JPH11140008A - Method for producing fluorine-containing ether compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method capable of supplying a fluorine-containing ether compound which can be used for a solvent, a cosmetic, a detergent composition, an emulsifier, a surface treatment agent and the like in a high yield in a simple and inexpensive manner. SOLUTION: A hydroxy compound and a carbonyl compound,
Alternatively, in producing an ether compound by reacting only a carbonyl compound in a hydrogen atmosphere using a catalyst,
A fluorine-containing compound having a fluorine substituent is used as at least one of the hydroxy compound and the carbonyl compound, and is reacted in the presence of a Lewis acid to obtain a fluorine-containing ether compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a fluorinated ether compound. More specifically, the present invention relates to a method for producing a fluorinated ether compound which can be easily and inexpensively supplied in a high yield to a fluorinated ether compound which can be widely used for solvents, cosmetics, detergent compositions, emulsifiers, surface treatment agents and the like. .

[0002]

2. Description of the Related Art Conventionally, as a method for producing a fluorine-containing ether compound, for example, the following formula (3) R-CH ₂ OH (3) (wherein, R represents an alkyl group or a fluorine-containing alkyl group). A method of synthesizing a fluorinated ether compound by converting a hydrocarbon or fluorinated alcohol into an alcoholate such as Na, K or the like and then reacting it with an alkyl halide or a halogenated fluorinated alkyl (Williamson synthesis method) is known. Have been.

In Japanese Patent Publication No. 8-30021, a fluoroolefin is used by reacting a fluoroolefin with a fluorine-containing carbonyl compound in the presence of AgF in an aprotic polar solvent having a hydrogen atom. Methods for obtaining the compounds are disclosed.

However, the former method requires an alkali such as Na or K which is equivalent to the alcohol used, and furthermore, a large amount of salt is produced after the reaction, which is not industrially preferable. In the latter method, the catalyst AgF used is a fluorine atom constituting the fluorinated ether compound, so that
More than an equimolar amount is required for the fluorine-containing carbonyl compound as a raw material, and further, there is a problem that it cannot be recovered and reused.

A fluorine-containing ether compound can be synthesized from a fluorine-containing alcohol and an ester compound.
Ester compounds are limited to dimethyl sulfate, diethyl sulfate, and the like, and are preferable for the synthesis of methyl ether and ethyl ether. However, it is difficult to synthesize a fluorine-containing ether compound having more carbon atoms than these compounds.

[0006]

As described above, fluorine-containing ether compounds are expected to be used, but are difficult to produce because they are difficult to use, and cannot be used for general purposes. There has been a need for a method of producing compounds. Accordingly, an object of the present invention is to provide a production method capable of supplying a fluorine-containing ether compound which can be used for a solvent, a cosmetic, a detergent composition, an emulsifier, a surface treatment agent, and the like in a high yield in a simple and inexpensive manner. is there.

[0007]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on a simple and inexpensive method for producing a fluorine-containing ether compound which can be used for general purposes. Alternatively, when producing an ether compound by reacting only a carbonyl compound under a hydrogen atmosphere using a catalyst, at least one of a hydroxy compound or a carbonyl compound, or a fluorine compound having a fluorine substituent as at least one of the carbonyl compounds is used. The present inventors have found that a fluorine-containing ether compound can be obtained in one step and in a high yield by the presence of a Lewis acid in the reaction system, and have completed the present invention.

That is, according to the present invention, when a hydroxy compound and a carbonyl compound are reacted in a hydrogen atmosphere using a catalyst to produce an ether compound, a fluorine compound having a fluorine substituent as at least one of the hydroxy compound and the carbonyl compound is used. Use compound and Lewis
(Lewis) It is intended to provide a process for producing a fluorinated ether compound, which comprises reacting in the presence of an acid.

Further, the present invention provides a method for producing an ether compound by reacting a carbonyl compound in a hydrogen atmosphere using a catalyst, wherein a fluorine compound having a fluorine substituent is used as at least one of the carbonyl compounds; (Lewis) It is intended to provide a process for producing a fluorinated ether compound, which comprises reacting in the presence of an acid.

[0010]

Embodiments of the present invention will be described below in detail.

In the present invention, when reacting a hydroxy compound with a carbonyl compound, a fluorine compound having a fluorine substituent is used as at least one of the hydroxy compound and the carbonyl compound, and both the hydroxy compound and the carbonyl compound have a fluorine substituent. When the reaction is carried out using a fluorine compound, a fluorine-containing ether compound in which both sides of the ether compound are substituted with fluorine can be produced. When reacting a hydroxy compound with a carbonyl compound using a fluorine compound having only one fluorine substituent, only one of the ether compounds is substituted with fluorine, and a fluorine-containing ether compound can be produced. it can.

Furthermore, in the present invention, when only the carbonyl compound is reacted with only the carbonyl compound having a fluorine substituent, a fluorine-containing ether compound in which both sides of the ether compound are substituted with fluorine can be produced.

