JP2000191578A - Method for producing fluorine-containing ether compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a fluorine-containing ether compound from an alkenyl ether compound by addition reaction of fluorine with a high yield. SOLUTION: A fluorine-containing alkenyl ether compound having at least one fluorine atom bonded to a carbon atom adjacent to a double bond is used as a fluorinating agent as (i) metal fluoride, (ii) xenon difluoride, (iii) ) A combination of lead dioxide or lead tetraacetate and anhydrous hydrogen fluoride or (iv) a combination of iodotoluene difluoride and an amine-hydrogen fluoride adduct to add fluorine to the alkenyl group. A method for producing a fluorine ether compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a fluorinated ether compound using an alkenyl ether compound as a starting material.

[0002]

2. Description of the Related Art Fluorine-containing organic compounds are widely used industrially as polymer materials, refrigerants, detergents, foaming agents, pharmaceuticals, agricultural chemicals, and intermediates thereof. Among them, the fluorinated ether compounds have been used in the medical field and the like. For example, among the fluorinated ether compounds represented by the following general formula (2) which is the object of the present invention, R ¹
= CHF ₂ , R ² = F, R ³ = H, R ⁴ = Cl (CH
F ₂ OCF ₂ CHFCl) has been used as an anesthetic (New Fluorine Chemistry, Chemical Review, 27, Chapter 2, 198).
0 years).

[0003] Further, recently, fluorine-containing ether compounds are expected to be used as refrigerants, especially as substitutes for CFCs. For example, among the fluorine-containing organic compounds represented by the general formula (2) described below, which are objects of the present invention, R ¹
= CH ₃ , R ² = R ³ = R ⁴ = F (CH ₃ OCF ₂ CF
₃ ), R ¹ = CH ₃ , R ² = CF ₃ , R ³ = R ⁴ = F (CH ₃ OCF (CF ₃ ) ₂ ), and R ¹ = CH ₃ , R ² =
R ³ = F, R ⁴ = CF ₃ (CH ₃ OCF ₂ CF ₂ C
F ₃ ) is expected to be used as a new refrigerant with little effect on the environment (Chemtech, 26,
44 (1996)).

[0004] As a method for producing a fluorinated ether compound, particularly an alkyl-perfluoroalkyl ether expected as a substitute for chlorofluorocarbon, conventionally, metal fluoride salts such as perfluoro acid halides or perfluoroketones, potassium fluoride, and the like, A method using an alkylating agent such as dimethyl sulfate or methyl paratoluenesulfonate has been adopted (ECO INDUSTRY, 1,
October issue, p5, 1996).

[0005] However, dimethyl sulfate, which is one of the alkylating agents used in this method, is extremely toxic and requires careful handling. Furthermore, since these alkylating agents are expensive, a method of synthesizing these fluorinated ether compounds at lower cost and more simply has been desired for industrial large-scale production.

On the other hand, a fluorine-containing alkenyl ether compound represented by the following general formula (1), in particular, R ¹ ＣC
H ₃ , R ² = R ³ = R ⁴ = F (CH ₃ OCF = C
F _2), alkyl such as those of _{^{R 1 = CH 3, R 2}} = R 3 = F, R 4 = CF 3 (CH 3 OCF = CFCF 3) - perfluoroalkenyl ethers, sodium alkoxides such as CH ₃ ONa _{CF 2 = CF 2, CF 2} = CFCF can be easily obtained by the reaction of a perfluoroalkene of ₃ like (fluorine compounds, Kodansha, Chapter 3, 1979
Year). The reaction of adding fluorine to a carbon-carbon unsaturated compound is one of the most basic and representative methods for introducing fluorine into an organic compound, and if fluorine can be added to these fluorine-containing alkenyl ether compounds, Although a fluorine-containing ether compound can be produced inexpensively and easily, such a general method has not been developed so far.

[0007] The reaction of adding fluorine by reacting a fluorinating agent with an alkenyl ether compound containing no fluorine atom in the alkenyl group has been reported but is limited to special compounds (Tetrahedron Lett. 197).
7,363), in the case of a normal alkenyl ether compound, when a fluorinating agent is reacted, polymerization of a substrate occurs, and almost no fluorine-added compound is obtained (refer to Reference Example 1 described later).
reference).

