CN106622385B - A kind of double-core magnesium-germanium tungsten oxygen cluster catalyst, preparation method and its usage - Google Patents
A kind of double-core magnesium-germanium tungsten oxygen cluster catalyst, preparation method and its usage Download PDFInfo
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- CN106622385B CN106622385B CN201611177171.7A CN201611177171A CN106622385B CN 106622385 B CN106622385 B CN 106622385B CN 201611177171 A CN201611177171 A CN 201611177171A CN 106622385 B CN106622385 B CN 106622385B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/22—Magnesium
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Abstract
The invention belongs to thioether class catalyst material preparation technical fields, are specifically related to a kind of preparation method and application of double-core magnesium-germanium tungsten oxygen cluster catalyst.The selective oxidation reaction of thio-ether type compounds may be implemented in this kind of catalyst, and for high conversion rate up to 92.7%, selectivity is up to 94.9%.
Description
Technical field
The invention belongs to multi-metal oxygen cluster catalyst material preparation technical fields, are directed to a kind of double-core magnesium-germanium tungsten
The technology of preparing of oxygen cluster catalyst lays the foundation for its catalytic applications.
Technical background
Multi-metal oxygen cluster chemical developer has been subjected to nearly more than 200 years history so far, has become in current inorganic chemistry
One of with fastest developing speed, field that intersection is most wide.The multi-metal oxygen cluster chemistry of early stage thinks inorganic oxacid (such as phosphoric acid, sulfuric acid, tungsten
Acid, molybdic acid etc.) through condensation can form dehydroamino acid.Multi-metal oxygen cluster chemistry is exactly the chemistry about isopolyacid and heteropoly acid, the former
It is related to same polyanionic, the latter is related to heteropolyanion.In multi-metal oxygen cluster, tungsten can form many same more and miscellaneous more tungsten oxygen
Cluster compound.Experiment show such compound have in terms of catalysis, phase transfer, selective oxidation and the pharmaceutical chemistry it is preferable before
Scape.
Sulfide oxidation is that corresponding sulfone compound is organic synthesis and industrial important reaction.Trace it to its cause be because
There is good bioactivity for sulfide oxide sulfoxide and sulfone, widely answered in the fine chemicals such as pesticide, medicine
With.Importantly, sulfone and sulfoxide are synthetic intermediates important in organic synthesis, in synthesis functional material and molecular recombination
Deng reaction in have broad application prospects.It is mainly used as the important centres such as manufacture dyestuff, medicine, fragrance, flavouring, pesticide
The raw material of body.In sulfide oxidation reaction, H2O2It is concerned as Green Oxidant, but H2O2Exist as oxidant
The problem of be that its oxidability is medium.Therefore, in order to preferably with H2O2Green oxidation sulfide compound is realized as oxidant
Main problem is to establish efficient, highly selective catalyst system.Therefore select suitable catalyst to solve this problem
It is crucial.
In recent years, in document report organic inorganic hybridization tungsten phosphorus oxygen cluster (Ezzat Rafie, et al, Journal
Of Molecular Catalysis A:Chemical, 2013,380,18-27) oxidation diphenyl sulfide, but reacting above
In there is catalyst synthesis it is complex the problems such as.
On the basis of document above, designing a sulfide oxidation and generating sulfone, synthesize simple efficient catalytic system is
Very necessary.By retrieval, patent document related with the present patent application is not yet found.
Summary of the invention
The purpose of this invention is to solve the selective oxidation process of previous catalyst thioether in the case where hydrogen peroxide is oxidant
It is middle to synthesize the problems such as complex.Provide a kind of preparation method of synthesizing new double-core magnesium-germanium tungsten oxygen cluster catalyst, to
There is preferable catalytic action in the selective oxidation of thioether, realize the target of thioether molecule selective oxidation.
The scheme of the invention is double-core magnesium-germanium tungsten oxygen cluster catalyst, characterized in that structural formula are as follows:
Double-core magnesium-germanium tungsten oxygen cluster catalyst preparation method, metal magnesium salts, DMF are reacted with germanotungstic acid in aqueous solution
Construct metal double-core magnesium-germanium tungsten oxygen cluster；Double-core magnesium-germanium tungsten oxygen cluster catalyst monocrystalline is obtained using nature volatility process.
