) Weighing MgFe-MOF catalyst (30 mg), placing in a three-neck flask with a condenser tube, adding ethanol (10 mL), introducing oxygen into 1mmol cyclopentanol at a flow rate of 30mL/min, stirring at 50deg.C for reacting for 4h, and dropwise adding isovaleraldehyde 2mmol during the reaction;
(b) After the reaction is finished, taking mesitylene as an internal standard, quantitatively analyzing each component in the catalytic system by using an Shimadzu gas chromatograph, and calculating the yield of the cyclopentanol on the basis of the quantitative analysis.
Example 3
The catalyst in this embodiment is a MgCo-MOF catalyst, and the preparation method thereof comprises the following steps:
(1) Magnesium acetate (0.3 mmol), cobalt nitrate hexahydrate (0.2 mmol) and 3-hydroxy-4, 4-biphenyl dicarboxylic acid (0.23 mmol) are dissolved in a mixed solution composed of N, N-dimethylformamide (10 mL), ethanol (2 mL) and water (3 mL), and the precursor solution is prepared by stirring;
(2) Transferring the precursor solution in the step (1) into a reaction kettle, and reacting for 30 hours at the temperature of 100 ℃;
(3) And (3) centrifugally separating the prepared bimetallic MgCo-MOF, washing with DMF and methanol for several times, and drying in vacuum at 100 ℃ for 8 hours to obtain the MgCo-MOF catalyst.
The method for synthesizing the cyclic lactone by catalyzing the cyclic alcohol in series comprises the following steps:
(a) MgCo-MOF catalyst (20 mg) is weighed and placed in a three-neck flask with a condenser tube, ethyl acetate (10 mL) and 1mmol of cyclohexanol are added, oxygen is introduced at the flow rate of 20mL/min, stirring is carried out for 5h at 60 ℃, and 3mmol of benzaldehyde is dropwise added in the reaction process;
(b) After the reaction is finished, taking mesitylene as an internal standard, quantitatively analyzing each component in the catalytic system by using an Shimadzu gas chromatograph, and calculating the yield of the cyclohexanolide to be 85 percent on the basis.
After 5 applications of the bimetallic MOF catalyst described in this example, the yield of the 5-th applied cyclohexanolide was 80%.
Example 4
The catalyst in this embodiment is a MgNi-MOF catalyst, and the preparation method comprises the following steps:
(1) Magnesium chloride (0.4 mmol), nickel nitrate hexahydrate (0.1 mmol) and 3, 3-dihydroxyl-4, 4-biphthalic acid (0.22 mmol) are dissolved in a mixed solution composed of N, N-dimethylformamide (10 mL), ethanol (1 mL) and water (4 mL), and the precursor solution is prepared by stirring;
(2) Transferring the precursor solution into a reaction kettle, and reacting for 36 hours at 110 ℃;
(3) And centrifugally separating the prepared bimetallic MgNi-MOF, washing with DMF and methanol for several times, and vacuum drying at 110 ℃ for 9 hours to obtain the MgNi-MOF catalyst.
The method for synthesizing the cyclic lactone by catalyzing the cyclic alcohol in series comprises the following steps:
(a) MgNi-MOF catalyst (10 mg) was weighed and placed in a three-necked flask with a condenser, N-dimethylformamide (10 mL) was added, 1mmol of cycloheptyl alcohol was introduced into the flask at a flow rate of 10mL/min, and the mixture was stirred and reacted for 6 hours at 70℃with dropwise addition of 4mmol of m-chlorobenzaldehyde during the reaction.
(b) After the reaction is finished, taking mesitylene as an internal standard, adopting an Shimadzu gas chromatograph to quantitatively analyze each component in the catalytic system, and calculating the yield of the cycloheptalactone to be 95 percent on the basis.
Example 5
The catalyst in this embodiment is a MgCu-MOF catalyst, and the preparation method thereof comprises the following steps:
(1) Magnesium nitrate hexahydrate (0.15 mmol), copper nitrate trihydrate (0.35 mmol), 2-hydroxy terephthalic acid (0.11 mmol), 2, 5-dihydroxy terephthalic acid (0.1 mmol) are dissolved in a mixed solution composed of N, N-dimethylformamide (10 mL), ethanol (3.5 mL) and water (1.5 mL), and the precursor solution is prepared by stirring;
(2) Transferring the precursor solution into a reaction kettle, and reacting at 120 ℃ for 42h;
(3) And (3) centrifugally separating the prepared bimetallic MgCu-MOF, washing with DMF and methanol for several times, and vacuum drying at 120 ℃ for 10 hours to obtain the MgCu-MOF catalyst.
