CN102153582B - Method for synthesizing bromotrimethylsilane - Google Patents
Method for synthesizing bromotrimethylsilane Download PDFInfo
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- CN102153582B CN102153582B CN201110057265.1A CN201110057265A CN102153582B CN 102153582 B CN102153582 B CN 102153582B CN 201110057265 A CN201110057265 A CN 201110057265A CN 102153582 B CN102153582 B CN 102153582B
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- bromotrimethylsilane
- silicon ether
- temperature
- phosphorus tribromide
- reaction
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Abstract
The invention discloses a method for synthesizing bromotrimethylsilane, and relates to a synthetic production technology for a chemical product. The method comprises the following steps of: under oxygen-free conditions, stirring in a reaction kettle in which phosphorus tribromide and silyl ether are sequentially added, raising the temperature to 1005 DEG C, keeping the temperature, performing reflux reaction for 60.5 hours, rectifying under normal pressure to obtain the bromotrimethylsilane, and stopping to receive a finished product of the bromotrimethylsilane when the temperature in the kettle is raised to 135 DEG C. By the method, a silyl ether-phosphorus tribromide method is improved and innovated, side reactions are avoided, the obtained product has purity, and the finished product of the bromotrimethylsilane which has the content of about 99 percent can be obtained; and the stirring at normal temperature is changed into high-temperature reflux, so that the reaction time is greatly shortened.
Description
Technical field
The present invention relates to a kind of production technical field of Chemicals, particularly the method for chemosynthesis bromotrimethylsilane.
Background technology
Bromotrimethylsilane is a kind of novel organosilicon synthetic agent, be mainly used in the synthetic aspect of antiviral, it is the necessary raw material of synthetic anti-hepatic-B virus medicine PMEA (adefovir, PMEA) and synthetic AIDS drug tynofovir (tenofovir, PMPA).
Have at present the synthetic method of bibliographical information to have several as follows:
1, hexamethyldisilane method: Me
3siSiMe
3+ Br
2→ 2Me
3siBr, the method product yield is high, but reacts violent and wayward, easily blasts, and raw material hexamethyldisilane is expensive in addition, loses gradually the meaning of suitability for industrialized production.
2, silicon ether---aluminium powder method: Me
3siOSiMe
3+ Br
2+ 2/3 Al → 2Me
3siBr+1/3 Al
2o
3, the method temperature of reaction is high, and the more and 120 ℃ of left and right of by product will be solidified, and are difficult to process, and are mingled with dimethyl two bromo-silicanes of 15% left and right in product, and separation difficulty affect product use.
3, silicon ether---triphenylphosphine method: Me
3siOSiMe
3+ Br
2+ Ph
3p → 2Me
3siBr+Ph
3pO, the raw material triphenylphosphine that the method adopts is expensive, and the by product triphen phosphine oxide of generation is difficult to process, and is unfavorable for suitability for industrialized production.
4, phenyl-trimethylsilicane method: PhSiMe
3+ Br
2→ Me
3siBr+PhBr, because a small amount of hydrogen bromide producing in reaction can cause phenyl-trimethylsilicane to resolve into benzene, causes the benzene that contains 5% left and right in the method the finished product, and benzene and bromotrimethylsilane boiling point are very approaching, cannot separate, and affects product use.
5, silicon ether---phosphorus tribromide method: Me
3siOSiMe
3+ PBr
3→ Me
3siBr, the method is because needs are used iron trichloride as catalyzer, and owing to there being following side reaction: Me
3siBr+FeCl
3→ Me
3siCl+FeBr
3thereby, cause in product, containing having an appointment 3% trimethylchlorosilane impurity, affect product and use, and by product being more, be difficult to processing.
Summary of the invention
The object of the invention is to propose a kind ofly to overcome prior art deficiency, avoids side reaction, product purity is high, a kind of synthetic method of safety, the bromotrimethylsilane that produces without the three wastes.