The preparation method, it is preferred that sequentially add magnesium chloride, N, N '-dimethyl in a clean beaker
Formamide (DMF) is dissolved in water, stirring and dissolving, adds germanotungstic acid, and heating stirring filters, and filtrate is slowly steamed at room temperature
Hair, obtains clear crystal, yield about 47 ~ 62% after 4 ~ 6 days.
The preparation method, it is preferred that 6 ~ 10h(of stirring is preferred at 30 ~ 50 DEG C, and 8 are stirred at 40 DEG C h).
The preparation method, it is preferred that magnesium chloride: N, N '-dimethyl formamide: the ratio between the amount of germanotungstic acid substance is
2~4 : 15~30 : 1~3。
The present invention also provides the strontium-purposes of the germanium tungsten oxygen cluster catalyst in thioether selective oxidation.Thioether is benzene
Methyl sulfide, to chlorobenzene methyl sulfide, p-nitrophenyl methyl sulfide, to methoxybenzene methyl sulfide etc..
Mentality of designing of the invention is as follows:
Metal magnesium salts and DMF with germanotungstic acid to that substitution reaction occur in aqueous solution and construct double-core magnesium-germanium tungsten oxygen cluster cooperation
Object；And double-core magnesium-germanium tungsten oxygen cluster catalyst monocrystalline has been obtained using nature volatility process；
Double-core magnesium with clear structure-germanium tungsten oxygen cluster catalyst is applied to selectively to urge under the conditions of the hydrogen peroxide of thioether
Change in oxidation, realizes the highly selective target of the high conversion of thioether selective oxidation.
What the crystal structure information of this kind of catalyst obtained by the following method:
It synthesizes to obtain double-core magnesium-germanium tungsten oxygen cluster catalyst crystal by conventional solution reaction, specific description experiment
Method is as follows:
Magnesium chloride (2 ~ 4mmol), DMF (15 ~ 30mmol) and water 50 ~ 80 are sequentially added in the beaker of 100mL
ML, stirring and dissolving add germanotungstic acid (1 ~ 3mmol), and 6 ~ 10h is stirred at 30 ~ 50 DEG C, is cooled to room temperature, and filter, filter
Liquid slow evaporation at room temperature, obtains clear crystal [Mg (HCON (CH after 4 ~ 6 days3)6]2GeW12O40.Yield about 47 ~ 59%.
Product is characterized by single crystal X diffraction, elemental analysis, obtains the accurate information about crystal structure.Specifically
As a result as follows:
The molecular formula of crystal is [Mg (HCON (CH3)6]2GeW12O40, wherein cationic portion is that magnesium metal is formed with DMF
Match cations, anion GeW12O40, the two by electrostatic attraction interaction be combined together.
This invention mainly synthesis double-core magnesium-germanium tungsten oxygen cluster catalyst, has been applied to thio-ether type compounds
Selective oxidation.The selective oxidation of sulfide compound may be implemented in this kind of catalyst, and for high conversion rate up to 92.7%, selectivity is high
Up to 94.9%.The preparation method reaction process of such catalyst is simple.
Above-mentioned thioether be thioanisole, to chlorobenzene methyl sulfide, to methyl thiobenzoxide, to methoxybenzene methyl sulfide etc., turn
Rate selectively passes through gas chromatographic detection.
The present invention provides double-core magnesium tungsten oxygen cluster catalyst and has the following characteristics that
Preparation method is simple and catalyst all has specific molecular structure, is conducive to study mechanism of catalytic reaction.
Catalyst can be used for multiple times, and be still able to maintain good catalytic activity after processing, have convenient for can be easily separated
Conducive to industrialized production.
Detailed description of the invention
Fig. 1 compound [Mg (HCON (CH3)6]2GeW12O40Crystal structure.
Specific embodiment
Below with reference to embodiment, the present invention is described in detail, but the scope of protection is not limited by this.
