WO2007055212A1 - Process for production of compound having fluorosulfonyl group, and novel compound - Google Patents

Process for production of compound having fluorosulfonyl group, and novel compound Download PDF

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Publication number
WO2007055212A1
WO2007055212A1 PCT/JP2006/322199 JP2006322199W WO2007055212A1 WO 2007055212 A1 WO2007055212 A1 WO 2007055212A1 JP 2006322199 W JP2006322199 W JP 2006322199W WO 2007055212 A1 WO2007055212 A1 WO 2007055212A1
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group
compound
formula
represented
atom
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PCT/JP2006/322199
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French (fr)
Japanese (ja)
Inventor
Masao Iwaya
Eisuke Murotani
Kazuya Oharu
Hidekazu Okamoto
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Asahi Glass Company, Limited
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Priority claimed from JP2005323515A external-priority patent/JP2007131877A/en
Application filed by Asahi Glass Company, Limited filed Critical Asahi Glass Company, Limited
Publication of WO2007055212A1 publication Critical patent/WO2007055212A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/78—Halides of sulfonic acids
    • C07C309/79—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms
    • C07C309/84—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms of a carbon skeleton substituted by carboxyl groups

Definitions

  • the present invention relates to a method for producing a compound having a fluorosulfonyl group and a novel compound.
  • the present invention relates to a method for producing a compound having a fluorosulfonyl group and a novel compound.
  • R f indicates 1 CF, 1 CF, 1 CF or 1 CF. ;
  • Non-Patent Document 1 Chem. Soc., Chem. Comm., 1974, 323-324
  • Non-Patent Document 2 J. Chem. Soc., Perkin Trans. I, 1978, 202—209
  • Non-Patent Document 3 Tetrahedron, Vol. 47, 1991, 555-562
  • R f in the perfluorocarboxylic acid described in Non-Patent Document 1 and Non-Patent Document 2 is only a chemically stable perfluoroalkyl group such as CF, CF, CF, and CF.
  • the inventors of the present invention have prepared a reaction product having a fluorosulfonyl group retained when an electrode reaction is carried out between an ethylenic compound and a polyfluorocarboxylic acid having a fluorosulfonyl group. And a novel fluorine-containing compound having a fluorosulfonyl group, and a reaction of an electrode reaction between fluoroethylenes and polyfluorocarboxylic acid or a salt thereof.
  • the present invention provides the following inventions.
  • X, ⁇ , ⁇ Independently, an alkyl group, a closed alkyl group, a fluoroalkyl group, a hydroxyalkyl group, an alkoxycarbonyl group, a fluoroalkoxycarbonyl group, an alkylcarbonyloxy Or a fluoroalkylcarbonyloxy group having 1 to C carbon atoms: L0 ( ⁇ ), carboxyl group, cyan group, chlorine atom, fluorine atom or Hydrogen atom.
  • a group represented by the formula O is present between the carbon atom and carbon atom bond in the alkyl group.
  • a group represented by the formula C (O) —, a group represented by the formula C (O) 2 O 3, or a group represented by the formula oc (o) 1 may be inserted.
  • a group represented by the formula O may be inserted between the carbon atom and the carbon atom bond in Q.
  • the compound (2) is a compound (21) represented by the formula CR (SO F) (C (O) OH).
  • R a fluorine atom or a trifluoromethyl group.
  • n l, 2, or 3.
  • X a , Y a each independently an alkyl group, a closed alkyl group, a fluoroalkyl group, a hydroxyalkyl group, an alkoxy carbo group, a fluoro alkoxy carbo ol group, an alkyl carbo oxy group, or a fluoro It is a loalkylcarboxoxy group, which is a carbon number of 1 to: L0 group (A), carboxyl group, cyano group, chlorine atom, or hydrogen atom.
  • the alkyl group moiety having 2 or more carbon atoms which may contain a fluorine atom in the group (A).
  • a group represented by the formula O may be inserted between the carbon atom and the carbon atom bond in Q.
  • x al an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.
  • Y 31 an alkyl group, an alkoxy carbo group, or an alkyl carbo oxy group, a group having 1 to 10 carbon atoms (A a ) or a carboxyl group.
  • Y b , z b each independently an alkyl group, a closed alkyl group, a fluoroalkyl group, a hydroxyalkyl group, an alkoxycarbon group, a fluoroalkoxycarbol group, an alkyl A chlorocarboxoxy group or a fluoroalkylcarboxoxy group, which has a carbon number of 1 to: an L0 group (A), a carboxyl group, a cyano group, a chlorine atom, a fluorine atom, or a hydrogen atom;
  • a group represented by the formula O is present between the carbon atom and carbon atom bond in the alkyl group.
  • a group represented by the formula C (O) —, a group represented by the formula C (O) O 2, or a group represented by the formula oc (o) 1 may be inserted.
  • a group represented by the formula O may be inserted between the carbon atom and the carbon atom bond in Q.
  • Y bl an alkyl group, an alkoxycarbo group, or an alkylcarboxoxy group, a group having 1 to 10 carbon atoms (A b ) or a carboxyl group.
  • z bl a hydrogen atom or a fluorine atom.
  • a compound represented by the following formula (ll 2 ) (wherein Z 1 represents a hydrogen atom or a methyl group, R 1 represents a fluorine atom or a trifluoromethyl group.) O
  • a compound having a fluorosulfonyl group can be produced efficiently. Further, according to the present invention, a novel compound having a fluorosulfol group useful as a functional material such as a raw material of fluoromonomer and a surfactant is provided.
  • Electrode reaction is performed with the compound (2) represented by OH) or a salt thereof.
  • salt of the compound (2) and the compound (2) may be used alone or the compound (2) alone may be used alone (the following may be used) .
  • salt 2 is sodium salt of the compound (2): Q (SO F ) (C (O) 0 "Na +), or compound (2
  • X and Y forces are each independently an alkyl group, a closed alkyl group, a fluoroalkyl group, a hydroxyalkyl group, an alkoxycarbo group, A fluoroalkoxycarbol group, an alkylcarboxoxy group, or a fluoroalkylcarboxoxy group, which is a group having 1 to 10 carbon atoms (A), a carboxyl group, a cyano group, a chlorine atom, or
  • Z is a hydrogen atom
  • Y and Z are each independently an alkyl group, a closed alkyl group, a fluorinated alkyl group, a hydroxyalkyl group, an alkoxycarbo group, a fluoroalkoxycarbonyl Group, an alkylcarbonyloxy group or a fluoroalkylcarbonyloxy group, the group having 1 to C carbon atom
  • the group (A) may contain a fluorine atom, and when an alkyl group part having 2 or more carbon atoms is present, between the carbon atom and carbon atom bond in the alkyl group, OC ( O) — — C (O) O or — OC (O)-is inserted!
  • M in the compound (2) is preferably 1.
  • Q is particularly preferably a difluoromethylene group, preferably a perfluoroalkylene group having 1 to 3 carbon atoms!
  • the fluorosulfonyl group in the compound (2) is considered to be an unstable group in the electrode reaction, and the elimination of the fluorosulfonyl group was expected even in the electrode reaction in the present invention. Therefore, a compound (11), a compound (12), a compound (13) or a compound (14) which is a reaction product in which a fluorosulfol group is retained in an electrode reaction using the compound (2) can be obtained. Was an unexpected effect.
  • Compound (2) is preferably compound (21) represented by the formula CR (SO F) (C (O) OH).
  • the compound (211) represented by the formula CFR ⁇ SO F) (C (O) OH) is particularly preferred (the same applies hereinafter).
  • R and R 1 are a fluorine atom or a trifluoromethyl group, and a fluorine atom is particularly preferable.
  • n is preferably 1. In addition, when n is 1, the Rs may be the same or different.
  • Compound (21) and Compound (211) are each a fluorine-containing carboxylic acid having a fluorophore group at the a- position of the carboxyl group, and a reaction in which the ⁇ -position fluorosulfonyl group is retained in the electrode reaction. It was a particularly unexpected effect that the product was obtained.
  • compound (2) include CF (SO F) (C (O) OH) CF (CF) (SO F) (C (O)
  • the amount of the compound (3) relative to the total amount of the compound (2) and the salt of the compound (2) is preferably 0.25-1.
