JP5163659B2 - Method for producing fluorine-containing epoxide - Google Patents

Description

  The present invention relates to a chlorosulfonate compound which is a novel compound useful as an intermediate of a fluorine-containing epoxide, a method for producing the chlorosulfonate compound, and a method for producing a fluorine-containing epoxide using the chlorosulfonate compound.

  General formula

A perfluoroalkyl epoxide represented by the formula (wherein Rf is a perfluoroalkyl group) is a useful compound as a pharmaceutical intermediate, an intermediate such as a repellent, a resin / rubber monomer, and the like.

  As a method for producing the epoxide, for example, Patent Document 1 describes a method for producing a diol according to the following reaction process formula, and the diol obtained by this method is subjected to a dehydration reaction to obtain an epoxide. it can.

  However, in this method, the yield of the target perfluoroalkyl epoxide is about 30%, and an improvement in the yield is desired.

In Patent Document 2 below, mono- or bis (perfluoroalkyl) ethylene, SO ₃ and halongen are reacted to produce a sulfate or halosulfonate, and then the sulfate or halosulfonate is converted to a halohydrin by hydrolysis. Thereafter, a method of forming an epoxide by reaction with a base is described. However, in this method, hydrolysis of sulfate or halosulfonate is difficult, and halohydrin cannot be obtained in a sufficient yield. For this reason, when the above-described reaction process is employed, the yield of epoxide with respect to mono- or bis (perfluoroalkyl) ethylene as a raw material is not satisfactory.
JP 2004-18503 A Japanese Patent No. 3172173

  The present invention has been made in view of the above-mentioned problems of the prior art, and its main purpose is a novel process capable of producing a fluorine-containing epoxide in a high yield by a relatively simple reaction process using perfluoroalkylethylene as a raw material. Is to provide a simple method.

  The present inventor has intensively studied to achieve the above-described object. As a result, by using perfluoroalkylethylene as a raw material and reacting it with N-bromo or N-iodosuccinimide and chlorosulfuric acid, a chlorosulfonate compound having a chlorine atom at the terminal, which is a novel compound, is obtained in high yield. I found out that I can. This compound has good stability, but when hydrolyzed in the presence of an alkali metal iodide, it can be surprisingly converted into a halohydrin compound with very high efficiency. It was found that it can be easily converted into an epoxide by reacting with. Therefore, by adopting the above-described reaction process, it becomes possible to synthesize the fluorine-containing epoxide in a high yield using perfluoroalkylethylene as a raw material. The present invention has been completed based on these findings.

That is, the present invention provides a chlorosulfonate compound which is a novel compound useful as an intermediate of the following fluorine-containing epoxide, a method for producing the chlorosulfonate compound, and a method for producing the fluorine-containing epoxide.
1. General formula: Rf-CHX-CH ₂ OSO ₂ Cl
(Wherein Rf is a perfluoroalkyl group and X is a bromine atom or an iodine atom).
2. Item 2. The fluorine-containing chlorosulfonate compound according to Item 1, wherein Rf is a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms.
3. General formula: RfCH = CH ₂
(Wherein Rf is a perfluoroalkyl group) is reacted with at least one succinimide compound selected from the group consisting of N-bromosuccinimide and N-iodosuccinimide, and chlorosulfuric acid. General formula: Rf-CHX-CH ₂ OSO ₂ Cl
(Wherein, Rf is the same as above, and X is a bromine atom or an iodine atom).
4). A fluorine-containing chlorosulfonate compound represented by the general formula: Rf—CHX—CH ₂ OSO ₂ Cl (wherein Rf is a perfluoroalkyl group and X is a bromine atom or an iodine atom) is represented by the formula: MI Hydrolysis in the presence of an alkali metal iodide represented by the formula (wherein M is Li, Na or K): Rf—CHX—CH ₂ OH (wherein Rf and X are as defined above) The same applies to the fluorine-containing halohydrin compound represented by the following formula, and then reacting the obtained halohydrin compound with a base:

(Wherein Rf is the same as above).
5. General formula: Rf-CHX-CH ₂ OSO fluorinated chloro sulfonate compound represented by ₂ Cl The method for producing a fluorinated epoxide according to Item 4 is obtained by the method according to Item 3.