Technical solution of the present invention is: under oxygen free condition, by throwing successively, there is the stirring of the reactor of phosphorus tribromide and silicon ether to be warming up to 100 ℃ ± 5 ℃, and keep this temperature back flow reaction after 6 ± 0.5 hours, carry out atmospheric distillation, obtain bromotrimethylsilane, when temperature in the kettle rises to 135 ℃, stop receiving bromotrimethylsilane finished product.
The present invention is to silicon ether---and phosphorus tribromide method has carried out improving innovation, has avoided the generation of side reaction, and products obtained therefrom purity is high, can obtain the bromotrimethylsilane finished product of content in 99% left and right; Change stirring at normal temperature into high temperature reflux, greatly shortened the reaction times.
The molar ratio of phosphorus tribromide of the present invention and silicon ether is 1.4～1.5 ︰ 1.
In order to improve product yield, the present invention also drops into catalyzer---ferric bromide after input silicon ether.
Described ferric bromide and silicon ether mol ratio are 0.001～0.01 ︰ 1.
The present invention also fully reclaims phosphorus tribromide by the following method, has reduced the usage quantity of phosphorus tribromide to silicon ether, by product success conversion processing is become to the raw materials for production of other products, in whole building-up process, without the three wastes, produces, and clean environment firendly, can be used for suitability for industrialized production.
When the first reactor temperature rises to more than 175 ℃ and while steaming without material, stop distillation again, reclaim and obtain phosphorus tribromide.
To in the first reactor, be down to below 80 ℃, again to the disposable silicon ether that adds in the first reactor, after stirring half an hour, be transferred to the second reactor, control the second reactor temperature below 60 ℃, to the second reactor, add water while stirring and be hydrolyzed, obtain respectively organic phase silicon ether, water phosphate aqueous solution and solid red phosphorus; To solid red phosphorus, drip bromine again and be reacted into raw phosphorus tribromide.
Silicon ether is by after further dewatering, can drop in the reaction of next batch and recycle, (Hydrogen bromide content is 1.5% left and right to the phosphate aqueous solution that contains a small amount of Hydrogen bromide, phosphorous acid and iron bromide, phosphorous acid is 0.5% left and right, ferric bromide is 0-0.9%, phosphorus acid content is 50% left and right) can be used as byproduct sale (or can further pass through fractionation by distillation Hydrogen bromide and phosphoric acid), red phosphorus can change into phosphorus tribromide use again by dripping bromine.
Innovative point of the present invention is:
1, select different catalyzer, avoided the generation of side reaction.In existing bibliographical information, use iron trichloride as catalyzer, but had following side reaction: Me
3siBr+FeCl
3→ Me
3siCl+FeBr
3, and the present invention directly selects ferric bromide as catalyzer, and catalytic effect is better, and has successfully avoided the generation of above-mentioned side reaction, and the purity of the finished product is increased, and a rectifying can reach more than 99%.In addition, by process optimization, further reduced the usage quantity of catalyzer, even can be without catalyzer (without catalyzer, yield can be in a slight decrease).
2, the stirring at normal temperature in bibliographical information is changed into high temperature reflux reaction, the reaction times was shortened to about 6 hours above from original 12 hours.
3, distillation still residue has been carried out processing again.In existing bibliographical information, do not relate to the processing for distillation still residue, in fact, document is when obtaining bromotrimethylsilane by distillation, in still, residual a large amount of still is residual, wherein, comprise other materials that catalyzer, unreacted phosphorus tribromide (three valent phosphors), estersil (pentavalent phosphorus), red phosphorus (elemental phosphorous) and silicon ether and multivalence phosphorus generate, formed dangerous solid waste, and be difficult to process, for suitability for industrialized production has been brought difficulty.We reclaim a part of unreacted phosphorus tribromide by pyrogenic distillation and recycle, also other Substance Transformations that impel silicon ether and multivalence phosphorus to generate are estersil and red phosphorus, then to remaining still, residual by first adding the method being hydrolyzed again after silicon ether, (reason that adopts this method is direct hydrolysis, not only reaction is violent but also have the danger of blasting) phosphate aqueous solution and the red phosphorus that obtain silicon ether, contain a small amount of Hydrogen bromide and phosphorous acid, phosphate aqueous solution can be used as byproduct and sells, and red phosphorus can change into phosphorus tribromide use again by dripping bromine.So, whole distillation still residue all transforms and processes, and the utilization ratio of phosphorus tribromide and silicon ether is greatly enhanced, and has further reduced production cost, and can successfully be committed to suitability for industrialized production, and meaning is very great.