  • the current density in the electrode reaction is preferably 0.015 OA Zcm 2 from the viewpoint of reaction control and reaction efficiency.
  • the total amount of current in the electrode reaction is compound (2), compound (2) 0.1 to 5. OFZmol is preferable with respect to the total amount of the salt and the compound (3).
  • the reaction temperature in the electrode reaction is preferably -20 ° C to + 100 ° C, particularly preferably -20 ° C to + 60 ° C.
  • the reaction pressure in the electrode reaction may be atmospheric pressure, reduced pressure, or increased pressure, and atmospheric pressure is preferable.
  • the electrode reaction is preferably performed in the presence of a solvent which may be performed in the absence of a solvent or in the presence of a solvent.
  • the solvent is not particularly limited as long as it is a solvent that dissolves compound (3) and compound (2) or a salt thereof.
  • the solvent is preferably an aprotic solvent.
  • Non-protonic solvents include tetrahydrofuran, 1,2-dimethoxyethane, propylene carbonate, acetonitrile, dimethylformamide, dimethyl sulfoxide, dioxane and the like.
  • the electrode reaction is preferably performed in the presence of a supporting electrolyte.
  • the supporting electrolyte is particularly preferably an alcohol (methanol, ethanol, etc.) or water for which a protic solvent is preferred.
  • the reaction vessel used for the electrode reaction is preferably a known electrolytic cell. From the viewpoint of good insulation of the battery case, a glass battery case or a fluorine resin battery case is preferred V ,. Also, let the battery case function as an anode or cathode.
  • the anode and cathode in the electrode are preferably electrodes having a high acid reduction potential.
  • the electrode is particularly preferably an electrode made of platinum or a carbon material, preferably an electrode made of magnesium, copper, aluminum, platinum, and an electrode material made of at least one kind of electrode material that is also selected as a group force.
  • post-treatment is preferably performed to obtain compound (11), compound (12), compound (13), or compound (14) having a purity suitable for the purpose.
  • the post-treatment method include water washing, extraction, chromatography, distillation, recrystallization and the like.
  • the post-treatment may be performed by combining these two or more methods.
  • the electrode reaction may be performed by a batch method that is performed after the reaction substrate is collectively supplied to the battery case, or may be performed by a continuous reaction method that is performed while the reaction substrate is continuously supplied to the battery case.
  • the reason why the compound (13) is formed is considered to be that the radical (I 1 ) and the proton undergo a radical coupling reaction.
  • radical (2 1 ) and radical (I 1 ) undergo a radical coupling reaction.
  • a compound (3 a ) represented by the formula CX a Y a CH,
  • X a in the compound (3 a ) is preferably an alkyl group having 1 to carbon atoms or a hydrogen atom, particularly preferably a methyl group or a hydrogen atom, from the viewpoint of reaction yield.
  • Y a in the compound (3 a ) is an alkyl group, an alkoxy carbo yl group, or an alkyl carbo oxy group in which the group (A) or the carboxyl group is preferable from the viewpoint of the reaction yield, and has 1 carbon atom.
  • Methoxyca is particularly preferred for groups of ⁇ 10 (A a ) or carboxyl groups. Most preferred is a sulfonyl group, a hydroxymethyl group or a carboxy group.
  • the group (A a ) contains a fluorine atom! /, May! /, An alkyl group part having 2 or more carbon atoms is present, and a carbon atom in the alkyl group is bonded between carbon atom bonds, and OC (O) C
  • the number of inserted groups is preferably 1 to 4, particularly preferably 1.
  • the number of carbon atoms in the group (A a ) is preferably 2 to 10 and particularly preferably 2 to 8.
  • Preferred embodiments of Y 3 include C (0) OCH, -CH OH CH OC (0) CH,-
  • the compound (2) is particularly preferably the compound (211) preferred by the compound (21).
  • the compound (3 a ) and the compound (2) or a salt thereof are electrode-reacted to produce the following compound (ll a ), the following compound (12 a ), and the following compound:
  • An embodiment of obtaining any one compound selected from ( 13a ) is mentioned.
  • the configuration of compound ( 12a ) may be either cis or trans! /.
  • the compound (3 a ) in which X a is a group (A), a carboxyl group, a cyano group, or a chlorine atom is used, the compound (12 a ) and the compound (13 a ) are Since the compound can be obtained with high selectivity, it is preferable to obtain the compound (12 a ) or the compound (13 a ).
  • the compound (3 a ) in which X a is a hydrogen atom is used, the compound (1 l a ) can be obtained with high selectivity. Therefore, it is preferable to obtain the compound (ll a ).
  • the amount of the compound (3 a ) relative to the total amount of the compound (2) and the salt of the compound (2) is preferably 0.4 to 1.0 times monoreca, preferably 0.5 to 0.8. Double monore power is especially preferred!
  • the current density in the electrode reaction from the viewpoint of reaction control and reaction efficiency, 0. 01 ⁇ 5.
  • OA Zcm 2 is preferably tool 0. 05 ⁇ 2. 5AZcm 2 more preferably tool 0. 1 ⁇ 1. OAZcm 2 Is particularly preferred.
  • OFZmol is preferred instrument 0.2 ⁇ 2.5 F / mol force, more preferably 0.3 to 1. OFZmol is particularly preferred.
  • the above conditions are preferably applied to the reaction temperature, reaction pressure, presence / absence of solvent, type of reactor, and type of anode and cathode in the electrode reaction.
  • the reason why the compound (ll a ), the compound (12 a ), or the compound (13 a ) is efficiently produced is not necessarily clear, but is considered to be due to the following reasons, respectively. It is done.
  • the reason why the compound (ll a ) is generated is that the electrode ( 1 ) generates a radical (2 1 ) due to the electrode reaction, and then the radical (2 1 ) is converted into a radical (2 a) into the compound (3 a ). This is thought to be because the following radical (1 ⁇ was generated by the addition reaction, and two radicals (I 31 ) were further radical-coupled.
  • the following compound (ll al ), the following compound (12 al ), and the following compound (13 al ) are prepared by subjecting the compound (3 al ) and the compound (21) or a salt thereof to an electrode reaction.
  • it is a method for producing any one selected compound.
  • the configuration of the compound (12 al ) may be cis or trans! /. [0050] [Chemical 16] x a1
  • (211) or a salt thereof is particularly preferably a method for producing any one compound selected from the following compounds (11, the following compounds (12), and the following compounds (13 1 ).
  • the configuration of the compound (12 1 ) may be cis or trans.
  • the compound (II 1 ) is a characteristic novel compound having two fluorosulfol groups and two groups represented by the formula C (0) OZ 1 .
  • the compound (II 1 ) is useful as a functional material such as a raw material for fluoromonomers and a surfactant.
  • Specific examples of the compound (II 1 ) include the following compounds.
  • the CH 3 CH 3 compound (12 1 ) is a novel ethylenic compound having a characteristic structure having a fluorosulfol group and a group represented by the formula C (O) OZ 1 .
  • the compound (12 1 ) is useful as a functional material such as a fluoromonomer or a surfactant. Specific examples of the compound (12 1 ) include the following compounds.
  • the compound (13 1 ) is a novel compound having a characteristic structure having a fluorosulfol group and a group represented by the formula C (O) OZ 1 .
  • the compound (13 1 ) is useful as a functional material such as a raw material for fluoromonomers and a surfactant. Specific examples of the compound (13 1 ) include the following compounds.
  • Y b in the compound (3 b ) is an alkyl group, an alkoxy carbo yl group, or an alkyl carbo oxy group in which the group (A) or the carboxyl group is preferable from the viewpoint of the reaction yield, A methoxycarbonyl group, a hydroxymethyl group or a carboxy group is most preferred, and a group having 1 to 10 carbon atoms (A b ) or a carboxyl group is particularly preferred.
  • the group (A b ) may contain a fluorine atom, but there may be an alkyl group part having 2 or more carbon atoms, and a carbon atom in the alkyl group may be bonded with an O 1 or a C (O ) —, 1 C (O) 0—, or 1 OC (O) — is inserted, the number of inserted groups is preferably 1 to 4, and particularly preferably 1. When these groups are inserted between carbon atoms in carbon atoms in the alkyl group, the number of carbon atoms in the group (A bl ) is preferably from 2 to 10, and particularly preferably from 2 to 8.