The raw materials used in the present invention can all be bought from market, such as DMF full name N, N '-dimethyl formamide, be purchased from traditional Chinese medicines collection
Chemical reagent Co., Ltd of group.
Embodiment 1: compound [[Mg (HCON (CH3)6]2GeW12O40Preparation
Sequentially add magnesium chloride (2mmol), DMF (16mmol) and water 50mL in the beaker of 100mL, stirring and dissolving,
Germanotungstic acid (1mmol) is added, 6h is stirred at 40 DEG C, is cooled to room temperature, is filtered, filtrate slow evaporation at room temperature, 4 ~ 6 days
After obtain clear crystal [Mg (HCON (CH3)6]2GeW12O40.Yield about 56%.
Embodiment 2: compound [[Mg (HCON (CH3)6]2GeW12O40Preparation
50 mL of magnesium chloride (3mmol), DMF (30mmol) and water is sequentially added in the beaker of 100mL, is stirred molten
Solution, adds germanotungstic acid (2mmol), stirs 10h at 50 DEG C, be cooled to room temperature, and filters, filtrate slow evaporation at room temperature, and 4
Clear crystal [Mg (HCON (CH is obtained after ~ 6 days3)6]2GeW12O40.Yield about 52%.
Embodiment 3: compound [[Mg (HCON (CH3)6]2GeW12O40Preparation
80 mL of magnesium chloride (4mmol), DMF (15mmol) and water is sequentially added in the beaker of 100mL, is stirred molten
Solution, adds germanotungstic acid (3mmol), stirs 6h at 30 DEG C, be cooled to room temperature, and filters, filtrate slow evaporation at room temperature, 4 ~
Clear crystal [Mg (HCON (CH is obtained after 6 days3)6]2GeW12O40.Yield about 49%.
Embodiment 4: compound [[Mg (HCON (CH3)6]2GeW12O40Preparation
Sequentially add magnesium chloride (4mmol), DMF (30mmol) and water 50mL in the beaker of 100mL, stirring and dissolving,
Germanotungstic acid (1mmol) is added, 8h is stirred at 30 DEG C, is cooled to room temperature, is filtered, filtrate slow evaporation at room temperature, 4 ~ 6 days
After obtain clear crystal [Mg (HCON (CH3)6]2GeW12O40.Yield about 47%.
Embodiment 5: compound [[Mg (HCON (CH3)6]2GeW12O40Preparation
70 mL of magnesium chloride (3mmol), DMF (20mmol) and water is sequentially added in the beaker of 100mL, is stirred molten
Solution, adds germanotungstic acid (2mmol), stirs 10h at 50 DEG C, be cooled to room temperature, and filters, filtrate slow evaporation at room temperature,
Clear crystal [Mg (HCON (CH is obtained after 4 ~ 6 days3)6]2GeW12O40.Yield about 61%.
Embodiment 6: compound [[Mg (HCON (CH3)6]2GeW12O40Preparation
Sequentially add magnesium chloride (4mmol), DMF (30mmol) and water 50mL in the beaker of 100mL, stirring and dissolving,
Germanotungstic acid (2mmol) is added, 8h is stirred at 40 DEG C, is cooled to room temperature, is filtered, filtrate slow evaporation at room temperature, 4 ~ 6
Clear crystal [Mg (HCON (CH is obtained after it3)6]2GeW12O40.Yield about 55%.
Embodiment 7: compound [[Mg (HCON (CH3)6]2GeW12O40Preparation
Sequentially add magnesium chloride (2mmol), DMF (15mmol) and water 60mL in the beaker of 100mL, stirring and dissolving,
Germanotungstic acid (3mmol) is added, 6h is stirred at 30 DEG C, is cooled to room temperature, is filtered, filtrate slow evaporation at room temperature, 4 ~ 6 days
After obtain clear crystal [Mg (HCON (CH3)6]2GeW12O40.Yield about 51%.
