JP4292412B2 - Method for producing fluorine-containing ether compound - Google Patents

Description

  The present invention relates to a method for producing a fluorine-containing ether compound.

  As a method for producing a fluorinated ether, a method of reacting an alcohol with a fluorinated olefin compound in the presence of an alkali metal hydroxide or an alkali metal hydride is widely known (see Patent Document 1 below). However, this method requires relatively high temperature and high pressure conditions, has a low reaction rate, and has a problem that a large amount of precipitate is produced after the reaction, which is a satisfactory method in terms of productivity. Absent.

Further, it is known that a fluorine-containing ether can be obtained under mild conditions by performing the above reaction in an organic solvent (see Patent Document 2 below). However, in this method, in addition to the target fluorine-containing ether, by-products such as olefin compounds in which fluorine atoms are eliminated from the carbanion intermediate tend to be produced in a large amount, and the amount of solvent relative to the raw material is large. The amount of fluorine-containing ether obtained by one reaction is relatively small.
Moreover, the manufacturing method which uses water as a reaction solvent is also known (refer the following patent document 3). In this method, the target fluorine-containing ether compound can be obtained with high selectivity and the post-treatment process is simple, but there is a problem in productivity because the reaction rate is greatly reduced. Although it is possible to increase the reaction rate by reducing the amount of water used, the advantage that the post-treatment step is simple is lost because a large amount of precipitate is generated after the reaction.
US Pat. No. 3,557,294 JP-A-9-263559 JP 2002-20152 A

The main object of the present invention is to provide a novel production method in which a fluorine-containing ether compound can be obtained with high selectivity in a relatively short time and the post-treatment process is simple.

  As a result of intensive studies to achieve the above object, the present inventor has achieved the selectivity of the target product according to the method of reacting the fluorinated alcohol and the fluorinated olefin compound in the presence of the basic compound and the alcohol. The present inventors have found that a fluorine-containing ether can be obtained in a relatively short time without losing, and have completed the present invention.

  That is, this invention provides the manufacturing method of the following fluorine-containing ether compound.

1. In the presence of a basic compound and at least one selected from the group consisting of secondary alcohols and tertiary alcohols, the general formula (I):
Rf—CH ₂ —OH (I)
(In the formula, Rf is a C 1-18 perfluoroalkyl group, a C 1-18 polyfluoroalkyl group, a C 6-18 perfluoroaryl group, or a C 6-18 polyfluoroaryl group. A fluorine-containing alcohol represented by the general formula (II):
CF ₂ = CR ¹ R ² (II)
(In the formula, R ¹ and R ² are the same or different and are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group having 1 to 10 carbon atoms, a perfluoroalkyl group having 1 to 10 carbon atoms, And a fluorine-containing olefin compound represented by a C 1-10 polyfluoroalkyl group, a C 6-18 perfluoroaryl group or a C 6-18 polyfluoroaryl group). And general formula (III):
Rf—CH ₂ —O—CF ₂ —CHR ¹ R ² (III)
(Wherein Rf, R ¹ and R ² are as defined above).

  2. The fluorine-containing alcohol represented by the general formula (I) is 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,3,4,4,4- Hexafluorobutanol, 2,2,3,3-tetrafluoropropanol, 3,3,4,4,4-pentafluorobutanol, 3,3,4,4-tetrafluorobutanol, 2,2,3,3, 4,4,5,5-octafluoropentanol, 3,3,4,4,5,5,6,6,6-nonafluorohexanol, 3,3,4,4,5,5,6,6 -Octafluorohexanol, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanol, 3,3,4,4,5,5,6, 6,7,7,8,8-dodecafluorooctanol, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadeca Fluorodecanol, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-hexadecafluorodecanol, 3,3,4,4, 5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heneicosafluorododecanol, 3,3,4,4,5 , 5,6,6,7,7,8,8,9,9,10,10,11,11,12,12-eicosafluoro Decanol, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14, 14-pentacosafluorotetradecanol, and 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12, Item 2. The method according to Item 1, which is at least one compound selected from the group consisting of 13,13,14,14-tetracosafluorotetradecanol.

  3. The fluorine-containing alcohol represented by the general formula (I) is 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol and 2,2,3,4,4,4- Item 2. The method according to Item 1, which is at least one compound selected from the group consisting of hexafluorobutanol.

  4). The fluorine-containing olefin compound represented by the general formula (II) is at least one compound selected from the group consisting of vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, and octafluoroisobutene. Item 4. The method according to any one of Items 1 to 3.