  Hereinafter, the present invention will be specifically described.

Starting material In the present invention, a perfluoroalkylethylene represented by the following general formula: RfCH═CH ₂ (wherein Rf is a perfluoroalkyl group) is used as a starting material.

In the above compound, as the perfluoroalkyl group represented by Rf, a linear or branched perfluoroalkyl group having 1 to 20 carbon waters can be exemplified, and specific examples thereof include the formula: CF ₃ (CF ₂ ) _n - (wherein, the group represented by n = 0 to 19), the _{formula: (CF 3) 2 CA (} CF 2 CF 2) n- ( where n = 0 to 8, A is a fluorine atom or a A group represented by CF ₃ — and the like. Specific examples of the alkyl group in the perfluoroalkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, n-pentyl, iso-pentyl, n-hexyl, heptyl, n-octyl and nonyl. , N-decyl and the like.

Production process of fluorine-containing chlorosulfonate compound In the method of the present invention, first, the perfluoroalkylethylene is converted into at least one succinimide compound selected from the group consisting of N-bromosuccinimide and N-iodosuccinimide, and chlorosulfuric acid (HSO ₃ Cl)
General formula: Rf-CHX-CH ₂ OSO ₂ Cl
(In the formula, Rf is a perfluoroalkyl group, and X is a bromine atom or an iodine atom).

  According to this reaction, a fluorine-containing chlorosulfonate compound can be obtained in a high yield.

The fluorine-containing chlorosulfonate compound represented by the general formula: Rf—CHX—CH ₂ OSO ₂ Cl obtained by the above-described method is a novel compound. For example, the fluorine-containing epoxide is obtained in a high yield by the method described later. Can do. In addition, the chlorosulfonate compound is a compound in which a chlorine atom is bonded to the terminal of the sulfonate group, and has better stability than a compound having an iodine atom, a bromine atom, etc. at the terminal, and is left in the air. However, hydrolysis and oxidative degradation hardly occur and handling is simple. Therefore, the chlorosulfonate compound is a highly useful compound as an intermediate for producing a fluorine-containing epoxide. Furthermore, the —OSO ₂ Cl group in the chlorosulfonate compound is a good reactive functional group and can be converted into various functional groups.

  In the above reaction, the amount of the succinimide compound used is preferably about 0.01 to 10 times mol, more preferably about 0.1 to 5 times mol, of perfluoroalkylethylene used as a raw material.

  As the succinimide compound, N-bromosuccinimide is particularly preferable from the viewpoint of being inexpensive and easy to purchase, and by using this, the above reaction can proceed stably.

  The amount of chlorosulfuric acid used is preferably about 0.01 to 10 times mol, more preferably about 0.1 to 5 times mol for perfluoroalkylethylene.

  This reaction can be carried out without solvent or in a solvent. As the solvent, a solvent that is stable to the above reaction can be used. Examples of such solvents include chlorine-containing compounds such as methylene chloride and chloroform, saturated hydrocarbon compounds such as n-hexane, n-pentane, n-heptane, and n-octane, perfluorohexane, perfluorooctane, and perfluoro. Examples include polyethers, fluorine-containing compounds such as HFC-141b and HFC-225. Although there is no limitation in particular about the usage-amount of a solvent, For example, it can be set as about 0.01-100 times capacity | capacitance with respect to perfluoroethylene.

  The above reaction can be performed in a wide temperature range from cooling to heating. The specific reaction temperature can be, for example, about −80 to 200 ° C., and preferably about −30 to 100 ° C.

  The pressure during the reaction may be any of reduced pressure, atmospheric pressure, and increased pressure. For example, when the reaction is performed in a closed container at a temperature exceeding the boiling point of the raw material, the reaction proceeds in a pressurized state. Moreover, when performing reaction at the temperature below a boiling point using a high boiling-point raw material, reaction can be performed under reduced pressure or atmospheric pressure. Therefore, the actual pressure during the reaction depends on the reaction temperature, the boiling point of perfluoroethylene as a raw material, and the like.

