Eureka AIR delivers breakthrough ideas for toughest innovation challenges, trusted by R&D personnel around the world.

Bimetal MOF catalyst for synthesizing cyclic lactone by tandem catalysis of cyclic alcohol as well as preparation method and application of bimetal MOF catalyst

A technology for catalyzing cyclic alcohols and bimetals, applied in organic compound/hydride/coordination complex catalysts, physical/chemical process catalysts, catalytic reactions, etc., can solve problems such as explosion and expensive, and achieve simple equipment and low cost. , highly selective effect

Pending Publication Date: 2021-11-26
THE NAT CENT FOR NANOSCI & TECH NCNST OF CHINA
View PDF3 Cites 4 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] At present, the most reliable class of reactions for the preparation of cyclic lactones is to synthesize cyclic ketones from cyclic ketones by Baeyer-Villiger Oxidation (Baeyer-Villiger Oxidation); however, this reaction usually requires the use of hydrogen peroxide Strong oxidizing agents such as peroxyacids (such as peracetic acid, trifluoroperoxyacetic acid, and m-chloroperoxybenzoic acid) are used as oxidizing agents, which are explosive hazards and are usually very expensive (see literature: R.A.Sheldon et al. The Baeyer-Villiger Reaction: New Developments toward Greener Procedures.Chem.Rev., 2004,104,4105-4123.); Avelino Corma et al. in dioxane solvent, with H 2 o 2 (35%) as an oxidant, using Sn-β molecular sieve as a catalyst to catalyze the oxidation of cyclohexanone, after reacting for 3 hours at 90°C, the yield of cyclohexanolactone reached 52% (see literature: Avelino Corma et al. "Sn -zeolite beta as a heterogeneous chemoselective catalyst for Baeyer-Villiger oxidations."Nature, 2001, 412(6845), 423-425.)
In the preparation process of cyclic ketones, especially cyclohexanone, the formation of cyclohexanol is usually unavoidable. However, there are few reports on the synthesis method of directly preparing the corresponding cyclic lactones by using cyclic alcohols as raw materials through a heterogeneous catalytic oxidation process.

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0063] Catalyst described in this embodiment is MgMn-MOF catalyst, and its preparation method comprises the following steps:

[0064] (1) Dissolve magnesium nitrate hexahydrate (0.1mmol), manganese nitrate (0.4mmol) and 2-hydroxyterephthalic acid (0.25mmol) in N,N-dimethylformamide (10mL), ethanol (4mL) In a mixed solution composed of water (1mL), stir to prepare the precursor solution;

[0065] (2) Move the precursor solution in step (1) into the reaction kettle, and react at 80°C for 18h;

[0066] (3) Centrifuge the prepared bimetallic MgMn-MOF, wash it several times with DMF and methanol, and dry it in vacuum at 80° C. for 6 hours to obtain the MgMn-MOF catalyst;

[0067] The method of catalyzing cyclic alcohols in series to synthesize cyclic lactones:

[0068] (a) Weigh the MgMn-MOF catalyst (40mg) into a three-necked flask with a condenser, add toluene (10mL), 1mmol cyclobutanol, feed oxygen at a flow rate of 40mL / min, and stir the reaction at 40°C 3h, during the react...

Embodiment 2

[0071] Catalyst described in this embodiment is MgFe-MOF catalyst, and its preparation method comprises the following steps:

[0072] (1) Dissolve magnesium sulfate (0.2mmol), ferrous nitrate (0.3mmol) and 2,5-dihydroxyterephthalic acid (0.24mmol) in N,N-dimethylformamide (10mL), ethanol ( 3mL) and water (2mL) in the mixed solution that forms, stir preparation precursor solution;

[0073] (2) Move the precursor solution in step (1) into the reaction kettle, and react at 90°C for 24h;

[0074] (3) The prepared bimetallic MgFe-MOF was separated by centrifugation, washed several times with DMF and methanol, and dried in vacuum at 90° C. for 7 hours to obtain the MgFe-MOF catalyst.

[0075] The method of catalyzing cyclic alcohols in series to synthesize cyclic lactones:

[0076] (a) Weigh the MgFe-MOF catalyst (30mg) into a three-necked flask with a condenser, add ethanol (10mL), 1mmol cyclopentanol, feed oxygen at a flow rate of 30mL / min, and stir the reaction at 50°C 4h, 2mm...

Embodiment 3

[0079] The catalyst described in this embodiment is a MgCo-MOF catalyst, and its preparation method comprises the following steps:

[0080] (1) Dissolve magnesium acetate (0.3mmol), cobalt nitrate hexahydrate (0.2mmol) and 3-hydroxy-4,4-biphenyldicarboxylic acid (0.23mmol) in N,N-dimethylformamide (10mL) , ethanol (2mL) and water (3mL) in the mixed solution that forms, stir preparation precursor solution;

[0081] (2) Move the precursor solution in step (1) into the reaction kettle, and react at 100°C for 30h;

[0082] (3) The prepared bimetallic MgCo-MOF was separated by centrifugation, washed several times with DMF and methanol, and dried in vacuum at 100 °C for 8 h to obtain the MgCo-MOF catalyst.

[0083] The method of catalyzing cyclic alcohols in series to synthesize cyclic lactones:

[0084](a) Weigh the MgCo-MOF catalyst (20mg) into a three-necked flask with a condenser, add ethyl acetate (10mL), 1mmol cyclohexanol, and feed oxygen at a flow rate of 20mL / min, at 60°C...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention relates to a bimetallic MOF catalyst for synthesizing cyclic lactone by tandem catalysis of cyclic alcohol as well as a preparation method and application of the bimetal MOF catalyst. The 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 form one or a combination of at least two of 2-hydroxyterephthalic acid, 2, 5-dihydroxyterephthalic acid, 3-hydroxy-4, 4-diphenyldicarboxylic acid or 3, 3-dihydroxy-4, 4-diphenyldicarboxylic acid. the bimetallic MOF catalyst disclosed by the invention is used for preparing the cyclic lactone by 'one-pot ' tandem catalysis of the cyclic alcohol, and has the advantages of high reaction rate, mild reaction conditions, high yield and selectivity of the cyclic lactone and universality.

Description

technical field [0001] The invention belongs to the field of catalytic synthesis, and relates to a bimetallic MOF catalyst for catalyzing ring alcohols to synthesize ring lactones in series, a preparation method and application thereof. Background technique [0002] The preparation of cyclic lactones is a valuable reaction in organic synthesis, which has many possible applications, for example, the synthesis of expensive intermediates or products such as antibiotics, steroids, pheromones, and polymerized monomers. [0003] At present, the most reliable class of reactions for the preparation of cyclic lactones is to synthesize cyclic ketones from cyclic ketones by Baeyer-Villiger Oxidation (Baeyer-Villiger Oxidation); however, this reaction usually requires the use of hydrogen peroxide Strong oxidizing agents such as peroxyacids (such as peracetic acid, trifluoroperoxyacetic acid, and m-chloroperoxybenzoic acid) are used as oxidizing agents, which are explosive hazards and ar...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22C07D307/33C08G83/00
CPCB01J31/2239B01J31/1691C08G83/008C07D307/33B01J2531/22B01J2531/72B01J2531/842B01J2531/845B01J2531/847B01J2531/16B01J2531/26B01J2231/70
Inventor 薛光信李国栋唐智勇
Owner THE NAT CENT FOR NANOSCI & TECH NCNST OF CHINA
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Eureka Blog
Learn More
PatSnap group products