CN103755734A - Synthesis method of trimethylsilyl acetate - Google Patents
Synthesis method of trimethylsilyl acetate Download PDFInfo
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- CN103755734A CN103755734A CN201410013427.5A CN201410013427A CN103755734A CN 103755734 A CN103755734 A CN 103755734A CN 201410013427 A CN201410013427 A CN 201410013427A CN 103755734 A CN103755734 A CN 103755734A
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- acetic acid
- trimethylsilyl group
- synthetic method
- acid trimethylsilyl
- filtrate
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Abstract
The invention discloses a synthesis method of trimethylsilyl acetate, and relates to a silylating reagent. The synthesis method comprises the steps of adding 0.63-0.84 part by mass of sodium acetate, 0.5-5 parts by mass of a solvent and 0.0001-0.005 part by mass of a phase transfer catalyst to a reaction kettle, and uniformly stirring at 20-30 DEG C; dropwise adding 1 part of trimethyl chlorosilane to the reaction kettle at an addition speed of 1-2g/min, stirring and reacting for 2-4 hours at 10-60 DEG C to obtain liquid to be filtered; separating the liquid to be filtered to obtain filtrate; and distilling the filtrate, collecting distillate at 106-108 DEG C to obtain a finished trimethylsilyl acetate product. The synthesis method disclosed by the invention is relatively high in reaction activity, thorough in reaction, high in yield of the finished trimethylsilyl acetate product and short in reaction time; and the finished trimethylsilyl acetate product is easy to separate, and is relatively high in purity.
Description
Technical field
The present invention relates to a kind of silylating reagent, be specifically related to a kind of synthetic method of acetic acid trimethylsilyl group.
Background technology
Acetic acid trimethylsilyl group is a kind of application trimethyl silicone hydride reagent more widely, is mainly used in the silanization of alcohol, mercaptan, phenol, ketone, crafty acid, phenylacetylene etc., and obtains three (trimethyl silane) boric acid ester with acid reaction.
Existing acetic acid trimethylsilyl group is to make by chlorosilane and acetic acid reaction, and because chlorosilane is substitution reaction with reacting of acetic acid, reactive behavior is lower, and reaction is difficult to thoroughly carry out, and the yield that obtains product is lower; Due to the boiling point of acetic acid trimethylsilyl group, more approaching with the boiling point of byproduct of reaction Acetyl Chloride 98Min., therefore not only more difficult separation of reaction product, and also the purity of the acetic acid trimethylsilyl group obtaining is lower.
Summary of the invention
For the defect existing in prior art, the object of the present invention is to provide a kind of synthetic method of acetic acid trimethylsilyl group, reactive behavior is higher, the yield that more thoroughly obtains product that reaction is carried out is higher, reaction times is shorter, and product easily separates, and the purity of product is higher.
For reaching above object, the technical scheme that the present invention takes is: a kind of synthetic method of acetic acid trimethylsilyl group, comprises the following steps:
A, by mass parts, 0.63～0.84 part of sodium acetate, 0.5～5 part of solvent and 0.0001～0.005 portion of phase-transfer catalyst are added in reactor, at the temperature of 20 ℃～30 ℃, stir; Under the condition that is 1g/min～2g/min at rate of addition, in reactor, drip 1 part of trimethylchlorosilane, at the temperature of 10 ℃～60 ℃, stirring reaction 2h～4h, forms liquid to be filtered;
B, liquid to be filtered is carried out to filtrate separation, obtain filtrate; Filtrate is distilled, and collecting temperature is 106 ℃～108 ℃ distillates under condition, obtains acetic acid trimethylsilyl group product.
On the basis of technique scheme, described solvent is DMF, N,N-dimethylacetamide, acid anhydrides or acetic acid.
On the basis of technique scheme, described phase-transfer catalyst is Tetrabutyl amonium bromide, tetrabutylammonium chloride or Dimethylamino pyridine.
On the basis of technique scheme, described phase-transfer catalyst is DMF or acid anhydrides.