  5). Item 5. The method according to Item 4, wherein the fluorine-containing olefin compound represented by the general formula (II) is at least one compound selected from the group consisting of tetrafluoroethylene and hexafluoropropylene.

  6). Any one of Items 1 to 5, wherein the basic compound is at least one compound selected from the group consisting of alkali metal oxides, alkaline earth metal oxides, alkali metal hydroxides, and alkaline earth metal hydroxides. The method described.

  -Secondary alcohol and tertiary alcohol are each represented by the following general formula (IV)

(In formula, R < ³ >, R < ⁴ > and R < ⁵ > are the same or different, respectively, a hydrogen atom, a C1-C18 alkyl group, a C1-C10 perfluoroalkyl group, C1-C10, respectively. A polyfluoroalkyl group, an aryl group having 6 to 18 carbon atoms, a perfluoroaryl group having 6 to 18 carbon atoms, or a polyfluoroaryl group having 6 to 18 carbon atoms; provided that R ³ , R ⁴ and R ⁵ are Item 7. The method according to any one of Items 1 to 6, wherein all of them are not hydrogen atoms, or one is a hydrogen atom and the other two are not hydrogen atoms.

  8). At least one selected from the group consisting of secondary alcohols and tertiary alcohols is isopropanol, 3-pentanol, 3-methyl-3-pentanol, 3-ethyl-3-pentanol, tert-butanol, trityl alcohol And the method according to any one of Items 1 to 7, which is at least one selected from the group consisting of 1,1,1,3,3,3-hexafluoro-2-propanol.

  9. Item 9. The method according to any one of Items 1 to 8, which is carried out in the presence of water.

The fluorine-containing alcohol used as a raw material in the method of the present invention is represented by the following general formula (I):
_Rf-CH 2 OH (I)
{Wherein Rf is a C 1-18 perfluoroalkyl group, general formula: C _m H _n F _p (where m is an integer of 1-18, n is an integer of 1-2 m, p is 2m + 1) -N) is a polyfluoroalkyl group having 1 to 18 carbon atoms, a perfluoroaryl group having 6 to 18 carbon atoms, or a polyfluoroaryl group having 6 to 18 carbon atoms. is there.

In the general formula (I), the structure of the alkyl group in the perfluoroalkyl group and polyfluoroalkyl group represented by Rf may be either linear or branched.
Examples of the perfluoroalkyl group having 1 to 18 carbon atoms include groups represented by C _q F _{2q + 1} (q is an integer of 1 to 18), and particularly a linear or branched chain having about 1 to 10 carbon atoms. Are preferred.
General _formula: C _m H n _{F p} (where, m is 1 to 18 integer, n is an integer of 1 to 2 m, p is a is 2m + 1-n) polyfluoro 1 to 18 carbon atoms represented by The alkyl group is particularly preferably a linear or branched chain having about 1 to 10 carbon atoms.
Examples of the C 6-18 perfluoroaryl group include pentafluorophenyl, heptafluoronaphthyl, perfluorotoluyl, perfluoroxylyl, perfluoroanthranyl, perfluorophenanthryl, perfluorodiphenyl, and the like.
Examples of the polyfluoroaryl group having 6 to 18 carbon atoms include (mono, di, tri, or tetra) fluorophenyl, (mono, di, tri, tetra, penta, or hexa) fluoronaphthyl.

  As the fluorine-containing alcohol, any compound represented by the general formula (I) can be used without particular limitation. In particular, considering the availability, for example, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,3,3-tetrafluoropropanol, 2, 2,3,4,4,4-hexafluorobutanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 3,3,4,4,4-pentafluorobutanol, 3,3 , 4,4-tetrafluorobutanol, 2,2,3,3,4,4,5,5-octafluoropentanol, 3,3,4,4,5,5,6,6,6-nonafluoro Hexanol, 3,3,4,4,5,5,6,6-octafluorohexanol, 3,3,4,4,5,5,6,6,7,7,8,8,8-trideca Fluorooctanol, 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluorooctanol, 3,3,4,4,5,5,6,6,7,7 , 8,8,9,9,10,10,10-heptadecafluorodecanol, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10 , 10-Hexadecafluorodecanol, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12 -Henicosafluorododecanol, 3,3,4,4,5,5,6,6,7,7,8 , 8,9,9,10,10,11,11,12,12-eicosafluorododecanol, 3,3,4,4,5,5,6,6,7,7,8,8,9 , 9,10,10,11,11,12,12,13,13,14,14,14-pentacosafluorotetradecanol, 3,3,4,4,5,5,6,6,7, 7,8,8,9,9,10,10,11,11,12,12,13,13,14,14-tetracosafluorotetradecanol and the like are preferable. Of these, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2, 2,3,4,4,4-hexafluorobutanol is particularly preferred.

