CN102153582A - Method for synthesizing bromotrimethylsilane - Google Patents
Method for synthesizing bromotrimethylsilane Download PDFInfo
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- CN102153582A CN102153582A CN2011100572651A CN201110057265A CN102153582A CN 102153582 A CN102153582 A CN 102153582A CN 2011100572651 A CN2011100572651 A CN 2011100572651A CN 201110057265 A CN201110057265 A CN 201110057265A CN 102153582 A CN102153582 A CN 102153582A
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- Prior art keywords
- bromotrimethylsilane
- silicon ether
- reactor
- phosphorus tribromide
- synthetic method
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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 100+/-5 DEG C, keeping the temperature, performing reflux reaction for 6+/-0.5 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, be that (adefovir is PMEA) with synthetic AIDS drug tynofovir (tenofovir, necessary raw material PMPA) for synthetic anti-hepatic-B virus medicine A Difuwei.
Have the synthetic method of bibliographical information to have following several at present:
1, hexamethyldisilane method: Me
3SiSiMe
3+ Br
2→ 2Me
3SiBr, this method product yield height, but react violent and wayward, and blast easily, the raw material hexamethyldisilane costs an arm and a leg in addition, loses the meaning of suitability for industrialized production gradually.
2, silicon ether---aluminium powder method: Me
3SiOSiMe
3+ Br
2+ 2/3 Al → 2Me
3SiBr+1/3 Al
2O
3, this method temperature of reaction height, by product more and about 120 ℃ will solidify, be difficult to handle, be mingled with dimethyl two bromo-silicanes about 15% in the product, separation difficulty influence the product use.
3, silicon ether---triphenylphosphine method: Me
3SiOSiMe
3+ Br
2+ Ph
3P → 2Me
3SiBr+Ph
3PO, the raw material triphenylphosphine that this method adopts costs an arm and a leg, and the by product triphen phosphine oxide of generation is difficult to handle, 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 that produces in the reaction can cause phenyl-trimethylsilicane to resolve into benzene, causes the benzene that contains in these method the finished product about 5%, and benzene is very approaching with the bromotrimethylsilane boiling point, can't separate, and influences the product use.
5, silicon ether---phosphorus tribromide method: Me
3SiOSiMe
3+ PBr
3→ Me
3SiBr, this method is owing to need to use iron trichloride as catalyzer, and owing to has following side reaction: Me
3SiBr+FeCl
3→ Me
3SiCl+FeBr
3Thereby, cause containing in the product 3% the trimethylchlorosilane impurity of having an appointment, influence product and use, and by product is more, be difficult to handle.
Summary of the invention
A kind of synthetic method of the bromotrimethylsilane that the object of the invention is to propose a kind ofly to overcome the prior art deficiency, avoids side reaction, product purity height, safety, the no three wastes produce.
Technical solution of the present invention is: under oxygen free condition, be warming up to 100 ℃ ± 5 ℃ with throwing the reactor stirring that phosphorus tribromide and silicon ether are arranged successively, 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 to receive the bromotrimethylsilane finished product.
The present invention is to silicon ether---and the phosphorus tribromide method has carried out improving innovation, has avoided the generation of side reaction, and products obtained therefrom purity height can obtain the bromotrimethylsilane finished product of content about 99%; Change stirring at normal temperature into high temperature reflux, shortened the reaction times greatly.
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 dropping into 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, and by product success conversion processing is become the raw materials for production of other products, no three wastes generation in the entire synthesis process, and clean environment firendly can be used for suitability for industrialized production.
Stop distillation when material steams when first reactor temperature rises to more than 175 ℃ and do not have, reclaim and obtain phosphorus tribromide.
To reduce in first reactor below 80 ℃, disposable adding silicon ether in first reactor again, be transferred to second reactor after stirring half an hour, control second reactor temperature below 60 ℃, add water to second reactor while stirring and be hydrolyzed, obtain organic phase silicon ether, water phosphate aqueous solution and solid red phosphorus respectively; Drip bromine to solid red phosphorus again and be reacted into living phosphorus tribromide.
Silicon ether is by after further dewatering, can drop in the reaction of next batch and recycle, (Hydrogen bromide content is about 1.5% to contain the phosphate aqueous solution of a small amount of Hydrogen bromide, phosphorous acid and iron bromide, phosphorous acid is about 0.5%, ferric bromide is 0-0.9%, phosphorus acid content is about 50%) can be used as byproduct sale (perhaps can further pass through fractionation by distillation Hydrogen bromide and phosphoric acid), red phosphorus can change into the phosphorus tribromide use again by dripping bromine.