The method for synthesizing the cyclic lactone by catalyzing the cyclic alcohol in series comprises the following steps:
(a) MgCu-MOF catalyst (40 mg) is weighed and placed in a three-neck flask with a condenser tube, tetrahydrofuran (10 mL) and 1mmol of 2-methyl-cyclobutanol are added, oxygen is introduced at the flow rate of 40mL/min, stirring is carried out for 3h at the temperature of 40 ℃, and 1.5mmol of p-nitrobenzaldehyde is dropwise added in the reaction process;
(b) After the reaction is finished, taking mesitylene as an internal standard, quantitatively analyzing each component in the catalytic system by using an Shimadzu gas chromatograph, and calculating the yield of the butyrolactone on the basis of the quantitative analysis.
Example 6
The catalyst in this embodiment is MgZn-MOF catalyst, and the preparation method comprises the following steps:
(1) Magnesium nitrate hexahydrate (0.25 mmol), zinc nitrate hexahydrate (0.25 mmol) and 3-hydroxy-4, 4-biphthalic acid (0.1 mmol), 3-dihydroxy-4, 4-biphthalic acid (0.1 mmol) were dissolved in a mixed solution composed of N, N-dimethylformamide (10 mL), ethanol (3.5 mL) and water (1.5 mL), and the precursor solution was prepared by stirring;
(2) Transferring the precursor solution into a reaction kettle, and reacting for 48 hours at 130 ℃;
(3) And centrifugally separating the prepared bimetallic MgZn-MOF, washing with DMF and methanol for several times, and vacuum drying at 130 ℃ for 11 hours to obtain the MgZn-MOF catalyst.
The method for synthesizing the cyclic lactone by catalyzing the cyclic alcohol in series comprises the following steps:
(a) MgZn-MOF catalyst (30 mg) is weighed and placed in a three-neck flask with a condenser tube, dichloroethane (10 mL) is added, 1mmol of 3-ethylcyclopentanol is introduced into the flask at a flow rate of 30mL/min, oxygen is introduced into the flask at 50 ℃, stirring is carried out for 4 hours, and 2.5mmol of trifluoroacetaldehyde is dropwise added in the reaction process;
(b) After the reaction is finished, taking mesitylene as an internal standard, adopting an Shimadzu gas chromatograph to quantitatively analyze each component in the catalytic system, and calculating the yield of the cyclopentanol to be 79 percent on the basis.
Example 7
The catalyst in this example is a MnFe-MOF catalyst, and the preparation method thereof comprises the following steps:
(1) Manganese dichloride (0.35 mmol), ferrous nitrate (0.15 mmol) and 2-hydroxy terephthalic acid (0.19 mmol) are dissolved in a mixed solution consisting of N, N-dimethylformamide (10 mL), ethanol (2.5 mL) and water (2.5 mL), and the mixed solution is stirred to prepare a precursor solution;
(2) Transferring the precursor solution into a reaction kettle, and reacting for 54 hours at 140 ℃;
(3) And centrifugally separating the prepared bimetal MnFe-MOF, washing the bimetal MnFe-MOF with DMF and methanol for a plurality of times, and vacuum drying the bimetal MnFe-MOF at 140 ℃ for 12 hours to obtain the MnFe-MOF catalyst.
The method for synthesizing the cyclic lactone by catalyzing the cyclic alcohol in series comprises the following steps:
(a) Weighing MnFe-MOF catalyst (20 mg), placing the catalyst into a three-neck flask with a condenser tube, adding dioxane (10 mL), introducing oxygen into 1mmol of 4-methoxycyclohexanol at a flow rate of 20mL/min, stirring and reacting for 5h at 60 ℃, and dropwise adding 3.5mmol of isovaleraldehyde in the reaction process;
(b) After the reaction is finished, taking mesitylene as an internal standard, quantitatively analyzing each component in the catalytic system by using an Shimadzu gas chromatograph, and calculating the yield of the cyclohexanolide to be 89% on the basis.
Example 8
The catalyst in this embodiment is a MnCo-MOF catalyst, and the preparation method thereof includes the following steps:
(1) Manganese sulfate (0.45 mmol), cobalt acetate hexahydrate (0.05 mmol) and 2, 5-dihydroxyterephthalic acid (0.18 mmol) are dissolved in a mixed solution composed of N, N-dimethylformamide (10 mL), ethanol (1.5 mL) and water (3.5 mL), and the precursor solution is prepared by stirring;
(2) Transferring the precursor solution into a reaction kettle, and reacting for 60 hours at 150 ℃;
(3) And centrifugally separating the prepared bimetal MnCo-MOF, washing the bimetal MnCo-MOF with DMF and methanol for several times, and drying the bimetal MnCo-MOF in vacuum at 150 ℃ for 13 hours to obtain the MnCo-MOF catalyst.