The hydroxy compound used in the present invention includes a compound represented by the following general formula (1): R _1- (OA) _n -OH (1) wherein R ₁ is a hydrogen atom, a straight or branched chain having 1 to 40 carbon atoms. An alkyl or alkenyl group, a cycloalkyl group having 3 to 12 carbon atoms, or a fluorine substituent in which at least one hydrogen atom of these groups is substituted with a fluorine atom. A represents a linear or branched alkylene group having 2 to 12 carbon atoms which may have a hydroxy group as a substituent, and n A's may be the same or different. n is 0
Indicates a number of 500. ] The compound represented by this is mentioned.

Among the compounds represented by the general formula (1), those having no fluorine substituent include methyl alcohol, ethyl alcohol, propyl alcohol, n
-Butyl alcohol, n-hexyl alcohol, n-octyl alcohol, n-decyl alcohol, n-undecyl alcohol, n-dodecyl alcohol, n-tridecyl alcohol, n-tetradecyl alcohol, n-pentadecyl alcohol, n- Hexadecyl alcohol,
linear saturated alcohols such as n-octadecyl alcohol and n-eicosyl alcohol, isopropyl alcohol,
Isobutyl alcohol, 2-ethylhexyl alcohol, 2-hexyldecyl alcohol, 2-heptylundecyl alcohol, 2-octyldodecyl alcohol,
2-decyltetradecyl alcohol, 2- (1,3,3
-Trimethylbutyl) -5,7,7-trimethyloctyl alcohol;

[0015]

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(Where a and b are a + b = 14, and a = b
= With a distribution having a peak at 7), saturated branched alcohols such as methyl-branched isostearyl alcohol, 2-tetradecyloctadecyl alcohol, 2-hexadecyleicosyl alcohol, 9-octadecenyl alcohol, oleyl alcohol Alkenyl alcohols, such as ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monoisopropyl ether (isopropyl cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monoisoamyl ether, ethylene glycol Monoethers of ethylene glycol such as monohexyl ether, diethylene glycol monomethyl ether (methyl carbitol Monoethylene ethers such as diethylene glycol monoethyl ether (ethyl carbitol), diethylene glycol monoisopropyl ether (isopropyl carbitol), diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monomethyl ether, triethylene glycol monoethyl Monoethers of triethylene glycol such as ether, triethylene glycol monohexyl ether, triethylene glycol monododecyl ether, and triethylene glycol monotetradodecyl ether; 1,4-butanediol monohexyl ether; 2-methyl-1,3 -Propanediol monooctyl ether, 1,6-pentanediol monohexyl ether, 3-methyl Alkylene glycol monoethers such as -1,5-pentanediol monohexyl ether, ethylene oxide, propylene oxide or butylene oxide adducts of the above alcohols, cyclopentanol, cyclohexanol, cycloheptanol, etc. It is not limited to these.

Among these hydroxy compounds, aliphatic alcohols having 1 to 22 carbon atoms, particularly 6 to 22 carbon atoms, methyl cellosolve, ethyl cellosolve, isopropyl cellosolve,
Butyl cellosolve, methyl carbitol, ethyl carbitol, isopropyl carbitol, butyl carbitol, or an ethylene oxide or / and propylene oxide adduct of an aliphatic alcohol having 1 to 22 carbon atoms, particularly 6 to 22 carbon atoms (average mole number 0.1 to 0.1) 200), cycloalkanols having 5 to 8 carbon atoms and diols having 2 to 10 carbon atoms are preferable, and aliphatic alcohols having 6 to 22 carbon atoms; cyclohexanol; ethylene glycol, 1,4-butanediol, 1,6 Diols such as -hexanediol and 1,9-nonanediol are preferred. These hydroxy compounds can be used alone or as a mixture of two or more.

In addition, general formula (1) having a fluorine substituent
Examples of the hydroxy compound represented by include fluorine-containing hydroxy compounds having a fluorine substituent in which at least one hydrogen atom of the hydroxy compound having no fluorine substituent shown above is substituted with a fluorine atom. Specific examples include 2,2,3,3,3-pentafluoropropanol, 2- (perfluorohexyl) ethanol, 2- (perfluorooctyl) ethanol,
(Perfluorodecyl) ethanol, 6- (perfluoroethyl) hexanol, 6- (perfluorobutyl)
Hexanol, 6- (perfluorohexyl) hexanol, 6- (perfluorooctyl) hexanol,
2,2,3,4,4,4-hexafluorobutanol,
2,2,3,3-tetrafluoropropanol, 1H,
1H, 5H-octafluoropentanol, 1H, 1
H, 7H-dodecafluoroheptanol, 1H, 1H,
Linear fluorinated alcohols such as 9H-hexadecafluorononanol, 2- (perfluoro-3-methylbutyl) ethanol, 2- (perfluoro-5-methylhexyl) ethanol, 2- (perfluoro-7-methyl) (Octyl) ethanol, 2- (perfluoro-9-methyldodecyl) ethanol, 6- (perfluoro-1-methylethyl) hexanol, 6- (perfluoro-3-methylbutyl) hexanol, 6- (perfluoro-5-
Methylhexyl) hexanol, 6- (perfluoro-
Branched fluorine-containing alcohols such as 7-methyloctyl) hexanol, 3- (perfluoro-3-methylbutyl)
-1,2-propanediol, 3- (perfluoro-5
-Methylhexyl) -1,2-propanediol, 3-
Fluorine-containing diols such as (perfluoro-7-methyloctyl) -1,2-propanediol, ethylene oxide of these fluorine-containing alcohols or diols,
Examples include propylene oxide and butylene oxide adducts, but are not necessarily limited thereto.