Innovative point of the present invention is:
1, selects different catalyzer for use, avoided the generation of side reaction.Use iron trichloride as catalyzer in the existing bibliographical information, but had following side reaction: Me
3SiBr+FeCl
3→ Me
3SiCl+FeBr
3, and the present invention directly selects for use ferric bromide as catalyzer, and catalytic effect is better, and has successfully avoided the generation of above-mentioned side reaction, makes the purity of the finished product increase, and a rectifying can reach more than 99%.In addition,, further reduced the usage quantity of catalyzer by process optimization, even can be without catalyzer (without catalyzer, yield can have reduction slightly).
2, the stirring at normal temperature in the bibliographical information is changed into the high temperature reflux reaction, make the reaction times from original shortening to about 6 hours more than 12 hours.
3, distillation still residue has been carried out handling again.Do not relate to processing in the existing bibliographical information for distillation still residue, in fact, document is when obtaining bromotrimethylsilane by distillation, residual a large amount of still is residual in the still, 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 useless, and be difficult to handle, for suitability for industrialized production has been brought difficulty.We reclaim a part of unreacted phosphorus tribromide by pyrogenic distillation and recycle, other materials that also impel silicon ether and multivalence phosphorus to generate are converted into estersil and red phosphorus, residual (reason that adopts this method is a direct hydrolysis by adding earlier the method that is hydrolyzed again behind the silicon ether to remaining still then, not only reaction is violent but also have the danger of blasting) obtain silicon ether, contain the phosphate aqueous solution and the red phosphorus of 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 again by dripping bromine and use.So, whole distillation still residue all transforms and handles, 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.The molar ratio of phosphorus tribromide and silicon ether is 1.69:1 in the former document report, and phosphorus tribromide is excessive greatly, produces a large amount of solid useless simultaneously; The present invention is by the recycling to phosphorus tribromide, effectively reduce the usage quantity of phosphorus tribromide, the molar ratio of phosphorus tribromide and silicon ether is 1.4～1.5: 1 when reacting initial, 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 document report is 73%, and adopt this method, product yield after the rectifying can reach (in silicon ether) more than 92.7%, by recycle phosphorus tribromide, silicon ether and a small amount of red phosphorus, final product yield can will be higher than the yield of former document report far away up to (in silicon ether) more than 98%.
Embodiment
Example 1: adopting ferric bromide is the embodiment of catalyzer
In the exsiccant 2000L enamel electricity still that has the condensing reflux system, pump into 1800kg(6.65kmol successively) phosphorus tribromide and 721kg(4.45kmol) silicon ether; add 3kg (0.01kmol) ferric bromide from solid feed inlet; to closed system displacement 3～5 times, whole material and reaction process thereof all are under the protection of nitrogen atmosphere with nitrogen.
Point is opened and is stirred, heat by jacket steam, be warming up to 100 ℃ ± 5 ℃ gradually, and kept this temperature back flow reaction 6 ± 0.5 hours, begin to carry out atmospheric distillation (rectifying tower is by two joint Dg200, and the common enamel rectifying tower joint of H1.5m constitutes) after reaction finishes, when temperature in the kettle rises to 130-135 ℃, stop rectifying, obtain content greater than 99% bromotrimethylsilane finished product 1270kg(8.25kmol), a rectifying yield is that 92.7%(is in silicon ether).
Excessive phosphorus tribromide is reclaimed in distillation, stops distillation when material steams when temperature in the kettle rises more than 175 ℃ and do not have, reclaims and obtains phosphorus tribromide 1050kg(3.88kmol), residue 200kg still is residual in the still.
Be cooled to below 80 ℃, disposable adding silicon ether 200kg in still again stirs the enamel reaction still that is transferred to another 1500L after half an hour, and control still temperature is below 60 ℃, dripping 200kg water while stirring in still is hydrolyzed, obtain organic phase silicon ether 245 kg, water phosphate aqueous solution 320 kg(wherein, containing Hydrogen bromide is 1.52%, containing iron bromide is 0.93%, containing phosphorous acid is 0.51%, and phosphoric acid is 50.5%), solid red phosphorus is 34kg(1.10 kmol).
Silicon ether can recycle after dewatering, and phosphate aqueous solution can directly externally be sold (perhaps can further pass through fractionation by distillation Hydrogen bromide and phosphoric acid, externally sell), and red phosphorus can be converted into phosphorus tribromide by the method that drips bromine.
