JP3530975B2 - Method for producing fluorine-containing ether compound - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a fluorine-containing 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 their intermediates. Among them, fluorine-containing ether compounds have been used in the medical field, etc., and, for example, among the fluorine-containing ether compounds represented by the following general formula (2) which is the subject of the present invention, R ¹
= CHF ₂ , R ² = F, R ³ = H, R ⁴ = Cl (CH
F ₂ OCF ₂ CHFCl) is used as an anesthetic (New Fluorine Chemistry, Chemistry Review, 27, Chapter 2, 198).
0 years).

Further, recently, a fluorine-containing ether compound is highly expected to be used as a refrigerant, especially as a CFC substitute. For example, among the fluorine-containing organic compounds represented by the following general formula (2), which is the subject 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 ones _{(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 that has little effect on the environment (Chemtech, 26,
44 (1996)).

As a method for producing a fluorine-containing ether compound, particularly an alkyl-perfluoroalkyl ether expected as a CFC substitute, perfluoro acid halides or perfluoro ketones, metal fluoride salts such as potassium fluoride, and A method using an alkylating agent such as dimethylsulfate and methyl paratoluenesulfonate has been adopted (ECO INDUSTRY, 1,
October issue, p5, 1996).

However, dimethyl sulfate, which is one of the alkylating agents used in this method, is extremely toxic and requires careful handling. Further, since these alkylating agents are expensive, a method for synthesizing these fluorine-containing ether compounds at a lower cost and more conveniently 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), among which R ¹ = C
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 of introducing fluorine into an organic compound, and if fluorine can be added to these fluorine-containing alkenyl ether compounds, Although a fluorinated ether compound can be produced inexpensively and conveniently, such a general method has not been developed so far.

The reaction of reacting a fluorinating agent with an alkenyl ether compound containing no fluorine atom in the alkenyl group to add fluorine is limited to a special compound, although there are reported cases (Tetrahedron Lett. 197).
7, 363), when a fluorinating agent is reacted with an ordinary alkenyl ether compound, polymerization of a substrate occurs, and a compound to which fluorine is added is hardly obtained (Reference Example 1 described later).
reference).

More recently, methyl-perfluoroiso
Butenyl ether (CH₃OCF = C (CF₃)₂)
Methyl-perfluoroisobutyl by reacting with nitrogen gas
Ether (CH₃OCF₂CF (CF₃)₂)
The law was reported (US Pat. No. 5,741,950). Shi
However, in this method, the yield is as low as 40%, and
The side reaction of fluorination of the methyl group is unavoidable,
By-product (CFH ₂OCF₂CF (CF₃)₂) Is the purpose
About one-third of the items will occur. Reduce the amount of this by-product
To reduce the amount of fluorine gas to be reacted
However, in this case, the yield of the target product was only about 10%.
I can't. Also, CH₃OCF = C (CF₃)₂Other than
Even fluorine alkenyl ether compounds do not react with fluorine gas.
Fluorination to the methyl group will occur (see below).
See Reference Example 2).

[0009]

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

[0010]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies on a method for producing a fluorine-containing ether compound, and have 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 therewith, a reaction such as polymerization thereof is unlikely to occur, and if a fluorinating agent milder than fluorine gas is used, fluorination to a methyl group does not proceed, It was found that the fluorine addition reaction proceeds smoothly and a fluorine-containing ether compound can be synthesized with a high yield, and the present invention has been completed.

That is, according to the present invention, (i) a metal fluoride as a fluorinating agent for a fluorinated alkenyl ether compound having at least one fluorine atom bonded to a carbon atom adjacent to a double bond, (ii) Xenon difluoride,
(Iii) reacting 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 the fluorine-containing ether compound is provided.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION According to the present invention, a fluorinated ether compound represented by the following general formula (2) can be obtained from a fluorinated alkenyl ether compound represented by the following general formula (1). General formula (1):

[Chemical 5] (In the formula, R ¹ is an alkyl group which may have a substituent,
An aralkyl group or an aryl group, and 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. Shown, R ^{1 to} R ⁴
May each combine to form a ring) General formula (2):

[Chemical 6] (In the formula, R ^{1 to} R ⁴ have the same meanings as described above)

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

The above-mentioned alkyl group, aralkyl group and aryl group may have a substituent, but the substituent is not particularly limited as long as it does not participate in this reaction, and a substituted or unsubstituted aryl group, 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), R²~ R^FourLittle
At least one is a fluorine atom, R ²~ R^FourAll of
It may be a silicon atom. Also, among them
Non-children are halogen atoms other than hydrogen atom and fluorine atom.
Child, optionally substituted alkyl group, aralkyl
Is an alkyl group or an aryl group.
As the aralkyl group or the aryl group, the above R¹Regarding
The ones shown are listed. Also, by binding to those groups
As the substituent which may be present, the above R¹Various shown about
The following are listed. With halogen atoms other than the above fluorine
Examples include chlorine, bromine and iodine.

