WO2007126194A1 - Method of preparing fluorinated alkoxytrialkylsilanes - Google Patents
Method of preparing fluorinated alkoxytrialkylsilanes Download PDFInfo
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- WO2007126194A1 WO2007126194A1 PCT/KR2006/005348 KR2006005348W WO2007126194A1 WO 2007126194 A1 WO2007126194 A1 WO 2007126194A1 KR 2006005348 W KR2006005348 W KR 2006005348W WO 2007126194 A1 WO2007126194 A1 WO 2007126194A1
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- Prior art keywords
- fluorinated
- formula
- reaction
- imidazole compound
- chlorotrialkylsilane
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
Definitions
- the present invention relates to a process for preparing fluorinated
- alkoxytrialkylsilanes from the reaction of chlorosilanes with fluoro alcohol, and in
- the first process relates to a reaction between a
- the second process relates to a reaction between a hexamethyldisilazine and
- the present invention provides an improved process for the production of
- an imidazole compound which is used as a reaction medium, reacts with a generated hydrogen chloride to form an
- alkoxytrialkylsilane and the by-products such as the imidazolium chloride
- the present invention relates to a process for preparing fluorinated
- alkoxytrialkylsilanes wherein an imidazole compound is added to the reaction of a
- R 1 , R 2 and R3 are a Ci-C 6 hydrocarbon or a phenyl group, respectively;
- R f is a Ci-C 6 fluorinated hydrocarbon containing 1-8 fluorine atoms.
- chlorotrialkylsilane reacts with a
- R 4 is a Ci-C 6 alkyl or a C 2 -C 6 alkenyl group.
- Scheme 1 The process of Scheme 1 comprises two reaction steps as shown in Scheme 2.
- chlorotrialkylsilane of formula (2) reacts with an imidazole
- salt of formula (6) is also formed as a by-product.
- an imidazole compound of formula (4) is used as a
- reaction vehicle in the present invention to produce a silylimidazolium salt of
- alkoxytrialkylsilane is manufactured at a relatively high temperature of 80 0 C.
- imidazolium salt of formula (6) are ionic compounds having a higher specific gravity
- fluorinated alkoxytrialkylsilane of formula (1) remains in an upper liquid layer
- fluorinated alkoxytrialkylsilane of formula (1) may also be obtained with
- ⁇ of formula (6) may be collected after it is converted into an imidazole compound of
- formula (4) by adding a suitable base.
- the base include an alkali metal
- R 4 is a Ci-C 6 alkyl or a C 2 -C 6 alkenyl group; M is an alkali
- X is a hydroxyl (OH) or a Ci-C 6 alkoxy group.
- compound of formula (4) may be used in the amount of 1.2 moles, respectively, relative to one mole of the fluorinated alcohol of formula (3). If the amount of the
- chlorotrialkylsilane of formula (2) or the imidazole compound of formula (4) is less
- chlorotrialkylsilane may remain unreacted, thus making the separation and
- reaction may be performed at a
- reaction temperature is preferred to be as low as possible only if the
- reaction temperature may be 100%, respectively. However, if the reaction temperature is lower than -
- the reaction rate may be too low, thus resulting in low economical efficiency.
- reaction temperature above 50 0 C is not preferred because it would result in
- reaction of the present invention may be performed in the
- the solvent may be used in the amount of up to 300 vol%,
- the reaction may be more stably performed at room temperature due to the
- alkoxytrialkylsilane and the imidazolium salt, an ionic liquid alkoxytrialkylsilane and the imidazolium salt, an ionic liquid.
- Example 1 except that the solvent was changed as shown in Table 5. The results are
- a chlorotrialkylsilane derivative reacts with a
- the imidazolium salt may be any substantial boiling point.
- the imidazolium salt may be any substantial boiling point.
- imidazolium salt may be converted into the initial imidazole compound
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The present invention relates to a process for preparing alkoxytrialkylsilane, and in particular to a process, wherein an imidazole compound is added as a HCl scavenger and a reaction promoter, thereby enhancing the yield of fluorinated alkoxytrialkylsilanes and reducing corrosion problem.