On the basis of technique scheme, in steps A, 0.63～0.84 part of sodium acetate, 2～3 parts of solvents and 0.001～0.002 portion of phase-transfer catalyst are added in reactor, at the temperature of 20 ℃～30 ℃, stir; Under the condition that is 1g/min～2g/min at rate of addition, in reactor, drip 1 part of trimethylchlorosilane, at the temperature of 30 ℃～50 ℃, after stirring reaction 2h～4h, form liquid to be filtered.
On the basis of technique scheme, described sodium acetate is 0.72 part.
On the basis of technique scheme, described solvent is 2.5 parts.
On the basis of technique scheme, described phase-transfer catalyst is 0.0015 part.
On the basis of technique scheme, step B comprises the following steps: liquid to be filtered is carried out to filtrate separation, obtain filtrate; In temperature, be 107 ℃, pressure is under 1 atmospheric condition, and filtrate is distilled, and obtains acetic acid trimethylsilyl group product.
On the basis of technique scheme, the yield of described acetic acid trimethylsilyl group is 98%～98.5%.
Compared with prior art, the invention has the advantages that:
(1) the present invention adopts sodium acetate to react with trimethylchlorosilane, for acid-base neutralisation reaction, compared with substitution reaction of the prior art, the activity of reaction is higher, react more thorough, the quality of the product acetic acid trimethyl silicane product obtaining is larger, and the yield of acetic acid trimethylsilyl group is 90.9%～96.68%, and yield is higher.
(2) by product of the present invention is sodium-chlor, larger with the boiling point difference of acetic acid trimethylsilyl group, therefore the present invention can be by distilling to obtain the overhead product of 106 ℃～107 ℃, overhead product is acetic acid trimethylsilyl group product, in acetic acid trimethylsilyl group product, the content of acetic acid trimethylammonium silicone grease is 98%～98.5%, and purity is higher.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
The embodiment of the present invention provides a kind of synthetic method of acetic acid trimethylsilyl group, comprise the following steps: by mass parts by 0.63～0.84 sodium acetate, 0.5～5 part of solvent and 0.0001～0.005 portion of phase-transfer catalyst add in reactor, at the temperature of 20 ℃～30 ℃, stir, under the condition that is 1g/min～2g/min at rate of addition, in reactor, drip 1 part of trimethylchlorosilane, stirring reaction 2h～4h at the temperature of 10 ℃～60 ℃, obtain liquid to be filtered, liquid to be filtered is carried out to filtrate separation and obtain filtrate, at pressure, be under an atmospheric condition, filtrate to be distilled, collect the overhead product of 106 ℃～108 ℃, obtain acetic acid trimethyl silicane fat prod.
By GC(Gas Chromatography vapor-phase chromatography) detect acetic acid trimethyl silicane fat prod, the content that obtains acetic acid trimethylammonium silicone grease in acetic acid trimethyl silicane fat prod is 98%～98.5%.
By reaction equation (CH
3)
3siCl+CH
3cOONa → CH
5h
12o
2si+NaCl, in the embodiment of the present invention, the mol ratio of trimethylchlorosilane and sodium acetate is 1:0.9～1:1.2, therefore: when the mol ratio of trimethylchlorosilane and sodium acetate is 1:0.9～1:1, the theoretical yield of acetic acid trimethylammonium silicone grease is: (charging capacity/82 of sodium acetate) × 132; When the mol ratio of trimethylchlorosilane and sodium acetate is 1:0.9～1:1, the theoretical yield of acetic acid trimethylammonium silicone grease is: (charging capacity/108.6 of trimethylchlorosilane) × 132.The yield calculation formula of acetic acid trimethylammonium silicone grease is: (theoretical yield of actual output/acetic acid trimethylammonium silicone grease of acetic acid trimethylammonium silicone grease) × 100%.
Reactor is the 1000ml four-hole glass round-bottomed flask that is provided with agitator, thermometer, reflux condensing tube, constant pressure funnel and well heater; Solvent is DMF, N,N-dimethylacetamide, acid anhydrides or acetic acid; Phase-transfer catalyst is Tetrabutyl amonium bromide, tetrabutylammonium chloride or Dimethylamino pyridine.