The method for synthesizing the cyclic lactone by catalyzing the cyclic alcohol in series comprises the following steps:
(a) Weighing MnCo-MOF catalyst (10 mg), placing the catalyst into a three-neck flask with a condenser tube, adding toluene (10 mL), 1mmol of 2-bromocycloheptyl alcohol, introducing oxygen at a flow rate of 10mL/min, stirring and reacting for 6 hours at 70 ℃, and dropwise adding 4mmol of benzaldehyde in the reaction process;
(b) After the reaction is finished, taking mesitylene as an internal standard, adopting an Shimadzu gas chromatograph to quantitatively analyze each component in the catalytic system, and calculating the yield of the cycloheptalactone to be 99 percent on the basis.
Example 9
The catalyst in this embodiment is a MnNi-MOF catalyst, and the preparation method thereof comprises the following steps:
(1) Manganese acetate (0.1 mmol), nickel acetate hexahydrate (0.4 mmol) and 3-hydroxy-4, 4-biphenyl dicarboxylic acid (0.17 mmol) are dissolved in a mixed solution composed of N, N-dimethylformamide (11 mL), ethanol (3 mL) and water (1 mL), and the precursor solution is prepared by stirring;
(2) Transferring the precursor solution into a reaction kettle, and reacting for 66 hours at 160 ℃;
(3) And centrifugally separating the prepared bimetal MnNi-MOF, washing with DMF and methanol for several times, and vacuum drying at 160 ℃ for 14h to obtain the MnNi-MOF catalyst.
The method for synthesizing the cyclic lactone by catalyzing the cyclic alcohol in series comprises the following steps:
(a) Weighing MnNi-MOF catalyst (40 mg), placing the catalyst into a three-neck flask with a condenser tube, adding ethanol (10 mL), 1mmol of 2-iodocyclobutanol, introducing oxygen at a flow rate of 40mL/min, stirring and reacting for 3h at 40 ℃, and dropwise adding 1.5mmol of m-chlorobenzaldehyde in the reaction process;
(b) After the reaction is finished, taking mesitylene as an internal standard, quantitatively analyzing each component in the catalytic system by using an Shimadzu gas chromatograph, and calculating the yield of the butyrolactone on the basis that the yield is 65%.
Example 10
The catalyst in this embodiment is a MnCu-MOF catalyst, and the preparation method thereof includes the following steps:
(1) Manganese dichloride (0.15 mmol), copper nitrate trihydrate (0.35 mmol) and 3, 3-dihydroxyl-4, 4-biphthalic acid (0.16 mmol) are dissolved in a mixed solution composed of N, N-dimethylformamide (9 mL), ethanol (3 mL) and water (3 mL), and precursor solution is prepared by stirring;
(2) Transferring the precursor solution into a reaction kettle, and reacting at 80 ℃ for 72 hours;
(3) And centrifugally separating the prepared bimetal MnCu-MOF, washing the bimetal MnCu-MOF with DMF and methanol for several times, and drying the bimetal MnCu-MOF in vacuum at 170 ℃ for 15 hours to obtain the MnCu-MOF catalyst.
The method for synthesizing the cyclic lactone by catalyzing the cyclic alcohol in series comprises the following steps:
(a) Weighing MnCu-MOF catalyst (30 mg), placing the catalyst into a three-neck flask with a condenser tube, adding ethyl acetate (10 mL), introducing oxygen into 1mmol cyclopentanol at a flow rate of 30mL/min, stirring and reacting for 4 hours at 50 ℃, and dropwise adding 2mmol of p-nitrobenzaldehyde in the reaction process;
(b) After the reaction is finished, taking mesitylene as an internal standard, adopting an Shimadzu gas chromatograph to quantitatively analyze each component in the catalytic system, and calculating the yield of the cyclopentanol to be 91 percent on the basis.
Example 11
The catalyst in this example is a MnZn-MOF catalyst, and the preparation method thereof comprises the following steps:
(1) Manganese nitrate (0.2 mmol), zinc nitrate hexahydrate (0.3 mmol) and 2-hydroxy terephthalic acid (0.05 mmol) and 2, 5-dihydroxyterephthalic acid (0.1 mmol) are dissolved in a mixed solution composed of N, N-dimethylformamide (8 mL), ethanol (3 mL) and water (4 mL), and precursor solution is prepared by stirring;
(2) Transferring the precursor solution into a reaction kettle, and reacting for 18 hours at 90 ℃;
(3) And centrifugally separating the prepared bimetal MnZn-MOF, washing the bimetal MnZn-MOF with DMF and methanol for several times, and drying the bimetal MnZn-MOF in vacuum at 180 ℃ for 16 hours to obtain the MnZn-MOF catalyst.