  The reaction time depends on the type, amount, reaction temperature, and the like of the perfluoroethylene compound as a substrate, and the reaction can usually be carried out in the range of several seconds to several hours.

  Suitable reaction vessels are those made of materials that are inert under the reaction conditions, such as glass, Hastelloy 22, Hastelloy 276, and the like.

  The chlorosulfonate compound obtained by the reaction can be isolated by a known method such as crystallization, distillation, and liquid separation operation.

Production process of fluorine-containing halohydrin compound Next, the fluorine-containing chlorosulfonate compound obtained by the above-described method is treated in the presence of an alkali metal iodide represented by the formula: MI (wherein M is Li, Na or K). By hydrolyzing to
General formula: Rf-CHX-CH ₂ OH
(Wherein Rf is a perfluoroalkyl group and X is a bromine atom or an iodine atom).

  According to the above-described method, by performing the hydrolysis in the presence of a specific alkali metal iodide, the hydrolysis reaction of the chlorosulfonate compound, which is a stable compound, easily proceeds, and has a high yield exceeding 90%. A fluorine-containing halohydrin compound can be obtained at a high rate.

  The hydrolysis reaction can be performed by reacting a fluorine-containing chlorosulfonate compound with at least one proton donating compound selected from the group consisting of water and alcohols in the presence of an alkali metal iodide. As alcohols, for example, methanol, ethanol, isopropanol, butanol, octanol and the like can be used. Examples of the alkali metal iodide include LiI, NaI, KI and the like.

  The amount of at least one proton donor compound selected from the group consisting of water and alcohols is preferably about 0.01 to 1000 times by volume, for example, about 0.1 to 100 times by volume with respect to the fluorine-containing chlorosulfonate compound. More preferably.

  In addition, the amount of alkali metal iodide used is preferably about 0.01 to 10 times mol, more preferably about 0.01 to 10 times mol for the fluorinated chlorosulfonate compound.

  The hydrolysis reaction can be performed without a solvent or in a solvent. As the solvent, any of a polar solvent and a nonpolar solvent may be used. For example, acetonitrile, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), nitrobenzene, benzonitrile, n-hexane , N-pentane, n-heptane, n-octane, monoglyme, diglyme, triglyme, tetraglyme and other hydrocarbon compounds that may have functional groups; chlorine-containing compounds such as methylene chloride and chloroform; perfluorohexane, par Fluorine-containing compounds such as fluorooctane, perfluoropolyether, HFC-141b, and HFC-225 can be used.

  The above-mentioned solvents can be used alone or in combination, and the amount used can be, for example, 0.01 to 100 times the volume of the fluorine-containing chlorosulfonate compound.

  The hydrolysis reaction can be performed in a wide temperature range from cooling to heating. Specific reaction temperature can be made into the range of about -20-200 degreeC, for example, and it is preferable to set it as the range of about 0-100 degreeC. However, the lower limit of the reaction temperature is preferably a temperature at which the solvent and the substrate used do not coagulate.

  The pressure during the reaction may be any of reduced pressure, atmospheric pressure, and increased pressure. For example, when the reaction is performed in a closed container at a temperature exceeding the boiling point of the raw material to be used, the reaction proceeds in a pressurized state. Moreover, when performing reaction at the temperature below a boiling point using a high boiling-point raw material, reaction can be performed under reduced pressure or atmospheric pressure.

  The reaction time depends on the type, amount, reaction temperature, and the like of the fluorine-containing chlorosulfonate compound as a substrate, and the reaction is carried out in the range of several seconds to several hours.

  In addition, when a nonpolar catalyst having poor compatibility with the raw material is used, the reaction may proceed slowly. In this case, the reaction can be promoted by using a phase transfer catalyst.

As the phase transfer catalyst, a general formula: R ¹ R ² R ³ R ⁴ NX (wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and each is a hydrocarbon group, and X is a halogen atom) R ⁵ R ⁶ R ⁷ R ⁸ PX (wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and are each a hydrocarbon group) , X is a halogen atom) and the like can be used singly or in combination of two or more. Here, as the hydrocarbon group, a linear or branched alkyl group having about 1 to 10 carbon atoms, an aryl group, an aralkyl group and the like are preferable, and in particular, a methyl group, an ethyl group, an n-propyl group, an isopropyl group. Group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, octyl group, phenyl group, benzyl group and the like are preferable. X is a halogen atom such as F, Cl, Br, or I, and is preferably F, Cl, Br, or the like, and particularly preferably Cl, Br, or the like because of availability.