Below by 5 embodiment, be specifically described:
Embodiment 1: selective solvent is DMF, phase-transfer catalyst is tetrabutylammonium chloride.
In the four-hole glass round-bottomed flask of 1000ml, add 86g sodium acetate, 209gN, dinethylformamide and 0.216g tetrabutylammonium chloride, four-hole glass round-bottomed flask is with agitator, thermometer, reflux condensing tube, constant pressure funnel and well heater.At the temperature of 30 ℃, sodium acetate, DMF and tetrabutylammonium chloride are stirred, in constant pressure funnel, add 108.5g trimethylchlorosilane, the rate of addition of constant pressure funnel is adjusted to 2g/min; Trimethylchlorosilane in constant pressure funnel is dropped to four-hole glass round-bottomed flask.After trimethylchlorosilane dropwises, be warming up to 60 ℃ of stirring reaction 2h, obtain liquid to be filtered, liquid to be filtered is carried out to filtrate separation and obtain filtrate, at pressure, be under an atmospheric condition, filtrate to be distilled, collect the overhead product of 108 ℃, obtain 120g acetic acid trimethyl silicane fat prod.
Embodiment 2: selective solvent is N,N-dimethylacetamide, phase-transfer catalyst is Tetrabutyl amonium bromide.
In 1000ml four-hole glass round-bottomed flask, add 98.4g sodium acetate, 542.5gN, N-N,N-DIMETHYLACETAMIDE and 0.54g Tetrabutyl amonium bromide, four-hole glass round-bottomed flask is with agitator, thermometer, reflux condensing tube, constant pressure funnel and well heater.At the temperature of 20 ℃, by sodium acetate, N, N-N,N-DIMETHYLACETAMIDE and Tetrabutyl amonium bromide stir, in constant pressure funnel, add 108.5g trimethylchlorosilane, the rate of addition of constant pressure funnel is adjusted to 1g/min, trimethylchlorosilane in constant pressure funnel is dropped to four-hole glass round-bottomed flask, after trimethylchlorosilane dropwises, be warming up to 40 ℃, stirring reaction 3h, obtain liquid to be filtered, liquid to be filtered is carried out to filtrate separation and obtain filtrate, at pressure, be under an atmospheric condition, filtrate to be distilled, collect the overhead product of 106 ℃, obtain 120g acetic acid trimethyl silicane fat prod.
Embodiment 3: selective solvent is acetic acid, phase-transfer catalyst is Tetrabutyl amonium bromide.
In 1000ml four-hole glass round-bottomed flask, add 73.8g sodium acetate, 554.25g acetic acid and 0.0108g Tetrabutyl amonium bromide, four-hole glass round-bottomed flask is with agitator, thermometer, reflux condensing tube, constant pressure funnel and well heater.At the temperature of 25 ℃, by sodium acetate, acetic acid and Tetrabutyl amonium bromide stir, in constant pressure funnel, add 108.5g trimethylchlorosilane, the rate of addition of constant pressure funnel is adjusted to 1.5g/min, trimethylchlorosilane in constant pressure funnel is dropped to four-hole glass round-bottomed flask, after trimethylchlorosilane dropwises, stirring reaction 2h at the temperature of 10 ℃, obtain liquid to be filtered, liquid to be filtered is carried out to filtrate separation and obtain filtrate, at pressure, be under an atmospheric condition, filtrate to be distilled, collect the overhead product of 107 ℃, obtain 115g acetic acid trimethyl silicane fat prod.
Embodiment 4: selective solvent is aceticanhydride, phase-transfer catalyst is Dimethylamino pyridine.
