CN101804340B - Activating method of silicon dioxide and application thereof in catalyzing silicon cyanation of benzaldehyde - Google Patents
Activating method of silicon dioxide and application thereof in catalyzing silicon cyanation of benzaldehyde Download PDFInfo
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Abstract
The invention discloses an activating method of silicon dioxide, comprising the following steps of: adding silicon dioxide into a vacuum tubular furnace; vacuumizing to 10-20Pa by using a molecular pump unit; raising the temperature to 100-500DEG C at the temperature raising speed of 1DEG C/min; activating at constant temperature for 12 hours to obtain activated silicon dioxide; and sealing and preserving the activated silicon dioxide in an N2 atmosphere. The activating method of the silicon dioxide is simple and raw materials are low in prices and easily obtained. The activated silicon dioxide is used for catalyzing the silicon cyanation of benzaldehyde without adding other assistants, the reaction condition is mild and the yield is high; a catalyst is separated from a product by simple filter, so the invention overcomes the technical problem that the catalyst is difficult to separate in the silicon cyanation; and in addition, the catalyst can be recycled and still has high catalytic activity after being used for 4 times. The activated silicon dioxide can be used for catalyzing the silicon cyanation of other aldehyde substances.
Description
Technical field
The invention belongs to catalyst technical field, refer more particularly to the activation of silicon-dioxide and the application in catalyzing silicon cyanation of benzaldehyde thereof.
Background technology
Silicon cyanation is one of most important reaction that forms in the organic synthesis on the C-C key.Through the cyanalcohol that silicon cyanation obtained is the important intermediate of more synthetic polyfunctional compounds; And the chiral cyanohydrin that the asymmetrical siloxy cyanation obtains one of important chiral source in the asymmetric synthesis especially; Its two functional groups transform through multistep, can synthesize a series of optically pure chipal compounds.Simultaneously, cyanalcohol also is the starting raw material of synthetic many medicines and the important composition segment of some natural products and agricultural chemicals.
The silicon eyeball reaction of catalysis aldehyde can roughly be divided into two big types: no metal participates in catalysis and metal is participated in catalysis; And the catalysis of not having the metal participation can be divided into enzyme, peptide and small molecules catalysis etc.; These materials show good activity in the catalysis silicon cyanation, but are one because many catalyzer and reaction system are dissolved, and cause relatively difficulty of separation; And in most cases need column chromatography to separate, thereby operation is also more loaded down with trivial details.Metal complexes is that catalyzer often has clear and definite active site and higher activity, but in catalytic process, reaction conditions is required relatively harshlyer, and has problem such as separation difficulty equally.Though the immobilized problem that can solve separation difficulty to the catalyzer of inorganic carrier surface preparation of metal complexes; But because its building-up process more complicated; Catalyzer is immobilized possibly to cause active reduction etc. to be still the problem that is difficult to overcome, and therefore, the application in silicon cyanation is also few.At present, a letter technical problem to be solved just provides and a kind ofly has high reactivity, is easy to isolating catalyzer in the silicon cyanation field.
Silicon-dioxide has big specific surface area and porousness, often is used as sorbent material, siccative and support of the catalyst etc.Use silicon-dioxide to make catalyzer in the chemical reaction and have mild condition, simple to operate, the easy and isolating advantage of product usually.In addition, silicon-dioxide also has nontoxic, non-environmental-pollution, low cost and other advantages.At present, silicon-dioxide has shown good performance and prospects for commercial application aspect catalysis in olefine polymerization.But the silicon cyanation that silicon-dioxide is used for the catalysis aldehydes is not seen bibliographical information as yet.
Summary of the invention
A technical problem to be solved by this invention is to provide the activation method that a kind of method is simple, be easy to separate, reuse the high silicon-dioxide of catalytic activity.
Another technical problem to be solved by this invention is for silicon-dioxide a kind of new purposes to be provided.