The fluorine-containing olefin compound as the other raw material of the present invention has the following general formula (II):
CF ₂ = CR ¹ R ² (II)
(In the formula, R ¹ and R ² are the same or different and are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group having 1 to 10 carbon atoms, a perfluoroalkyl group having 1 to 10 carbon atoms, general _formula: C _m H n _{F p} (where, m is an integer of from 1 to 10, n is an integer of 1 to 2 m, p is a is 2m + 1-n) polyfluoro having 1 to 10 carbon atoms represented by An alkyl group, a perfluoroaryl group having 6 to 18 carbon atoms, or a polyfluoroaryl group having 6 to 18 carbon atoms).

  In the general formula (II), the alkyl group portion of the alkoxy group having 1 to 10 carbon atoms may be either linear or branched.

Preferred functional groups as R ¹ and R ² include methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoro Fluorobutyl, perfluoropentyl, perfluorohexyl, difluoromethyl, 2H-perfluoroethyl, 3H-perfluoropropyl, 4H-perfluorobutyl, 5H-perfluoropentyl, 6H-perfluoro Examples include a hexyl group, a pentafluorophenyl group, a perfluoronaphthyl group, and a fluoroanthranyl group.

  Among the fluorine-containing olefins represented by the general formula (II), preferred compounds include vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, octafluoroisobutene and the like. Of these, tetrafluoroethylene and hexafluoropropylene are particularly preferable.

The amount of the fluorine-containing olefin represented by the general formula (II) is not particularly limited, but considering economy, it may be about 0.7 to 2 mol with respect to 1 mol of the fluorine-containing alcohol. Preferably, it is more preferably about 0.9 to 1.3 mol.
According to the present invention, in the presence of a basic compound and at least one selected from the group consisting of a secondary alcohol and a tertiary alcohol, the general formula (I):
_Rf-CH 2 OH (I)
(Wherein Rf is as defined above) and a general formula (II):
CF ₂ = CR ¹ R ² (II)
(Wherein, R ¹ and R ² are as defined above) to react with a fluorine-containing olefin compound represented by the general formula (III):
Rf—CH ₂ —O—CF ₂ —CHR ¹ R ² (III)
A fluorine-containing ether compound represented by the formula (wherein Rf, R ¹ and R ² are the same as above) can be obtained.

  An important feature of the method of the present invention is to use at least one selected from the group consisting of a secondary alcohol and a tertiary alcohol together with a basic compound. As a result, the secondary / tertiary alcohol used as an additive reacts with the fluorine-containing olefin compound, thereby reducing the purity of the product and greatly increasing the reaction rate, allowing high selection in a short time. In particular, the intended fluorine-containing ether compound can be obtained.

  As the basic compound, a metal oxide, a metal hydroxide, or the like can be used. As the metal hydroxide, an alkali metal hydroxide (for example, sodium hydroxide, potassium hydroxide, lithium hydroxide), alkaline earth, or the like can be used. Examples include metal hydroxides (eg, magnesium hydroxide, calcium hydroxide, barium hydroxide). In particular, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide are preferred because they are easily available and inexpensive. Examples of the alkali metal oxide include sodium oxide, potassium oxide, and lithium oxide, and examples of the alkaline earth metal oxide include calcium oxide, magnesium oxide, and barium oxide.

  A basic compound can be used individually by 1 type or in mixture of 2 or more types.

  The amount of the basic compound used is not particularly limited, but considering the reaction rate, economy, etc., it is preferably about 0.01 to 2 mol with respect to 1 mol of the fluorinated alcohol. It is more preferable to set it to about -0.6 mol.

  The at least one selected from the group consisting of secondary alcohols and tertiary alcohols is not particularly limited. For example, the following general formula (IV)

(Wherein R ³ , R ⁴ and R ⁵ are as defined above) can be used, but the hydroxyl group is sterically sterically like a tertiary alcohol. A bulky material is preferred. Among them, considering the availability, remarkable effect, and selectivity of the target product, isopropanol, 3-pentanol, 3-methyl-3-pentanol, 3-ethyl-3-pentanol, tert-butanol, trityl Alcohol, 1,1,1,3,3,3-hexafluoro-2-propanol and the like are preferable. In particular, tert-butanol, 1,1,1,3,3,3-hexafluoro-2-propanol and the like are preferable.