More recently, methyl-perfluoroiso
Butenyl ether (CH_ThreeOCF = C (CF_Three)_Two)
Methyl perfluoroisobutyl by reacting with nitrogen gas
Ether (CH_ThreeOCF_TwoCF (CF_Three)_TwoWho manufactures
A law was reported (US Pat. No. 5,741,950). I
However, in this method, the yield is as low as about 40%, and
The side reaction of fluorination of the methyl group is inevitable.
By-product (CFH _TwoOCF_TwoCF (CF_Three)_Two) Is the purpose
About one-third of the object is generated. Reduce the amount of this by-product
Only to reduce the amount of fluorine gas to be reacted.
However, in this case, the yield of the target product is only about 10%.
I can't. Also, CH_ThreeOCF = C (CF_Three)_TwoIncluding
Even with fluorine alkenyl ether compounds, fluorine gas
Fluorination to the methyl group occurs (see
Refer to Reference Example 2).

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a fluorine-containing ether compound from an alkenyl ether compound by addition of fluorine at a high yield.

[0010]

Means for Solving the Problems The present inventors have conducted intensive studies on a method for producing a fluorine-containing ether compound, and have found that a fluorine-containing compound having a structure in which a fluorine atom is bonded to a carbon atom adjacent to a double bond of an alkenyl group. In the case of a fluorine alkenyl ether compound, even if a fluorinating agent is reacted with the compound, a reaction such as polymerization is unlikely to occur, and if a fluorinating agent milder than fluorine gas is used, fluorination to a methyl group does not proceed, The present inventors have found that the addition reaction of fluorine proceeds smoothly and that a fluorine-containing ether compound can be synthesized with good yield, and the present invention has been completed.

That is, according to the present invention, a fluorine-containing alkenyl ether compound in which at least one fluorine atom is bonded to a carbon atom adjacent to a double bond is used as a fluorinating agent (i) metal fluoride, (ii) Xenon difluoride,
(Iii) reacting a combination of lead dioxide or lead tetraacetate with anhydrous hydrogen fluoride or (iv) a combination of iodotoluene difluoride and an amine-hydrogen fluoride adduct to add fluorine to the alkenyl group. A method for producing a fluorinated ether compound is provided.

[0012]

According to the present invention, a fluorine-containing ether compound represented by the following general formula (2) can be obtained from a fluorine-containing alkenyl ether compound represented by the following general formula (1). General formula (1):

Embedded image (Wherein, R ¹ is an alkyl group which may have a substituent,
An aralkyl group or an aryl group; R ^{2 to} R ^{4 each} represent a hydrogen atom, a halogen atom, a substituted or unsubstituted linear or branched alkyl group, an aralkyl group or an aryl group, at least one of which is a fluorine atom; And R ^{1 to} R ⁴
May combine with each other to form a ring.) General formula (2):

Embedded image (Wherein, R ^{1 to} R ⁴ have the same meaning as described above)

In the general formula (1), R ¹ represents an alkyl group, an aralkyl group or an aryl group which may have a substituent. In this case, the alkyl group is not particularly limited and may be any of Although a chain or branched alkyl group can be used, the number of carbon atoms is usually 30 or less, preferably 20 or less, and more preferably 15 or less. Specifically, for example, a methyl group, an ethyl group,
n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, 2-methylbutyl, 1-methylbutyl, n-hexyl, isohexyl Group, 3-
Methylpentyl, 2-methylpentyl, 1-methylpentyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl And a cyclic alkyl group such as a chain alkyl group such as an eicosyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group. The aralkyl group is not particularly limited, but usually has 7 to 30 carbon atoms.
, Preferably 7 to 20, more preferably 7 to 15
Range. Specific examples include a benzyl group and a phenethyl group. The aryl group is not particularly limited, but usually has 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms,
More preferably, the number is in the range of 6 to 14. Specific examples include a phenyl group, a naphthyl group and an anthranyl group.