Solving the problems of the technologies described above the technical scheme that is adopted is: silicon-dioxide is placed vacuum tube furnace, be evacuated to 10 with the molecular pump unit
-2Pa is warming up to 100～500 ℃ with 1 ℃/minute temperature rise rate, and constant temperature activation 12 hours is reduced to room temperature, naturally at N
2Sealing is preserved in the atmosphere.
The particle diameter of above-mentioned silicon-dioxide is 20～60 μ m, and specific surface area is 480～540m
2/ g is produced by alpha-acetol Sha company.
The present invention places vacuum tube furnace with silicon-dioxide, is evacuated to 10 with the molecular pump unit
-2Pa, best temperature rise rate with 1 ℃/minute is warming up to 500 ℃, constant temperature activation 12 hours.
The purposes of activatory silicon-dioxide of the present invention in silicon cyanation of benzaldehyde, its method of use is following:
Get activatory silicon-dioxide, be dissolved in the Shrek bottle that fills solvent, add phenyl aldehyde, trimethyl silicane nitrile, the volume ratio of solvent and phenyl aldehyde, trimethyl silicane nitrile is 1: 0.02: 0.04, and the mol ratio of phenyl aldehyde and activatory silicon-dioxide is 1: 2.5～5, fills N
2As protection gas, sealing bottleneck, stirring at room reaction 7～15 hours; With Shrek strainer tube filter reaction mixture; Obtain product 2-phenyl-2-(trimethylsiloxy group) acetonitrile, with the product in the gas chromatographic detection filtrating, and with toluene with gained solids wash 5～6 times; Vacuum-drying is promptly recyclablely used again.
Above-mentioned solvent is any one in toluene, methylene dichloride, trichloromethane, normal hexane, the THF.
The present invention with silicon-dioxide under vacuum state through 100～500 ℃ of activation treatment 12 hours, obtain activatory silicon-dioxide, method is simple, low in raw material cost is easy to get.Activatory silicon-dioxide is used for catalyzing silicon cyanation of benzaldehyde, need add other auxiliary agents, reaction conditions is gentle, and product yield is high.The present invention adopts simple filtering just can realize separating of catalyzer and product, has overcome the problem that catalyst separating in the silicon cyanation of aldehyde reclaims difficulty, and reusable after the catalyst recovery, and it is high to reuse catalytic activity.Activatory silicon-dioxide of the present invention also can be used for the silicon cyanation of other aldehyde materials of catalysis.
Description of drawings
Fig. 1 is the sem photograph of the silicon-dioxide of instance 1 tongueization of the present invention.
Embodiment
To further explain of the present invention, but the invention is not restricted to these embodiment below in conjunction with accompanying drawing and embodiment.
Embodiment 1
The activation method of present embodiment silicon-dioxide is: 2g silicon-dioxide is placed vacuum tube furnace, be evacuated to 10 with the molecular pump unit
-2Pa is warming up to 500 ℃ with 1 ℃/minute temperature rise rate, and room temperature is reduced in constant temperature activation 12 hours naturally, obtains activatory silicon-dioxide, at N
2Sealing is preserved in the atmosphere.
The particle diameter of above-mentioned silicon-dioxide is 20～60 μ m, and specific surface area is 480～540m
2/ g is produced by alpha-acetol Sha company.
Adopt present embodiment activation method activatory silicon-dioxide to observe with ESEM, the sem photograph of activatory silicon-dioxide is seen Fig. 1.Visible by Fig. 1, activatory silica sphere regular shape, particles dispersed is even, does not occur reuniting.
Embodiment 2
The activation method of present embodiment silicon-dioxide is: 2g silicon-dioxide is placed vacuum tube furnace, be evacuated to 10 with the molecular pump unit
-2Pa is warming up to 100 ℃ with 1 ℃/minute temperature rise rate, constant temperature activation 12 hours, and other steps are identical with embodiment 1, obtain activatory silicon-dioxide.