  The amount of the phase transfer catalyst used is preferably about 0.001 to 10 times molar equivalent, more preferably about 0.01 to 5 times molar equivalent to the fluorine-containing chlorosulfonate compound.

  As the reaction vessel, a material that is inert under the reaction conditions, for example, glass, stainless steel such as SUS304 or SUS316, Hastelloy 22, Hastelloy 276, or the like is suitable.

  The fluorine-containing halohydrin compound obtained by the reaction can be isolated by a known method such as crystallization, distillation, or liquid separation operation.

Production process of fluorine-containing epoxide By reacting the fluorine-containing halohydrin compound obtained by the above-described method with a base,
General formula:

A fluorine-containing epoxide represented by the formula (wherein Rf is a perfluoroalkyl group) can be obtained.

In the above reaction, as the base, LiOH, NaOH, KOH, CsOH , Mg (OH) 2, Ca (OH) 2, Ba (OH) 2, Li 2 CO 3, Na 2 CO 3, Cs 2 CO 3, MgCO ₃ , CaCO ₃ , BaCO _{3 and the} like can be used, and NaOH, KOH, Ca (OH) ₂ , Na ₂ CO ₃ , CaCO _{3 and the} like are particularly preferable because they are inexpensive and easily available.

  The amount of the base used is preferably about 0.01 to 10 times mol, more preferably about 0.01 to 10 times mol for the fluorine-containing halohydrin compound.

  The above reaction can be carried out without solvent or in a solvent. As the solvent, any of a polar solvent and a nonpolar solvent may be used. For example, water; acetonitrile, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), nitrobenzene, benzonitrile, Hydrocarbon compounds that may have functional groups such as n-hexane, n-pentane, n-heptane, n-octane, monoglyme, diglyme, triglyme and tetraglyme; chlorine-containing compounds such as methylene chloride and chloroform; perfluoro Fluorine-containing compounds such as hexane, perfluorooctane, perfluoropolyether, HFC-141b, and HFC-225 can be used.

  The above-mentioned solvents can be used singly or in combination, and the amount used can be, for example, 0.01 to 100 times the volume of the fluorine-containing halohydrin compound.

  The hydrolysis reaction can be performed in a wide temperature range from cooling to heating. Specific reaction temperature can be made into the range of about -20-200 degreeC, for example, and it is preferable to set it as the range of about 0-100 degreeC. However, the lower limit of the reaction temperature is preferably a temperature at which the solvent and the substrate used do not coagulate.

  The pressure during the reaction may be any of reduced pressure, atmospheric pressure, and increased pressure. For example, when the reaction is performed in a closed container at a temperature exceeding the boiling point of the raw material to be used, the reaction proceeds in a pressurized state. Moreover, when performing reaction at the temperature below a boiling point using a high boiling-point raw material, reaction can be performed under reduced pressure or atmospheric pressure. Therefore, the actual pressure during the reaction depends on the reaction temperature, the boiling point of the fluorine-containing halohydrin compound used as the raw material, the boiling point of the product fluorine-containing epoxide, and the like.

  The reaction time depends on the type, amount, reaction temperature, and the like of the fluorine-containing halohydrin compound as a substrate, and the reaction is carried out in the range of several seconds to several hours.

  According to the reaction step described above, the fluorine-containing epoxide can be obtained from the fluorine-containing halohydrin compound in a high yield.

  After completion of the reaction, the target fluorine-containing epoxide can be isolated and purified by conventional separation means such as solvent extraction, recrystallization, distillation, chromatography and the like.

  According to the present invention, a halohydrin compound can be obtained in a very high yield from a chlorosulfonate compound which is a novel compound obtained by reacting perfluoroalkylethylene with N-bromo or N-iodosuccinimide and chlorosulfuric acid. . Therefore, it is possible to produce perfluoroalkyl epoxide in high yield from perfluoroalkylethylene as a raw material by passing through the above-described chlorosulfonate compound production process, halohydrin compound production process and epoxide production process. .