The alkyl group, aralkyl group and aryl group may have a substituent. The substituent is not particularly limited as long as it does not participate in the reaction, and may be a substituted or unsubstituted aryl group, a carbonyl group. Group, alkoxy group, alkoxycarbonyl group, acyl group, acyloxy group, alkyl or arylsulfonyl group, nitro group,
Halogen (fluorine, chlorine, bromine, iodine) and the like are exemplified. The number of carbon atoms contained in these substituents is not particularly limited, but is usually 0 to 30, preferably 0 to 20, and more preferably 0 to 15.

In the general formula (1), R^Two~ R^FourFew
At least one is a fluorine atom; ^Two~ R^FourIs all
It may be a nitrogen atom. Among them, fluorine
Non-child atoms are halogen atoms other than hydrogen and fluorine atoms
An alkyl group, an aralkyl
And an alkyl group or an aryl group.
As the aralkyl group or the aryl group, the aforementioned R¹About
Those shown are listed. Also, by bonding to those groups
The optional substituents include the aforementioned R¹Various shown for
One. With a halogen atom other than the fluorine
Examples include chlorine, bromine and iodine.

Further, R ^{1 to} R ⁴ in the general formula (1)
May be two of each, for example, R ¹ and R ² , R ² and R ³ , R ³ and R ^{4, and the} like to form a ring. In this case, the alkylene group forming a ring has, for example, 10 or less carbon atoms,
It is preferably 1 to 8, more preferably 2 to 6, which may be an alkylene group which may be branched. Such alkene compounds include 1-fluoro-1-alkoxycyclopentene, 1-fluoro-1-
Alkoxycyclohexene and the like can be exemplified.

According to the present invention, a fluorine-containing ether compound represented by the following general formula (4) can be obtained from a fluorine-containing alkenyl ether compound represented by the following general formula (3). General formula (3):

Embedded image General formula (4):

Embedded image In the above formula, R ⁵ represents an alkyl group which may have a substituent. As specific examples include those described with respect to the R ^1. R ^{6 to} R ⁸ represent a fluorine atom or a perfluoroalkyl group, at least one of which represents a fluorine atom. As the perfluoroalkyl group, one having 1 carbon atom
-30, preferably 1-20 perfluoroalkyl groups are indicated. Two of R ^{6 to} R ⁸ , for example, R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ^{8, and the} like may be bonded to form a ring. In this case, the perfluoroalkylene group forming a ring has, for example, 10 or less carbon atoms, preferably 1 to 8 carbon atoms.
And more preferably 2 to 6 optionally branched perfluoroalkylene groups. Examples of such an alkene compound include 1-alkoxyperfluorocyclopentene, 1-alkoxyperfluorocyclohexene, and the like.

The fluorinating agent used in the present invention includes:
The addition reaction of fluorine occurs at the carbon-carbon unsaturated bond,
An alkyl group such as a methyl group that does not easily cause fluorination or an alkyl group that does not cause fluorination is used, and a combination of a plurality of reagents may be used.
Examples of such a fluorinating agent include metal fluorides such as cobalt trifluoride, potassium tetrafluorocobaltate (KCoF ₄ ), manganese trifluoride, silver difluoride, and cerium tetrafluoride; xenon difluoride; A combination of lead or lead tetraacetate with anhydrous hydrogen fluoride and a combination of iodotoluene difluoride with an amine-hydrogen fluoride adduct may be used. Among them, cobalt trifluoride, potassium tetrafluorocobaltate, manganese trifluoride,
Metal fluorides such as silver difluoride and cerium tetrafluoride, and xenon difluoride are preferred. The reaction method may be either a batch method or a flow method.

The amount of the fluorinating agent depends on the reaction method, the fluorinating agent,
It is appropriately selected depending on the kind of the substrate and the like, and is not particularly limited as long as it is usually 1 equivalent or more, and preferably 1 to 500 equivalent.