Description
METHOD OF PREPARING FLUORINATED ALKOXYTRIALKYLSILANES
TECHNICAL FIELD
The present invention relates to a process for preparing fluorinated
alkoxytrialkylsilanes from the reaction of chlorosilanes with fluoro alcohol, and in
particular to a process, wherein an imidazole compound is added as a HCl
scavenger as well as a reaction promoter, thereby enhancing the yield of fluorinated
alkoxytrialkylsilanes and reducing corrosion problem.
RELATED PRIOR ART
Fluorinated alkoxytrialkylsilanes have attracted much attention as
promising candidates for the third-generation cleaning agent, because they are zero
ozone-depleting, low global warming, thermally stable, and highly capable of
cleaning the surfaces of metals, plastics, and elastomers without any damage.
Besides the application as cleaning agents, fluorinated alkoxytrialkysilanes
can be used in diverse areas including chemical reaction media, lubricants, foaming
agents, polymer modifying agents and insulating agents, due to their excellent
physical and chemical properties.
Two useful processes have been known useful for manufacturing
fluorinated alkoxytrialkylsilanes. The first process relates to a reaction between a
chlorotrialkylsilane and a fluorinated alcohol [Collect. Czech. Chem. Commun. 44,
750, (1979)]. However, this process envitably produces hydrochloric acid as a by¬
product, which is apt to cause the corrosion of facilities and makes product
separation process difficult.
The second process relates to a reaction between a hexamethyldisilazine and
a fluorinated alcohol for making fluorinated alkoxytrialkylsilane [Publications of
Japanese patent application Nos. 7-247293 and 6-108096]. However, this process
also should be performed at high temperatures for a long reaction time with a
moderate yield of about 80%. Furthermore, the process suffers from relatively high
cost of raw material, hexamethyldisilazane and formation of corrosive ammonia as a
by-product.
The present invention provides an improved process for the production of
fluorinated alkoxytrialkylsilanes from the reaction between a chlorotrialkylsilane
and a fluorinated alcohol in the presence of an imidazolium compound.
According to the process of the present invention, the generation of the
corrosive material is fundamentally prevented, thus remarkably increasing reaction
stability.
Further, according to the process herein, an imidazole compound, which is
used as a reaction medium, reacts with a generated hydrogen chloride to form an
imidazolium chloride salt which has a relatively low melting point. The big
difference in specific gravity and polarity between the produced fluorinated
alkoxytrialkylsilane and the by-products, such as the imidazolium chloride, results
in the formation of a two-phase system, thereby facilitating the separation of the
products from the reaction mixture via layer separation.
DETAILED DESCRIPTION OF INVENTION
The present invention relates to a process for preparing fluorinated
alkoxytrialkylsilanes, wherein an imidazole compound is added to the reaction of a
chlorotrialkylsilane and a fluorinated alcohol as acid scavangers, thereby increasing
the yield of the resulting fluorinated alkoxytrialkylsilane.
Hereunder is provided a more detailed description of the present invention.
The present invention is characterized in maximizing the yield of a reaction
for preparing a fluorinated alkoxytrialkylsilane of formula (1) from the reaction of a
chlorotrialkylsilane and a fluorinated alcohol in the presence of an imidazole
compound:
wherein R1, R2 and R3 are a Ci-C6 hydrocarbon or a phenyl group, respectively; and
Rf is a Ci-C6 fluorinated hydrocarbon containing 1-8 fluorine atoms.
According to the present invention, chlorotrialkylsilane reacts with a
fluorinated alcohol in the presence of an imidazole compound for preparing a
fluorinated alkoxytrialkylsilane of formula (1) as shown in Scheme 1.
Scheme 1
R
In Scheme 1, Ri, R2, R3 and Rf are same as defined in formula (1) above; and
R4 is a Ci-C6 alkyl or a C2-C6 alkenyl group.
The process of Scheme 1 comprises two reaction steps as shown in Scheme 2.
Scheme 2
(5) (1 ) (6)
In Scheme 2, R1, R2, R3, R4, and Rf are same as defined in Scheme 1.
That is, chlorotrialkylsilane of formula (2) reacts with an imidazole
compound of formula (4) to form an ionic compound, a silylimidazolium salt of
formula (5), which further reacts with a fluorinated alcohol of formula (3) to form a
target material, a fluorinated alkoxytrialkylsilane of formula (1). An immidazolium
salt of formula (6) is also formed as a by-product.