  • Preferred embodiments of Y b include one C (0) OCH, one CH OH, one CH OC (0) CH,-
  • Z b in the compound (3 b ) is preferably a hydrogen atom or a fluorine atom.
  • the compound (3 b ) was oc fluoroethylenes, and the carbon atom in the compound (3 b ) had a low activity, so it was considered that no electrode reaction occurred. Therefore, it is an unexpected effect that the compound (3 b ) undergoes an electrode reaction, and the formation of the compound (14 b ) at a high selectivity in the electrode reaction is a particularly unexpected effect. It was.
  • Compound (2) is particularly preferably compound (211), more preferably compound (21).
  • the compound (3 b ) and the compound (2) or a salt thereof are electrode-reacted to produce the following compound (ll b ), the following compound (12 b ), and the following compound. Any one compound selected from ( 14b ) is obtained.
  • the configuration of the compound ( 12a ) may be cis type or trans type.
  • the amount of the compound (3 b ) relative to the total amount of the salt of the compound (2) and the compound (2) is preferably 0.25 to 0.5 times the monoreaction power, preferably 0.3 to 0. 4 times monore power is especially preferred!
  • the current density in the electrode reaction is preferably 0.01 to 5.
  • OA / cm 2 from the viewpoint of reaction control and reaction efficiency, and particularly preferably 0.1 to 1.
  • OA / cm 2 The total amount of electric current in the electrode reaction is preferably 0.1 to 5.
  • the above conditions are preferably applied to the reaction temperature, reaction pressure, presence / absence of solvent, type of reactor, and type of anode and cathode in the electrode reaction.
  • the reason why the compound (ll b ), the compound (12 b ), or the compound (14 b ) is efficiently produced is not necessarily clear, but is considered to be due to the following reasons, respectively.
  • the following compound (ll bl ), the following compound (12 bl ), and the following compound (14 bl ) are prepared by subjecting the compound (3 bl ) to the compound (21) or a salt thereof.
  • the method for producing any one compound selected from (1) is preferred.
  • the configuration of the compound (12 bl ) may be cis or trans.
  • the compound (14 bl ) is preferably obtained because the compound (14 bl ) can be obtained with high selectivity.
  • the method is a method for producing one kind of compound.
  • the configuration of the compound (12 2 ) may be cis or trans. In the production method, since the compound (14 2 ) can be obtained with high selectivity, it is preferable to obtain the compound (14 2 ).
  • the compound (ll 2 ) is a novel fluorine-containing compound having a characteristic structure having a fluorosulfol group and a group represented by the formula ⁇ ⁇ ⁇ 1 .
  • the compound (II 2 ) is useful as a functional material such as a raw material for fluoromonomers and a surfactant.
  • the compound (12 2 ) has a fluorosulfol group and the formula C (O) A novel ethylenic fluorine-containing compound having a characteristic structure having a group represented by OZ 1 .
  • the compound (12 2 ) is useful as a functional material such as a fluoromonomer or a surfactant. Specific examples of the compound (12 2 ) include the following compounds.
  • Compound (14 2 ) has two fluorosulfol groups and It is a unique novel compound having a group represented by one formula (1).
  • the compound (14 2 ) is useful as a functional material such as a raw material for fluoromonomers and a surfactant. Specific examples of the compound (14 2 ) include the following compounds.
  • GC gas chromatography and GC-M for gas chromatography mass spectrometry S
  • EI—MS electron ionization mass spectrometry
  • CI MS chemical ionization mass spectrometry
  • GC yield for the yield determined from the peak area ratio of GC
  • mF millifaradaic
  • a stirring blade was installed in a battery tank (made of glass, internal volume 50 mL) equipped with a refrigerant distribution jacket and a discharge valve at the bottom, and 0 ° C refrigerant was circulated.
  • Two platinum nets (length 3 cm x width 3 cm, 80 mesh) were installed in the battery case as anodes and anodes so as not to interfere with the stirring blades.
  • the platinum mesh was used in a polyethylene mesh bag to prevent short circuit.
  • Acetonitrile (30 mL) as a solvent and ion-exchanged water (5 mL) as a supporting electrolyte were placed in a battery case.
  • a stirring blade was installed in a battery tank (made of glass, internal volume 50 mL) equipped with a refrigerant distribution jacket and a discharge valve at the bottom, and 0 ° C refrigerant was circulated.
  • Two platinum nets (length 3 cm x width 3 cm, 80 mesh) were installed in the battery case as anodes and anodes so as not to interfere with the stirring blades.
  • the platinum mesh was used in a polyethylene mesh bag to prevent short circuit.
  • Acetonitrile (30 mL) as a solvent and ion-exchanged water (5 mL) as a supporting electrolyte were placed in a battery case.
  • fluorine-containing compounds having various structures particularly compounds having a fluorosulfol group can be easily produced.
  • the compound of the present invention is useful as a functional material such as a raw material of a fluoromonomer, a fluoromonomer, and a surfactant.

Abstract

The object is to provide a process for production of a compound having a fluorosulfonyl group and a novel compound. Thus, disclosed is a process for producing any one selected from the compounds (11) to (14) shown below. The process comprises the step of subjecting a compound: CXY=CHZ and a compound: Q(SO2F)m(C(O)OH) or a salt thereof to an electrode reaction (wherein symbols are as follows: X, Y and Z independently represent a group (A) selected from an alkyl group, a chloroalkyl group, a fluoroalkyl group, a hydroxyalkyl group, an alkoxycarbonyl group, a fluoroalkoxycarbonyl group, an alkylcarbonyloxy group and a fluoroalkylcarbonyloxy group each having 1-10 carbon atoms, a crboxyl group, a cyano group, or a chlorine, fluorine or hydrogen atom, provided that, when the group (A) contains an alkyl group moiety having 2 or more carbon atoms which may contain a fluorine atom, a group represented by the formula -O-, -C(O)-, -C(O)O- or -OC(O)- may be inserted between a carbon-carbon bond in the alkyl group; Q represents a polyfluoro saturated hydrocarbon group having 1-10 carbon atoms and has a valency of (m+1), provided that a group represented by the formula -O- may be inserted between a carbon-carbon bond in Q; and m represents 1, 2 or 3. Also disclosed is a compound (111), (112), (121), (122), (131) or (142) shown below, wherein R1 represents a fluorine atom or a trifluoromethyl group; and Z1 represents a hydrogen atom or a methyl group.

Description

フルォロスルホニル基を有する化合物の製造方法、および新規化合物 技術分野  TECHNICAL FIELD The present invention relates to a method for producing a compound having a fluorosulfonyl group and a novel compound.
[0001] 本発明は、フルォロスルホニル基を有する化合物の製造方法、および新規化合物 に関する。  The present invention relates to a method for producing a compound having a fluorosulfonyl group and a novel compound.
背景技術  Background art
[0002] エチレン性化合物とペルフルォロアルキルカルボン酸との電極反応として、非特許 文献 1および非特許文献 2には、式 CHW=CHで表される化合物と式 RfC (0) OH [0002] As an electrode reaction between an ethylenic compound and a perfluoroalkylcarboxylic acid, Non-Patent Document 1 and Non-Patent Document 2 include a compound represented by the formula CHW = CH and a formula R f C (0) OH.
2  2
で表される化合物とを電極反応させて下記化合物 (PP1)、下記化合物 (PP2)、また は下記化合物（PP3)を得たと記載されている（ただし、 Wは— C (0) OCH 、— C H It is described that the following compound (P P 1), the following compound (P P 2), or the following compound (P P 3) was obtained by electrode reaction with a compound represented by the formula (where W is —C (0) OCH, — CH
3 3 7 または一 CNを、 Rfは一 CF 、 一 C F 、 一 C Fまたは一 C F を、示す。；)。 3 3 7 or 1 CN, R f indicates 1 CF, 1 CF, 1 CF or 1 CF. ;).