Embodiment 3
The activation method of present embodiment silicon-dioxide is: 2g silicon-dioxide is placed vacuum tube furnace, be evacuated to 10 with the molecular pump unit
-2Pa is warming up to 300 ℃ with 1 ℃/minute temperature rise rate, constant temperature activation 12 hours, and other steps are identical with embodiment 1, obtain activatory silicon-dioxide.
Embodiment 4
Adopt embodiment 1 application of activatory silicon-dioxide in silicon cyanation of benzaldehyde, its method of use is following:
Get activatory silicon-dioxide 0.2g; Be dissolved in the Shrek bottle that fills 5mL toluene, add phenyl aldehyde 0.1mL, trimethyl silicane nitrile 0.2mL, the volume ratio of toluene and phenyl aldehyde, trimethyl silicane nitrile is 1: 0.02: 0.04; The mol ratio of phenyl aldehyde and activatory silicon-dioxide is 1: 3.33, fills N
2As protection gas, sealing bottleneck, stirring at room reaction 7 hours; With Shrek strainer tube filter reaction mixture; Obtaining product 2-phenyl-2-(trimethylsiloxy group) acetonitrile, is 100% with the productive rate of product 2-phenyl-2-(trimethylsiloxy group) acetonitrile in the gas chromatographic detection filtrating, and with toluene with gained solids wash 5～6 times; Vacuum-drying is promptly recyclablely used again.
Embodiment 5
Adopt embodiment 1 application of activatory silicon-dioxide in silicon cyanation of benzaldehyde, its method of use is following:
Get activatory silicon-dioxide 0.15g; Be dissolved in the Shrek bottle that fills 5mL toluene, add phenyl aldehyde 0.1mL, trimethyl silicane nitrile 0.2mL, the volume ratio of toluene and phenyl aldehyde, trimethyl silicane nitrile is 1: 0.02: 0.04; The mol ratio of phenyl aldehyde and SiO 2 catalyst is 1: 2.5, fills N
2As protection gas; The sealing bottleneck; Stirring at room reaction 7 hours, with Shrek strainer tube filter reaction mixture, other steps are identical with embodiment 4; Obtain product 2-phenyl-2-(trimethylsiloxy group) acetonitrile, the productive rate of product 2-phenyl-2-(trimethylsiloxy group) acetonitrile is 70% in filtrating with gas chromatographic detection.
Embodiment 6
Adopt embodiment 1 application of activatory silicon-dioxide in silicon cyanation of benzaldehyde, its method of use is following:
Get activatory silicon-dioxide 0.3g; Be dissolved in the Shrek bottle that fills 5mL toluene, add phenyl aldehyde 0.1mL, trimethyl silicane nitrile 0.2mL, the volume ratio of toluene and phenyl aldehyde, trimethyl silicane nitrile is 1: 0.02: 0.04; The mol ratio of phenyl aldehyde and activatory silicon-dioxide is 1: 5, fills N
2As protection gas; The sealing bottleneck; Stirring at room reaction 7 hours, with Shrek strainer tube filter reaction mixture, other steps are identical with embodiment 4; Obtain product 2-phenyl-2-(trimethylsiloxy group) acetonitrile, the productive rate of product 2-phenyl-2-(trimethylsiloxy group) acetonitrile is 95% in filtrating with gas chromatographic detection.
Embodiment 7
Toluene in the foregoing description 4～6 can be used isopyknic methylene dichloride replacement, and other steps are identical with corresponding embodiment, obtain product 2-phenyl-2-(trimethylsiloxy group) acetonitrile.
Embodiment 8
Toluene in the foregoing description 4～6 can be used isopyknic trichloromethane replacement, and other steps are identical with corresponding embodiment, obtain product 2-phenyl-2-(trimethylsiloxy group) acetonitrile.
Embodiment 9
Toluene in the foregoing description 4～6 can be used isopyknic normal hexane replacement, and other steps are identical with corresponding embodiment, obtain product 2-phenyl-2-(trimethylsiloxy group) acetonitrile.