The method for synthesizing the cyclic lactone by catalyzing the cyclic alcohol in series comprises the following steps:
(a) Weighing MnZn-MOF (20 mg), placing the MnZn-MOF into a three-neck flask with a condenser tube, adding N, N-dimethylformamide (10 mL), introducing oxygen into the flask at a flow rate of 20mL/min, stirring the mixture for reaction for 5 hours at 60 ℃, and dropwise adding 2.5mmol of trifluoroacetaldehyde in the reaction process;
(b) After the reaction is finished, taking mesitylene as an internal standard, quantitatively analyzing each component in the catalytic system by using an Shimadzu gas chromatograph, and calculating the yield of the cyclohexanolide to be 92 percent on the basis.
Example 12
The catalyst in this embodiment is a FeCo-MOF catalyst, and the preparation method thereof comprises the following steps:
(1) Ferrous nitrate (0.25 mmol), cobalt nitrate hexahydrate (0.25 mmol) and 3-hydroxy-4, 4-biphthalic acid (0.04 mmol), 3-dihydroxy-4, 4-biphthalic acid (0.1 mmol) are dissolved in a mixed solution composed of N, N-dimethylformamide (8 mL), ethanol (4 mL) and water (3 mL), and the precursor solution is prepared by stirring;
(2) Transferring the precursor solution into a reaction kettle, and reacting for 24 hours at the temperature of 100 ℃;
(3) And centrifugally separating the prepared bimetallic FeCo-MOF, washing with DMF and methanol for several times, and vacuum drying at 190 ℃ for 17 hours to obtain the FeCo-MOF catalyst.
The method for synthesizing the cyclic lactone by catalyzing the cyclic alcohol in series comprises the following steps:
(a) Weighing FeCo-MOF catalyst (10 mg), placing in a three-neck flask with a condenser tube, adding tetrahydrofuran (10 mL), 1mmol of cycloheptyl alcohol, introducing oxygen at a flow rate of 10mL/min, stirring at 70 ℃ for reaction for 6 hours, and dropwise adding 3mmol of isovaleraldehyde in the reaction process;
(b) After the reaction is finished, taking mesitylene as an internal standard, adopting an Shimadzu gas chromatograph to quantitatively analyze each component in the catalytic system, and calculating the yield of the cycloheptalactone on the basis that the yield is 93%.
Example 13
The catalyst in this embodiment is a FeNi-MOF catalyst, and the preparation method thereof includes the following steps:
(1) Ferrous sulfate (0.3 mmol), nickel nitrate hexahydrate (0.2 mmol) and 2-hydroxy terephthalic acid (0.13 mmol) are dissolved in a mixed solution composed of N, N-dimethylformamide (7 mL), ethanol (4 mL) and water (4 mL), and the precursor solution is prepared by stirring;
(2) Transferring the precursor solution into a reaction kettle, and reacting for 30 hours at 110 ℃;
(3) And centrifuging to separate the prepared bimetallic FeNi-MOF, washing with DMF and methanol for several times, and vacuum drying at 200 ℃ for 18 hours to obtain the FeNi-MOF catalyst.
The method for synthesizing the cyclic lactone by catalyzing the cyclic alcohol in series comprises the following steps:
(a) Weighing FeNi-MOF catalyst (40 mg), placing in a three-neck flask with a condenser tube, adding dichloroethane (10 mL), introducing oxygen into 1mmol of 2-methyl cyclobutanol at a flow rate of 40mL/min, stirring and reacting for 3h at 40 ℃, and dropwise adding 3.5mmol of benzaldehyde in the reaction process;
(b) After the reaction is finished, taking mesitylene as an internal standard, quantitatively analyzing each component in the catalytic system by using an Shimadzu gas chromatograph, and calculating the yield of the butyrolactone on the basis that the yield is 95%.
Example 14
The catalyst in this embodiment is a FeCu-MOF catalyst, and the preparation method thereof comprises the following steps:
(1) Ferrous acetate (0.35 mmol), copper nitrate trihydrate (0.15 mmol) and 2, 5-dihydroxyterephthalic acid (0.125 mmol) are dissolved in a mixed solution composed of N, N-dimethylformamide (6 mL), ethanol (5 mL) and water (4 mL), and precursor solution is prepared by stirring;
(2) Transferring the precursor solution into a reaction kettle, and reacting for 36 hours at 120 ℃;
(3) The prepared bimetallic FeCu-MOF is centrifugally separated, washed by DMF and methanol for a plurality of times and dried in vacuum at 210 ℃ for 19 hours, so as to obtain the FeCu-MOF catalyst.