In 1000ml four-hole glass round-bottomed flask, add 82g sodium acetate, 325g aceticanhydride and 0.15g Dimethylamino pyridine, four-hole glass round-bottomed flask is with agitator, thermometer, reflux condensing tube, constant pressure funnel and well heater.At the temperature of 30 ℃, by sodium acetate, aceticanhydride and Dimethylamino pyridine stir, in constant pressure funnel, add 108.5g trimethylchlorosilane, the rate of addition of constant pressure funnel is adjusted to 2g/min, trimethylchlorosilane in constant pressure funnel is dropped to four-hole glass round-bottomed flask, after trimethylchlorosilane dropwises, stirring reaction 2h at the temperature of 50 ℃, obtain liquid to be filtered, liquid to be filtered is carried out to filtrate separation and obtain filtrate, at pressure, be under an atmospheric condition, filtrate to be distilled, collect the overhead product of 108 ℃, obtain 126g acetic acid trimethyl silicane fat prod.
Embodiment 5: selective solvent is DMF, phase-transfer catalyst is Dimethylamino pyridine.
In 1000ml four-hole glass round-bottomed flask, add 90g sodium acetate, 250gN, dinethylformamide and 0.108g Dimethylamino pyridine, four-hole glass round-bottomed flask is with agitator, thermometer, reflux condensing tube, constant pressure funnel and well heater.At the temperature of 30 ℃, by sodium acetate, N, dinethylformamide and Dimethylamino pyridine stir, in constant pressure funnel, add 108.5g trimethylchlorosilane, the rate of addition of constant pressure funnel is adjusted to 2g/min, trimethylchlorosilane in constant pressure funnel is dropped to four-hole glass round-bottomed flask, after trimethylchlorosilane dropwises, stirring reaction 4h at the temperature of 45 ℃, obtain liquid to be filtered, liquid to be filtered is carried out to filtrate separation and obtain filtrate, at pressure, be under an atmospheric condition, filtrate to be distilled, collect the overhead product of 107 ℃, obtain 126g acetic acid trimethyl silicane fat prod.
Through GC, analyze, according to the yield calculation formula of acetic acid trimethylammonium silicone grease: (theoretical yield of actual output/acetic acid trimethylammonium silicone grease of acetic acid trimethylammonium silicone grease) × 100% draws:
In embodiment 1, in acetic acid trimethyl silicane fat prod, the content of acetic acid trimethylsilyl group is 98.5%, and the yield of acetic acid trimethylammonium silicone grease is: 120/132 × 100%=90.9%.
In acetic acid trimethyl silicane fat prod in embodiment 2, the content of acetic acid trimethylsilyl group is 98.5%, and the yield of acetic acid trimethylammonium silicone grease is: 120/132 × 100%=90.9%.
In embodiment 3, in acetic acid trimethyl silicane fat prod, the content of acetic acid trimethylsilyl group is 98%, and the yield of acetic acid trimethylammonium silicone grease is: 115/(132 × 0.9) × 100%=96.68%.
In embodiment 4, in acetic acid trimethyl silicane fat prod, the content of acetic acid trimethylsilyl group is 98.2%, and the yield of acetic acid trimethylammonium silicone grease is: 126/132 × 100%=95.5%.
In embodiment 5 acetic acid trimethyl silicane fat prods, the content of acetic acid trimethylsilyl group is 98.5%, and the yield of acetic acid trimethylammonium silicone grease is: 126/132 × 100%=95.5%.
The present invention is not limited to above-mentioned embodiment, for those skilled in the art, under the premise without departing from the principles of the invention, can also make some improvements and modifications, within these improvements and modifications are also considered as protection scope of the present invention.The content not being described in detail in this specification sheets belongs to the known prior art of professional and technical personnel in the field.
Claims (10)
1. a synthetic method for acetic acid trimethylsilyl group, is characterized in that, comprises the following steps:
A, by mass parts, 0.63～0.84 part of sodium acetate, 0.5～5 part of solvent and 0.0001～0.005 portion of phase-transfer catalyst are added in reactor, at the temperature of 20 ℃～30 ℃, stir; Under the condition that is 1g/min～2g/min at rate of addition, in reactor, drip 1 part of trimethylchlorosilane, at the temperature of 10 ℃～60 ℃, stirring reaction 2h～4h, forms liquid to be filtered;
B, liquid to be filtered is carried out to filtrate separation, obtain filtrate; Filtrate is distilled, and collecting temperature is 106 ℃～108 ℃ distillates under condition, obtains acetic acid trimethylsilyl group product.