3 2 5 3 7 7 15  3 2 5 3 7 7 15
[0003] [化 1]  [0003] [Chemical 1]
Figure imgf000004_0001
Figure imgf000004_0001
また、非特許文献 3には、 CH (C (0) NH ) =CHと CF C (O) OHを電極反応させ  Non-Patent Document 3 describes that CH (C (0) NH) = CH and CF C (O) OH are reacted by an electrode.
2 2 3  2 2 3
て下記化合物（PP4)を得たと記載されて!ヽる。 The following compound (P P 4) was obtained.
[0004] [化 2]
Figure imgf000004_0002
非特許文献 1 : Chem. Soc. , Chem. Comm. , 1974, 323- 324 [0004] [Chemical 2]
Figure imgf000004_0002
Non-Patent Document 1: Chem. Soc., Chem. Comm., 1974, 323-324
非特許文献 2 :J. Chem. Soc. , Perkin Trans. I, 1978, 202— 209  Non-Patent Document 2: J. Chem. Soc., Perkin Trans. I, 1978, 202—209
非特許文献 3 : Tetrahedron, Vol. 47, 1991, 555- 562  Non-Patent Document 3: Tetrahedron, Vol. 47, 1991, 555-562
発明の開示  Disclosure of the invention
発明が解決しょうとする課題 [0005] 非特許文献 1および非特許文献 2に記載のペルフルォロカルボン酸における Rfは 、 CF、 C F、 C F、 C F 等の化学的に安定なペルフルォロアルキル基のみであProblems to be solved by the invention [0005] R f in the perfluorocarboxylic acid described in Non-Patent Document 1 and Non-Patent Document 2 is only a chemically stable perfluoroalkyl group such as CF, CF, CF, and CF.
3 2 5 3 7 7 15 3 2 5 3 7 7 15
る。したがって、エチレン性化合物と、 CF (C (O) OH) (SO F)のようなフルォロスル  The Therefore, ethylenic compounds and fluorosul such as CF (C (O) OH) (SO F)
2 2  twenty two
ホニル基を有し、化学的に不安定なポリフルォロカルボン酸とを電極反応させる試み は、その成否を含めて全く未知である。  Attempts to electrode-react with a chemically unstable polyfluorocarboxylic acid having a phonyl group, including its success or failure, are completely unknown.
また、フッ素原子を有するエチレン性ィ匕合物とポリフルォロカルボン酸を電極反応さ せる試みは、その成否を含めて全く未知である。  In addition, attempts to make an electrode reaction between an ethylenic compound having a fluorine atom and polyfluorocarboxylic acid are completely unknown including its success or failure.
課題を解決するための手段  Means for solving the problem
[0006] 本発明者らは、エチレン性ィ匕合物類とフルォロスルホニル基を有するポリフルォロ カルボン酸とを電極反応させた場合にはフルォロスルホニル基が保持された反応生 成物が得られること、 a フルォロエチレン類とポリフルォロカルボン酸またはその塩 とが電極反応すること、および、フルォロスルホニル基を有する新規含フッ素化合物 を見出した。  [0006] The inventors of the present invention have prepared a reaction product having a fluorosulfonyl group retained when an electrode reaction is carried out between an ethylenic compound and a polyfluorocarboxylic acid having a fluorosulfonyl group. And a novel fluorine-containing compound having a fluorosulfonyl group, and a reaction of an electrode reaction between fluoroethylenes and polyfluorocarboxylic acid or a salt thereof.
[0007] すなわち、本発明は下記の発明を提供する。  That is, the present invention provides the following inventions.
< 1 > 式 CXY=CHZで表される化合物（3)と、式 Q (SO F) (C (O) OH)で表さ  <1> The compound (3) represented by the formula CXY = CHZ and the formula Q (SO F) (C (O) OH)
2 m  2 m
れる化合物（2)またはその塩とを電極反応させる、下式（11)で表される化合物、下 式（ 12)で表される化合物、下式（ 13)で表される化合物および下式（14)で表される 化合物から選ばれるいずれか 1種の化合物の製造方法。  A compound represented by the following formula (11), a compound represented by the following formula (12), a compound represented by the following formula (13), and the following formula (2): A process for producing any one compound selected from the compounds represented by 14):
[0008] [化 3] [0008] [Chemical 3]
X X
Y— C— CHZQ(S02F)m X X X Y— C— CHZQ (S0 2 F) m XXX
I \ \ \ I \ \ \
Y-C-CHZQ(S02F)m ^^CZQiSOzF) CH— CHZQ(S02F)m Y— C-CHZQ(S02F)n X Y Y7 Q(S02F)m YC-CHZQ (S0 2 F) m ^^ CZQiSOzF) CH— CHZQ (S0 2 F) m Y— C-CHZQ (S0 2 F) n XYY 7 Q (S0 2 F) m
(11) (12) (13) (14) 式中の記号は、下記の意味を示す。  (11) (12) (13) (14) The symbols in the formulas have the following meanings.
[0009] X、 Υ、 Ζ：それぞれ独立に、アルキル基、クロ口アルキル基、フルォロアルキル基、ヒ ドロキシアルキル基、アルコキシカルボ-ル基、フルォロアルコキシカルボ-ル基、ァ ルキルカルボニルォキシ基、またはフルォロアルキルカルボニルォキシ基であって、 炭素数 1〜： L0の基 (Α)、カルボキシル基、シァノ基、塩素原子、フッ素原子もしくは 水素原子。 [0009] X, Υ, Ζ: Independently, an alkyl group, a closed alkyl group, a fluoroalkyl group, a hydroxyalkyl group, an alkoxycarbonyl group, a fluoroalkoxycarbonyl group, an alkylcarbonyloxy Or a fluoroalkylcarbonyloxy group having 1 to C carbon atoms: L0 (Α), carboxyl group, cyan group, chlorine atom, fluorine atom or Hydrogen atom.
ただし、基 (A)中にフッ素原子を含んでいてもよい炭素数 2以上のアルキル基部分 が存在する場合、該アルキル基中の炭素原子 炭素原子結合間には、式 O で 表される基、式 C (O)—で表される基、式 C (O) O で表される基、または式 oc(o)一で表される基が挿入されていてもよい。  However, when an alkyl group part having 2 or more carbon atoms that may contain a fluorine atom is present in the group (A), a group represented by the formula O is present between the carbon atom and carbon atom bond in the alkyl group. A group represented by the formula C (O) —, a group represented by the formula C (O) 2 O 3, or a group represented by the formula oc (o) 1 may be inserted.
Q：炭素数 1〜10の（m+ 1)価のポリフルォロ飽和炭化水素基。  Q: (m + 1) -valent polyfluoro saturated hydrocarbon group having 1 to 10 carbon atoms.
ただし、 Q中の炭素原子 炭素原子結合間には、式 O で表される基が挿入さ れていてもよい。  However, a group represented by the formula O may be inserted between the carbon atom and the carbon atom bond in Q.
m: l、 2、または 3。  m: l, 2, or 3.
[0010] < 2> 化合物（2)が、式 CR (SO F) (C (O) OH)で表される化合物（21)であ  [0010] <2> The compound (2) is a compound (21) represented by the formula CR (SO F) (C (O) OH).
3-n 2 n  3-n 2 n
る < 1 >に記載の製造方法。  <1> The production method according to <1>.
ただし、式中の記号は、下記の意味を示す。  However, the symbol in a formula shows the following meaning.
R:フッ素原子またはトリフルォロメチル基。  R: a fluorine atom or a trifluoromethyl group.
n: l、 2、または 3。  n: l, 2, or 3.
[0011] < 3 > 式 CXaYa=CHで表される化合物（3a)と、化合物（2)またはその塩とを電 [0011] <3> A compound (3 a ) represented by the formula CX a Y a = CH and a compound (2) or a salt thereof are
2  2
極反応させる下式（l la)で表される化合物、下式（12a)で表される化合物、および下 式（13a)で表される化合物から選ばれるいずれか 1種の化合物の製造方法。 Production of any one compound selected from a compound represented by the following formula (ll a ), a compound represented by the following formula (12 a ), and a compound represented by the following formula (13 a ) Method.