Example 2: the embodiment of catalyst-free
In the exsiccant 2000L enamel electricity still that has the condensing reflux system, pump into 1800kg(6.65kmol successively) phosphorus tribromide and 721kg(4.45kmol) silicon ether; to closed system displacement 3～5 times, whole material and reaction process thereof all are under the protection of nitrogen atmosphere with nitrogen.
Point is opened and is stirred, heat by jacket steam, be warming up to 100 ℃ ± 5 ℃ gradually, and kept this temperature back flow reaction 6 ± 0.5 hours, begin to carry out atmospheric distillation (rectifying tower is by two joint Dg200, and the common enamel rectifying tower joint of H1.5m constitutes) after reaction finishes, when temperature in the kettle rises to 130-135 ℃, stop rectifying, obtain content greater than 99% bromotrimethylsilane finished product 1110kg(7.25kmol), a rectifying yield is that 81.5%(is in silicon ether).
Change distillation into and reclaim excessive phosphorus tribromide, stop distillation when material steams, reclaim and obtain phosphorus tribromide 1150kg(4.25kmol when temperature in the kettle rises more than 175 ℃ and do not have), residue 250kg still is residual in the still.
Be cooled to below 80 ℃, disposable adding silicon ether 200kg in still again, stirring is transferred to the enamel reaction still of another 1500L after half an hour, control still temperature drips 200kg water while stirring and is hydrolyzed below 60 ℃ in still, obtain organic phase silicon ether 295kg, water phosphate aqueous solution 325kg(wherein, containing Hydrogen bromide is 1.82%, containing phosphorous acid is 0.61%, phosphoric acid is 50.8%), solid red phosphorus is 30kg(1.00 kmol).
Silicon ether can recycle after dewatering, and phosphate aqueous solution can directly externally be sold (perhaps can further pass through fractionation by distillation Hydrogen bromide and phosphoric acid, externally sell), and red phosphorus can be converted into phosphorus tribromide by the method that drips bromine.
Claims (6)
1. a kind of synthetic method of bromotrimethylsilane, it is characterized in that under the oxygen free condition, be warming up to 100 ℃ ± 5 ℃ with throwing first reactor stirring that phosphorus tribromide and silicon ether are arranged successively, and keep this temperature back flow reaction after 6 ± 0.5 hours, carry out atmospheric distillation, obtain bromotrimethylsilane, when first reactor temperature rises to 135 ℃, stop to receive the bromotrimethylsilane finished product.
2. according to a kind of synthetic method of the described bromotrimethylsilane of claim 1, the molar ratio that it is characterized in that described phosphorus tribromide and silicon ether is 1.4～1.5 ︰ 1.
3. according to a kind of synthetic method of claim 1 or 2 described bromotrimethylsilanes, it is characterized in that after dropping into silicon ether, also dropping into ferric bromide.
4. according to a kind of synthetic method of the described bromotrimethylsilane of claim 1, it is characterized in that described ferric bromide and silicon ether mol ratio are 0.001～0.01 ︰ 1.
5. according to a kind of synthetic method of the described bromotrimethylsilane of claim 1, it is characterized in that stopping distillation when material steams, reclaim and obtain phosphorus tribromide when first reactor temperature rises to more than 175 ℃ and do not have.
6. according to a kind of synthetic method of the described bromotrimethylsilane of claim 5, it is characterized in that and to reduce in first reactor below 80 ℃, disposable adding silicon ether in first reactor again, be transferred to second reactor after stirring half an hour, control second reactor temperature below 60 ℃, add water to second reactor while stirring and be hydrolyzed, obtain organic phase silicon ether, water phosphate aqueous solution and solid red phosphorus respectively; Drip bromine to solid red phosphorus and be reacted into living phosphorus tribromide.
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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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| CN102153582A true CN102153582A (en) | 2011-08-17 |
| CN102153582B CN102153582B (en) | 2014-04-23 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109928991A (en) * | 2019-04-08 | 2019-06-25 | 浙江海洲制药有限公司 | A method of preparing bromotrimethylsilane |
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 (1)
| Title |
|---|
| W.F.GILLIAM ET AL: "Methylbromosilanes", 《J.A.C.S.》, 31 December 1946 (1946-12-31), pages 1161 - 1163 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109928991A (en) * | 2019-04-08 | 2019-06-25 | 浙江海洲制药有限公司 | A method of preparing bromotrimethylsilane |
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| CN102153582B (en) | 2014-04-23 |
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