The reaction conditions are appropriately selected depending on the type of the fluorinating agent, the type of the substrate and the like, and the reaction temperature is usually from -75 ° C.
The range is 300 ° C, preferably -30 ° C to 200 ° C, and more preferably 0 ° C to 200 ° C. The reaction time or contact time varies depending on the reaction temperature, the fluorinating agent, the type of the substrate, and the like, but is usually 1 second to 100 hours, preferably several seconds to 6 hours.
0 hour, more preferably 0.01 to 50 hours.

At the time of the reaction, additives can be added. The additive is appropriately selected depending on the purpose, the fluorinating agent to be used, the type of the substrate, and the like. For example, when xenon difluoride is used as the fluorinating agent, silicon tetrafluoride, hydrogen fluoride, boron trifluoride ether complex, trifluoroacetic acid, hydrogen fluoride pyridine complex, etc. And the like can be added to carry out the reaction. The amount of the additive to be used is not particularly limited, but is usually 0.1 to 0.1 with respect to the substrate.
It is in the range of 01 to 100 times by weight, preferably 0.05 to 50 times by weight, and more preferably 0.1 to 20 times by weight.

In the reaction, a solvent can be present. The solvent is appropriately selected depending on the fluorinating agent, the type of the substrate, and the like, but is not particularly limited as long as it is inert to the reaction. For example, when using xenon difluoride as the fluorinating agent, dichloromethane, chloroform, halogenated hydrocarbons such as carbon tetrachloride, nitriles such as acetonitrile, and fluorocarbons such as hexafluorobenzene can be used. .

[0023]

Next, the present invention will be described in more detail with reference to Examples and Reference Examples. Note that the present invention is not limited to the embodiment.

EXAMPLE 1 Xenon difluoride (174 mg, 1.03 mm) was placed in a reaction vessel comprising a stop valve and a stainless steel reaction tube.
ol), and then using a vacuum line at -196 ° C. with methylpentafluoropropenyl ether (CH ₃ OC
F = CFCF ₃ , 0.865 mmol) and shaken at room temperature for 18 hours. The crude product is distilled using a vacuum line to give methyl heptafluoropropyl ether (CH
_{3 OCF 2 CF 2 CF 3,} 0.764mmol, to obtain a 88%). The product was ¹ H-NMR spectrum, ¹⁹ F-NMR
Identified by spectrum and IR spectrum.

IR: 3020, 2977, 2879, 1
460, 1350, 1237, 1204, 1180, 1
146, 1120, 1060, 1020, 961, 93
3,784,744cm ^-1

¹ H-NMR (CDCl ₃ , TMS) δ:
3.74 (s)

¹⁹ F-NMR (CDCl ₃ , CFCl ₃ )
φ: 82.1 (t, J = 7 Hz, 3F), 90.0 (t
q, J ₃ = 4 Hz, J ₄ = 7 Hz, 2F), 130.1
(T, J = 4 Hz, 2F) A compound in which a methyl group is fluorinated (CFH ₂ OC
F ₂ CF ₂ CF ₃ etc.) was not formed.

Example 2 Cobalt trifluoride (21.3 g, 183 mmo) was placed in a reaction vessel comprising a stop valve and a stainless steel reaction tube.
l), and then use a vacuum line at -196 ° C to prepare methylpentafluoropropenyl ether (1.014m
mol) was added. This was heated to room temperature over 30 minutes. The crude product was treated with sodium fluoride (0.80 g, 19 m
mol), shaken at room temperature for 1 hour, and distilled using a vacuum line to obtain methylheptafluoropropyl ether (0.562 mmol).
1, 55%). A compound having a fluorinated methyl group (CFH ₂ OCF ₂ CF ₂ CF ₃ ) was also produced, but the amount was 0.010 mmol (1%).

Example 3 A reaction vessel comprising a stop valve and a stainless steel reaction tube was charged with potassium tetrafluorocobaltate (KCo).
F ₄ , 30.7 g, 176 mmol) and then use a vacuum line at -196 ° C. at methyl trifluorovinyl ether (CH ₃ OCF = CF ₂ , 1.003 mmol).
l) was added. This was heated at 160 ° C. for 20 minutes. The crude product was treated with sodium fluoride (0.90 g, 21 mmol
1), shaken at room temperature for 1 hour, and distilled using a vacuum line to obtain methylpentafluoroethyl ether (CH ₃ OCF ₂ CF ₃ , 0.1.
(841 mmol, 85%). The product is ¹ H-NM
It was identified by R spectrum, ¹⁹ F-NMR spectrum, and IR spectrum.