[0012] [化 4] [0012] [Chemical 4]
Figure imgf000006_0001
Figure imgf000006_0001
(11 a) (12a) (13a) 式中の記号は、下記の意味を示す。 (11 a ) (12 a ) (13 a ) The symbols in the formula have the following meanings.
Xa、 Ya:それぞれ独立に、アルキル基、クロ口アルキル基、フルォロアルキル基、ヒド ロキシアルキル基、アルコキシカルボ-ル基、フルォロアルコキシカルボ-ル基、アル キルカルボ-ルォキシ基、またはフルォロアルキルカルボ-ルォキシ基であって、炭 素数 1〜： L0の基 (A)、カルボキシル基、シァノ基、塩素原子、もしくは水素原子。 ただし、基 (A)中にフッ素原子を含んでいてもよい炭素数 2以上のアルキル基部分 が存在する場合、該アルキル基中の炭素原子 炭素原子結合間には、式 o—で 表される基、式 c(o)—で表される基、式 c (0) 0—で表される基、または式 oc(o)一で表される基が挿入されていてもよい。 X a , Y a : each independently an alkyl group, a closed alkyl group, a fluoroalkyl group, a hydroxyalkyl group, an alkoxy carbo group, a fluoro alkoxy carbo ol group, an alkyl carbo oxy group, or a fluoro It is a loalkylcarboxoxy group, which is a carbon number of 1 to: L0 group (A), carboxyl group, cyano group, chlorine atom, or hydrogen atom. Provided that the alkyl group moiety having 2 or more carbon atoms, which may contain a fluorine atom in the group (A). Is present, a carbon atom in the alkyl group, a carbon atom bond, a group represented by the formula o—, a group represented by the formula c (o) —, and a formula c (0) 0— Or a group represented by the formula oc (o) 1 may be inserted.
Q：炭素数 1〜10の（m+ 1)価のポリフルォロ飽和炭化水素基。  Q: (m + 1) -valent polyfluoro saturated hydrocarbon group having 1 to 10 carbon atoms.
ただし、 Q中の炭素原子 炭素原子結合間には、式 O で表される基が挿入さ れていてもよい。  However, a group represented by the formula O may be inserted between the carbon atom and the carbon atom bond in Q.
m: l、 2、または 3。  m: l, 2, or 3.
[0013] <4> 化合物（3a)力 式 CXalYal = CH 2で表される化合物（3al)である < 3 >に 記載の製造方法。 <4> The production method according to <3>, wherein the compound (3 a ) is a compound (3 al ) represented by the formula CX al Y al = CH 2.
式中の記号は、下記の意味を示す。  The symbols in the formula have the following meanings.
xal:炭素数 1〜10のアルキル基または水素原子。 x al : an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.
Y31 :アルキル基、アルコキシカルボ-ル基、またはアルキルカルボ-ルォキシ基で あって、炭素数 1〜10の基 (Aa)もしくはカルボキシル基。 Y 31 : an alkyl group, an alkoxy carbo group, or an alkyl carbo oxy group, a group having 1 to 10 carbon atoms (A a ) or a carboxyl group.
ただし、基 (Aa)中に炭素数 2以上のアルキル基部分が存在する場合、該アルキル 基中の炭素原子-炭素原子結合間には、式— 0—で表される基、式— c(o)o で 表される基、または式 OC (O)—で表される基が挿入されていてもよい。 However, when an alkyl group having 2 or more carbon atoms is present in the group (A a ), a group represented by the formula —0—, a formula —c, is present between the carbon atom-carbon atom bonds in the alkyl group. (o) A group represented by o or a group represented by the formula OC (O) — may be inserted.
[0014] < 5 > 化合物（2)が化合物（21)である < 3 >または <4>に記載の製造方法。 [0014] <5> The production method according to <3> or <4>, wherein the compound (2) is the compound (21).
< 6 > 式 CFYb=CHZbで表される化合物（3b)と、化合物（2)またはその塩とを電 極反応させる下式（l lb)で表される化合物、下式（12b)で表される化合物、および下 式（ 14b)で表される化合物から選ばれる!/ヽずれか 1種の化合物の製造方法。 <6> A compound represented by the following formula (ll b ), wherein the compound (3 b ) represented by the formula CFY b = CHZ b and the compound (2) or a salt thereof is subjected to an electrode reaction, the following formula (12 b ) And a compound represented by the following formula ( 14b )! / A method for producing one kind of compound.
[0015] [化 5] [0015] [Chemical 5]
Yb— C-CHZbQ(S02F)n Y b — C-CHZ b Q (S0 2 F) n
Yb— C -CHZbQ(S02F)n Y b — C -CHZ b Q (S0 2 F) n
Figure imgf000007_0001
Figure imgf000007_0001
(11 ") (12b) (14b) 式中の記号は、下記の意味を示す。 (11 ") ( 12b ) ( 14b ) The symbols in the formula have the following meanings.
Yb、 zb:それぞれ独立に、アルキル基、クロ口アルキル基、フルォロアルキル基、ヒド ロキシアルキル基、アルコキシカルボ-ル基、フルォロアルコキシカルボ-ル基、アル キルカルボ-ルォキシ基、またはフルォロアルキルカルボ-ルォキシ基であって、炭 素数 1〜： L0の基 (A)、カルボキシル基、シァノ基、塩素原子、フッ素原子、もしくは水 素原子。 Y b , z b : each independently an alkyl group, a closed alkyl group, a fluoroalkyl group, a hydroxyalkyl group, an alkoxycarbon group, a fluoroalkoxycarbol group, an alkyl A chlorocarboxoxy group or a fluoroalkylcarboxoxy group, which has a carbon number of 1 to: an L0 group (A), a carboxyl group, a cyano group, a chlorine atom, a fluorine atom, or a hydrogen atom;
ただし、基 (A)中にフッ素原子を含んでいてもよい炭素数 2以上のアルキル基部分 が存在する場合、該アルキル基中の炭素原子 炭素原子結合間には、式 O で 表される基、式 C(O)—で表される基、式 C (O)O で表される基、または式 oc(o)一で表される基が挿入されていてもよい。  However, when an alkyl group part having 2 or more carbon atoms that may contain a fluorine atom is present in the group (A), a group represented by the formula O is present between the carbon atom and carbon atom bond in the alkyl group. In addition, a group represented by the formula C (O) —, a group represented by the formula C (O) O 2, or a group represented by the formula oc (o) 1 may be inserted.
Q：炭素数 1〜10の（m+ 1)価のポリフルォロ飽和炭化水素基。  Q: (m + 1) -valent polyfluoro saturated hydrocarbon group having 1 to 10 carbon atoms.
ただし、 Q中の炭素原子 炭素原子結合間には、式 O で表される基が挿入さ れていてもよい。  However, a group represented by the formula O may be inserted between the carbon atom and the carbon atom bond in Q.
m:l、 2、または 3。  m: l, 2, or 3.
[0016] <7> 化合物（3b)力 式 CFYbl = CHZblで表される化合物（3bl)である <6>に 記載の製造方法。 <7> The production method according to <6>, wherein the compound (3 b ) is a compound (3 bl ) represented by the formula CFY bl = CHZ bl .
式中の記号は、下記の意味を示す。  The symbols in the formula have the following meanings.
Ybl:アルキル基、アルコキシカルボ-ル基、またはアルキルカルボ-ルォキシ基で あって、炭素数 1〜10の基 (Ab)もしくはカルボキシル基。 Y bl : an alkyl group, an alkoxycarbo group, or an alkylcarboxoxy group, a group having 1 to 10 carbon atoms (A b ) or a carboxyl group.
ただし、基 (Ab)中に炭素数 2以上のアルキル基部分が存在する場合、該アルキル 基中の炭素原子-炭素原子結合間には、式— 0—で表される基、式— c(o)o で 表される基、または式 OC(O)—で表される基が挿入されていてもよい。 However, when an alkyl group having 2 or more carbon atoms is present in the group (A b ), a group represented by the formula —0—, a formula —c, is present between the carbon atom-carbon atom bonds in the alkyl group. (o) A group represented by o or a group represented by the formula OC (O) — may be inserted.
zbl：水素原子またはフッ素原子。 z bl : a hydrogen atom or a fluorine atom.