The method for synthesizing the cyclic lactone by catalyzing the cyclic alcohol in series comprises the following steps:
(a) FeCu-MOF catalyst (30 mg) was weighed and placed in a three-necked flask with a condenser tube, dioxane (10 mL) was added, 1mmol of 3-ethylcyclopentanol was introduced at a flow rate of 30mL/min, and the mixture was stirred and reacted for 4 hours at 50℃with dropwise addition of 4mmol of m-chlorobenzaldehyde during the reaction.
(b) After the reaction is finished, taking mesitylene as an internal standard, adopting an Shimadzu gas chromatograph to quantitatively analyze each component in the catalytic system, and calculating the yield of the cyclopentanol on the basis that the yield is 99%.
Example 15
The catalyst in this example is a FeZn-MOF catalyst, and the preparation method comprises the following steps:
(1) Ferrous chloride (0.4 mmol), zinc nitrate hexahydrate (0.1 mmol) and 3-hydroxy-4, 4-biphenyl dicarboxylic acid (0.25 mmol) are dissolved in a mixed solution composed of N, N-dimethylformamide (6 mL), ethanol (4 mL) and water (5 mL), and the precursor solution is prepared by stirring;
(2) Transferring the precursor solution into a reaction kettle, and reacting at 130 ℃ for 42h;
(3) And centrifugally separating the prepared bimetallic FeZn-MOF, washing with DMF and methanol for several times, and vacuum drying at 220 ℃ for 20 hours to obtain the FeZn-MOF catalyst.
The method for synthesizing the cyclic lactone by catalyzing the cyclic alcohol in series comprises the following steps:
(a) Weighing FeZn-MOF catalyst (20 mg), placing in a three-neck flask with a condenser tube, adding toluene (10 mL), 1mmol of 4-methoxycyclohexanol, introducing oxygen at a flow rate of 20mL/min, stirring at 60 ℃ for reaction for 5h, and dropwise adding 3.5mmol of p-nitrobenzaldehyde in the reaction process;
(b) After the reaction is finished, taking mesitylene as an internal standard, quantitatively analyzing each component in the catalytic system by using an Shimadzu gas chromatograph, and calculating the yield of the cyclohexanolide to be 98 percent on the basis.
Example 16
The catalyst in this example is a CoNi-MOF catalyst, and the preparation method comprises the following steps:
(1) Cobalt nitrate hexahydrate (0.35 mmol), nickel chloride (0.15 mmol) and 3, 3-dihydroxyl-4, 4-biphthalic acid (0.24 mmol) are dissolved in a mixed solution composed of N, N-dimethylformamide (5 mL), ethanol (5 mL) and water (5 mL), and the precursor solution is prepared by stirring;
(2) Transferring the precursor solution into a reaction kettle, and reacting for 48 hours at 140 ℃;
(3) The prepared bimetallic CoNi-MOF was centrifugally separated, washed with DMF and methanol several times and dried in vacuum at 230℃for 21 hours to obtain the CoNi-MOF catalyst.
The method for synthesizing the cyclic lactone by catalyzing the cyclic alcohol in series comprises the following steps:
(a) Weighing CoNi-MOF catalyst (10 mg), placing in a three-neck flask with a condenser tube, adding ethanol (10 mL), 1mmol of 2-bromocycloheptyl alcohol, introducing oxygen at a flow rate of 10mL/min, stirring at 70 ℃ for reaction for 6 hours, and dropwise adding 3mmol of trifluoroacetaldehyde in the reaction process;
(b) After the reaction is finished, taking mesitylene as an internal standard, adopting an Shimadzu gas chromatograph to quantitatively analyze each component in the catalytic system, and calculating the yield of the cycloheptalactone to be 88 percent on the basis.
Example 17
The catalyst in this example is a CoCu-MOF catalyst, and the preparation method comprises the following steps:
(1) Cobalt sulfate (0.1 mmol), copper acetate (0.4 mmol) and 2-hydroxy terephthalic acid (0.11 mmol), 2, 5-dihydroxy terephthalic acid (0.12 mmol) are dissolved in a mixed solution composed of N, N-dimethylformamide (12 mL), ethanol (2 mL) and water (1 mL), and the precursor solution is prepared by stirring;
(2) Transferring the precursor solution into a reaction kettle, and reacting for 54 hours at 150 ℃;
(3) The prepared bimetallic CoCu-MOF was centrifuged and washed several times with DMF and methanol and dried in vacuo at 240℃for 22h to give the CoCu-MOF catalyst.