IR: 3019, 2977, 2886, 1
463, 1235, 1183, 1120, 734 cm ^-1

¹ H-NMR (CDCl ₃ , TMS)
δ: 3.73 (s)

¹⁹ F-NMR (CDCl ₃ , CFCl ₃ )
φ: 86.6 (br, s, 3F), 94.1 (br,
s, 2F) In addition, a compound in which a methyl group is fluorinated (CFH ₂ OC
F ₂ CF ₃ ) was not formed.

Example 4 A reaction vessel comprising a stop valve and a stainless steel reaction tube was charged with cobalt trifluoride (21.3 g, 183 mmo).
l), and then use a vacuum line at -196 ° C to prepare methyl trifluorovinyl ether (1.002 mmol).
l) was added. This was heated to room temperature over 30 minutes.
The crude product was treated with sodium fluoride (0.82 g, 20 mmol
l) and further shaken at room temperature for 1 hour, and then distilled using a vacuum line to obtain methylpentafluoroethyl ether (0.697 mmol, 70%).
%). Compounds in which the methyl group is fluorinated (CFH
₂ OCF ₂ CF ₃ ) was not formed.

Example 5 Cerium tetrafluoride (25.7 g, 119 mmol) was placed in a reaction vessel comprising a stop valve and a stainless steel reaction tube.
l), and then use a vacuum line at -196 ° C at methyl trifluorovinyl ether (1.011 mmol).
l) was added. This was heated at 80 ° C. for 1 hour. The crude product was transferred to a reaction vessel containing sodium fluoride (0.73 g, 17 mmol), further shaken at room temperature for 1 hour, and distilled using a vacuum line to give methylpentafluoroethyl ether (0.222 mmol). , 22%). Compound in which methyl group is fluorinated (CFH ₂ OC
F ₂ CF ₃ ) was not formed.

EXAMPLE 6 Silver difluoride (24.6 g, 169 mmol) was placed in a reaction vessel consisting of a stop valve and a stainless steel reaction tube, and then methyltrifluorovinyl ether (1.006 mmol) was used at -196 ° C. using a vacuum line. ) Was added. This was heated to room temperature over 30 minutes. The crude product was transferred to a reaction vessel containing sodium fluoride (0.88 g, 21 mmol), further shaken at room temperature for 1 hour, and distilled using a vacuum line to obtain methylpentafluoroethyl ether (0.159 mmol). , 16%). A compound in which a methyl group is fluorinated (CFH ₂ OCF ₂
CF ₃ ) did not form.

Example 7 Manganese trifluoride (19.7 g, 176 mmo) was placed in a reaction vessel comprising a stop valve and a stainless steel reaction tube.
l), and then use a vacuum line at -196 ° C to prepare methyl trifluorovinyl ether (1.024 mmol).
l) was added. This was heated to room temperature over 30 minutes, and then shaken at room temperature for 1.5 hours. The crude product was transferred to a reaction vessel containing sodium fluoride (0.80 g, 19 mmol), further shaken at room temperature for 1 hour,
Distillation using a vacuum line gave methylpentafluoroethyl ether (0.199 mmol, 19%).
A compound in which a methyl group is fluorinated (CFH ₂ OCF ₂ CF
₃ ) was also produced, but the amount was 0.032 mmol (3
%)Met.

Example 8 Cobalt trifluoride (45.3 g, 389 mmol) was placed in a stainless steel flow-type reaction tube having an inner diameter of 3 cm.
Methyl trifluorovinyl ether (8.9 g, 79 m
mol) was introduced into the reaction tube at a reaction temperature of 50 ° C. while diluting with nitrogen gas. At this time, the nitrogen gas flow rate was 30 cc / m
in, the raw material flow rate was 11 cc / min. When the outlet gas was collected and analyzed by gas chromatography, methylpentafluoroethyl ether was found to have a yield of 60%.
It was found that the raw material recovery was 32%. Compound in which methyl group is fluorinated (CFH ₂ OCF ₂ CF ₃ )
Did not generate.