  A secondary alcohol and a tertiary alcohol can be used individually by 1 type or in mixture of 2 or more types.

  The amount of secondary alcohol and tertiary alcohol used is not particularly limited, but considering the reaction rate and economy, the amount is about 0.001 to 2 moles relative to 1 mole of the raw fluorine-containing alcohol. It is preferable that it is about 0.01-0.8 mol.

  The specific method for carrying out the production method of the present invention is not particularly limited, but an example of the production method is as follows.

  First, a fluorine-containing alcohol, a basic compound, and alcohol are put into a pressurizable reaction apparatus such as an autoclave, and the inside of the apparatus is replaced with an inert gas, and then the pressure is reduced by about 0.01 to 0.09 MPa from atmospheric pressure. At this time, the reaction apparatus may be cooled with an appropriate cryogen in order to prevent loss of raw materials due to reduced pressure.

  Next, the temperature of the reactor after depressurization is raised, and a gaseous fluorine-containing olefin compound is introduced while maintaining a predetermined temperature. Although reaction temperature can be changed according to the reaction rate of a raw material, when reaction rate and the selectivity of reaction are considered, it is about 0-200 degreeC normally, Preferably what is necessary is just about 50-100 degreeC. As a method for introducing the fluorine-containing olefin compound, in addition to a method of introducing the entire amount into the apparatus at the start of the reaction, a method of introducing continuously or intermittently by a method of keeping the introduction speed constant, a method of keeping the introduction pressure constant, etc. Is mentioned. In particular, a method of keeping the introduction pressure constant is preferable as a method that can make the most of the simplicity of the apparatus and operation and the effect of shortening the reaction time. The pressure at this time is not particularly limited, but is preferably about 0.1 to 3 MPa in consideration of the reaction rate and prevention of polymerization of the fluorinated olefin compound.

In the production method of the present invention, the above reaction may be performed in the presence of water. As a water supply source, water contained in the raw material can be used, and water can be added separately. The method of adding water separately is not particularly limited, but is selected from the group consisting of a method of adding water directly into the reaction system, a fluorine-containing alcohol, a basic compound, a secondary alcohol and a tertiary alcohol. The method of using at least 1 type of compound as aqueous solution is mentioned.

The amount of water to be used is not particularly limited. However, considering that the effect of shortening the reaction time by adding secondary alcohol and tertiary alcohol is maximized, the amount of water used is 1 The amount is preferably about 0.01 to 1.70 mol with respect to mol, and more preferably about 0.05 to 0.95 mol with respect to 1 mol of fluorine-containing alcohol. When water is added, the reaction rate decreases. However, in the production method of the present invention, the decrease in the reaction rate can be reduced as compared with the case where there is no secondary alcohol and tertiary alcohol.

  The obtained fluorine-containing ether compound may be further purified by a known method such as extraction, distillation, recrystallization, column chromatography, liquid separation, or washing according to a conventional method, if necessary.

  According to the present invention, a target fluorine-containing ether compound can be obtained with high selectivity in a relatively short time without impairing selectivity. The obtained ether compound can be effectively used for various applications such as a cleaning agent, a foaming agent, and a solvent.

  Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1
A stainless steel autoclave with a capacity of 200 ml was charged with 80.0 g of 2,2,2-trifluoroethanol, 13.5 g of 85% pure potassium hydroxide and 17.3 g of tert-butanol. The autoclave was cooled in a dry ice-acetone bath to deaerate the inside of the container and purged with nitrogen, and then the pressure was reduced again.

  Next, the autoclave was heated to 85 ° C., and tetrafluoroethylene was introduced with stirring while maintaining the internal pressure of 0.7 MPa. It took 127 minutes to introduce 84.3 g (1.05 mol per mol of trifluoroethanol) tetrafluoroethylene.

  The organic layer after the reaction was analyzed by gas chromatography. The target 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether was found to have a conversion rate of 99.99% or more and a selectivity of 99.0%. It was confirmed that it was generated.

  With respect to the conditions of Comparative Example 1 in which no alcohol was added, the reaction was completed in about half the time, and the conversion rate and selectivity of the resulting ether were almost the same.