4, the present invention has further optimized the molar ratio of phosphorus tribromide and silicon ether, has reduced the usage quantity of phosphorus tribromide.In former bibliographical information, the molar ratio of phosphorus tribromide and silicon ether is 1.69:1, and phosphorus tribromide is greatly excessive, produces a large amount of solid wastes simultaneously; The present invention is by the recycling to phosphorus tribromide, effectively reduce the usage quantity of phosphorus tribromide, while reacting initial, the molar ratio of phosphorus tribromide and silicon ether is 1.4～1.5: 1, by phosphorus tribromide is recycled, actual phosphorus tribromide is 0.62～0.65:1 (mol ratio) to the consumption of silicon ether.
5, product yield is greatly enhanced.The yield of former bibliographical information is 73%, and adopt this method, product yield after a rectifying can reach more than 92.7% (in silicon ether), by recycle phosphorus tribromide, silicon ether and a small amount of red phosphorus, final product yield can be up to more than 98% (in silicon ether), be far away higher than the yield of former bibliographical information.
Embodiment
Example 1: adopt the embodiment that ferric bromide is catalyzer
In the dry 2000L enamel electricity still with condensing reflux system, pump into successively 1800kg(6.65kmol) phosphorus tribromide and 721kg(4.45kmol) silicon ether; from solid feed inlet, add 3kg (0.01kmol) ferric bromide; with nitrogen, to closed system displacement 3～5 times, make whole material and reaction process thereof all under the protection in nitrogen atmosphere.
Point is opened and is stirred, by jacket steam, heat, be warming up to gradually 100 ℃ ± 5 ℃, and keep this temperature back flow reaction 6 ± 0.5 hours, after reaction finishes, start to carry out atmospheric distillation (rectifying tower is by two joint Dg200, and the common enamel rectifying tower joint of H1.5m forms), when temperature in the kettle rises to 130-135 ℃, stop rectifying, obtain the bromotrimethylsilane finished product 1270kg(8.25kmol that content is greater than 99%), a rectification yield is that 92.7%(is in silicon ether).
The phosphorus tribromide that Distillation recovery is excessive, stops distillation when temperature in the kettle rises more than 175 ℃ and while steaming without material, reclaim and obtain phosphorus tribromide 1050kg(3.88kmol again), in still, residue 200kg still is residual.
Be cooled to below 80 ℃, again to the disposable silicon ether 200kg that adds in still, stir the enamel reaction still that is transferred to another 1500L after half an hour, control still temperature below 60 ℃, to dripping 200kg water in still, be hydrolyzed while stirring, obtain organic phase silicon ether 245 kg, water phosphate aqueous solution 320 kg(wherein, are 1.52% containing Hydrogen bromide, containing iron bromide, be 0.93%, containing phosphorous acid, be 0.51%, phosphoric acid is 50.5%), solid red phosphorus is 34kg(1.10 kmol).
Silicon ether can recycle after dehydration, and phosphate aqueous solution can directly externally be sold (or can further pass through fractionation by distillation Hydrogen bromide and phosphoric acid, externally selling), and red phosphorus can be converted into phosphorus tribromide by the method for dropping bromine.
Example 2: the embodiment of catalyst-free
In the dry 2000L enamel electricity still with condensing reflux system, pump into successively 1800kg(6.65kmol) phosphorus tribromide and 721kg(4.45kmol) silicon ether; with nitrogen, to closed system displacement 3～5 times, make whole material and reaction process thereof all under the protection in nitrogen atmosphere.