Example 9 A three-piece stainless steel flow-through reaction tube having an inner diameter of 3 cm
Manganese iodide (50.6 g, 450 mmol)
Methyl trifluorovinyl ether (16.3 g, 14
6 mmol) while diluting with nitrogen gas.
C. was introduced into the reaction tube. At this time, the nitrogen gas flow rate was 11c
c / min, and the raw material flow rate was 3.6 cc / min.
Collect outlet gas and analyze by gas chromatography
As a result, methylpentafluoroethyl ether was collected.
It was found that the rate was 66%, and the raw material recovery was 5%.
Was. Compounds in which the methyl group is fluorinated (CFH_TwoOCF_Two
CF _Three) Did not generate.

Example 10 A counter valve comprising a stop valve and a stainless steel reaction tube
Cobalt trifluoride (21.3 g, 183 mmo)
l), and then use a vacuum line at -196 ° C.
Cylheptafluoroisobutenyl ether (CH_ThreeOC
F = C (CF_Three) _Two, 1.010 mmol). This
This was heated to room temperature over 45 minutes. Fluoride crude product
Reaction with sodium (1.08 g, 26 mmol)
Transfer to a container, shake at room temperature for 1 hour, and vacuum
Distillation using a line, methyl nonafluoroisobuty
Ruether (CH_ThreeOCF_TwoCF (CF_Three)_Two, 0.696
mmol, 69%). The product is¹H-NMR spec
Kutul,¹⁹F-NMR spectrum and IR spectrum
Identified.

IR: 3020, 2977, 2877, 1
460, 1302, 1262, 1234, 1176, 1
137, 1109, 1048, 1018, 986, 94
9, 781, 749, 731 cm ^-1

¹ H-NMR (CDCl ₃ , TMS) δ:
3.75 (s)

¹⁹ F-NMR (CDCl ₃ , CFCl ₃ )
φ: 74.0 (dt, J ₂ = 6 Hz, J ₃ = 10 Hz, 6
F), 82.5 (d, sep, J ₂ = 9 Hz, J ₇ = 10
Hz, 2F), 187.9 (t, sep, J ₃ = 6 Hz,
J ₇ = 9 Hz, 1F) A compound having a fluorinated methyl group (CFH ₂ OC
F ₂ CF (CF ₃ ) ₂ etc.) was not formed.

EXAMPLE 11 Xenon difluoride (193 mg, 1.14 mm) was placed in a reaction vessel comprising a stop valve and a stainless steel reaction tube.
ol), and then trifluoromethyl trifluorovinyl ether (CF ₃ OCF ＝ C
F ₂ , 0.955 mmol), silicon tetrafluoride (1.1
1 mmol) and shaken at room temperature for 48 hours. The crude product was distilled using a vacuum line to give trifluoromethylpentafluoroethyl ether (0.694 mmol
1, 73%). The product was identified by a ¹⁹ F-NMR spectrum and an IR spectrum.

IR: 3123, 3091, 1621, 1
594, 1523, 1495, 1347, 1246, 1
153, 1111, 1094, 1012, 855, 74
9,682,618cm ^-1

¹⁹ F-NMR (CDCl ₃ , CFCl ₃ )
φ: 55.7 (t, J = 9 Hz, 3F), 87.1
(T, J = 2 Hz, 3F), 91.0 (qq, J = 2H)
z, J = 9Hz, 2F)

Reference Example 1 Xenon difluoride (213 mg, 1.26 mm) was placed in a reaction vessel comprising a stop valve and a stainless steel reaction tube.
ol), and then, using a vacuum line, ethyl vinyl ether (C ₂ H ₅ OCH ＝ CH ₂ , 1.05 mmol)
l), silicon tetrafluoride (1.26 mmol) was added, and the mixture was shaken at room temperature for 30 minutes. As a result, ethyl vinyl ether was consumed to produce a tar-like substance, but a compound to which fluorine was added was not obtained.