In addition, R ^{1 to} R ⁴ in the above general formula (1)
Two of them, for example, R ¹ and R ² , R ² and R ³ , R ³ and R ^{4 and the} like may combine to form a ring. In this case, the alkylene group forming the ring has, for example, 10 or less carbon atoms,
It can be shown as preferably 1 to 8 and more preferably 2 to 6 optionally branched alkylene groups. Such alkene compounds include 1-fluoro-1-alkoxycyclopentene and 1-fluoro-1-
Examples thereof include alkoxycyclohexene.

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

[Chemical 7] General formula (4):

[Chemical 8] In the above formula, R ⁵ represents an alkyl group which may have a substituent. Specific examples thereof include those shown for R ¹ . R ^{6 to} R ⁸ represent a fluorine atom or a perfluoroalkyl group, and at least one of them represents a fluorine atom. Perfluoroalkyl group has 1 carbon atom
~ 30, preferably 1-20, perfluoroalkyl groups are indicated. Two of R ^{6 to} R ⁸ may be bonded to each other to form a ring, for example, R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ^{8 and the} like. In this case, the perfluoroalkylene group forming the ring has, for example, 10 or less carbon atoms, preferably 1 to 8 carbon atoms.
, More preferably 2 to 6 optionally branched perfluoroalkylene groups and the like can be shown. Examples of such alkene compounds include 1-alkoxyperfluorocyclopentene and 1-alkoxyperfluorocyclohexene.

The fluorinating agent used in the present invention includes:
A carbon-carbon unsaturated bond causes an addition reaction of fluorine,
An alkyl group such as a methyl group that hardly causes 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; dioxide. Examples include a combination of lead or lead tetraacetate and anhydrous hydrogen fluoride and a combination of iodotoluene difluoride and an amine-hydrogen fluoride adduct. Among these, cobalt trifluoride, potassium tetrafluorocobaltate, manganese trifluoride,
Metal fluorides such as silver difluoride and cerium tetrafluoride, and xenon difluoride are preferred. Further, 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,
There is no particular limitation as long as it is appropriately selected depending on the type of substrate and the like, and is usually 1 equivalent or more, preferably 1 to 500 equivalents.

The reaction conditions are appropriately selected depending on the fluorinating agent, the type of substrate, etc., but the reaction temperature is usually from -75 ° C to
The temperature 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, fluorinating agent, type of substrate, etc., but is usually 1 second to 100 hours, preferably several seconds to 6
It is 0 hour, more preferably 0.01 to 50 hours.

Additives may be added during the reaction. The additive is appropriately selected depending on its purpose, the fluorinating agent used, the type of 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 may be used to improve reactivity. Etc. can be added to carry out the reaction. The amount of the additive used is not particularly limited, but is usually 0.
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.

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

[0023]

EXAMPLES The present invention will be described in more detail with reference to Examples and Reference Examples. The present invention is not limited to this embodiment.

Example 1 Xenon difluoride (174 mg, 1.03 mm) was placed in a reaction vessel consisting of a stop valve and a stainless steel reaction tube.
ol), and then methyl pentafluoropropenyl ether (CH ₃ OC) at −196 ° C. using a vacuum line.
F = CFCF ₃ , 0.865 mmol) was added and shaken at room temperature for 18 hours. The crude product was distilled using a vacuum line to give methyl heptafluoropropyl ether (CH
₃ OCF ₂ CF ₂ CF ₃ , 0.764 mmol, 88%) was obtained. The product is ¹ H-NMR spectrum, ¹⁹ F-NMR
It was identified by the spectrum and IR spectrum.

IR: 3020, 2977, 2879, 1
460, 1350, 1237, 1204, 1180, 1
146, 1120, 1060, 1020, 961, 93
3,784,744 cm ^-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) Incidentally, a compound (CFH ₂ OC) in which a methyl group is fluorinated.
F ₂ CF ₂ CF ₃ etc.) was not produced.

Example 2 Cobalt trifluoride (21.3 g, 183 mmo) was placed in a reaction vessel consisting of a stop valve and a stainless steel reaction tube.
l), and then using a vacuum line at -196 ° C. methylpentafluoropropenyl ether (1.014 m
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) and then shaken at room temperature for 1 hour and then distilled using a vacuum line to obtain methylheptafluoropropyl ether (0.562 mmo).
l, 55%). A compound (CFH ₂ OCF ₂ CF ₂ CF ₃ ) in which the methyl group was fluorinated was also produced, but the amount was 0.010 mmol (1%).

