CN101804340A - 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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- CN101804340A CN101804340A CN201010156183A CN201010156183A CN101804340A CN 101804340 A CN101804340 A CN 101804340A CN 201010156183 A CN201010156183 A CN 201010156183A CN 201010156183 A CN201010156183 A CN 201010156183A CN 101804340 A CN101804340 A CN 101804340A
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- Y02P20/584—Recycling of catalysts
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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 silica 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.By 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 syntheses especially, its two functional groups transform through multistep, can synthesize a series of optically pure chipal compounds.Simultaneously, cyanalcohol also is the initiation 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 classes: no metal participates in catalysis and metal participates in catalysis, and the catalysis of not having the metal participation can be divided into enzyme, peptide and little Journal of Molecular Catalysis etc., these materials show good activity in the catalysis silicon cyanation, but since many catalyst and reaction system molten be one, 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 complex is that catalyst often has clear and definite activated centre and higher activity, but reaction condition is required relatively harshlyer in catalytic process, and has problem such as separation difficulty equally.Though the immobilized problem that can solve separation difficulty to the catalyst of inorganic carrier surface preparation of metal complex, but because its building-up process more complicated, catalyst is immobilized may 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, just provide a kind of catalyst that has high activity, is easy to separate in a silicon cyanation field letter technical problem to be solved.
Silica has big specific area and porous, through being often used as adsorbent, drier and catalyst carrier etc.Use silica to make catalyst in the chemical reaction and have mild condition, advantage simple to operate, that separate with product easily usually.In addition, silica also has nontoxic, non-environmental-pollution, low cost and other advantages.At present, silica has shown good performance and prospects for commercial application aspect catalysis in olefine polymerization.But the silicon cyanation that silica 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 silica of catalytic activity.
Another technical problem to be solved by this invention is to provide a kind of new purposes for silica.
Solving the problems of the technologies described above the technical scheme that is adopted is: silica is placed vacuum tube furnace, be evacuated to 10 with the molecular pump unit
-2Pa is warming up to 100～500 ℃ with 1 ℃/minute heating 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 silica is 20～60 μ m, and specific area is 480～540m
2/ g is produced by Alpha Sha company.
The present invention places vacuum tube furnace with silica, is evacuated to 10 with the molecular pump unit
-2Pa, best heating rate with 1 ℃/minute is warming up to 500 ℃, constant temperature activation 12 hours.
The purposes of silica in silicon cyanation of benzaldehyde of the present invention's activation, its using method is as follows:
Get the silica of activation, be dissolved in the Shrek bottle that fills solvent, add benzaldehyde, trimethyl silicane nitrile, the volume ratio of solvent and benzaldehyde, trimethyl silicane nitrile is 1: 0.02: 0.04, and the mol ratio of the silica of benzaldehyde and activation is 1: 2.5～5, fills N
2As protection gas; the sealing bottleneck; stirring at room reaction 7～15 hours; with Shrek screen pipe filter reaction mixture; obtain product 2-phenyl-2-(trimethylsiloxy group) acetonitrile, with the product in the gas chromatographic detection filtrate, 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, carrene, chloroform, n-hexane, the oxolane.
The present invention with silica under vacuum state through 100～500 ℃ of activation processing 12 hours, the silica that obtains activating, method is simple, raw material is cheap and easy to get.The silica of activation is used for catalyzing silicon cyanation of benzaldehyde, need add other auxiliary agents, reaction condition gentleness, product yield height.The present invention adopts simple filtering just can realize separating of catalyst and product, has overcome the problem that catalyst separation in the silicon cyanation of aldehyde reclaims difficulty, and reusable after the catalyst recovery, reuses the catalytic activity height.The silica of the present invention's activation 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 silica of example 1 tongueization of the present invention.
The specific embodiment
The present invention is described in more detail below in conjunction with drawings and Examples, but the invention is not restricted to these embodiment.
Embodiment 1
The activation method of present embodiment silica is: 2g silica is placed vacuum tube furnace, be evacuated to 10 with the molecular pump unit
-2Pa is warming up to 500 ℃ with 1 ℃/minute heating rate, and room temperature is reduced in constant temperature activation 12 hours naturally, and the silica that obtains activating is at N
2Sealing is preserved in the atmosphere.
The particle diameter of above-mentioned silica is 20～60 μ m, and specific area is 480～540m
2/ g is produced by Alpha Sha company.
Adopt the silica of present embodiment activation method activation to observe with ESEM, the sem photograph of the silica of activation is seen Fig. 1.As seen from Figure 1, the silica surface regular shape of activation, particle is uniformly dispersed, and does not occur reuniting.