2. the synthetic method of acetic acid trimethylsilyl group as claimed in claim 1, is characterized in that: solvent described in steps A is DMF, N,N-dimethylacetamide, acid anhydrides or acetic acid.
3. the synthetic method of acetic acid trimethylsilyl group as claimed in claim 1, is characterized in that: phase-transfer catalyst described in steps A is Tetrabutyl amonium bromide, tetrabutylammonium chloride or Dimethylamino pyridine.
4. the synthetic method of acetic acid trimethylsilyl group as claimed in claim 3, is characterized in that: phase-transfer catalyst described in steps A is DMF or acid anhydrides.
5. the synthetic method of acetic acid trimethylsilyl group as claimed in claim 1, it is characterized in that: in steps A, 0.63～0.84 part of sodium acetate, 2～3 parts of solvents and 0.001～0.002 portion of phase-transfer catalyst are added in reactor, at the temperature of 20 ℃～30 ℃, stir; Under the condition that is 1g/min～2g/min at rate of addition, in reactor, drip 1 part of trimethylchlorosilane, at the temperature of 30 ℃～50 ℃, after stirring reaction 2h～4h, form liquid to be filtered.
6. the synthetic method of acetic acid trimethylsilyl group as claimed in claim 5, is characterized in that: described sodium acetate is 0.72 part.
7. the synthetic method of acetic acid trimethylsilyl group as claimed in claim 5, is characterized in that: described solvent is 2.5 parts.
8. the synthetic method of acetic acid trimethylsilyl group as claimed in claim 5, is characterized in that: described phase-transfer catalyst is 0.0015 part.
9. the synthetic method of the acetic acid trimethylsilyl group as described in claim 1 to 8 any one, is characterized in that, step B comprises the following steps: liquid to be filtered is carried out to filtrate separation, obtain filtrate; In temperature, be 107 ℃, pressure is under 1 atmospheric condition, and filtrate is distilled, and obtains acetic acid trimethylsilyl group product.
10. adopt the acetic acid trimethylsilyl group that synthetic method is made described in claim 1 to 10 any one, it is characterized in that: the yield of described acetic acid trimethylsilyl group is 98%～98.5%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010072532A1 (en) * | 2008-12-16 | 2010-07-01 | Basf Se | Method for silylation of monocarboxylic acids |
| CN101880392A (en) * | 2010-07-22 | 2010-11-10 | 溧阳巨神科技材料有限公司 | Method for preparing hydroxyl silicone oil by taking sodium acetate as acylating agent |
| CN102286018A (en) * | 2011-08-08 | 2011-12-21 | 浙江大学 | Preparation method of acetoxysilane |
-
2014
- 2014-01-13 CN CN201410013427.5A patent/CN103755734A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010072532A1 (en) * | 2008-12-16 | 2010-07-01 | Basf Se | Method for silylation of monocarboxylic acids |
| CN101880392A (en) * | 2010-07-22 | 2010-11-10 | 溧阳巨神科技材料有限公司 | Method for preparing hydroxyl silicone oil by taking sodium acetate as acylating agent |
| CN102286018A (en) * | 2011-08-08 | 2011-12-21 | 浙江大学 | Preparation method of acetoxysilane |
Non-Patent Citations (3)
| Title |
|---|
| YUN-FEI DU ET AL.: "A study on the heterogeneous reaction of trialkylsilyl chlorides with inorganic salts and monocarboxylates catalysed by PEG400", 《JOURNAL OF CHEMICAL RESEARCH》 * |
| 叶非等: "《有机合成化学》", 30 September 2010, 化学工业出版社 * |
| 姚蒙正等: "《精细化工产品合成原理》", 31 March 2000, 中国石化出版社 第2版 * |
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Application publication date: 20140430 |