[0017] <8> 化合物（2)が化合物（21)である <6>または <7>に記載の製造方法。 <8> The production method according to <6> or <7>, wherein the compound (2) is the compound (21).
<9> 下式（II1)で表される化合物（ただし、 X1および Z1はそれぞれ独立に、水 素原子またはメチル基を、 R1はフッ素原子またはトリフルォロメチル基を、示す。 )o <9> Compound represented by the following formula (II 1 ) (X 1 and Z 1 each independently represent a hydrogen atom or a methyl group, and R 1 represents a fluorine atom or a trifluoromethyl group. ) o
[0018] [化 6] [0018] [Chemical 6]
Figure imgf000008_0001
<10> 下式（ll2)で表される化合物（ただし、 Z1は水素原子またはメチル基を、 R1はフッ素原子またはトリフルォロメチル基を、示す。 )o
Figure imgf000008_0001
<10> A compound represented by the following formula (ll 2 ) (wherein Z 1 represents a hydrogen atom or a methyl group, R 1 represents a fluorine atom or a trifluoromethyl group.) O
[0019] [化 7]  [0019] [Chemical 7]
∑10(0)C-C-CH2CFR1S02F ∑ 1 0 (0) CC-CH 2 CFR 1 S0 2 F
(112)(11 2 )
10(0)C— C一 CH2CFR1S02F 10 (0) C—C 1 CH 2 CFR 1 S0 2 F
<11> 下式（121)で表される化合物（ただし、 X1および Z1はそれぞれ独立に、水 素原子またはメチル基を、 R1はフッ素原子またはトリフルォロメチル基を、示す。 )o<11> Compound represented by the following formula (12 1 ) (X 1 and Z 1 each independently represent a hydrogen atom or a methyl group, and R 1 represents a fluorine atom or a trifluoromethyl group. ) o
[0020] [化 8]
Figure imgf000009_0001
[0020] [Chemical 8]
Figure imgf000009_0001
<12> 下式（122)で表される化合物（ただし、 Z1は水素原子またはメチル基を、 R1はフッ素原子またはトリフルォロメチル基を、示す。 )o <12> A compound represented by the following formula (12 2 ) (wherein Z 1 represents a hydrogen atom or a methyl group, R 1 represents a fluorine atom or a trifluoromethyl group) o
[0021] [化 9]
Figure imgf000009_0002
[0021] [Chemical 9]
Figure imgf000009_0002
[0022] <13> 下式（131)で表される化合物（ただし、 X1および Z1はそれぞれ独立に、水 素原子またはメチル基を、 R1はフッ素原子またはトリフルォロメチル基を、示す。 )o[0022] <13> A compound represented by the following formula (13 1 ) (wherein X 1 and Z 1 are each independently a hydrogen atom or a methyl group, and R 1 is a fluorine atom or a trifluoromethyl group. ) O
[0023] [化 10]
Figure imgf000009_0003
[0023] [Chemical 10]
Figure imgf000009_0003
[0024] <14> 下式（142)で表される化合物（ただし、 Z1は水素原子またはメチル基を、 R1はフッ素原子またはトリフルォロメチル基を、示す。 )o <14> A compound represented by the following formula (14 2 ) (wherein Z 1 represents a hydrogen atom or a methyl group, R 1 represents a fluorine atom or a trifluoromethyl group) o
[0025] [化 11]
Figure imgf000010_0001
発明の効果 [0025] [Chemical 11]
Figure imgf000010_0001
The invention's effect
[0026] 本発明の製造方法によれば、フルォロスルホニル基を有する化合物を効率的に製 造できる。また本発明によれば、フルォロモノマーの原料、界面活性剤等の機能性 材料として有用なフルォロスルホ-ル基を有する新規ィ匕合物が提供される。  [0026] According to the production method of the present invention, a compound having a fluorosulfonyl group can be produced efficiently. Further, according to the present invention, a novel compound having a fluorosulfol group useful as a functional material such as a raw material of fluoromonomer and a surfactant is provided.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0027] 本明細書における、基中の記号は特に記載しない限り前記と同義である。また、本 明細書において、式（1)で表される化合物をィ匕合物（1)と、式（I1)で表されるラジカ ルをラジカル（I1)と、式 O で表される基を単に O と、記すことがある。他の化 合物と、他のラジカルと、他の基も、同様に記す。 [0027] In the present specification, symbols in groups are as defined above unless otherwise specified. In this specification, the compound represented by the formula (1) is represented by the compound (1), the radical represented by the formula (I 1 ) is represented by the radical (I 1 ), and the formula O. This group is sometimes simply written as O. Other compounds, other radicals, and other groups are similarly described.
本発明においては、式 CXY=CHZで表される化合物（3)と、式 Q (SO F) (C (0  In the present invention, the compound (3) represented by the formula CXY = CHZ and the formula Q (SO F) (C (0
2 m 2 m
) OH)で表される化合物（2)またはその塩とを電極反応させる。 ) Electrode reaction is performed with the compound (2) represented by OH) or a salt thereof.
本発明においては、化合物（2)およびィ匕合物（2)の塩を用いてもよぐ化合物（2) のみを用いてもよぐ化合物（2)の塩のみを用いてもよい（以下同様。 ) 0化合物（2) の塩は、化合物（2)のナトリウム塩： Q (SO F) (C (O) 0"Na+)、または、化合物（2 In the present invention, the salt of the compound (2) and the compound (2) may be used alone or the compound (2) alone may be used alone (the following may be used) . Similarly) 0 compound (salt 2) is sodium salt of the compound (2): Q (SO F ) (C (O) 0 "Na +), or compound (2
2 m  2 m
)のカリウム塩： Q (SO F) (C (O) 0"K+)が好まし!/ヽ。 ) Potassium salt: Q (SO F) (C (O) 0 "K + ) is preferred! / ヽ.
2 m  2 m
[0028] 化合物（3)における X、 Yおよび Zの好まし 、態様としては、 Xおよび Y力 それぞれ 独立に、アルキル基、クロ口アルキル基、フルォロアルキル基、ヒドロキシアルキル基 、アルコキシカルボ-ル基、フルォロアルコキシカルボ-ル基、アルキルカルボ-ル ォキシ基、またはフルォロアルキルカルボ-ルォキシ基であって、炭素数 1〜10の基 (A)、カルボキシル基、シァノ基、塩素原子、もしくは水素原子であり、 Zが水素原子 である態様、 Yおよび Zが、それぞれ独立に、アルキル基、クロ口アルキル基、フルォ 口アルキル基、ヒドロキシアルキル基、アルコキシカルボ-ル基、フルォロアルコキシ カルボニル基、アルキルカルボニルォキシ基、またはフルォロアルキルカルボニルォ キシ基であって、炭素数 1〜： L0の基 (A)、カルボキシル基、シァノ基、塩素原子、フッ 素原子、もしくは水素原子であり、 Xがフッ素原子である態様が挙げられる。 [0029] ただし、基 (A)中にフッ素原子を含んで 、てもよ 、炭素数 2以上のアルキル基部分 が存在する場合、該アルキル基中の炭素原子 炭素原子結合間には、 O C (O)— — C (O) O 、または― OC (O) -が挿入されて!、てもよ!/ヽ。 [0028] Preference is given to X, Y and Z in the compound (3). As an embodiment, X and Y forces are each independently an alkyl group, a closed alkyl group, a fluoroalkyl group, a hydroxyalkyl group, an alkoxycarbo group, A fluoroalkoxycarbol group, an alkylcarboxoxy group, or a fluoroalkylcarboxoxy group, which is a group having 1 to 10 carbon atoms (A), a carboxyl group, a cyano group, a chlorine atom, or An embodiment wherein Z is a hydrogen atom, Y and Z are each independently an alkyl group, a closed alkyl group, a fluorinated alkyl group, a hydroxyalkyl group, an alkoxycarbo group, a fluoroalkoxycarbonyl Group, an alkylcarbonyloxy group or a fluoroalkylcarbonyloxy group, the group having 1 to C carbon atoms: L0 (A), carboxyl group, Anomoto, a chlorine atom, a fluorine atom or a hydrogen atom, include embodiments wherein X is fluorine atom. [0029] However, the group (A) may contain a fluorine atom, and when an alkyl group part having 2 or more carbon atoms is present, between the carbon atom and carbon atom bond in the alkyl group, OC ( O) — — C (O) O or — OC (O)-is inserted!