Among these fluorinated hydroxy compounds, aliphatic alcohols having a fluorine substituent and having 1 to 22 carbon atoms are preferred, and particularly, the general formula (4) Rf ₁ (CH ₂ ) _p OH (4) Rf ₁ represents a linear or branched fluorinated alkyl group having 1 to 12 carbon atoms, and p represents a number of 1 to 10). These fluorinated hydroxy compounds can be used alone or as a mixture of two or more.

In the present invention, the carbonyl compound includes a compound having a carbonyl group as well as a compound having a carbonyl group easily by an acid or heating. As the carbonyl compound used in the present invention, general formula (2)

[0021]

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[Wherein R ₂ and R ₃ are hydrogen atoms and have 1 to 20 carbon atoms.
Represents a linear or branched alkyl or alkenyl group, or a fluorine substituent in which at least one of the hydrogen atoms of these groups has been replaced by a fluorine atom, and R ₂ and R ₃ may be the same or different Good. Further, a cyclic structure in which R ₂ and R ₃ are bonded may be used. Or a polymer thereof.

Among the compounds represented by the general formula (2), those having no fluorine substituent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, Methyl isobutyl ketone (4-methyl-2-pentanone), pinacolone, methyl-n-amyl ketone, methyl-n-hexyl ketone, diethyl ketone, ethyl-
n-butyl ketone, di-n-propyl ketone, diisopropyl ketone, diisobutyl ketone, 2,6,6-trimethylnonanone-4, 6-methyl-5-heptenone-2
And other cyclic ketones such as cyclohexanone, 2-methylcyclohexanone, isophorone, cyclopentanone and cycloheptanone, formaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, pentylaldehyde, hexylaldehyde, heptylaldehyde, octylaldehyde, and nonyl. Linear aldehydes such as aldehyde, decylaldehyde, undecylaldehyde, dodecylaldehyde, hexadecylaldehyde, octadecylaldehyde, eicosylaldehyde, isobutyraldehyde, 2-ethylhexylaldehyde, 2-
Ethyl butyraldehyde, isononyl aldehyde (3,
Branched aldehydes such as 5,5-trimethylhexanal) and methylheptadecylaldehyde; and examples of the polymer of the compound represented by the general formula (2) include paraformaldehyde and paraaldehyde (trimer of acetaldehyde). But are not necessarily limited to these.

Among these carbonyl compounds, chain ketones having 3 to 19 carbon atoms, aldehydes having 1 to 19 carbon atoms, cyclic ketones having 5 to 8 carbon atoms, paraformaldehyde and paraaldehyde are preferable, and acetone, methyl ethyl ketone, A chain ketone having 3 to 6 carbon atoms, such as methyl isobutyl ketone (4-methyl-2-pentanone), formaldehyde, acetaldehyde, butyraldehyde, isobutyraldehyde, octylaldehyde, isononylaldehyde (3,5,5-trimethylhexanal) ), Aliphatic aldehydes having 1 to 12 carbon atoms such as dodecyl aldehyde,
Particularly preferred are cyclic ketones having 5 to 6 carbon atoms, such as cyclohexanone, paraformaldehyde and paraaldehyde, and more preferably acetone, methyl ethyl ketone, methyl isobutyl ketone (4-methyl-2-pentanone), butyraldehyde, isobutyraldehyde, octylaldehyde, Nonylaldehyde (3,5,5-trimethylhexanal) and paraaldehyde are particularly preferred. These carbonyl compounds can be used alone or as a mixture of two or more.

In addition, general formula (2) having a fluorine substituent
Examples of the carbonyl compound represented by include a fluorine-containing carbonyl compound having a fluorine substituent in which at least one of the hydrogen atoms of the carbonyl compound having no fluorine substituent shown above is substituted with a fluorine atom. Specific examples include fluoroacetone, 1,1,1-trifluoroacetone, 1,1,1-trifluoro-2-butanone, 1,1,1-trifluoro-2-pentanone,
1,1,1-trifluoro-2-hexanone, bis (trifluoromethyl) ketone, bis (pentafluoroethyl) ketone, bis (heptafluoropropyl) ketone,
Fluorinated ketones such as trifluoromethylpentafluoroethylketone and trifluoromethylheptafluoropropylketone, 3,3,3-trifluoropropylaldehyde, 4,4,4-trifluorobutyraldehyde,
5,5,5-trifluoropentylaldehyde, 6,
Fluorine-containing aldehydes such as 6,6-trifluorohexylaldehyde, trifluoroethanoyl fluoride, pentafluoropropionoyl fluoride, heptafluorobutanoyl fluoride, nonafluoropentanoyl fluoride and the like, but not necessarily It is not limited to these. Among these fluorinated carbonyl compounds, a fluorinated chain ketone having 1 to 12 carbon atoms and a fluorinated chain aldehyde having 1 to 12 carbon atoms are preferable, and particularly a fluorinated ketone represented by the general formula (5) The fluorine-containing aldehyde represented by the general formula (6) is preferable.