Embodiment 10
Toluene in the foregoing description 4～6 can be used isopyknic THF replacement, and other steps are identical with corresponding embodiment, obtain product 2-phenyl-2-(trimethylsiloxy group) acetonitrile.
In order to confirm optimised process step of the present invention, the contriver has carried out a large amount of laboratory study tests, and various test situation are following:
Laboratory apparatus: Agilent 7890A gas chromatograph, chromatographic column are CYCLODEX-B (30m, 0.32mm, 0.25 μ) type capillary column, adopt fid detector, are produced by U.S.'s Agilent (Agilent) scientific & technical corporation.
1, the selection of silicon-dioxide activation temperature
(1) activation of silicon-dioxide
Get totally 5 parts of silica 1 .0g, place vacuum tube furnace respectively, be evacuated to 10 with the molecular pump unit
-2Pa is warming up to 100 ℃, 200 ℃, 300 ℃, 400 ℃, 500 ℃ respectively with 1 ℃/minute temperature rise rate, and room temperature is reduced in constant temperature activation 12 hours naturally, obtains activatory silicon-dioxide, at N
2Sealing is preserved in the atmosphere.
(2) silicon cyanation of benzaldehyde
Get each 0.2g of step 1 activatory silicon-dioxide; Place the 10mL Shrek bottle that fills 5mL toluene respectively; Add phenyl aldehyde 0.1mL, trimethyl silicane nitrile 0.2mL; The volume ratio of toluene and phenyl aldehyde, trimethyl silicane nitrile is 1: 0.02: 0.04, and the mol ratio of phenyl aldehyde and activatory silicon-dioxide is 1: 3.33, fills N
2As protection gas, the sealing bottleneck, stirring at room reaction is followed the tracks of reaction with gc, treat that phenyl aldehyde transforms fully after, with Shrek strainer tube filter reaction mixture, the product in filtrating with gas Chromatographic Determination.Test-results is seen table 1.
The different activation temperature activatory of table 1 silicon-dioxide is to silicon cyanation of benzaldehyde result's influence
| Activation temperature (℃) | Reaction times (hour) | Productive rate (%) |
| 100 | 15 | 96 |
| 200 | 8 | 98 |
| 300 | 12 | 99 |
| 400 | 11 | 96 |
| 500 | 7 | 100 |
Visible by table 1, when the silicon-dioxide activation temperature was 100～500 ℃, the productive rate of product 2-phenyl-2-(trimethylsiloxy group) acetonitrile was all higher, i.e. the better catalytic activity of activatory silicon-dioxide catalysis phenyl aldehyde; When activation temperature was 500 ℃, the reaction required time was the shortest and catalytic effect is best, and product yield is the highest.It is 100～500 ℃ that the present invention selects the activation temperature of silicon-dioxide, and the best is 500 ℃.
2, the selection of catalyst levels
(1) activation of silicon-dioxide
Get silicon-dioxide 2.0g and place vacuum tube furnace, be evacuated to 10 with the molecular pump unit
-2Pa is warming up to 500 ℃ with 1 ℃/minute temperature rise rate, and room temperature is reduced in constant temperature activation 12 hours naturally, obtains activatory silicon-dioxide, at N
2Sealing is preserved in the atmosphere.
(2) silicon cyanation of phenyl aldehyde
Get step 1 activatory silicon-dioxide 0.05g, 0.1g, 0.15g, 0.2g, 0.25g, 0.3g; Place 6 25mL Shrek bottles that fill 5mL toluene; Add phenyl aldehyde 0.1mL, trimethyl silicane nitrile 0.2mL respectively; The volume ratio of toluene and phenyl aldehyde, trimethyl silicane nitrile is 1: 0.02: 0.04, and the mol ratio of phenyl aldehyde and activatory silicon-dioxide was respectively 1: 0.83,1: 1.67,1: 2.5,1: 3.33,1: 4.17,1: 5, filled N
2As protection gas, the sealing bottleneck, stirring at room reaction 7 hours is followed the tracks of reaction with gc, treat that phenyl aldehyde transforms fully after, with Shrek strainer tube filter reaction mixture, the product in filtrating with gas Chromatographic Determination.Test-results is seen table 2.