REFERENCE EXAMPLE 2 Methylpentafluoropropenyl ether (CH ₃ OCF = CFC) was added to a reaction vessel comprising a stop valve and a stainless steel reaction tube at −196 ° C. using a vacuum line.
F ₃ , 0.897 mmol) and fluorine (1.07 mmol)
l) was added, and the temperature was gradually raised from -113 ° C to room temperature over 19 hours. The crude product was transferred to a reaction vessel containing sodium fluoride (1.16 g, 28 mmol), further shaken at room temperature for 1 hour, and then distilled using a vacuum line. Methyl heptafluoropropyl ether, which is a compound to which fluorine is added, has a yield of 31% (0.2%).
80 mmol,), but simultaneously the compounds CFH ₂ OCF ₂ CF ₂ CF ₃ and CF ₂ in which the methyl group was fluorinated
HOCF ₂ CF ₂ CF ₃ yields 31% (0.27
7 mmol) and 3% (0.028 mmol).

[0048]

According to the present invention, a fluorinated ether compound can be obtained easily and with high yield from an alkenyl ether compound by a fluorine addition reaction to a carbon-carbon unsaturated bond. The fluorinated ether compound obtained by this method is useful as a refrigerant, a medicine and the like.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Akira Sekiya 1-1-1 Higashi, Tsukuba City, Ibaraki Pref., National Institute of Advanced Industrial Science and Technology (72) Inventor Seiji Takubo 2-40-17 Hongo Wakai Hongo, Bunkyo-ku, Tokyo 6th floor of the building

Claims (5)

[Claims] 1. A fluorinated alkenyl ether compound in which at least one fluorine atom is bonded to a carbon atom adjacent to a double bond, (i) metal fluoride, (ii) xenon difluoride, iii) reacting a combination of lead dioxide or lead tetraacetate with anhydrous hydrogen fluoride or (iv) a combination of iodotoluene difluoride and an amine-hydrogen fluoride adduct to add fluorine to the alkenyl group. A method for producing a fluorinated ether compound. 2. The alkenyl compound represented by the following general formula (1)
The method according to claim 1, wherein the fluorine-containing ether compound is a compound represented by the following general formula (2). General formula (1): (Wherein, R ¹ is an alkyl group which may have a substituent,
An aralkyl group or an aryl group; R ^{2 to} R ^{4 each} represent a hydrogen atom, a halogen atom, a substituted or unsubstituted linear or branched alkyl group, an aralkyl group or an aryl group, at least one of which is a fluorine atom; And R ^{1 to} R ⁴
May combine with each other to form a ring.) General formula (2): (In the formula, R ^{1 to} R ⁴ have the same meaning as described above.) 3. The alkenyl compound represented by the following general formula (3)
The method according to claim 1, wherein the fluorine-containing ether compound is a compound represented by the following general formula (4). General formula (3): (Wherein, R ⁵ represents an alkyl group which may have a substituent, and R ^{6 to} R ^{8 each} represent a fluorine atom or a perfluoroalkyl group, at least one of which represents a fluorine atom;
R ^{6 to} R ⁸ may be bonded to each other to form a ring) General formula (4): (In the formula, R ^{5 to} R ⁸ have the same meaning as described above.) 4. The method according to claim 1, wherein the alkenyl compound is CH ₃ OCF ＝ C.
F ₂ or CH ₃ OCF ＝ CFCF ₃ , and the fluorinated ether compound is CH ₃ OCF ₂ CF ₃ or CH ₃ OCF ₂ C
The method of claim 1 wherein F ₂ CF _3. 5. The alkenyl compound is CH ₃ OCF ル C
F ₂ or CH ₃ OCF ＝ CFCF ₃ , and the fluorinated ether compound is CH ₃ OCF ₂ CF ₃ or CH ₃ OCF ₂ C
The method of claim 1 wherein the fluorinating agent is F ₂ CF ₃ and the fluorinating agent is metal fluoride or xenon difluoride.