[0026]

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(In the formula, Rf ₂ represents a fluorine-containing alkyl group having 1 to 10 carbon atoms, and R ₄ represents an alkyl group having 1 to 10 carbon atoms.) Rf ₃ (CH ₂ ) _q CHO (6) ( In the formula, Rf ₃ represents a fluorine-containing alkyl group having 1 to 10 carbon atoms, and q represents a number of 1 to 10.) These fluorine-containing carbonyl compounds can be used alone or as a mixture of two or more kinds. .

In the production method of the present invention, in the method of reacting a hydroxy compound and a carbonyl compound, the charge ratio of the hydroxy compound and the carbonyl compound is not particularly limited, but usually, the hydroxy compound / carbonyl compound (molar ratio) is used. = 30/1 to 1/30, particularly 5
/ 1/1/5 is preferred. If the hydroxy compound has a low molecular weight and can be easily removed, it is preferable to use the hydroxy compound in excess to react all of the carbonyl compound. In addition, the molecular weight of the hydroxy compound is large,
Further, as long as the compound solidifies at room temperature or the like, it is preferable to use an excess of the carbonyl compound and react all of the hydroxy compounds that are difficult to remove. If the molar ratio of the hydroxy compound / carbonyl compound is out of the above range, the yield is not significantly affected, but it is not economical.

In the present invention, when reacting a hydroxy compound with a carbonyl compound, or when reacting only a carbonyl compound, the reaction is carried out in the presence of a Lewis acid. The Lewis acid used in the present invention may be any electron-pair acceptor. For example, BF ₃ · OEt ₂ (boron trifluoride / diethyl ether complex), BF ₃ · 2CH ₃ CO ₂ H
(Boron trifluoride / acetic acid complex), BF ₃・ (CH ₃ ) ₃ COCH
₃ (boron trifluoride / t-butyl methyl ether complex), BF ₃ · CH ₃ OH (boron trifluoride / methanol complex), BF ₃ · CH ₃ (CH ₂ ) ₂ OH (boron trifluoride / propanol complex) ) BF ₃ complexes, such as, TiCl ₄ (titanium tetrachloride), SnCl ₄
(Tin tetrachloride), AlCl ₃ (aluminum trichloride), TMSOTf
(Trimethylsilyl trifluoromethanesulfonate),
Ti (O- ⁱ Pr) ₄ (tetraisopropyl titanate), ZnCl ₂ (zinc dichloride), FeCl ₃ (iron trichloride) and the like are particularly preferable. BF ₃ .OEt ₂ (boron trifluoride.diethyl) Ether complex).

The amount of the Lewis acid to be used is not particularly limited, but is preferably 0.01 to 20 times, more preferably 0.1 to 10 times, the molar amount of the hydroxy compound used when the hydroxy compound is reacted with the carbonyl compound. Mole,
More preferably 0.5 to 5 moles, preferably 0.01 to 20 moles, more preferably 0.1 to 10 moles, more particularly preferably 0.1 to 10 moles with respect to the carbonyl compound used when reacting only the carbonyl compound. It is 0.5 to 5 times mol.

In the present invention, the catalyst used when reacting the hydroxy compound with the carbonyl compound or when reacting only the carbonyl compound is not particularly limited as long as it has a hydrogenating ability. Palladium compounds such as palladium and palladium oxide; ruthenium, rhodium and platinum catalysts; and ruthenium oxide, rhodium oxide and platinum oxide. Further, a catalyst such as iridium, osmium, rhenium or the like can be used. These catalysts may be appropriately supported on a carrier such as carbon, alumina, silica-alumina, silica and zeolite. Among these catalysts, preferably, a palladium catalyst, more preferably a palladium catalyst supported on carbon, alumina, silica alumina, silica or zeolite, palladium hydroxide or palladium oxide, particularly palladium supported on carbon Catalysts are preferred.

In the present invention, the catalyst is usually used while being supported at a ratio of 2 to 10% by weight based on a carrier such as carbon or alumina, but it may be used without being supported on the carrier. It may be a water-containing product of about 20 to 60% by weight.

If the catalyst is, for example, 5% by weight supported on a carrier, it is preferable to use 0.1 to 10% by weight based on the hydroxy compound or carbonyl compound used. If the amount is less than 0.1% by weight, the reaction proceeds, but the reaction is slow and not preferable. If the amount is more than 10% by weight, the reaction is fast, but on the contrary, a side reaction proceeds, which is not preferable. More preferably, it is 0.5 to 5% by weight.

The catalyst can be used in all pH ranges, but preferably a catalyst having a pH of 8 to 2, more preferably a pH of 7.5 to 3. Here, the pH of the catalyst refers to the pH of an aqueous solution obtained by dispersing 2 g of the catalyst powder in 30 g of ion-exchanged water.

In the present invention, the hydroxy compound and the carbonyl compound are reacted in a hydrogen atmosphere, or only the carbonyl compound is reacted in a hydrogen atmosphere. The hydrogen pressure is not particularly limited, and is usually 1 (atmospheric pressure) to 1 (atmospheric pressure). 200k
g / cm ² , preferably 1 (atmospheric pressure) to 100 kg / cm ² ,
In particular, the effect of the present invention is remarkable at a low pressure reaction of 1 (atmospheric pressure) to 30 kg / cm ² .

