CN106622385A - Double-core magnesium-germanium tungsten oxide cluster catalyst and preparing method and application thereof - Google Patents
Double-core magnesium-germanium tungsten oxide cluster catalyst and preparing method and application thereof Download PDFInfo
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- CN106622385A CN106622385A CN201611177171.7A CN201611177171A CN106622385A CN 106622385 A CN106622385 A CN 106622385A CN 201611177171 A CN201611177171 A CN 201611177171A CN 106622385 A CN106622385 A CN 106622385A
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- 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
- B01J31/26—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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- 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
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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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- 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
- 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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- 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
- 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 the technical field of preparation of sulfur ether type catalyst materials, and particularly relates to a preparing method of a magnesium-germanium tungsten oxide cluster catalyst and application. The kind of catalysts can achieve selective oxidation reactions of sulfur ether type chemical compounds, the conversion rate is up to 92.7%, and the selectivity is up to 94.9%.
Description
Technical field
The invention belongs to multi-metal oxygen cluster catalyst material preparing technical field, is directed to a kind of double-core magnesium-germanium tungsten
The technology of preparing of oxygen clusters catalyst, is that its catalytic applications lays the foundation.
Technical background
Multi-metal oxygen cluster chemical developer has been subjected to so far the history of nearly more than 200 years, in having become 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, sulphuric acid, tungsten
Acid, molybdic acid etc.）Jing condensations can form dehydroamino acid.Multi-metal oxygen cluster chemistry is exactly the chemistry with regard to 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 same many and miscellaneous many tungsten oxygen of many
Cluster compound.Experiment shows, before such compound has preferably in terms of catalysis, phase transfer, selective oxidation and pharmaceutical chemistry
Scape.
Sulfide oxidation is organic synthesiss and industrial important reaction for corresponding sulfone compound.Trace it to its cause be because
There is good biological activity for sulfide oxide sulfoxide and sulfone, widely should obtain in the fine chemicals such as pesticide, medicine
With.Importantly, sulfone and sulfoxide are synthetic intermediates important in organic synthesis, in complex functionality material and molecular recombination
Deng reaction in have broad application prospects.It is mainly used as manufacturing the important centres such as dyestuff, medicine, spice, flavoring agent, pesticide
The raw material of body.In sulfide oxidation reaction, H2O2Receive much concern as Green Oxidant, but H2O2Exist as oxidant
Problem be that its oxidability is medium.Therefore, in order to preferably with H2O2Green oxidation sulfide compound is realized as oxidant
Subject matter is to set up the efficient, catalyst system and catalyzing of high selectivity.Therefore select suitable catalyst to become and 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 react more than
In there are problems that catalyst synthesize.
On the basis of document above, one sulfide oxidation of design generates sulfone, synthesizes simple efficient catalytic system is
It is very necessary.By retrieval, patent document related with the present patent application is not yet found.
The content of the invention
The purpose of this invention is the selective oxidation process for solving conventional catalyst thioether in the case where hydrogen peroxide is oxidant
It is middle synthesis it is complex the problems such as.There is provided a kind of preparation method of synthesizing new double-core magnesium-germanium tungsten oxygen clusters catalyst, to
There is preferable catalytic action in the selective oxidation of thioether, the target of thioether molecule selective oxidation is realized.
The solution of the present invention is that double-core magnesium-germanium tungsten oxygen clusters catalyst is characterized in that, structural formula is：
The preparation method of double-core magnesium-germanium tungsten oxygen clusters catalyst, metal magnesium salt, DMF are constructed in aqueous with germanotungstic acid reaction
Metal double-core magnesium-germanium tungsten oxygen clusters；The monocrystalline of double-core magnesium-germanium tungsten oxygen clusters catalyst is obtained using nature volatility process.
Described preparation method, it is preferred that magnesium chloride, N, N '-dimethyl are sequentially added in the beaker of a cleaning
Methanamide (DMF) is dissolved in water, stirring and dissolving, adds germanotungstic acid, and heated and stirred is filtered, and filtrate is slowly steamed at room temperature
Send out, clear crystal, yield about 47 ~ 62% are obtained after 4 ~ 6 days.
Described preparation method, it is preferred that 6 ~ 10h is stirred at 30 ~ 50 DEG C（Preferably, 8 h are stirred at 40 DEG C）.
Described preparation method, it is preferred that magnesium chloride：N, N '-dimethyl Methanamide：The ratio of the amount of germanotungstic acid material is
2~4 : 15~30 : 1~3。
Present invention also offers the strontium-purposes of the germanium tungsten oxygen clusters catalyst in thioether selective oxidation.Thioether is benzene
Methyl sulfide, to chlorobenzene methyl sulfide, p-nitrophenyl methyl sulfide, to methoxybenzene methyl sulfide etc..