[0030] 化合物（3)の好ま 、態様としては、後述の化合物（3a)と後述の化合物（3b)とが挙 げられる。 [0030] Preferred of the compounds (3), as the embodiment, the compound described below (3 a) and the compound described below (3 b) Togakyo is down.
化合物（2)における mは、 1が好ましい。 Qは、炭素数 1 3のペルフルォロアルキ レン基が好ましぐジフルォロメチレン基が特に好まし!/、。  M in the compound (2) is preferably 1. Q is particularly preferably a difluoromethylene group, preferably a perfluoroalkylene group having 1 to 3 carbon atoms!
化合物（2)中のフルォロスルホニル基は電極反応においては不安定な基と考えら れており、本発明における電極反応にぉ 、てもフルォロスルホニル基の脱離が予想 された。したがって、化合物（2)を用いた電極反応においてフルォロスルホ-ル基が 保持された反応生成物である、化合物（11)、化合物（12)、化合物（13)または化合 物（14)が得られるのは予想外の効果であった。  The fluorosulfonyl group in the compound (2) is considered to be an unstable group in the electrode reaction, and the elimination of the fluorosulfonyl group was expected even in the electrode reaction in the present invention. Therefore, a compound (11), a compound (12), a compound (13) or a compound (14) which is a reaction product in which a fluorosulfol group is retained in an electrode reaction using the compound (2) can be obtained. Was an unexpected effect.
[0031] 化合物（2)は、式 CR (SO F) (C (O) OH)で表される化合物（21)が好ましぐ [0031] Compound (2) is preferably compound (21) represented by the formula CR (SO F) (C (O) OH).
3-n 2 n  3-n 2 n
式 CFR^SO F) (C (O) OH)で表される化合物（211)が特に好ましい（以下同様で  The compound (211) represented by the formula CFR ^ SO F) (C (O) OH) is particularly preferred (the same applies hereinafter).
2  2
ある。 ) o Rおよび R1は、フッ素原子またはトリフルォロメチル基であり、特に、フッ素原 子が好ましい。 nは、 1が好ましい。また、 nが 1である場合の Rは、同一であっても異な つていてもよい。 is there. o R and R 1 are a fluorine atom or a trifluoromethyl group, and a fluorine atom is particularly preferable. n is preferably 1. In addition, when n is 1, the Rs may be the same or different.
[0032] 化合物（21)と化合物（211)は、それぞれ、カルボキシル基の a位にフルォロスル ホ-ル基を有する含フッ素カルボン酸であり、電極反応において α位のフルォロスル ホニル基が保持された反応生成物が得られるのは特に予想外の効果であった。 [0032] Compound (21) and Compound (211) are each a fluorine-containing carboxylic acid having a fluorophore group at the a- position of the carboxyl group, and a reaction in which the α-position fluorosulfonyl group is retained in the electrode reaction. It was a particularly unexpected effect that the product was obtained.
[0033] 化合物（2)の具体例としては、 CF (SO F) (C (O) OH) CF (CF ) (SO F) (C (  [0033] Specific examples of compound (2) include CF (SO F) (C (O) OH) CF (CF) (SO F) (C (
2 2 3 2 2 2 3 2
O) OH) CF (SO F) (C (O) OH) C (CF ) (SO F) (C (O) OH) C (SO F) (C O) OH) CF (SO F) (C (O) OH) C (CF) (SO F) (C (O) OH) C (SO F) (C
2 2 3 2 2 2 3 2 2 3 2 2 2 3
(0) OH)、 (FSO ) CF CF (C (O) OH) (FSO ) CF CF CF (C (O) OH) (FS (0) OH), (FSO) CF CF (C (O) OH) (FSO) CF CF CF (C (O) OH) (FS
2 2 2 2 2 2 2  2 2 2 2 2 2 2
O ) CF CF OCF (CF ) (C (O) OH)等が挙げられる。  O) CF CF OCF (CF) (C (O) OH) and the like.
2 2 2 3  2 2 2 3
[0034] 本発明における電極反応にぉ 、て、化合物（2)と化合物（2)の塩との総量に対す る化合物（3)の量は、 0. 25-1. 0倍モルが好ましい。  [0034] In the electrode reaction in the present invention, the amount of the compound (3) relative to the total amount of the compound (2) and the salt of the compound (2) is preferably 0.25-1.
電極反応における電流密度は、反応制御と反応効率の観点から、 0. 01 5. OA Zcm2が好ましい。電極反応における電流の総通電量は、化合物（2)、化合物（2) の塩、および化合物（3)の総量に対して、 0. 1〜5. OFZmolが好ましい。 The current density in the electrode reaction is preferably 0.015 OA Zcm 2 from the viewpoint of reaction control and reaction efficiency. The total amount of current in the electrode reaction is compound (2), compound (2) 0.1 to 5. OFZmol is preferable with respect to the total amount of the salt and the compound (3).
電極反応における反応温度は、—20°C〜 + 100°Cが好ましぐ—20°C〜 + 60°C が特に好ましい。電極反応における反応圧力は、大気圧、減圧、加圧のいずれであ つてもよく、大気圧が好ましい。  The reaction temperature in the electrode reaction is preferably -20 ° C to + 100 ° C, particularly preferably -20 ° C to + 60 ° C. The reaction pressure in the electrode reaction may be atmospheric pressure, reduced pressure, or increased pressure, and atmospheric pressure is preferable.
[0035] 電極反応は、無溶媒下で行ってもよぐ溶媒の存在下で行ってもよぐ溶媒の存在 下で行うのが好ましい。溶媒は、化合物（3)ならびに化合物（2)またはその塩を溶解 する溶媒であれば特に限定されない。溶媒は、非プロトン性溶媒が好ましい。非プロ トン性溶媒としては、テトラヒドロフラン、 1, 2—ジメトキシェタン、プロピレンカーボネ ート、ァセトニトリル、ジメチルホルムアミド、ジメチルスルホキシド、ジォキサン等が挙 げられる。また電極反応は、支持電解質の存在下に行うのが好ましい。支持電解質 は、プロトン性溶媒が好ましぐアルコール (メタノール、エタノール等。）または水が特 に好ましい。 [0035] The electrode reaction is preferably performed in the presence of a solvent which may be performed in the absence of a solvent or in the presence of a solvent. The solvent is not particularly limited as long as it is a solvent that dissolves compound (3) and compound (2) or a salt thereof. The solvent is preferably an aprotic solvent. Non-protonic solvents include tetrahydrofuran, 1,2-dimethoxyethane, propylene carbonate, acetonitrile, dimethylformamide, dimethyl sulfoxide, dioxane and the like. The electrode reaction is preferably performed in the presence of a supporting electrolyte. The supporting electrolyte is particularly preferably an alcohol (methanol, ethanol, etc.) or water for which a protic solvent is preferred.
[0036] 電極反応に用いる反応容器は、公知の電解装置の電槽を用いるのが好ま 、。電 槽は絶縁性が良好である観点から、ガラス製電槽またはフッ素榭脂製電槽が好まし V、。また電槽本体を陽極または陰極として機能させてもょ 、。  [0036] The reaction vessel used for the electrode reaction is preferably a known electrolytic cell. From the viewpoint of good insulation of the battery case, a glass battery case or a fluorine resin battery case is preferred V ,. Also, let the battery case function as an anode or cathode.
電極における陽極と陰極は、それぞれ、酸ィ匕還元電位の高い電極が好ましい。該 電極は、マグネシウム、銅、アルミニウム、白金、および炭素材料力もなる群力も選ば れる少なくとも 1種の電極材料からなる電極が好ましぐ白金または炭素材料カゝらなる 電極が特に好ましい。  The anode and cathode in the electrode are preferably electrodes having a high acid reduction potential. The electrode is particularly preferably an electrode made of platinum or a carbon material, preferably an electrode made of magnesium, copper, aluminum, platinum, and an electrode material made of at least one kind of electrode material that is also selected as a group force.