The method for synthesizing the cyclic lactone by catalyzing the cyclic alcohol in series comprises the following steps:
(a) Weighing CoCu-MOF catalyst (40 mg) and placing in a three-neck flask with a condenser, adding ethyl acetate (10 mL), 1mmol of 2-iodocyclobutanol, introducing oxygen at a flow rate of 40mL/min, stirring at 40 ℃ for 3h, and dropwise adding 2.5mmol of isovaleraldehyde in the reaction process;
(b) After the reaction is finished, taking mesitylene as an internal standard, quantitatively analyzing each component in the catalytic system by using an Shimadzu gas chromatograph, and calculating the yield of the butyrolactone on the basis that the yield is 77%.
Example 18
The catalyst in this example is a CoZn-MOF catalyst, and the preparation method comprises the following steps:
(1) Cobalt acetate (0.2 mmol), zinc nitrate hexahydrate (0.3 mmol) and 3-dihydroxy-4, 4-biphthalic acid (0.10 mmol), 3-dihydroxy-4, 4-biphthalic acid (0.12 mmol) are dissolved in a mixed solution composed of N, N-dimethylformamide (12 mL), ethanol (1 mL) and water (2 mL), and a precursor solution is prepared by stirring;
(2) Transferring the precursor solution into a reaction kettle, and reacting at 160 ℃ for 60 hours;
(3) The prepared bimetallic CoZn-MOF was centrifuged and washed several times with DMF and methanol and dried in vacuo at 250℃for 23h to give the CoZn-MOF catalyst.
The method for synthesizing the cyclic lactone by catalyzing the cyclic alcohol in series comprises the following steps:
(a) Weighing CoZn-MOF catalyst (30 mg) and placing in a three-neck flask with a condenser tube, adding N, N-dimethylformamide (10 mL), introducing oxygen into 1mmol cyclopentanol at a flow rate of 30mL/min, stirring and reacting for 4 hours at 50 ℃, and dropwise adding 2mmol of benzaldehyde in the reaction process;
(b) After the reaction is finished, taking mesitylene as an internal standard, quantitatively analyzing each component in the catalytic system by using an Shimadzu gas chromatograph, and calculating the yield of the cyclopentanol on the basis of the quantitative analysis.
Example 19
The catalyst in this example is a NiCu-MOF catalyst, and the preparation method thereof comprises the following steps:
(1) Nickel nitrate hexahydrate (0.3 mmol), copper sulfate (0.2 mmol) and 2-hydroxy terephthalic acid (0.21 mmol) are dissolved in a mixed solution composed of N, N-dimethylformamide (13 mL), ethanol (1 mL) and water (1 mL), and the precursor solution is prepared by stirring;
(2) Transferring the precursor solution into a reaction kettle, and reacting for 66 hours at 80 ℃;
(3) The prepared bimetallic NiCu-MOF was centrifugally separated, washed with DMF and methanol several times and dried in vacuo at 80℃for 24h to give the NiCu-MOF catalyst.
The method for synthesizing the cyclic lactone by catalyzing the cyclic alcohol in series comprises the following steps:
(a) Weighing NiCu-MOF catalyst (20 mg), placing in a three-neck flask with a condenser tube, adding tetrahydrofuran (10 mL), introducing oxygen at a flow rate of 20mL/min, stirring and reacting for 5h at 60 ℃, and dropwise adding 3mmol of m-chlorobenzaldehyde in the reaction process;
(b) After the reaction is finished, taking mesitylene as an internal standard, quantitatively analyzing each component in the catalytic system by using an Shimadzu gas chromatograph, and calculating the yield of the cyclohexanolide on the basis of the quantitative analysis.
Example 20
The catalyst in this example is a NiZn-MOF catalyst, and the preparation method thereof comprises the following steps:
(1) Nickel sulfate (0.4 mmol), zinc sulfate (0.1 mmol) and 2, 5-dihydroxyterephthalic acid (0.20 mmol) are dissolved in a mixed solution composed of N, N-dimethylformamide (10 mL), ethanol (1 mL) and water (4 mL), and a precursor solution is prepared by stirring;
(2) Transferring the precursor solution into a reaction kettle, and reacting at 90 ℃ for 72h;
(3) The prepared bimetallic NiZn-MOF was centrifugally separated, washed with DMF and methanol several times and dried in vacuo at 90℃for 6h to give the NiZn-MOF catalyst.
The method for synthesizing the cyclic lactone by catalyzing the cyclic alcohol in series comprises the following steps:
(a) Weighing NiZn-MOF catalyst (10 mg), placing in a three-neck flask with a condenser tube, adding dichloroethane (10 mL), introducing oxygen at a flow rate of 10mL/min, stirring and reacting for 6h at 70 ℃, and dropwise adding 4mmol of p-nitrobenzaldehyde in the reaction process;
(b) After the reaction is finished, taking mesitylene as an internal standard, adopting an Shimadzu gas chromatograph to quantitatively analyze each component in the catalytic system, and calculating the yield of the cycloheptalactone to be 98 percent on the basis.