In the present invention, the reaction temperature when reacting the hydroxy compound with the carbonyl compound or only the carbonyl compound is not particularly limited.
C., preferably 15 to 100.degree. C., especially at a low temperature of 15 to 50.degree. C. because of the high activity of this reaction. The reaction time may be appropriately selected depending on the reaction temperature, hydrogen pressure, amount of catalyst, and the like, but is usually 1 to 50 hours, preferably 1 to 50 hours.
~ 28 hours.

When the carbonyl compound is an aldehyde, the reaction is preferably carried out while dropping the aldehyde into the reaction system. By reacting the aldehyde while dropping it into the reaction system, a side reaction (aldol reaction) of the aldehyde can be avoided, and an ether compound can be obtained in high yield. In addition, the amount of aldehydes added can be reduced, and usually 1
The reaction can be completed with ２2 equivalents.

The dropping of the aldehyde into the reaction system includes not only the case where the aldehyde is added little by little at a constant rate but also the case where it is added intermittently. The dropping method is not particularly limited, but may be added in a divided manner in the reaction system, and it is preferable to drop the solution using a pump or the like. The dropping rate of the aldehyde may be appropriately selected according to the scale of the reaction. For example, on a 0.5 liter scale, it is preferably 0.1 to 180 g / hr, and 0.6 to 60 g / hr.
g / hr is more preferred.

In the reaction of the present invention, the reaction may be optionally carried out using a solvent which does not adversely affect the reaction. Examples of the solvent having no adverse effect on the reaction include, but are not necessarily limited to, hydrocarbon solvents such as hexane, heptane and octane. When a solvent that does not adversely affect the reaction is used, the amount of the solvent used is not particularly limited, but is preferably 0.5 to 2 times the volume of the reaction solution.

In this reaction, an equimolar amount of water is produced together with the desired fluorinated ether compound, but it is preferable to carry out the reaction while removing the produced water, since the reaction is accelerated. Specific methods for removing water include a method of removing water by performing a reaction in the presence of a dehydrating agent, a method of removing water while passing a gas such as hydrogen, and a method of removing water by azeotropic dehydration. And the like. Among these methods, a method of removing water by performing a reaction in the presence of a dehydrating agent or a method of removing water while flowing hydrogen is preferable, and particularly, a method of flowing hydrogen using a reactor equipped with a dehydrating tube. It is preferable to remove water produced as a by-product of the reaction outside the system while performing the reaction and return only unreacted raw materials to the system.

In the method of removing water by performing a reaction in the presence of a dehydrating agent, specific examples of the dehydrating agent used include anhydrous magnesium sulfate, anhydrous sodium sulfate,
Examples thereof include anhydrous calcium sulfate, anhydrous calcium chloride, and molecular sieve. Of these, anhydrous magnesium sulfate and anhydrous sodium sulfate are preferred, and anhydrous magnesium sulfate is most preferred. The amount of the dehydrating agent varies depending on the type of the dehydrating agent to be used. For example, when anhydrous magnesium sulfate is used, the molar amount is preferably 0.05 to 2 times, more preferably 0.1 to 1 time, based on the hydroxy compound. When only the carbonyl compound is reacted, the content is preferably 0.1 to 50 mol% based on the carbonyl compound, and 1 to 30 mol%.
Mole% is more preferred.

In the method of removing water outside the system while flowing a gas such as hydrogen, the flow rate of hydrogen may be appropriately selected according to the reaction scale. Liter / min is preferred,
More preferably, it is 0.01 to 10 liter / min. By setting the flow rate of hydrogen to 0.01 liter / min or more, water is easily removed from the system, and the reaction speeds up. Further, it is preferable that the flow rate of hydrogen is 30 liters / min or less, since the amount of the raw material hydroxy compound or carbonyl compound removed together with water is reduced. However, even in this case, the hydroxy compound or the carbonyl compound that is removed together with the water is removed, for example, by removing the water with a fractional distillation or a dehydrating agent, and then returned to the reactor again.
The reaction can be performed without delay. In addition, the flow of hydrogen may be continuous or intermittent during the reaction, but a continuous flow is preferable in order for the reaction to proceed smoothly.

As the method of azeotropic dehydration, for example, not only a method of continuously performing the reaction and the distillation of water using an azeotropic dehydrator, but also, for example, once the reaction is performed, the azeotropic dehydration is performed. A method in which the reaction and the distillation of water are performed stepwise, such as performing the reaction again, may be used. It is preferable to carry out the reaction continuously to make the reaction proceed smoothly. Further, in order to perform dehydration efficiently, azeotropic dehydration may be performed while flowing hydrogen.

In the method of the present invention in which water is removed by azeotropic dehydration to carry out the reaction, as the azeotropic solvent to be used, not only a carbonyl compound or a hydroxy compound as a reaction raw material but also a solvent having no adverse effect on the reaction is used. May be. When azeotropic dehydration is performed using a solvent having no adverse effect on the reaction, preferred solvents used include, but are not necessarily limited to, toluene, xylene, benzene and the like. When a solvent that does not adversely affect the reaction is used, the amount of the solvent used is not particularly limited, but is preferably 1 to 2 times the volume of the reaction solution.