As described above, an imidazole compound of formula (4) is used as a
reaction vehicle in the present invention to produce a silylimidazolium salt of
formula (5) as an intermediate, which is non-toxic and non-corrosive. Further, due
to the use of an imidazole compound of formula (4), the reaction yield can be greatly
increased even at room temperature. Conventionally, a fluorinated
alkoxytrialkylsilane is manufactured at a relatively high temperature of 80 0C.
Moreover, both the imidazole compound of formula (4) and the
imidazolium salt of formula (6) are ionic compounds having a higher specific gravity
than the fluorinated alkoxytrialkylsilane of formula (1). Thus, the final product,
fluorinated alkoxytrialkylsilane of formula (1) remains in an upper liquid layer,
while the intermediate and the by-product stay in a lower liquid layer.
Accordingly, the final product can be easily collected via layer separation.
Moreover, fluorinated alkoxytrialkylsilane of formula (1) may also be obtained with
high purity via simple distillation due to their much lower boiling point than those
of the intermediate and the by-product.
Further, as shown in Scheme 3, the by-product herein, an imidazolium salt
^ of formula (6) may be collected after it is converted into an imidazole compound of
formula (4) by adding a suitable base. Examples of the base include an alkali metal
salt, more specifically a water-soluble salt of an alkali metal-based compound, such
as sodium hydroxide and a Ci-C6 sodium alkoxide.
0 Scheme 3
In Scheme 3, R4 is a Ci-C6 alkyl or a C2-C6 alkenyl group; M is an alkali
metal; and X is a hydroxyl (OH) or a Ci-C6 alkoxy group.
For the preparation of the fluorinated alkoxytrialkylsilane of formula (1), 1-
1.5 moles of the chlorotrialkylsilane of formula (2) and 1-2 moles of the imidazole
5 compound of formula (4) may be used relative to one mole of the fluorinated alcohol
of formula (3). Preferably, the chlorotrialkylsilane of formula (2) and the imidazole
compound of formula (4) may be used in the amount of 1.2 moles, respectively,
relative to one mole of the fluorinated alcohol of formula (3). If the amount of the
chlorotrialkylsilane of formula (2) or the imidazole compound of formula (4) is less
than one mole relative to one mole of the fluorinated alcohol of formula (3), the raw
material, chlorotrialkylsilane may remain unreacted, thus making the separation and
purification of the product difficult.
Further, according to the process herein, the reaction may be performed at a
lower temperature, i.e., at a temperature of -20 to 50 °C, preferably -10 to 25 °C. In
particular, a reaction temperature is preferred to be as low as possible only if the
conversion of the raw material, i.e., a fluorinated alcohol and a chlorotrialkylsilane
may be 100%, respectively. However, if the reaction temperature is lower than -
20 0C, the reaction rate may be too low, thus resulting in low economical efficiency.
The reaction temperature above 50 0C is not preferred because it would result in
decomposition of products.
Moreover, the reaction of the present invention may be performed in the
absence of a solvent or, if necessary, in the presence of an appropriate aprotic
organic solvent. The solvent may be used in the amount of up to 300 vol%,
preferably 100-200 vol% relative to the volume of an imidazole compound. In a
solvent, the reaction may be more stably performed at room temperature due to the
dilution effect of raw materials, i.e., an imidazole compound and a
chlorotrialkylsilane, resulting in effective control of reaction heat. The solvent also
facilitates the layer separation between the products, i.e., the fluorinated
alkoxytrialkylsilane and the imidazolium salt, an ionic liquid.
5 EXAMPLES
The present invention is described more specifically by the following
Examples. Examples herein are meant only to illustrate the present invention, and
they should not be construed as limiting the scope of the claimed invention.
10 Example 1
12.9 g (0.12 mol) of chlorotrimethylsilane was dropwised to the solution of
10 g (0.1 mol) of 2,2,2-trifluoroethanol in 9.8 g (0.12 mol) of 1-methylimidazole at
0 0C, and stirred at room temperature for 1 hour. Upper layer was separated and
analyzed via gas chromatography equipped with column. The conversion of
^5 fluorinated alcohol was 99.6%. Distilling the upper layer gave a colorless
transparent liquid of 2,2,2-trifluoroethoxytrialkylsilane with a yield of 96.4%.