Example 3 In a reaction vessel consisting of a stop valve and a stainless steel reaction tube, potassium tetrafluorocobaltate (KCo
F _4, 30.7 g, put 176 mmol), followed by methyl trifluoromethyl ether at -196 ° C. using a vacuum line _{(CH 3 OCF = CF 2,} 1.003mmo
l) was added. This was heated at 160 ° C. for 20 minutes. The crude product was treated with sodium fluoride (0.90 g, 21 mmo
1) was placed in a reaction vessel and further shaken at room temperature for 1 hour, and then distilled using a vacuum line to obtain methyl pentafluoroethyl ether (CH ₃ OCF ₂ CF ₃ , 0.
841 mmol, 85%) was obtained. The product is ¹ H-NM
It was identified by an R spectrum, a ¹⁹ F-NMR spectrum, and an 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 produced.

Example 4 Cobalt trifluoride (21.3 g, 183 mmo) was placed in a reaction vessel consisting of a stop valve and a stainless steel reaction tube.
l), and then methyltrifluorovinyl ether (1.002 mmo) at -196 ° C using a vacuum line.
l) was added. This was heated to room temperature over 30 minutes.
The crude product was treated with sodium fluoride (0.82 g, 20 mmo
l) was transferred to a reaction vessel and further shaken at room temperature for 1 hour, and then distilled using a vacuum line to give methyl pentafluoroethyl ether (0.697 mmol, 70%).
%) Was obtained. Compounds with fluorinated methyl groups (CFH
₂ OCF ₂ CF ₃ ) did not form.

Example 5 Cerium tetrafluoride (25.7 g, 119 mmo) was placed in a reaction vessel consisting of a stop valve and a stainless steel reaction tube.
1) and then methyltrifluorovinyl ether (1.011 mmo at -196 ° C. using a vacuum line).
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 then distilled using a vacuum line to obtain methyl pentafluoroethyl ether (0.222 mmol). , 22%). Compounds in which the methyl group is fluorinated (CFH ₂ OC
F ₂ CF ₃ ) was not produced.

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 added 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 then distilled using a vacuum line to obtain methyl pentafluoroethyl ether (0.159 mmol). , 16%). A compound in which a methyl group is fluorinated (CFH ₂ OCF ₂
CF ₃ ) was not produced.

Example 7 Manganese trifluoride (19.7 g, 176 mmo) was placed in a reaction vessel consisting of a stop valve and a stainless steel reaction tube.
1), and then methyltrifluorovinyl ether (1.024 mmo) at -196 ° C using a vacuum line.
l) was added. After heating this to room temperature over 30 minutes, it was shaken for another 1.5 hours at room temperature. The crude product was transferred to a reaction vessel containing sodium fluoride (0.80 g, 19 mmol) and further shaken at room temperature for 1 hour.
Distillation using a vacuum line gave methyl pentafluoroethyl ether (0.199 mmol, 19%).
Compounds in which the 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, and
Methyl trifluorovinyl ether (8.9g, 79m
(mol) was diluted with nitrogen gas and introduced into the reaction tube at a reaction temperature of 50 ° C. At this time, the flow rate of nitrogen gas is 30 cc / m
in, the raw material flow rate was 11 cc / min. The outlet gas was collected and analyzed by gas chromatography to find that methyl pentafluoroethyl ether had 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 stainless steel flow-type reaction tube with an inner diameter of 3 cm
Add manganese fluoride (50.6g, 450mmol),
Methyl trifluorovinyl ether (16.3 g, 14
6 mmol) while diluting it with nitrogen gas at a reaction temperature of
It was introduced into the reaction tube at ° C. At this time, the flow rate of nitrogen gas is 11c
c / min, the raw material flow rate was 3.6 cc / min.
Collect outlet gas and analyze by gas chromatography
The methyl pentafluoroethyl ether
It was found that the rate was 66% and the raw material recovery was 5%
It was Compounds with fluorinated methyl groups (CFH₂OCF₂
CF ₃) Was not generated.