Embodiment 2
The activation method of present embodiment silica is: 2g silica is placed vacuum tube furnace, be evacuated to 10 with the molecular pump unit
-2Pa is warming up to 100 ℃ with 1 ℃/minute heating rate, constant temperature activation 12 hours, and other steps are identical with embodiment 1, the silica that obtains activating.
Embodiment 3
The activation method of present embodiment silica is: 2g silica is placed vacuum tube furnace, be evacuated to 10 with the molecular pump unit
-2Pa is warming up to 300 ℃ with 1 ℃/minute heating rate, constant temperature activation 12 hours, and other steps are identical with embodiment 1, the silica that obtains activating.
Embodiment 4
Adopt the application of silica in silicon cyanation of benzaldehyde of embodiment 1 activation, its using method is as follows:
Get the silica 0.2g of activation, be dissolved in the Shrek bottle that fills 5mL toluene, add benzaldehyde 0.1mL, trimethyl silicane nitrile 0.2mL, the volume ratio of toluene and benzaldehyde, trimethyl silicane nitrile is 1: 0.02: 0.04, the mol ratio of the silica of benzaldehyde and activation is 1: 3.33, fills N
2As protection gas; the sealing bottleneck; stirring at room reaction 7 hours; with Shrek screen pipe 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 filtrate, and with toluene with gained solids wash 5～6 times; vacuum drying is promptly recyclablely used again.
Embodiment 5
Adopt the application of silica in silicon cyanation of benzaldehyde of embodiment 1 activation, its using method is as follows:
Get the silica 0.15g of activation, be dissolved in the Shrek bottle that fills 5mL toluene, add benzaldehyde 0.1mL, trimethyl silicane nitrile 0.2mL, the volume ratio of toluene and benzaldehyde, trimethyl silicane nitrile is 1: 0.02: 0.04, the mol ratio of benzaldehyde and SiO 2 catalyst is 1: 2.5, fills N
2As protection gas; the sealing bottleneck; stirring at room reaction 7 hours; with Shrek screen pipe filter reaction mixture; other steps are identical with embodiment 4; obtaining product 2-phenyl-2-(trimethylsiloxy group) acetonitrile, is 70% with the productive rate of product 2-phenyl-2-(trimethylsiloxy group) acetonitrile in the gas chromatographic detection filtrate.
Embodiment 6
Adopt the application of silica in silicon cyanation of benzaldehyde of embodiment 1 activation, its using method is as follows:
Get the silica 0.3g of activation, be dissolved in the Shrek bottle that fills 5mL toluene, add benzaldehyde 0.1mL, trimethyl silicane nitrile 0.2mL, the volume ratio of toluene and benzaldehyde, trimethyl silicane nitrile is 1: 0.02: 0.04, the mol ratio of the silica of benzaldehyde and activation is 1: 5, fills N
2As protection gas; the sealing bottleneck; stirring at room reaction 7 hours; with Shrek screen pipe filter reaction mixture; other steps are identical with embodiment 4; obtaining product 2-phenyl-2-(trimethylsiloxy group) acetonitrile, is 95% with the productive rate of product 2-phenyl-2-(trimethylsiloxy group) acetonitrile in the gas chromatographic detection filtrate.
Embodiment 7
Toluene in the foregoing description 4～6 can be replaced with isopyknic carrene, 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 replaced with isopyknic chloroform, 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 replaced with isopyknic n-hexane, 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 replaced with isopyknic oxolane, and other steps are identical with corresponding embodiment, obtain product 2-phenyl-2-(trimethylsiloxy group) acetonitrile.
In order to determine optimised process step of the present invention, the inventor has carried out a large amount of laboratory research tests, and various test situation are as follows:
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 silica activation temperature
(1) activation of silica
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 heating rate, and room temperature is reduced in constant temperature activation 12 hours naturally, and the silica that obtains activating is at N
2Sealing is preserved in the atmosphere.
(2) silicon cyanation of benzaldehyde
Get each 0.2g of silica of step 1 activation, place the 10mL Shrek bottle that fills 5mL toluene respectively, add benzaldehyde 0.1mL, trimethyl silicane nitrile 0.2mL, the volume ratio of toluene and benzaldehyde, trimethyl silicane nitrile is 1: 0.02: 0.04, the mol ratio of the silica of benzaldehyde and activation is 1: 3.33, fills N
2As protection gas, the sealing bottleneck, stirring at room reaction is followed the tracks of reaction with gas-chromatography, treat that benzaldehyde transforms fully after, with Shrek screen pipe filter reaction mixture, with the product in the gas Chromatographic Determination filtrate.Result of the test sees Table 1.