Embodiment 8: compound [[Mg (HCON (CH3)6]2GeW12O40Preparation
70 mL of magnesium chloride (2mmol), DMF (30mmol) and water is sequentially added in the beaker of 100mL, is stirred molten
Solution, adds germanotungstic acid (2mmol), stirs 8h at 40 DEG C, be cooled to room temperature, and filters, filtrate slow evaporation at room temperature, 4 ~
Clear crystal [Mg (HCON (CH is obtained after 6 days3)6]2GeW12O40.Yield about 58%.
Embodiment 9: compound [[Mg (HCON (CH3)6]2GeW12O40Multi-metal oxygen cluster catalyst is to thio-ether type compounds
Catalysis oxidation application
With compound [[Mg (HCON (CH3)6]2GeW12O40For: take 0.25mmol thioether to be dissolved in 1 mL methanol,
0.3mmol hydrogen peroxide is added catalyst 20mg, reacts 4-8 hours under 40 °C, with gas chromatographic detection, specific sulfide oxidation
Data be shown in Table 2.
2. compound of table [Mg (HCON (CH3)6]2GeW12O40 To thioether selective oxidation the results list
Fig. 1 is compound [[Mg (HCON (CH3)6]2GeW12O40Crystal structure.
Table 1 is the crystallographic data of the compound.
Table 1
Claims (7)
1. double-core magnesium-germanium tungsten oxygen cluster catalyst, characterized in that structural formula are as follows:
。
2. double-core magnesium-germanium tungsten oxygen cluster catalyst preparation method according to claim 1, characterized in that double-core magnesium-germanium tungsten oxygen
Metal magnesium salts, DMF are reacted with germanotungstic acid in aqueous solution and construct metal double-core magnesium-germanium tungsten oxygen by the preparation method of cluster catalyst
Cluster；Double-core magnesium-germanium tungsten oxygen cluster catalyst monocrystalline is obtained using nature volatility process.
3. preparation method according to claim 2, characterized in that sequentially added in a clean beaker magnesium chloride,
N, N '-dimethyl formamide (DMF) are dissolved in water, stirring and dissolving, add germanotungstic acid, heating stirring, at 30 ~ 50 DEG C
6 ~ 10h, filtering are stirred, filtrate slow evaporation at room temperature obtains clear crystal, yield 47 ~ 62% after 4 ~ 6 days.
4. preparation method according to claim 3, characterized in that stir 8 h at 40 DEG C.
5. preparation method according to claim 3, characterized in that magnesium chloride: N, N '-dimethyl formamide: germanotungstic acid object
The ratio between amount of matter is 2 ~ 4: 15 ~ 30: 1 ~ 3.
6. double-core magnesium-purposes of the germanium tungsten oxygen cluster catalyst in thioether selective oxidation according to claim 1.
7. purposes according to claim 6, characterized in that thioether is thioanisole, to chlorobenzene methyl sulfide, p-nitrophenyl first
Thioether, to methoxybenzene methyl sulfide.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2008222597A (en) * | 2007-03-09 | 2008-09-25 | Nagoya Institute Of Technology | METHOD FOR PRODUCING beta-FLUOROMETHYLCARBONYL DERIVATIVE |
| CN101890346A (en) * | 2009-05-19 | 2010-11-24 | 中国石油化工股份有限公司 | Heteropoly acid catalyst and preparation method thereof |
| CN103787843A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Method for preparing tert-amyl methyl ether |
| CN105618151A (en) * | 2015-12-22 | 2016-06-01 | 聊城大学 | Strontium-germanium tungsten oxygen cluster catalyst, preparation method and application of strontium-germanium tungsten oxygen cluster catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008222597A (en) * | 2007-03-09 | 2008-09-25 | Nagoya Institute Of Technology | METHOD FOR PRODUCING beta-FLUOROMETHYLCARBONYL DERIVATIVE |
| CN101890346A (en) * | 2009-05-19 | 2010-11-24 | 中国石油化工股份有限公司 | Heteropoly acid catalyst and preparation method thereof |
| CN103787843A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Method for preparing tert-amyl methyl ether |
| CN105618151A (en) * | 2015-12-22 | 2016-06-01 | 聊城大学 | Strontium-germanium tungsten oxygen cluster catalyst, preparation method and application of strontium-germanium tungsten oxygen cluster catalyst |
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