The mentality of designing of the present invention is as follows：
Be there is into substitution reaction with germanotungstic acid in aqueous in metal magnesium salt and DMF and construct double-core magnesium-germanium tungsten oxygen clusters coordination compound；And
The monocrystalline of double-core magnesium-germanium tungsten oxygen clusters catalyst has been obtained using nature volatility process；
Double-core with clear and definite structure magnesium-germanium tungsten oxygen clusters catalyst is applied to into selective catalysis oxygen under the conditions of the hydrogen peroxide of thioether
In change, the target of the high conversion high selectivity of thioether selective oxidation is realized.
What the crystal structure information of this kind of catalyst was obtained by the following method：
The crystal of double-core magnesium-germanium tungsten oxygen clusters catalyst is obtained by conventional solution reaction synthesis, experimental technique is specifically described
It is as follows：
Magnesium chloride (2 ~ 4mmol), DMF (15 ~ 30mmol) and the mL of water 50 ~ 80 are sequentially added in the beaker of 100mL,
Stirring and dissolving, adds germanotungstic acid (1 ~ 3mmol), and 6 ~ 10h is stirred at 30 ~ 50 DEG C, is cooled to room temperature, filters, and filtrate exists
Slow evaporation under 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, elementary analysiss, obtains the accurate information with regard to crystal structure.Specifically
As a result it is as follows：
The molecular formula of crystal is [Mg (HCON (CH3)6]2GeW12O40, wherein cationic moiety is magnesium metal and matching somebody with somebody that DMF is formed
Cations, anion is GeW12O40, the two is interacted by electrostatic attraction and is combined together.
This invention mainly synthesis double-core magnesium-germanium tungsten oxygen clusters catalyst, has been applied to thio-ether type compounds
Selective oxidation.This kind of catalyst can realize the selective oxidation of sulfide compound, and high conversion rate is up to 92.7%, and selectivity is high
Up to 94.9%.The preparation method course of reaction of such catalyst is simple.
Above-mentioned thioether be thioanisole, to chlorobenzene methyl sulfide, to methyl thiobenzoxide, to methoxybenzene methyl sulfide etc., turn
Rate, selectivity passes through gas chromatographic detection.
The present invention provides double-core magnesium tungsten oxygen clusters catalyst and has the characteristics that：
Preparation method is simple and catalyst all has clear and definite molecular structure, is conducive to studying mechanism of catalytic reaction.
Catalyst is easy to can be easily separated, and can be used for multiple times Jing after processing, and remains to keep good catalysis activity, has
Beneficial to industrialized production.
Description of the drawings
Fig. 1. compound [Mg (HCON (CH3)6]2GeW12O40Crystal structure.
Specific embodiment
With reference to embodiment, the present invention is described in detail, but protection domain is not limited by this.
The present invention is raw materials used all can be bought from market, such as DMF full name N, N '-dimethyl Methanamide, purchased from traditional Chinese medicines collection
Chemical reagent company limited of group.
Embodiment 1：Compound [[Mg (HCON (CH3)6]2GeW12O40Preparation
Magnesium chloride (2mmol), DMF (16mmol) and water 50mL, stirring and dissolving are sequentially added in the beaker of 100mL, then is added
Enter germanotungstic acid (1mmol), at 40 DEG C 6h is stirred, be cooled to room temperature, filter, filtrate slow evaporation at room temperature, after 4 ~ 6 days
To clear crystal [Mg (HCON (CH3)6]2GeW12O40.Yield about 56%.
Embodiment 2：Compound [[Mg (HCON (CH3)6]2GeW12O40Preparation
Sequentially add magnesium chloride (3mmol), DMF (30mmol) and the mL of water 50 in the beaker of 100mL, stirring and dissolving, then
Germanotungstic acid (2mmol) is added, at 50 DEG C 10h is stirred, be cooled to room temperature, filtered, filtrate slow evaporation at room temperature, 4 ~ 6 days
After obtain clear crystal [Mg (HCON (CH3)6]2GeW12O40.Yield about 52%.
Embodiment 3：Compound [[Mg (HCON (CH3)6]2GeW12O40Preparation
Sequentially add magnesium chloride (4mmol), DMF (15mmol) and the mL of water 80 in the beaker of 100mL, stirring and dissolving, then
Germanotungstic acid (3mmol) is added, at 30 DEG C 6h is stirred, be cooled to room temperature, filtered, filtrate slow evaporation at room temperature, after 4 ~ 6 days
Obtain clear crystal [Mg (HCON (CH3)6]2GeW12O40.Yield about 49%.
Embodiment 4：Compound [[Mg (HCON (CH3)6]2GeW12O40Preparation
Magnesium chloride (4mmol), DMF (30mmol) and water 50mL, stirring and dissolving are sequentially added in the beaker of 100mL, then is added
Enter germanotungstic acid (1mmol), at 30 DEG C 8h is stirred, be cooled to room temperature, filter, filtrate slow evaporation at room temperature, after 4 ~ 6 days
To clear crystal [Mg (HCON (CH3)6]2GeW12O40.Yield about 47%.