Example 21
The catalyst in this embodiment is a CuZn-MOF catalyst, and the preparation method thereof comprises the following steps:
(1) Copper chloride (0.25 mmol), zinc acetate hexahydrate (0.25 mmol) and 2, 5-dihydroxyterephthalic acid (0.19 mmol) are dissolved in a mixed solution composed of N, N-dimethylformamide (10 mL), ethanol (2.5 mL) and water (2.5 mL), and the precursor solution is prepared by stirring;
(2) Transferring the precursor solution into a reaction kettle, and reacting for 24 hours at the temperature of 100 ℃;
(3) And centrifugally separating the prepared bimetal CuZn-MOF, washing the bimetal CuZn-MOF with DMF and methanol for a plurality of times, and drying the bimetal CuZn-MOF in vacuum at 100 ℃ for 12 hours to obtain the CuZn-MOF catalyst.
The method for synthesizing the cyclic lactone by catalyzing the cyclic alcohol in series comprises the following steps:
(a) Weighing CuZn-MOF catalyst (40 mg), placing in a three-neck flask with a condenser tube, adding dioxane (10 mL), 1mmol of cyclobutanol, introducing oxygen at a flow rate of 40mL/min, stirring at 70 ℃ for reaction for 6 hours, and dropwise adding 4mmol of benzaldehyde in the reaction process;
(b) After the reaction is finished, taking mesitylene as an internal standard, quantitatively analyzing each component in the catalytic system by using an Shimadzu gas chromatograph, and calculating the yield of the butyrolactone on the basis that the yield is 85%.
Comparative example 1
The comparative example differs from example 1 only in that the catalyst contains only Mg, i.e. is a single metal MOF catalyst; in the preparation process, the equimolar amount of manganese nitrate is replaced by magnesium nitrate hexahydrate, and other parameters and conditions are identical to those of the example 1.
Under the same synthesis conditions as in example 1, the yield of the cyclic lactone was 2%.
Comparative example 2
The comparative example differs from example 1 only in that the catalyst contains only Mn, i.e. is a monometal MOF catalyst, and in its preparation, equimolar amounts of magnesium nitrate hexahydrate are replaced by manganese nitrate, other parameters and conditions being exactly the same as in example 1.
Under the same synthesis conditions as in example 1, the yield of the cyclic lactone was 20%.
Comparative example 3
The comparative example differs from example 2 only in that the catalyst contains only Fe, i.e., is a single metal MOF catalyst, and in its preparation, the equimolar amount of magnesium sulfate is replaced with ferrous nitrate, and other parameters and conditions are exactly the same as those of example 2.
Under the same synthesis conditions as for the cyclic lactone of example 2, the yield of the cyclic lactone was 17%.
Comparative example 4
The comparative example differs from example 3 only in that the catalyst contains only Co, i.e., is a monometal MOF catalyst, and in its preparation, the equimolar amount of magnesium acetate is replaced by cobalt nitrate hexahydrate, and other parameters and conditions are exactly the same as in example 3.
Under the same synthesis conditions as in example 3, the yield of the cyclic lactone was 5%.
Comparative example 5
The comparative example differs from example 4 only in that the catalyst contains only Ni, i.e. is a monometal MOF catalyst, and in its preparation, the equimolar amount of magnesium chloride is replaced by nickel nitrate hexahydrate, and other parameters and conditions are exactly the same as in example 4.
Under the same synthesis conditions as in example 4, the yield of the cyclic lactone was 35%.
Comparative example 6
The comparative example differs from example 5 only in that the catalyst contains only Cu, i.e., is a monometal MOF catalyst, and in its preparation, equimolar amounts of magnesium nitrate hexahydrate are replaced with copper nitrate hexahydrate, and other parameters and conditions are exactly the same as those of example 5.
Under the same synthesis conditions as in example 5, the yield of the cyclic lactone was 10%.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.

Claims (29)

1. A method for synthesizing cyclic lactone by catalyzing cyclic alcohol in series, which is characterized in that a catalytic system of the method comprises a bimetallic MOF catalyst, a solvent, aldehyde, oxygen and cyclic alcohol;
wherein the bimetal in the bimetal MOF catalyst is selected from any two of Mg, mn, fe, co, ni, cu or Zn, and the organic ligand of the bimetal MOF catalyst is selected from any one or a combination of at least two of 2-hydroxy terephthalic acid, 2, 5-dihydroxy terephthalic acid, 3-hydroxy-4, 4-biphenyl dicarboxylic acid or 3, 3-dihydroxy-4, 4-biphenyl dicarboxylic acid.