[0045]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 1,3-dimethylbutyl {2- represented by the following formula (7)
Production of (perfluorohexyl) ethyl ether

[0047]

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In a 200 ml flask equipped with a stirrer,
(Perfluorohexyl) ethanol 30.0 g (80 mmol), 4-methyl-2-pentanone 16.0 g (160 mmol), 0.6 g of 5% Pd-C (pH 6.6) as catalyst, boron trifluoride / diethyl as Lewis acid Ether complex 2
3.4 g (160 mmol) was charged, and the mixture was stirred at room temperature for 28 hours under a hydrogen atmosphere (normal pressure).

After completion of the reaction, the catalyst was removed by filtration, neutralized with a saturated aqueous solution of sodium bicarbonate, purified by silica gel column chromatography, and 1,3-dimethylbutyl {2- (perfluorohexyl) ethyl} ether 2
8.4 g (64 mmol) were obtained as a clear, colorless liquid. The isolation yield was 80%.

Comparative Example 1 A 200 ml flask equipped with a stirrer was charged with 30.0 g (80 mmol) of 2- (perfluorohexyl) ethanol, 16.0 g (160 mmol) of 4-methyl-2-pentanone, and 5% Pd- as a catalyst. 0.6 g of C (pH 6.6) was charged, and the mixture was stirred at room temperature for 30 hours under a hydrogen atmosphere (normal pressure).

After completion of the reaction, the catalyst was removed by filtration, neutralized with a saturated aqueous solution of sodium bicarbonate, purified by silica gel column chromatography, and 1,3-dimethylbutyl {2- (perfluorohexyl) ethyl} ether
0.7 g (1.6 mmol) was obtained as a clear, colorless liquid.
The isolation yield was 2%.

Examples 2 to 13 Hydroxy compounds and carbonyl compounds shown in Tables 1 and 2 were used in the presence of the catalysts and Lewis acids shown in Tables 1 and 2 except for the reaction conditions shown in Tables 1 and 2. The reaction was carried out in the same manner as in Example 1. The obtained products and their isolation yields are shown in Tables 1 and 2.

[0053]

[Table 1]

[0054]

[Table 2]

Note) *: After charging the hydroxy compound, the catalyst and the Lewis acid, the carbonyl compound was added dropwise under the indicated reaction conditions.

Comparative Examples 2 to 13 The hydroxy compounds and carbonyl compounds shown in Tables 3 and 4 were used in the presence of the catalysts shown in Tables 3 and 4 in the same manner as in Comparative Example 1 except for the reaction conditions shown in Tables 3 and 4. The reaction was performed in the same manner. The obtained products and their isolation yields are shown in Tables 3 and 4.

[0057]

[Table 3]

[0058]

[Table 4]

Note) *: After charging the hydroxy compound and the catalyst, the carbonyl compound was added dropwise under the indicated reaction conditions.

Example 14 1,3-dimethylbutyl {2- represented by the above formula (7)
Production method of (perfluorohexyl) ethyl @ ether In a 200 ml flask equipped with a hydrogen gas inlet tube and a stirrer, 30.0 g (80%) of 2- (perfluorohexyl) ethanol was added.
Mmol), 16.0 g of 4-methyl-2-pentanone (160
Mmol), 5% Pd-C (pH 6.6) 0.6 as a catalyst
g, 23.4 g (160 mmol) of boron trifluoride / diethyl ether complex as a Lewis acid and 2.8 g (23 mmol) of anhydrous magnesium sulfate as a dehydrating agent were stirred under a hydrogen atmosphere (normal pressure) at 90 ° C. for 7 hours. went.

After completion of the reaction, the catalyst was removed by filtration, neutralized with a saturated aqueous solution of sodium bicarbonate, and purified by silica gel column chromatography to obtain 1,3-dimethylbutyl {2- (perfluorohexyl) ethyl} ether 3
2.6 g (72.8 mmol) were obtained as a clear, colorless liquid.
The isolation yield was 92%.

Comparative Example 14 1,3-dimethylbutyl {2- represented by the above formula (7)
Production method of (perfluorohexyl) ethyl @ ether In a 200 ml flask equipped with a hydrogen gas inlet tube and a stirrer, 30.0 g (80%) of 2- (perfluorohexyl) ethanol was added.
Mmol), 16.0 g of 4-methyl-2-pentanone (160
Mmol), 5% Pd-C (pH 6.6) 0.6 as a catalyst
g, anhydrous magnesium sulfate (2.8 g, 23 mmol) as a dehydrating agent was charged and stirred at 90 ° C. for 7 hours under a hydrogen atmosphere (normal pressure).

After completion of the reaction, the catalyst was removed by filtration, neutralized with a saturated aqueous solution of sodium bicarbonate, purified by silica gel column chromatography, and 1,3-dimethylbutyl {2- (perfluorohexyl) ethyl} ether 2
0.0 g (44 mmol) was obtained as a clear, colorless liquid. The isolation yield was 55%.

Examples 15 to 26 The hydroxy compounds and carbonyl compounds shown in Tables 5 and 6 were reacted with the catalysts shown in Tables 5 and 6 in the presence of a Lewis acid and a dehydrating agent in the reaction conditions shown in Tables 5 and 6. Except for Example 14
The reaction was carried out in the same manner as described above. The products obtained and their isolation yields are shown in Tables 5 and 6.