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

Example 1
(1) Synthesis process of C ₄ F ₉ CHBrCH ₂ OSO ₂ Cl
_{C 4 F 9 CH = CH 2} + NBS + HSO 3 Cl → C 4 F 9 CHBrCH 2 OSO 2 Cl + NHS
A three-necked flask equipped with a Dimroth was charged with 16.0 g (90.4 mmol) of N-bromosuccinimide (NBS) and 20.0 g (80.5 mmol) of 99% nC ₄ F ₉ CH═CH ₂ . The flask was immersed in an ice bath and a dropping funnel containing 20.0 g (171.7 mmol) of HSO ₃ Cl was attached.

Thereafter, HSO ₃ Cl was added dropwise over about 10 minutes so as not to exceed 30 ° C. After completion of the addition, the ice bath was removed and the reaction was allowed to stir overnight.

  After completion of the reaction, it was opened on ice taking care of heat generation. Since the two layers were separated, they were separated into a lower layer (organic layer) and an upper layer (acid aqueous solution layer) with a separating funnel, and both layers were subjected to NMR analysis and quantified. The lower layer was subjected to GC and GC / MS analysis and qualitative analysis was performed.

As a result of the analysis, the C ₄ F ₉ CH═CH ₂ conversion was 97.9%, and the yield of C ₄ F ₉ CHBrCH ₂ OSO ₂ Cl was 92.9%.
Analysis results for C ₄ F ₉ CHBrCH ₂ OSO ₂ Cl:
GC / MS (EI ⁺ ) results:
m / z [CF ₃ ⁺ ] = 69, [SO ₂ Cl ⁺ ] = 99, [CH ₂ OSO ₂ Cl ⁺ ] = 129, [CF ₂ CBr = CH ₂ ⁺ ] = 155, [C ₄ F ₉ CBr = CH ₂ ⁺ ] = 324, [C ₄ F ₉ CHBrCH ₂ ⁺ ] = 325, [C ₄ F ₉ CHBrCH ₂ O ⁺ ] = 341
¹ H-NMR result:
¹ H-NMR (270 MHz, CDCl3, TMS)
δ ppm: 4.32 ppm (m, 1H, —CF ₂ CH BrCH ₂ —) 4.56 ppm (m, 2H, —CHBr CH ₂ OSO ₂ Cl)
¹⁹ F-NMR result:
¹⁹ FNMR (254 MHz, CDCl ₃ , CFCl ₃ ),
δppm: -84.3ppm (brs, 3F, CF _3- ), -123.1ppm (dt, 2F, J = 4.6Hz, 2F, CF ₃ CF _2- ),
-114.5ppm (dt, 2F, J = 4.4Hz), -128.9ppm (m, 2F, CF ₃ - CF ₂ -CF ₂ )

(2) Synthesis process of C ₄ F ₉ CHBrCH ₂ OH
C ₄ F ₉ CHBrCH ₂ OSO ₂ Cl + NaI → C ₄ F ₉ CHBrCH ₂ OH + SO ₂ + I ₂ + NaCl
15 ml of water as a solvent was placed in a 50 ml three-necked flask, and 3.4 g (22.8 mmol) of NaI was added at room temperature. Thereto was added 0.05 g of benzyltriethylammonium chloride (PhCH ₂ N (Et) ₃ Cl) as a phase transfer catalyst, and the mixture was stirred until a homogeneous solution was obtained.

Thereafter, 5.03 g (10.6 mmol) of 93 mass% C ₄ F ₉ CHBrCH ₂ OSO ₂ Cl obtained in the above step (1) was added, and the mixture was stirred for about 2.5 hours. Since the two layers were separated after completion of the reaction, the upper layer (aqueous layer) / lower layer (organic layer) were separated and subjected to GC, GC / MS, and NMR measurements. As a result of the analysis, the conversion ratio of C ₄ F ₉ CHBrCH ₂ OSO ₂ Cl was 100%, and the yield of C ₄ F ₉ CHBrCH ₂ OH was 100%.