Embodiment 5：Compound [[Mg (HCON (CH3)6]2GeW12O40Preparation
Sequentially add magnesium chloride (3mmol), DMF (20mmol) and the mL of water 70 in the beaker of 100mL, stirring and dissolving, then
Germanotungstic acid (2mmol) is added, at 50 DEG C 10h is stirred, be cooled to room temperature, filtered, filtrate slow evaporation at room temperature, 4 ~ 6 days
After obtain clear crystal [Mg (HCON (CH3)6]2GeW12O40.Yield about 61%.
Embodiment 6：Compound [[Mg (HCON (CH3)6]2GeW12O40Preparation
Magnesium chloride (4mmol), DMF (30mmol) and water 50mL, stirring and dissolving are sequentially added in the beaker of 100mL, then is added
Enter germanotungstic acid (2mmol), at 40 DEG C 8h is stirred, be cooled to room temperature, filter, filtrate slow evaporation at room temperature, after 4 ~ 6 days
Obtain clear crystal [Mg (HCON (CH3)6]2GeW12O40.Yield about 55%.
Embodiment 7：Compound [[Mg (HCON (CH3)6]2GeW12O40Preparation
Magnesium chloride (2mmol), DMF (15mmol) and water 60mL, stirring and dissolving are sequentially added in the beaker of 100mL, then is added
Enter germanotungstic acid (3mmol), at 30 DEG C 6h is stirred, be cooled to room temperature, filter, filtrate slow evaporation at room temperature, after 4 ~ 6 days
To clear crystal [Mg (HCON (CH3)6]2GeW12O40.Yield about 51%.
Embodiment 8：Compound [[Mg (HCON (CH3)6]2GeW12O40Preparation
Sequentially add magnesium chloride (2mmol), DMF (30mmol) and the mL of water 70 in the beaker of 100mL, stirring and dissolving, then
Germanotungstic acid (2mmol) is added, at 40 DEG C 8h is stirred, be cooled to room temperature, filtered, filtrate slow evaporation at room temperature, after 4 ~ 6 days
Obtain clear crystal [Mg (HCON (CH3)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]2GeW12O40As a example by：Take 0.25mmol thioethers to be dissolved in 1 mL methanol, 0.3mmol
Hydrogen peroxide, adds catalyst 20mg, and 4-8 hours are reacted under 40 °C, and with gas chromatographic detection, the data of concrete sulfide oxidation are shown in
Table 2.
The compound of table 2. [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 clusters catalyst, is characterized in that, structural formula is：
。
2. the preparation method of double-core magnesium-germanium tungsten oxygen clusters catalyst according to claim 1, is characterized in that, double-core magnesium-germanium tungsten oxygen
The preparation method of cluster catalyst, metal double-core magnesium-germanium tungsten oxygen is constructed by metal magnesium salt, DMF with germanotungstic acid reaction in aqueous
Cluster；The monocrystalline of double-core magnesium-germanium tungsten oxygen clusters catalyst is obtained using nature volatility process.
3. preparation method according to claim 2, is characterized in that, sequentially add in the beaker of a cleaning magnesium chloride,
N, N '-dimethyl Methanamide (DMF) is dissolved in water, stirring and dissolving, adds germanotungstic acid, and heated and stirred is filtered, and filtrate exists
Slow evaporation under room temperature, obtains clear crystal, yield about 47 ~ 62% after 4 ~ 6 days.
4. preparation method according to claim 3, is characterized in that, 6 ~ 10h is stirred at 30 ~ 50 DEG C（Preferably, at 40 DEG C
8 h of lower stirring）.
5. preparation method according to claim 3, is characterized in that, magnesium chloride：N, N '-dimethyl Methanamide：Germanotungstic acid thing
The ratio of the amount of matter is 2 ~ 4: 15~30 : 1~3.
6. double-core magnesium-purposes of the germanium tungsten oxygen clusters catalyst in thioether selective oxidation according to claim 1.
7. purposes according to claim 6, is characterized in that, present invention also offers the strontium-germanium tungsten oxygen clusters catalyst exists
Purposes in thioether selective oxidation；Thioether be thioanisole, to chlorobenzene methyl sulfide, p-nitrophenyl methyl sulfide, to methoxybenzene
Methyl sulfide etc..
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111065715A (en) * | 2017-07-21 | 2020-04-24 | 圣地亚哥德孔波斯特拉大学 | Process for oxidizing organosulfur compounds |
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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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Patent Citations (4)
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111065715A (en) * | 2017-07-21 | 2020-04-24 | 圣地亚哥德孔波斯特拉大学 | Process for oxidizing organosulfur compounds |
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