Comparative Example 1
A stainless steel autoclave having a capacity of 200 ml was charged with 80.0 g of 2,2,2-trifluoroethanol and 13.6 g of potassium hydroxide having a purity of 85%. The autoclave was cooled in a dry ice-acetone bath to deaerate the inside of the container and purged with nitrogen, and then the pressure was reduced again.

  Next, the temperature of the autoclave was raised to 85 ° C., and tetrafluoroethylene was introduced with stirring while maintaining the internal pressure of 0.7 MPa. It took 237 minutes to introduce 84.0 g (1.05 mol per 1 mol of trifluoroethanol) tetrafluoroethylene.

The organic layer after the reaction was analyzed by gas chromatography. The target 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether was found to have a conversion rate of 99.99% or more and a selectivity of 98.7%. It was confirmed that it was generated.
Example 2
Excellent in the same manner as in Example 1 except that 120.0 g of 2,2,3,3,3-pentafluoropropanol was used instead of 80.0 g of 2,2,2-trifluoroethanol used in Example 1. Further, 1,1,2,2-tetrafluoroethyl-2,2,3,3,3-pentafluoropropyl ether can be obtained with a high conversion and selectivity.
Example 3
The same procedure as in Example 1 was used except that 145.6 g of 2,2,3,4,4,4-hexafluorobutanol was used instead of 80.0 g of 2,2,2-trifluoroethanol used in Example 1. 1,1,2,2-tetrafluoroethyl-2,2,3,4,4,4-hexafluorobutyl ether can be obtained with excellent conversion and selectivity.

Claims (8)

In the presence of at least one basic compound selected from the group consisting of alkali metal oxides, alkaline earth metal oxides, alkali metal hydroxides and alkaline earth metal hydroxides, and tert-butanol , ):
Rf—CH ₂ —OH (I)
(In the formula, Rf is a C 1-18 perfluoroalkyl group, a C 1-18 polyfluoroalkyl group, a C 6-18 perfluoroaryl group, or a C 6-18 polyfluoroaryl group. A fluorine-containing alcohol represented by the general formula (II):
CF ₂ = CR ¹ R ² (II)
(In the formula, R ¹ and R ² are the same or different and are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group having 1 to 10 carbon atoms, a perfluoroalkyl group having 1 to 10 carbon atoms, And a fluorine-containing olefin compound represented by a C 1-10 polyfluoroalkyl group, a C 6-18 perfluoroaryl group or a C 6-18 polyfluoroaryl group). And general formula (III):
Rf—CH ₂ —O—CF ₂ —CHR ¹ R ² (III)
(Wherein Rf, R ¹ and R ² are as defined above). The method according to claim 1, wherein the amount of tert-butanol used is 0.001 to 2 mol per mol of the fluorinated alcohol. The method according to claim 2, wherein the amount of tert-butanol used is 0.01 to 0.8 mol with respect to 1 mol of the fluorinated alcohol. The fluorine-containing alcohol represented by the general formula (I) is 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,3,4,4,4- Hexafluorobutanol, 2,2,3,3-tetrafluoropropanol, 3,3,4,4,4-pentafluorobutanol, 3,3,4,4-tetrafluorobutanol, 2,2,3,3, 4,4,5,5-octafluoropentanol, 3,3,4,4,5,5,6,6,6-nonafluorohexanol, 3,3,4,4,5,5,6,6 -Octafluorohexanol, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanol, 3,3,4,4,5,5,6, 6,7,7,8,8-dodecafluorooctanol, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadeca Fluorodecanol, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-hexadecafluorodecanol, 3,3,4,4, 5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heneicosafluorododecanol, 3,3,4,4,5 , 5,6,6,7,7,8,8,9,9,10,10,11,11,12,12-eicosafluoro Decanol, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14, 14-pentacosafluorotetradecanol, and 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12, The method according to any one of claims 1 to 3, which is at least one compound selected from the group consisting of 13,13,14,14-tetracosafluorotetradecanol. The fluorine-containing alcohol represented by the general formula (I) is 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol and 2,2,3,4,4,4- The method according to claim 4 , which is at least one compound selected from the group consisting of hexafluorobutanol. The fluorine-containing olefin compound represented by the general formula (II) is at least one compound selected from the group consisting of vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene and octafluoroisobutene. The method according to any one of claims 1 to 5 . The method according to claim 6 , wherein the fluorine-containing olefin compound represented by the general formula (II) is at least one compound selected from the group consisting of tetrafluoroethylene and hexafluoropropylene. The method according to any one of claims 1 to 7 , which is carried out in the presence of water.