(3) Step of C ₄ F ₉ CH (O) CH ₂ Synthesis (Epoxidation Reaction) To a 50 ml three-necked flask equipped with a Dimroth, 0.84 g (12.8 mmol) of 85% KOH and 10 ml of diglyme were added. Thereafter, a dropping funnel containing 3.18 g (8.36 mmol) of 89.9 mass% C ₄ F ₉ CHBrCH ₂ OH was attached to the flask and dropped in about 2 minutes. After confirming that the exotherm had subsided and the internal temperature had dropped to room temperature, heating was performed in an oil bath.

The time when the internal temperature was within the range of about 95 to 105 ° C. was defined as the reaction time, and the reaction was stirred for about 1 hour. After completion of the reaction, the temperature is returned to room temperature and water quenching is performed. The organic layer was extracted with CHCl ₃ , and GC, GC / MS, and NMR measurements were performed on the aqueous layer and the organic layer.

As a result of quantification from NMR analysis, the conversion of C ₄ F ₉ CHBrCH ₂ OH was 100%, and the yield of C ₄ F ₉ CH (O) CH ₂ (epoxy) was 75.8%.

Example 2
(1) C ₂ F ₅ (CF ₂ CF ₂ ) ₃ CHBrCH ₂ OSO ₂ Cl synthesis process
C ₂ F ₅ (CF ₂ CF ₂ ) ₃ CH = CH ₂ + NBS + HSO ₃ Cl → C ₂ F ₅ (CF ₂ CF ₂ ) ₃ CHBrCH ₂ OSO ₂ Cl + NHS
A three-necked flask equipped with a Dimroth was charged with 9.1 g (51.4 mmol) of N-bromosuccinimide (NBS) and 20.08 g (45.0 mmol) of C ₂ F ₅ (CF ₂ CF ₂ ) ₃ CH═CH ₂ . The flask was immersed in an ice bath and a dropping funnel containing HSO ₃ Cl: 20.0 g (171.7 mmol) was attached.

Thereafter, HSO ₃ Cl was added dropwise over about 10 minutes so as not to exceed 30 ° C. After completion of the addition, the ice bath was removed and the reaction was allowed to stir for about 1 hour.

After the completion of the reaction, the mixture was allowed to stand to separate into two layers. The lower layer and the upper layer were subjected to NMR analysis and quantified. As a _{result, C 2 F 5 (CF 2} CF 2) of ₃ CH = CH _{2 conversion: 94.2%, C 2 F 5} (CF 2 CF 2) 3 CHBrCH 2 OSO 2 Cl Yield: was 87.2%.
GC / MS (EI +) results:
m / z [CF ₃ ⁺ ] = 69, [SO ₂ Cl ⁺ ] = 99, [CH ₂ OSO ₂ Cl ⁺ ] = 129, [CF ₂ CBr = CH ₂ ⁺ ] = 155, [C ₇ F ₁₅ CF = CBrCH ₂ ⁺ ] = 505, [C ₈ F ₁₇ CHBrCH ₂ ⁺ ] = 525,
¹ H-NMR (270 MHz, CDCl ₃ , TMS):
δ ppm: 4.68 ppm (m, 1H, —CF ₂ CH BrCH ₂ —), 4.45 ppm (m, 2H, —CHBr CH ₂ OSO ₂ Cl)
¹⁹ F-NMR result:
¹⁹ FNMR (254 MHz, CDCl ₃ , CFCl ₃ ),
δppm: -84.9ppm (brs, 3F, CF 3 -), - 115.0ppm (dt, 2F, J = 4.5Hz, -CF 2 -CHBr-),
-122.3ppm (dt, 2F, J = 4.6Hz, 2F, - CF 2 -CF 2 CHBr-),
-124.8ppm (m, 6F, CF ₃ CF ₂ CF ₂ - CF ₂ CF ₂ CF ₂ -CF ₂ ),
-125.9ppm (m, 2F, CF ₃ CF ₂ - CF _2- ), -129.6ppm (m, 2F, CF ₃ - CF _2- )

(2) C ₂ F ₅ (CF ₂ CF ₂ ) ₃ CHBrCH ₂ OH synthesis process
To a 50 ml three-necked flask was added 5.0 g (7.8 mmol) of C ₂ F ₅ (CF ₂ CF ₂ ) ₃ CHBrCH ₂ OSO ₂ Cl obtained in the above step and 20 ml of water as a solvent. Then, NaI was added at 2.4 g (16 mmol) at room temperature. Thereto was added 0.1 g of phase transfer catalyst PhCH ₂ N (Et) ₃ Cl, and the reaction was allowed to stir for about 3 hours.