Point is opened and is stirred, by jacket steam, heat, be warming up to gradually 100 ℃ ± 5 ℃, and keep this temperature back flow reaction 6 ± 0.5 hours, after reaction finishes, start to carry out atmospheric distillation (rectifying tower is by two joint Dg200, and the common enamel rectifying tower joint of H1.5m forms), when temperature in the kettle rises to 130-135 ℃, stop rectifying, obtain the bromotrimethylsilane finished product 1110kg(7.25kmol that content is greater than 99%), a rectification yield is that 81.5%(is in silicon ether).
Change the excessive phosphorus tribromide of Distillation recovery into, when temperature in the kettle rises, more than 175 ℃ and while steaming without material again, stop distillation, reclaim and obtain phosphorus tribromide 1150kg(4.25kmol), in still, residue 250kg still is residual.
Be cooled to below 80 ℃, again to the disposable silicon ether 200kg that adds in still, stir the enamel reaction still that is transferred to another 1500L after half an hour, control still temperature below 60 ℃, to dripping 200kg water in still, be hydrolyzed while stirring, obtain organic phase silicon ether 295kg, water phosphate aqueous solution 325kg(wherein, is 1.82% containing Hydrogen bromide, containing phosphorous acid, is 0.61%, phosphoric acid is 50.8%), solid red phosphorus is 30kg(1.00 kmol).
Silicon ether can recycle after dehydration, and phosphate aqueous solution can directly externally be sold (or can further pass through fractionation by distillation Hydrogen bromide and phosphoric acid, externally selling), and red phosphorus can be converted into phosphorus tribromide by the method for dropping bromine.
Claims (4)
1. a kind of synthetic method of bromotrimethylsilane, is characterized in that under oxygen free condition, will throw successively phosphorus tribromide and silicon ether Me
3siOSiMe
3the first reactor stir and be warming up to 100 ℃ ± 5 ℃, and keep this temperature back flow reaction after 6 ± 0.5 hours, carry out atmospheric distillation, obtain bromotrimethylsilane, when the first reactor temperature rises to 135 ℃, stop receiving bromotrimethylsilane finished product.
2. a kind of synthetic method of bromotrimethylsilane according to claim 1, is characterized in that described phosphorus tribromide and silicon ether Me
3siOSiMe
3molar ratio be 1.4～1.5 ︰ 1.
3. according to a kind of synthetic method of bromotrimethylsilane described in claim 1 or 2, it is characterized in that dropping into silicon ether Me
3siOSiMe
3after also drop into ferric bromide.
4. a kind of synthetic method of bromotrimethylsilane according to claim 1, is characterized in that described ferric bromide and silicon ether Me
3siOSiMe
3mol ratio is 0.001～0.01 ︰ 1.
Priority Applications (1)
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|---|---|---|---|
| CN201110057265.1A CN102153582B (en) | 2011-03-10 | 2011-03-10 | Method for synthesizing bromotrimethylsilane |
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|---|---|---|---|
| CN201110057265.1A CN102153582B (en) | 2011-03-10 | 2011-03-10 | Method for synthesizing bromotrimethylsilane |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD134954A1 (en) * | 1978-03-10 | 1979-04-04 | Hans Gross | PROCESS FOR THE PREPARATION OF TRIORGANOHALOGENILANES |
| CN101250195A (en) * | 2008-03-19 | 2008-08-27 | 华东理工大学 | Modified method for preparing trialkyl bromosilane |
-
2011
- 2011-03-10 CN CN201110057265.1A patent/CN102153582B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD134954A1 (en) * | 1978-03-10 | 1979-04-04 | Hans Gross | PROCESS FOR THE PREPARATION OF TRIORGANOHALOGENILANES |
| CN101250195A (en) * | 2008-03-19 | 2008-08-27 | 华东理工大学 | Modified method for preparing trialkyl bromosilane |
Non-Patent Citations (2)
| Title |
|---|
| Methylbromosilanes;W.F.Gilliam et al;《J.A.C.S.》;19461231;1161-1163 * |
| W.F.Gilliam et al.Methylbromosilanes.《J.A.C.S.》.1946,1161-1163. |
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