[0065]

[Table 5]

[0066]

[Table 6]

Note) *: After charging the hydroxy compound, the catalyst, the Lewis acid and the dehydrating agent, the carbonyl compound was added dropwise under the indicated reaction conditions.

Comparative Examples 15 to 26 The hydroxy compounds and carbonyl compounds shown in Tables 7 and 8 were combined with the catalysts and dehydrating agents shown in Tables 7 and 8
The reaction was carried out in the same manner as in Comparative Example 14 except for the reaction conditions shown in Tables 7 and 8. Table 7 shows the obtained products and their isolation yields.
And Table 8 below.

[0069]

[Table 7]

[0070]

[Table 8]

Note) *: After charging the hydroxy compound, the catalyst and the dehydrating agent,
The carbonyl compound was added dropwise under the indicated reaction conditions.

Example 27 1,3-dimethylbutyl {2- represented by the above formula (7)
Production method of (perfluorohexyl) ethyl @ ether In a 200 ml flask equipped with a hydrogen gas inlet tube and a stirrer, 30.0 g (80%) of 2- (perfluorohexyl) ethanol was added.
Mmol), 16.0 g of 4-methyl-2-pentanone (160
Mmol), 5% Pd-C (pH 6.6) 0.6 as a catalyst
g, 23.4 g (160 mmol) of boron trifluoride / diethyl ether complex as a Lewis acid, and at 40 ° C. while continuously flowing hydrogen at 0.2 liter / min under atmospheric pressure.
Stirring was performed for 12 hours.

After completion of the reaction, the catalyst was removed by filtration, neutralized with a saturated aqueous solution of sodium bicarbonate, purified by silica gel column chromatography, and 1,3-dimethylbutyl {2- (perfluorohexyl) ethyl} ether 3
3.4 g (74.4 mmol) were obtained as a clear, colorless liquid.
The isolation yield was 93%.

Comparative Example 27 The 1,3-dimethylbutyl {2-} represented by the above formula (7)
Production method of (perfluorohexyl) ethyl @ ether In a 200 ml flask equipped with a hydrogen gas inlet tube and a stirrer, 30.0 g (80%) of 2- (perfluorohexyl) ethanol was added.
Mmol), 16.0 g of 4-methyl-2-pentanone (160
Mmol), 5% Pd-C (pH 6.6) 0.6 as a catalyst
g, and the mixture was stirred at 40 ° C. for 12 hours while continuously flowing hydrogen at 0.2 L / min under atmospheric pressure.

After completion of the reaction, the catalyst was removed by filtration, neutralized with a saturated aqueous solution of sodium bicarbonate, purified by silica gel column chromatography, and 1,3-dimethylbutyl {2- (perfluorohexyl) ethyl} ether
3.9 g (8.8 mmol) were obtained as a clear, colorless liquid.
The isolation yield was 11%.

Examples 28 to 39 The hydroxy compounds and carbonyl compounds shown in Tables 9 and 10 were used in the presence of the catalysts and Lewis acids shown in Tables 9 and 10 except for the reaction conditions shown in Tables 9 and 10. The reaction was carried out in the same manner as in Example 27. The products obtained and their isolation yields are shown in Tables 9 and 10.

[0077]

[Table 9]

[0078]

[Table 10]

Note) *: After charging the hydroxy compound, the catalyst and the Lewis acid, the carbonyl compound was added dropwise under the indicated reaction conditions.

Comparative Examples 28 to 39 The hydroxy compounds and carbonyl compounds shown in Tables 11 and 12 were used in the presence of the catalysts shown in Tables 11 and 12 in the presence of the catalysts shown in Tables 11 and 12.
The reaction was carried out in the same manner as in Comparative Example 27 except for the reaction conditions shown in 12. The products obtained and their isolation yields are shown in Tables 11 and 12.

[0081]

[Table 11]

[0082]

[Table 12]

Note) *: After charging the hydroxy compound and the catalyst, the carbonyl compound was added dropwise under the indicated reaction conditions.

Example 40 Production of bis {1- (perfluoromethyl) propyl} ether represented by the following formula (8)

[0085]

Embedded image

In a 200 ml flask equipped with a stirrer,
100.9 g (80 mmol) of 1,1-trifluoro-2-butanone, 2.0 g of 5% Pd-C (pH 6.6) as a catalyst,
Boron trifluoride-diethyl ether complex as Lewis acid
23.4 g (160 mmol) was charged, and the mixture was stirred at room temperature for 15 hours under a hydrogen atmosphere (normal pressure).

After the completion of the reaction, the catalyst was removed by filtration, neutralized with a saturated aqueous solution of sodium bicarbonate, purified by silica gel column chromatography, and 71.8 g (30 mmol) of bis {1- (perfluoromethyl) propyl} ether was obtained.
Was obtained as a colorless transparent liquid. The isolation yield was 76%.

Example 41 Production of bis (4,4,4-trifluorobutyl) ether represented by the following formula (9) CF _3- (CH ₂ ) ₃ -O- (CH ₂ ) ₃ -CF ₃ ( 9) In a 200 ml flask equipped with a stirrer, 100.9 g (80 mmol) of 4,4,4-trifluorobutyraldehyde, 2.0 g of 5% Pd-C (pH 6.6) as a catalyst, and boron trifluoride as a Lewis acid. 23.4 g of diethyl ether complex (160
Mmol) at room temperature under a hydrogen atmosphere (normal pressure).
Stirring was performed for hours.