2. The method of claim 1, wherein the ratio of the molar amount of metal element to the molar amount of organic ligand in the bimetallic MOF catalyst is from 2 to 4.
3. The method of claim 2, wherein the ratio of the molar amount of metal element to the molar amount of organic ligand in the bimetallic MOF catalyst is from 2.2 to 3.3.
4. The method of claim 1, wherein the bimetal is selected from any two of Mn, fe, co, ni or Cu.
5. The process of claim 1 wherein the organic ligand is selected from the group consisting of a mixture of 2, 5-dihydroxyterephthalic acid and 3, 3-dihydroxy-4, 4-diphthalic acid, a mixture of 2-hydroxyterephthalic acid and 2, 5-dihydroxyterephthalic acid, and a mixture of 3-hydroxy-4, 4-diphthalic acid and 3, 3-dihydroxy-4, 4-diphthalic acid.
6. The method of claim 1, wherein the bimetallic MOF catalyst is prepared by a process comprising: dissolving a bimetallic salt and an organic ligand in a solvent to obtain a reaction solution, and then carrying out solvothermal reaction to obtain the bimetallic MOF catalyst.
7. The method of claim 6, wherein the bimetallic salt is selected from the group consisting of divalent metal salts.
8. The method of claim 7, wherein the anion of the divalent metal salt is selected from at least one of nitrate, sulfate, acetate, and chloride.
9. The method of claim 6, wherein the solvent is selected from the group consisting of N, N-dimethylformamide, ethanol, and water.
10. The method of claim 9, wherein the volume ratio of N, N-dimethylformamide, ethanol, and water in the mixed solvent is (5-15): 1-5.
11. The method according to claim 6, wherein the ratio of the molar amount of the metal ions in the reaction solution to the molar amount of the organic ligand is 2 to 4.
12. The method according to claim 6, wherein the molar concentration of the metal ions in the reaction solution is 0.02 to 0.04mmol/mL.
13. The method of claim 12, wherein the molar concentration of metal ions in the reaction solution is from 0.03 to 0.035mmol/mL.
14. The method of claim 6, wherein the solvothermal reaction is at a temperature of 80-160 ℃ and for a period of 18-72 hours.
15. The method of claim 6, wherein the solvothermal reaction is further followed by solid-liquid separation, washing, and vacuum drying.
16. The method of claim 15, wherein the method of solid-liquid separation comprises centrifugation.
17. The method of claim 15, wherein the washed detergent comprises N, N-dimethylformamide and/or methanol.
18. The method of claim 15, wherein the vacuum drying is performed at a temperature of 80-250 ℃ for a time of 6-24 hours.
19. The method of claim 6, wherein the method of preparing the bimetallic MOF catalyst comprises the steps of:
(a) Dissolving a bimetallic salt and an organic ligand in a mixed solvent of N, N-dimethylformamide, ethanol and water to obtain a reaction solution, wherein the ratio of the molar quantity of metal ions to the molar quantity of the organic ligand in the reaction solution is 2-4;
(b) And (c) placing the reaction liquid in the step (a) in a reaction kettle, performing solvothermal reaction for 18-72h at the temperature of 80-160 ℃, centrifugally separating, washing the solid with N, N-dimethylformamide and methanol, and then drying in vacuum for 6-24h at the temperature of 80-250 ℃ to obtain the bimetallic MOF catalyst.
20. The method of claim 1, wherein the solvent is selected from at least one of toluene, ethanol, ethyl acetate, N-dimethylformamide, tetrahydrofuran, dichloroethane, and dioxane.
21. The method of claim 1, wherein the aldehyde is selected from at least one of trifluoroacetaldehyde, isopentyl aldehyde, benzaldehyde, m-chlorobenzaldehyde, and p-nitrobenzaldehyde.
22. The method of claim 1, wherein the cyclic alcohol comprises at least one of cyclic butanol, cyclopentanol, cyclohexanol, and cycloheptanol having substituent R.
23. The method of claim 22, wherein the substituent R is selected from-CH 3 、-CH 2 CH 3 、-OCH 3 At least one of, -Br and-I.
24. The method of claim 22, wherein the position of substituent R in the cyclic alcohol comprises at least one of ortho, meta, and para.
25. The method of claim 1, comprising mixing a bimetallic MOF catalyst, a solvent and a cyclic alcohol to obtain a mixed solution, introducing oxygen into the mixed solution to react, and adding aldehyde during the reaction; obtaining the cyclic lactone.
26. The method of claim 25, wherein stirring is accompanied during the reaction.
27. The method of claim 25, wherein the temperature of the reaction is 40-70 ℃.
28. The method of claim 25, wherein the reaction is for a period of 3 to 6 hours.
29. The method of claim 25, wherein the aldehyde is added dropwise.
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