Example 10 An anti-stop valve and a stainless steel reaction tube
Cobalt trifluoride (21.3g, 183mmo)
l) and then using a vacuum line at -196 ° C.
Cylheptafluoroisobutenyl ether (CH₃OC
F = C (CF₃) ₂, 1.010 mmol) was added. This
It was warmed to room temperature over 45 minutes. Fluoride the crude product
Reaction with sodium (1.08 g, 26 mmol)
Transfer to a container and shake at room temperature for 1 hour, then vacuum.
Distilled using a line to obtain methyl nonafluoroisobuty
Ruether (CH₃OCF₂CF (CF₃)₂, 0.696
mmol, 69%). The product is¹H-NMR spectrum
Khutor,¹⁹F-NMR spectrum and IR spectrum
It was identified by

IR: 3020, 2977, 2877, 1
460, 1302, 1262, 1234, 1176, 1
137, 1109, 1048, 1018, 986, 94
9,781,749,731cm ^-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) In addition, a compound (CFH ₂ OC) in which a methyl group is fluorinated
F ₂ CF (CF ₃ ) ₂ etc.) was not produced.

Example 11 Xenon difluoride (193 mg, 1.14 mm) was placed in a reaction vessel consisting of a stop valve and a stainless steel reaction tube.
ol) and then using a vacuum line for trifluoromethyltrifluorovinyl ether (CF ₃ OCF = C
F ₂ , 0.955 mmol), silicon tetrafluoride (1.1
1 mmol) was added and shaken at room temperature for 48 hours. The crude product was distilled using a vacuum line to give trifluoromethyl pentafluoroethyl ether (0.694 mmo
1, 73%). The product was identified by ¹⁹ F-NMR spectrum and 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 consisting of 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 mmo
l) and silicon tetrafluoride (1.26 mmol) were added, and the mixture was shaken at room temperature for 30 minutes. Ethyl vinyl ether was consumed and a tar-like substance was produced, but no fluorine-added compound was obtained.

Reference Example 2 Methyl pentafluoropropenyl ether (CH ₃ OCF = CFC) was used at -196 ° C. using a vacuum line in a reaction vessel consisting of a stop valve and a stainless steel reaction tube.
F ₃ , 0.897 mmol) and fluorine (1.07 mmo
1) was added, and this was gradually heated to room temperature from -113 ° C 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. Methylheptafluoropropyl ether, which is a compound to which fluorine is added, has a yield of 31% (0.2
80 mmol,) but at the same time fluorinated methyl groups CFH ₂ OCF ₂ CF ₂ CF ₃ and CF ₂
HOCF ₂ CF ₂ CF ₃ yields 31% (0.27
7 mmol) and 3% (0.028 mmol).

[0048]

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

─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Akira Sekiya 1-1, Higashi, Tsukuba-shi, Ibaraki Industrial Technology Institute, Institute of Materials Science and Technology (72) Inventor Seiji Takubo 2-40-17 Hongo, Hongo, Bunkyo-ku, Tokyo Wakai Wakai Building 6th floor, Research Center for Global Environmental Industrial Technology, New Refrigerant Project Room (56) Reference JP-A-5-262685 (JP, A) JP-A-61-275233 (JP, A) JP-A-60-81134 (JP, A) Special Table 2001-506261 (JP, A) edited by The Chemical Society of Japan, "4th Edition Experimental Chemistry Lecture 19 Organic Synthesis I-Hydrocarbon / Halogen Compounds", Maruzen, 1992, p. 398-399 (58) Fields surveyed (Int.Cl. ⁷ , DB name) C07C 41/22 C07C 43/12

Claims (5)

(57) [Claims] 1. A (i) metal fluoride, (ii) xenon difluoride, (ii) as a fluorinating agent for a fluorinated alkenyl ether compound having at least one fluorine atom bonded to a carbon atom adjacent to a double bond. 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 is reacted to add fluorine to the alkenyl group. Process for producing fluorine-containing ether compound. 2. The alkenyl compound is 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): (In the formula, R ¹ is an alkyl group which may have a substituent,
An aralkyl group or an aryl group, and 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. Shown, R ^{1 to} R ⁴
May each combine to form a ring) General formula (2): (In the formula, R ^{1 to} R ⁴ have the same meanings as described above.) 3. The alkenyl compound is 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): (In the formula, R ⁵ represents an alkyl group which may have a substituent, and R ^{6 to} R ⁸ 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 meanings as described above.) 4. The alkenyl compound is CH ₃ OCF═C.
F ₂ or CH ₃ OCF = CFCF ₃ , and the fluorine-containing ether compound is CH ₃ OCF ₂ CF ₃ or CH ₃ OCF ₂ C.
The method of claim 1 which is F ₂ CF ₃ . 5. The alkenyl compound is CH ₃ OCF═C.
F ₂ or CH ₃ OCF = CFCF ₃ , and the fluorine-containing ether compound is CH ₃ OCF ₂ CF ₃ or CH ₃ OCF ₂ C.
The method of claim 1 which is F ₂ CF ₃ and the fluorinating agent is a metal fluoride or xenon difluoride.