After completion of the reaction, the catalyst was removed by filtration, neutralized with a saturated aqueous solution of sodium bicarbonate, purified by silica gel column chromatography, and 73.7 g (31 mmol) of bis (4,4,4-trifluorobutyl) ether was obtained. Was obtained as a colorless transparent liquid. The isolation yield was 78%.

Comparative Example 40 Production of bis {1- (perfluoromethyl) propyl} ether represented by the above formula (8) 1,1,1-trifluoro-2-butanone was placed in a 200 ml flask equipped with a stirrer. 100.9 g (80 mmol) and 2.0 g of 5% Pd-C (pH 6.6) as a catalyst were charged, and stirred at room temperature for 30 hours under a hydrogen atmosphere (normal pressure).

After completion of the reaction, the catalyst was removed by filtration, neutralized with a saturated aqueous solution of sodium bicarbonate, purified by silica gel column chromatography, and 4.7 g (2 mmol) of bis {1- (perfluoromethyl) propyl} ether was obtained.
Was obtained as a colorless transparent liquid. The isolation yield was 5%.

Comparative Example 41 Production of bis (4,4,4-trifluorobutyl) ether represented by the above formula (9) In a 200 ml flask equipped with a stirrer, 100.9% of 4,4,4-trifluorobutyraldehyde was added. g (80 mmol) and 2.0 g of 5% Pd-C (pH 6.6) as a catalyst were stirred under a hydrogen atmosphere (normal pressure) at room temperature for 24 hours.

After completion of the reaction, the catalyst was removed by filtration, neutralized with a saturated aqueous solution of sodium bicarbonate, purified by silica gel column chromatography, and 11.3 g (5 mmol) of bis (4,4,4-trifluorobutyl) ether Was obtained as a colorless transparent liquid. The isolation yield was 12%.

Claims (9)

[Claims] When producing an ether compound by reacting a hydroxy compound and a carbonyl compound in a hydrogen atmosphere using a catalyst, a fluorine compound having a fluorine substituent is used as at least one of the hydroxy compound and the carbonyl compound. A method for producing a fluorine-containing ether compound, wherein the reaction is carried out in the presence of a Lewis acid. 2. A process for producing an ether compound by reacting a carbonyl compound in a hydrogen atmosphere using a catalyst, wherein a fluorine compound having a fluorine substituent is used as at least one of the carbonyl compounds, and Lewis (Lewis)
A method for producing a fluorinated ether compound, which comprises reacting in the presence of an acid. 3. A compound represented by the general formula (1) R _1- (OA) _n -OH (1) wherein R ₁ is a hydrogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, An alkenyl group, a cycloalkyl group having 3 to 12 carbon atoms, or a fluorine substituent in which at least one hydrogen atom of these groups is substituted with a fluorine atom. A represents a linear or branched alkylene group having 2 to 12 carbon atoms which may have a hydroxy group as a substituent, and n A's may be the same or different. n is 0
Indicates a number of 500. The method according to claim 1, which is a compound represented by the formula: 4. The method according to claim 1, wherein the hydroxy compound is an aliphatic alcohol having 1 to 22 carbon atoms, methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, isopropyl carbitol, butyl carbitol, or one carbon atom. ~ 22 ethylene oxide or / and propylene oxide adduct of an aliphatic alcohol (average number of moles 0.1 to 200),
4. The compound according to claim 3, which is a cycloalkanol having 5 to 8 carbon atoms, a diol having 2 to 10 carbon atoms, or a fluorine-containing hydroxy compound having a fluorine substituent in which at least one of the hydrogen atoms of these compounds is substituted with a fluorine atom. Manufacturing method. 5. A carbonyl compound represented by the general formula (2): [Wherein, R ₂ and R ₃ represent a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 20 carbon atoms, or a fluorine substituent in which at least one hydrogen atom of these groups is substituted with a fluorine atom. And R ₂ and R ₃ may be the same or different. Further, a cyclic structure in which R ₂ and R ₃ are bonded may be used. The method according to any one of claims 1 to 4, wherein the compound is a compound represented by the formula: or a polymer thereof. 6. The carbonyl compound is a linear ketone having 3 to 19 carbon atoms, an aliphatic aldehyde having 1 to 19 carbon atoms, and a carbonyl compound having 5 to 5 carbon atoms.
6. The process according to claim 5, wherein the compound is a fluorine-containing carbonyl compound having a fluorine substituent in which at least one hydrogen atom of the cyclic ketone, paraformaldehyde, paraaldehyde or a compound thereof is substituted with a fluorine atom. 7. A Lewis acid comprising a BF ₃ complex, titanium tetrachloride,
The production method according to any one of claims 1 to 6, which is tin tetrachloride, aluminum trichloride, trimethylsilyl trifluoromethanesulfonate, tetraisopropyl titanate, zinc dichloride or iron trichloride. 8. The method according to claim 1, wherein the catalyst is a palladium catalyst supported on carbon, alumina, silica alumina, silica or zeolite, palladium hydroxide or palladium oxide. 9. The production method according to claim 1, wherein the reaction is carried out while removing water produced as a by-product of the reaction.