The silica of the different activation temperature activation of table 1 is to silicon cyanation of benzaldehyde result's influence
| Activation temperature (℃) | Reaction time (hour) | Productive rate (%) |
| ??100 | ??15 | ??96 |
| ??200 | ??8 | ??98 |
| ??300 | ??12 | ??99 |
| ??400 | ??11 | ??96 |
| ??500 | ??7 | ??100 |
By table 1 as seen, when the silica 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 Huo Hua silica catalysis benzaldehyde; 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 silica, and the best is 500 ℃.
2, the selection of catalyst amount
(1) activation of silica
Get silica 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 heating rate, and room temperature is reduced in constant temperature activation 12 hours naturally, and the silica that obtains activating is at N
2Sealing is preserved in the atmosphere.
(2) silicon cyanation of benzaldehyde
Get silica 0.05g, 0.1g, 0.15g, 0.2g, 0.25g, the 0.3g of step 1 activation, place 6 25mL Shrek bottles that fill 5mL toluene, add benzaldehyde 0.1mL, trimethyl silicane nitrile 0.2mL respectively, the volume ratio of toluene and benzaldehyde, trimethyl silicane nitrile is 1: 0.02: 0.04, the mol ratio of the silica of benzaldehyde and activation 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 gas-chromatography, treat that benzaldehyde transforms fully after, with Shrek screen pipe filter reaction mixture, with the product in the gas Chromatographic Determination filtrate.Result of the test sees Table 2.
The silica consumption of table 2 activation is to silicon cyanation of benzaldehyde result's influence
| Benzaldehyde: catalyst (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 |
By table 2 as seen, the mol ratio of the silica of benzaldehyde and activation 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 the silica of benzaldehyde and activation, and the best is 1: 3.33.
3, choice of Solvent
(1) activation of silica
Get silica 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 heating rate, and room temperature is reduced in constant temperature activation 12 hours naturally, and the silica that obtains activating is at N
2Sealing is preserved in the atmosphere.
(2) silicon cyanation of benzaldehyde
Get totally 5 parts of the silica 0.2g of step 1 activation, place 5 25mL Shrek bottles, add solvent toluene 5mL, carrene 5mL, chloroform 5mL, n-hexane 5mL, oxolane 5mL respectively, in 5 Shrek bottles, all add benzaldehyde 0.1mL, trimethyl silicane nitrile 0.2mL again, the volume ratio of solvent toluene or carrene or chloroform or n-hexane or oxolane and benzaldehyde, trimethyl silicane nitrile is 1: 0.02: 0.04, the mol ratio of the silica of benzaldehyde and activation 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 gas-chromatography, treat that benzaldehyde transforms fully after, with Shrek screen pipe filter reaction mixture, with the product in the gas Chromatographic Determination filtrate.Result of the test sees Table 3.
Table 3 solvent is to silicon cyanation of benzaldehyde result's influence
| Solvent | Toluene | Carrene | Chloroform | N-hexane | Oxolane |
| Productive rate (%) | ??100 | ??96 | ??73 | ??94 | ??93 |
By table 3 as seen, when solvent was in toluene, carrene, chloroform, n-hexane, the oxolane any one, it is all higher that the silica catalysis benzaldehyde of activation generates the productive rate of 2-phenyl-2-(trimethylsiloxy group) acetonitrile.The present invention selects toluene or carrene or chloroform or n-hexane or oxolane as solvent, and the best is a toluene.
In order to verify beneficial effect of the present invention, the inventor reuses according to the method for embodiment 4 reclaiming the silica of the activation that obtains in the embodiment of the invention 4, tests the influence of its repeated use to catalytic performance, and result of the test sees Table 4.
The silica repeat performance of table 4 activation
| Number of repetition | Reaction time (hour) | Productive rate (%) |
| ??0 | ??7 | ??100 |
| ??1 | ??20 | ??98 |
| ??2 | ??20 | ??97 |
| Number of repetition | Reaction time (hour) | Productive rate (%) |
| ??3 | ??24 | ??98 |
| ??4 | ??26 | ??90 |
By table 4 as seen, during with the silicon cyanation of silica catalysis benzaldehyde of activation, catalyst is reusable, reuse 4 times after, the activity of the silicon cyanation of catalysis benzaldehyde is still very high, and the productive rate of product 2-phenyl-2-(trimethylsiloxy group) acetonitrile reaches 90%.