Table 2 activatory silicon-dioxide consumption is to silicon cyanation of benzaldehyde result's influence
| Phenyl aldehyde: catalyzer (mol ratio) | 1∶0.83 | 1∶1.67 | 1∶2.5 | 1∶3.33 | 1∶4.17 | 1∶5 |
| Productive rate (%) | 30 | 58 | 70 | 100 | 95 | 95 |
Visible by table 2, the mol ratio of phenyl aldehyde and activatory silicon-dioxide is 1: 2.5～5 o'clock, and the productive rate of 2-phenyl-2-(trimethylsiloxy group) acetonitrile is all higher.It is 1: 2.5～5 that the present invention selects the mol ratio of phenyl aldehyde and activatory silicon-dioxide, and the best is 1: 3.33.
3, choice of Solvent
(1) activation of silicon-dioxide
Get silicon-dioxide 2.0g and place vacuum tube furnace, be evacuated to 10 with the molecular pump unit
-2Pa is warming up to 500 ℃ with 1 ℃/minute temperature rise rate, and room temperature is reduced in constant temperature activation 12 hours naturally, obtains activatory silicon-dioxide, at N
2Sealing is preserved in the atmosphere.
(2) silicon cyanation of phenyl aldehyde
Get totally 5 parts of step 1 activatory silicon-dioxide 0.2g; Place 5 25mL Shrek bottles; Add solvent toluene 5mL, methylene dichloride 5mL, trichloromethane 5mL, normal hexane 5mL, THF 5mL respectively; In 5 Shrek bottles, all add phenyl aldehyde 0.1mL, trimethyl silicane nitrile 0.2mL again; The volume ratio of solvent toluene or methylene dichloride or trichloromethane or normal hexane or THF and phenyl aldehyde, trimethyl silicane nitrile is 1: 0.02: 0.04, and the mol ratio of phenyl aldehyde and activatory silicon-dioxide was respectively 1: 3.33, filled N
2As protection gas, the sealing bottleneck, stirring at room reaction 7 hours is followed the tracks of reaction with gc, treat that phenyl aldehyde transforms fully after, with Shrek strainer tube filter reaction mixture, the product in filtrating with gas Chromatographic Determination.Test-results is seen table 3.
Table 3 solvent is to silicon cyanation of benzaldehyde result's influence
| Solvent | Toluene | Methylene dichloride | Trichloromethane | Normal hexane | THF |
| Productive rate (%) | 100 | 96 | 73 | 94 | 93 |
Visible by table 3, when solvent was in toluene, methylene dichloride, trichloromethane, normal hexane, the THF any one, it is all higher that activatory silicon-dioxide catalysis phenyl aldehyde generates the productive rate of 2-phenyl-2-(trimethylsiloxy group) acetonitrile.The present invention selects toluene or methylene dichloride or trichloromethane or normal hexane or THF as solvent, and the best is a toluene.
In order to verify beneficial effect of the present invention, the contriver reuses according to the method for embodiment 4 reclaiming the activatory silicon-dioxide that obtains in the embodiment of the invention 4, tests it and reuses the influence to catalytic performance, and test-results is seen table 4.
Table 4 activatory silicon-dioxide repeat performance
| Multiplicity | Reaction times (hour) | Productive rate (%) |
| 0 | 7 | 100 |
| 1 | 20 | 98 |
| 2 | 20 | 97 |
| 3 | 24 | 98 |
| 4 | 26 | 90 |
Visible by table 4; During with the silicon cyanation of activatory silicon-dioxide catalysis phenyl aldehyde, catalyzer is reusable, reuse 4 times after; The activity of the silicon cyanation of catalysis phenyl aldehyde is still very high, and the productive rate of product 2-phenyl-2-(trimethylsiloxy group) acetonitrile reaches 90%.