The conversion of fluorinated alcohol used as a starting material and the
yield of thus produced fluorinated alkoxytrialkylsilane were calculated using the
following equations.
Equat i on( l)
Amount of the remaining
Conversion of fluorinated fluorinated alcohol(mol) alcohol (%) 100 - [100 x
Amount of used fluorinated alcohol (mol)
Equat ion(2)
Amount of the produced fluorinated
Yield of fluorinated alkoxytrialkylsi laneCmol ) alkoxytrialkylsi Ian = 100 x -
Amount of used fluorinated alcohol (mol )
Examples 2-6
2,2,2-Trifluoroethoxytrialkylsilane was synthesized under the same
condition as in Example 1 except that the kind of chlorotrialkylsilane was changed as
shown in Table 1. The results are shown in Table 1.
Table 1
Fluorinated alkoxytrimethylsilane was synthesized under the same
condition as in Example 1 except that the kind of fluorinated alcohol was changed as
shown in Table 2. The results are shown in Table 2.
Table 2
Examples 13-16
2,2,2-trifluoroethoxytrimethylsilane was synthesized under the same
condition as in Example 1 except that the kind of imidazole was changed as shown
in Table 3. The results are shown in Table 3.
Table 3
Example 17
20.84 g (0.521 moles) of sodium hydroxide was added into the lower layer
separated from the reaction mixture in Example 1 at room temperature and then the
mixture was stirred for 1 hour. After filtration of thus produced NaCl, the resulting
filtrate was distilled at reduced pressure, thereby regenerating 1-methy limidazole
with a yield of 97.6%.
Examples 18-21
1- Alky limidazole used in Examples 13-16 was regenerated by using the
same procedure as in Example 17. The results are shown in Table 4.
Table 4
Example 22
1 -Methylimidazole was collected by using the same procedure as in
Example 17 except that sodium hydroxide was replaced with sodium methoxide
(NaOCHs). The recovery rate of 1 -methylimidazole was 98.5%.
Examples 23-26
2,2,2-Trifluoroethoxytrimethylsilane was synthesized under the same condition as in
Example 1 except that the solvent was changed as shown in Table 5. The results are
shown in Table 5.
Table 5
Examples 28-41
2,2,2-Trifluoroethoxytrimethylsilane was synthesized under the same
condition as in Example except that the molar ratios of chlorotrimethylsilane and 1-
methylimidazole to 2,2,2-trifluoroethanol are changed as shown in Table 6. The
results are shown in Table 6.
Table 6
Examples 42-47
2,2,2-Trifluoroethoxytrimethylsilane was synthesized under the same
condition as in Example 1 except by changing the reaction temperature as shown in
Table 7. The results are shown in Table 7.
Table 7
As described above, a chlorotrialkylsilane derivative reacts with a
fluorinated alcohol in the presence of an imidazole compound in the present
invention. This greatly improves the stability and efficiency of the process by
preventing formation of any corrosive materials, which are generally produced as
by-products in the conventional process. The process of the present invention also
facilitates the separation of products from a reaction mixture, thereby much
simplifying the entire process.
The aforementioned ionic liquid, i.e., an imidazolium salt of formula (6),
which is produced as a by-product in the process, is not corrosive because it is in a
salt state without having any substantial boiling point. The imidazolium salt may
also be easily separated from the product, i.e., the fluorinated alkoxytrialkylsilane.
Further, the imidazolium salt may be converted into the initial imidazole compound
by treating with a suitable base such as sodium hydroxide, and easily collected for
recovery. For the foregoing reasons, the process herein can be applied to mass
production and a continuous process.
Claims
1. A process of preparing fluorinated alkoxytrialkylsilanes of formula (1), which
comprises a step of performing a reaction between a fluorinated alcohol and a
chlorotrialkylsilane in the presence of an imidazole compound:
and Rf is a Ci-C6 fluorinated hydrocarbon containing 1-8 fluorine atoms.
2. The process of claim 1, wherein the chlorotrialkylsilane and the imidazole
compound are used in the amount of 1-1.5 moles and 1-2 moles, respectively,
relative to one mole of the fluorinated alcohol.