Conclusion
The activation method of silica of the present invention is simple, when being used for the silicon cyanation of catalysis benzaldehyde, and the reaction condition gentleness, separate easily with product, the productive rate height of product 2-phenyl-2-(trimethylsiloxy group) acetonitrile, it is reusable to reclaim the catalyst that obtains, and reuses the catalytic activity height.
Claims (5)
1. the activation method of a silica is characterized in that: silica is placed vacuum tube furnace, be evacuated to 10 with the molecular pump unit
-2Pa is warming up to 100～500 ℃ with 1 ℃/minute heating rate, and room temperature is reduced in constant temperature activation 12 hours naturally, and the silica that obtains activating is at N
2Sealing is preserved in the atmosphere;
The particle diameter of above-mentioned silica is 20～60 μ m, and specific area is 480～540m
2/ g.
2. according to the activation method of the described silica of claim 1, it is characterized in that: silica is placed vacuum tube furnace, be evacuated to 10 with the molecular pump unit
-2Pa is warming up to 500 ℃ with 1 ℃/minute heating rate, constant temperature activation 12 hours.
3. the purposes of silica in silicon cyanation of benzaldehyde of claim 1 activation.
4. according to the purposes of silica in silicon cyanation of benzaldehyde of the described activation of claim 3, it is characterized in that: the silica of getting activation, be dissolved in the Shrek bottle that fills solvent, add benzaldehyde, trimethyl silicane nitrile, the volume ratio of solvent and benzaldehyde, trimethyl silicane nitrile is 1: 0.02: 0.04, the mol ratio of the silica of benzaldehyde and activation is 1: 2.5～5, fills N
2As protection gas, the sealing bottleneck, stirring at room reaction 7～15 hours, with Shrek screen pipe filter reaction mixture, obtain product 2-phenyl-2-(trimethylsiloxy group) acetonitrile, with the product in the gas chromatographic detection filtrate, 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, carrene, chloroform, n-hexane, the oxolane.
5. according to the purposes of silica in silicon cyanation of benzaldehyde of the described activation of claim 3, it is characterized in that: the silica of getting activation, be dissolved in the Shrek bottle that fills toluene, add benzaldehyde, trimethyl silicane nitrile, the volume ratio of toluene and benzaldehyde, trimethyl silicane nitrile is 1: 0.02: 0.04, the mol ratio of the silica of benzaldehyde and activation is 1: 3.33, fills N
2As protection gas; the sealing bottleneck; stirring at room reaction 7 hours; with Shrek screen pipe filter reaction mixture; obtain product 2-phenyl-2-(trimethylsiloxy group) acetonitrile, with the product in the gas chromatographic detection filtrate, and with toluene with gained solids wash 5～6 times; vacuum drying is promptly recyclablely used again.
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| CN2010101561838A CN101804340B (en) | 2010-04-26 | 2010-04-26 | Activating method of silicon dioxide and application thereof in catalyzing silicon cyanation of benzaldehyde |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153572A (en) * | 2011-02-24 | 2011-08-17 | 罗梅 | Chiral zinc nitrogen complex and synthesis method thereof |
| CN102153571A (en) * | 2011-02-10 | 2011-08-17 | 罗梅 | Chirality zinc-nitrogen coordination compound |
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| WO2007027752A1 (en) * | 2005-08-30 | 2007-03-08 | Massachusetts Institute Of Technology | Catalytic reactions involving alkenes |
| 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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2010
- 2010-04-26 CN CN2010101561838A patent/CN101804340B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7314844B2 (en) * | 2000-08-02 | 2008-01-01 | King's College London | Process for the cyanation aldehydes |
| WO2007027752A1 (en) * | 2005-08-30 | 2007-03-08 | Massachusetts Institute Of Technology | Catalytic reactions involving alkenes |
| 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153571A (en) * | 2011-02-10 | 2011-08-17 | 罗梅 | Chirality zinc-nitrogen coordination compound |
| CN102153571B (en) * | 2011-02-10 | 2013-06-05 | 罗梅 | Chirality zinc-nitrogen coordination compound |
| CN102153572A (en) * | 2011-02-24 | 2011-08-17 | 罗梅 | Chiral zinc nitrogen complex and synthesis method thereof |
| CN102153572B (en) * | 2011-02-24 | 2013-06-05 | 罗梅 | Chiral zinc nitrogen complex and synthesis method thereof |
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| CN101804340B (en) | 2012-03-14 |
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