After completion of the reaction, the reaction mixture was cooled to room temperature, Na ₂ SO ₃ was added, and generated iodine was removed. The obtained solid was fractionated and subjected to GC, GC / MS, and NMR measurements. As a result of quantification, the conversion rate of C ₂ F ₅ (CF ₂ CF ₂ ) ₃ CHBrCH ₂ OSO ₂ Cl: 100% and the yield of C ₂ F ₅ (CF ₂ CF ₂ ) ₃ CHBrCH ₂ OH: 93.9% .

(3) C ₈ F ₁₇ CH (O) CH ₂ Synthesis (Epoxidation Reaction) Step 76.8 mass% C ₂ F ₅ (CF ₂ CF ₂ ) ₃ CHBrCH ₂ OH ( Bromohydrin) (1.0 g, 1.41 mmol), KOH (0.14 g, 2.21 mmol), and 10 ml of diglyme as a solvent were charged. After stirring at room temperature and confirming that there was no exotherm, the temperature was raised to 130 ° C. The reaction was allowed to proceed for about 2 hours after reaching 130 ° C. After completion of the reaction, the temperature was returned to room temperature and water quenching was performed. The organic layer was extracted with CHCl ₃ , and GC, GC / MS, and NMR measurements were performed on the aqueous layer and the organic layer.

As a result of the analysis, the conversion rate of C ₂ F ₅ (CF ₂ CF ₂ ) ₃ CHBrCH ₂ OH was 100%, and the yield of C ₈ F ₁₇ CH (O) CH ₂ (epoxy) was 70.9%.

Comparative Example 1
C ₂ F ₅ (CF ₂ CF ₂ ) ₃ CHBrCH ₂ OSO ₂ Cl: 1.0 g (1.56 mmol) obtained in step (1) of Example 2 was added to a sample bottle containing 10 ml of 20% NaOH aqueous solution. An exotherm occurred upon addition. After cooling to room temperature, the organic layer was subjected to GC and GC / MS analysis. As a _{result, C 2 F 5 (CF 2} CF 2) 3 CHBrCH 2 OH can not be obtained for purposes quantitatively _{C 2 F 5 (CF 2 CF} 2) 3 CBr = CH 2 was obtained.

  From this result, it is understood that the fluorine-containing chlorosulfonate compound obtained in the first step of the present invention is difficult to convert to a fluorine-containing halohydrin compound by a normal hydrolysis method.

Claims (3)

General formula: RfCH = CH ₂
(Wherein Rf is a perfluoroalkyl group) is reacted with at least one succinimide compound selected from the group consisting of N-bromosuccinimide and N-iodosuccinimide, and chlorosulfuric acid. General formula characterized by: Rf-CHX-CH ₂ OSO ₂ Cl
(Wherein, Rf is the same as above, and X is a bromine atom or an iodine atom). A fluorine-containing chlorosulfonate compound represented by the general formula: Rf—CHX—CH ₂ OSO ₂ Cl (wherein Rf is a perfluoroalkyl group and X is a bromine atom or an iodine atom) is represented by the formula: MI Hydrolysis in the presence of an alkali metal iodide represented by the formula (wherein M is Li, Na or K): Rf—CHX—CH ₂ OH (wherein Rf and X are as defined above) The same applies to the fluorine-containing halohydrin compound represented by the following formula, and then reacting the obtained halohydrin compound with a base:

(Wherein Rf is the same as above). General formula: Rf-CHX-CH ₂ OSO fluorinated chloro sulfonate compound represented by ₂ Cl The method for producing a fluorinated epoxide according to claim 2 are those obtained by the method of claim 1.