Conclusion
The activation method of silicon-dioxide of the present invention is simple, and when being used for the silicon cyanation of catalysis phenyl aldehyde, reaction conditions is gentle; Separate easily with product; The productive rate of product 2-phenyl-2-(trimethylsiloxy group) acetonitrile is high, and it is reusable to reclaim the catalyzer that obtains, and it is high to reuse catalytic activity.
Claims (3)
1. the purposes of an activatory silicon-dioxide in silicon cyanation of benzaldehyde is characterized in that: silicon-dioxide is placed vacuum tube furnace, be evacuated to 10 with the molecular pump unit
-2Pa is warming up to 100～500 ℃ with 1 ℃/minute temperature rise rate, and room temperature is reduced in constant temperature activation 12 hours naturally, obtains activatory silicon-dioxide, at N
2Sealing is preserved in the atmosphere;
The particle diameter of above-mentioned silicon-dioxide is 20～60 μ m, and specific surface area is 480～540m
2/ g.
2. according to the purposes of the described activatory silicon-dioxide of claim 1 in silicon cyanation of benzaldehyde; It is characterized in that: get activatory silicon-dioxide; Be dissolved in the Shrek bottle that fills solvent, add phenyl aldehyde, trimethyl silicane nitrile, the volume ratio of solvent and phenyl aldehyde, trimethyl silicane nitrile is 1: 0.02: 0.04; The mol ratio of phenyl aldehyde and activatory silicon-dioxide is 1: 2.5～5, fills N
2As protection gas, sealing bottleneck, stirring at room reaction 7～15 hours; With Shrek strainer tube filter reaction mixture; Obtain product 2-phenyl-2-(trimethylsiloxy group) acetonitrile, with the product in the gas chromatographic detection filtrating, and with toluene with gained solids wash 5～6 times; Vacuum-drying is promptly recyclablely used again;
Above-mentioned solvent is any one in toluene, methylene dichloride, trichloromethane, normal hexane, the THF.
3. according to the purposes of the described activatory silicon-dioxide of claim 1 in silicon cyanation of benzaldehyde; It is characterized in that: get activatory silicon-dioxide; Be dissolved in the Shrek bottle that fills toluene, add phenyl aldehyde, trimethyl silicane nitrile, the volume ratio of toluene and phenyl aldehyde, trimethyl silicane nitrile is 1: 0.02: 0.04; The mol ratio of phenyl aldehyde and activatory silicon-dioxide is 1: 3.33, fills N
2As protection gas, sealing bottleneck, stirring at room reaction 7 hours; With Shrek strainer tube filter reaction mixture; Obtain product 2-phenyl-2-(trimethylsiloxy group) acetonitrile, with the product in the gas chromatographic detection filtrating, and with toluene with gained solids wash 5～6 times; Vacuum-drying is promptly recyclablely used again.
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| CN101058423A (en) * | 2007-03-28 | 2007-10-24 | 张仁水 | Method of processing superfine activated silicon |
| US7314844B2 (en) * | 2000-08-02 | 2008-01-01 | King's College London | Process for the cyanation aldehydes |
| CN101239986A (en) * | 2008-03-17 | 2008-08-13 | 南京曙光硅烷化工有限公司 | Direct synthesis method for triethoxysilicane |
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| US7314844B2 (en) * | 2000-08-02 | 2008-01-01 | King's College London | Process for the cyanation aldehydes |
| CN101058423A (en) * | 2007-03-28 | 2007-10-24 | 张仁水 | Method of processing superfine activated silicon |
| CN101239986A (en) * | 2008-03-17 | 2008-08-13 | 南京曙光硅烷化工有限公司 | Direct synthesis method for triethoxysilicane |
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