3. The process of claim 1, wherein the reaction is performed at a temperature of
from -20 to 50 0C.
4. The process of claim 1, wherein the imidazole compound has a structure of formula (4):
.N^N (4)
R
wherein R4 is a Q-Cr3 alkyl or a C2-C6 alkenyl group.
^
5. The process of claim 1, wherein a silyl imidazolium salt of formula (5) is
produced as an intermediate product in the reaction:
R1
\ JR4 R2-Si s/
■ N" N Cl- (5)
R3 wherein R1, R2 and R3 are a Ci-C6 hydrocarbon or a phenyl group; and R4 is a C1-
C6 alkyl or a C2-C6 alkenyl group.
0
6. The process of claim 1, wherein the reaction is performed in the absence of
solvent or in the presence of a non-polar solvent.
7. The process of claim 1, wherein an imidazolium salt of formula (6) is produced as
5 a by-product in the reaction:
ci- y N. ^N (6)
R "H wherein R4 is a Ci-C6 alkyl or a C2-C6 alkenyl group.
8. The process of claim 7, wherein the imidazole compound is regenerated by
reacting an imidazolium compound with an alkali metal salt.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020060039532A KR100744834B1 (en) | 2006-05-02 | 2006-05-02 | Method for producing a fluorine-containing alkoxysilane derivative |
| KR10-2006-0039532 | 2006-05-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2007126194A1 true WO2007126194A1 (en) | 2007-11-08 |
Family
ID=38601545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2006/005348 Ceased WO2007126194A1 (en) | 2006-05-02 | 2006-12-08 | Method of preparing fluorinated alkoxytrialkylsilanes |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR100744834B1 (en) |
| WO (1) | WO2007126194A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103958532A (en) * | 2011-10-11 | 2014-07-30 | 汉高美国知识产权有限责任公司 | Novel fluorochemical articles, methods for their preparation, and compositions made therefrom |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06108096A (en) * | 1992-09-29 | 1994-04-19 | Agency Of Ind Science & Technol | Solvent composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5493044A (en) | 1994-10-20 | 1996-02-20 | Fmc Corporation | Process for preparing alkylsilyl or arylsilyl ethers |
| JP3128193B2 (en) * | 1995-12-06 | 2001-01-29 | 信越化学工業株式会社 | Method for producing alkoxysilane compound |
-
2006
- 2006-05-02 KR KR1020060039532A patent/KR100744834B1/en not_active Expired - Fee Related
- 2006-12-08 WO PCT/KR2006/005348 patent/WO2007126194A1/en not_active Ceased
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06108096A (en) * | 1992-09-29 | 1994-04-19 | Agency Of Ind Science & Technol | Solvent composition |
Non-Patent Citations (3)
| Title |
|---|
| MONTANARI V. ET AL.: "1-Iodo-polyfluoroalkanes from polyfluoroalkoxy trimethylsilanes and iodochloro triphenylphosphorane", TETRAHEDRON LETTERS, vol. 35, no. 12, 1994, pages 1941 - 1944, XP000434499, DOI: doi:10.1016/S0040-4039(00)73201-1 * |
| PATEL N.R. ET AL.: "Synthesis and Chemistry of Acyclic Mono and Disiloxanes: Useful Precursors to per- and Polyfluoroethers", INORGANIC CHEMISTRY, vol. 33, no. 24, 1994, pages 5463 - 5470 * |
| UNEYAMA K. ET AL.: "Preparation of 2,2-difluoroenol silyl ethers by electroreductive defluorination of trifluoromethyl ketones", TETRAHEDRON LETTERS, vol. 39, no. 22, 1998, pages 3741 - 3744, XP004118726, DOI: doi:10.1016/S0040-4039(98)00574-7 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103958532A (en) * | 2011-10-11 | 2014-07-30 | 汉高美国知识产权有限责任公司 | Novel fluorochemical articles, methods for their preparation, and compositions made therefrom |
| EP2766375A4 (en) * | 2011-10-11 | 2015-09-09 | Henkel US IP LLC | Preparation of novel fluorocompounds, methods of preparation and compositions made therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100744834B1 (en) | 2007-08-01 |
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