[0037] 本発明の製造方法においては、目的に応じた純度の化合物（11)、化合物（12)、 化合物（13)、または化合物（14)を得るために後処理を行うのが好ましい。後処理の 方法としては、水洗、抽出、クロマトグラフィー、蒸留、再結晶等による方法が挙げら れる。これらの 2種以上の方法を組み合わせて後処理を行ってもよい。また、電極反 応は、反応基質を電槽に一括供給した後に行うバッチ方式で実施してもよぐ反応基 質を電槽に連続供給しながら行う連続反応方式で実施してもよい。  [0037] In the production method of the present invention, post-treatment is preferably performed to obtain compound (11), compound (12), compound (13), or compound (14) having a purity suitable for the purpose. Examples of the post-treatment method include water washing, extraction, chromatography, distillation, recrystallization and the like. The post-treatment may be performed by combining these two or more methods. In addition, the electrode reaction may be performed by a batch method that is performed after the reaction substrate is collectively supplied to the battery case, or may be performed by a continuous reaction method that is performed while the reaction substrate is continuously supplied to the battery case.
[0038] 本発明の製造方法において、下記化合物（11)、下記化合物（12)、下記化合物（ 13)、または下記化合物（14)が生成する理由は、必ずしも明確ではないが、それぞ れ下記の理由によると考えられる。 [0039] [化 12] x [0038] The reason why the following compound (11), the following compound (12), the following compound (13), or the following compound (14) is produced in the production method of the present invention is not necessarily clear, The reason is considered to be. [0039] [Chemical 12] x
Y-C-CHZQ(S02F)m X X X YC-CHZQ (S0 2 F) m XXX
I \ ヽ ヽ  I \ ヽ ヽ
Y— C— CHZQ(S。2F)m /C=CZQ(S02F)m ,CH— CHZO(S02F)m Y— C-CHZQ(S02F)m X Y Y Q(S02F)m Y— C— CHZQ (S. 2 F) m / C = CZQ (S0 2 F) m , CH— CHZO (S0 2 F) m Y— C-CHZQ (S0 2 F) m XYYQ (S0 2 F) m
(11) (12) (13) (14) すなわち、化合物（11)が生成する理由としては、電極反応により、化合物（2)また はその塩から下記ラジカル（21) (ラジカル（21)中のラジカルの生成部位は、カルボキ シル基が結合していた炭素原子である。）が生成し、つぎにラジカル（21)が化合物（3 )にラジカル付加反応して下記ラジカル（I1)が生成し、さらに 2個のラジカル（I1)がラ ジカルカップリング反応したためと考えられる。 (11) (12) (13) (14) That is, the reason why the compound (11) is formed is that the following radical (2 1 ) (radical (2 1 )) is generated from the compound (2) or a salt thereof by an electrode reaction. The radical is generated at the carbon atom to which the carboxy group was bonded.) Next, the radical (2 1 ) undergoes a radical addition reaction to the compound (3), and the following radical (I 1 ) This is thought to be due to the radical coupling reaction of two radicals (I 1 ).
[0040] [化 13] [0040] [Chemical 13]
X X
\  \
•C— CHZQ(S02F)m • C—CHZQ (S0 2 F) m
•Q(S02F)m / Q (S0 2 F) m /
Y  Y
(2r) (1 r) 化合物（ 12)が生成する理由としては、ラジカル（ I1)のプロトンが脱離したためと考 えられる。 The reason why (2 r ) (1 r ) compound (12) is formed is thought to be because the proton of radical (I 1 ) has been eliminated.
[0041] 化合物（13)が生成する理由としては、ラジカル（I1)とプロトンがラジカルカップリン グ反応したためと考えられる。 [0041] The reason why the compound (13) is formed is considered to be that the radical (I 1 ) and the proton undergo a radical coupling reaction.
化合物（14)が生成する理由としては、ラジカル（21)とラジカル（I1)がラジカルカツ プリング反応したためと考えられる。 The reason why the compound (14) is formed is considered to be that radical (2 1 ) and radical (I 1 ) undergo a radical coupling reaction.
[0042] 本発明の第 1の好ましい態様としては、式 CXaYa=CHで表される化合物（3a)と、 As a first preferred embodiment of the present invention, a compound (3 a ) represented by the formula CX a Y a = CH,
2  2
化合物（2)またはその塩とを電極反応させる態様が挙げられる。  An embodiment in which the compound (2) or a salt thereof is subjected to an electrode reaction is mentioned.
化合物（3a)における Xaは、反応収率の観点から、炭素数 1〜： LOのアルキル基また は水素原子が好ましく、メチル基または水素原子が特に好まし 、。 X a in the compound (3 a ) is preferably an alkyl group having 1 to carbon atoms or a hydrogen atom, particularly preferably a methyl group or a hydrogen atom, from the viewpoint of reaction yield.
化合物（3a)における Yaは、反応収率の観点から、基 (A)またはカルボキシル基が 好ましぐアルキル基、アルコキシカルボ-ル基、またはアルキルカルボ-ルォキシ基 であって、炭素数 1〜10の基 (Aa)もしくはカルボキシル基が特に好ましぐメトキシカ ルポ二ル基、ヒドロキシメチル基またはカルボキシ基が最も好まし 、。 Y a in the compound (3 a ) is an alkyl group, an alkoxy carbo yl group, or an alkyl carbo oxy group in which the group (A) or the carboxyl group is preferable from the viewpoint of the reaction yield, and has 1 carbon atom. Methoxyca is particularly preferred for groups of ~ 10 (A a ) or carboxyl groups. Most preferred is a sulfonyl group, a hydroxymethyl group or a carboxy group.
基 (Aa)中にフッ素原子を含んで!/、てもよ!/、炭素数 2以上のアルキル基部分が存在 し該アルキル基中の炭素原子 炭素原子結合間に、 O C(O) C(O) O 、または一 OC(O)—が挿入されている場合、挿入される基の数は、 1〜4個が好 ましぐ 1個が特に好ましい。前記アルキル基中の炭素原子 炭素原子結合間にこ れらの基が挿入された場合、基 (Aa)の炭素数は、 2〜 10が好ましぐ 2〜8が特に好 ましい。 The group (A a ) contains a fluorine atom! /, May! /, An alkyl group part having 2 or more carbon atoms is present, and a carbon atom in the alkyl group is bonded between carbon atom bonds, and OC (O) C When (O) 2 O or 1 OC (O) — is inserted, the number of inserted groups is preferably 1 to 4, particularly preferably 1. When these groups are inserted between carbon atoms in carbon atoms in the alkyl group, the number of carbon atoms in the group (A a ) is preferably 2 to 10 and particularly preferably 2 to 8.
[0043] Y3の好ましい態様としては、 C(0)OCH、 -CH OH CH OC(0)CH、 -[0043] Preferred embodiments of Y 3 include C (0) OCH, -CH OH CH OC (0) CH,-
3 2 2 33 2 2 3
C(O) OH等が挙げられる。 C (O) OH etc. are mentioned.
化合物（3a)は、式 CXalYal = CHで表される化合物（3al)が好ましい。 The compound (3 a ) is preferably a compound (3 al ) represented by the formula CX al Y al = CH.
2  2
化合物（3a)の具体例としては、 CH(C(0)OH)二 CH、CH(C(0)OCH )=CH Specific examples of the compound (3 a ) include CH (C (0) OH) diCH, CH (C (0) OCH) = CH
2 3 twenty three
、 C(CH ) (C(0)OH)=CH、 C(CH ) (C(O)OCH )=CH、 C(CH ) (OCOC, C (CH) (C (0) OH) = CH, C (CH) (C (O) OCH) = CH, C (CH) (OCOC
2 3 2 3 3 2 3 2 3 2 3 3 2 3
H ) =CH、 CH(CH OH) =CH、 CH(CH OCOCH ) =CH等が挙げられる。  H) = CH, CH (CH OH) = CH, CH (CH OCOCH) = CH, and the like.
3 2 2 2 2 3 2  3 2 2 2 2 3 2
[0044] 化合物（2)は、化合物（21)が好ましぐ化合物（211)が特に好ましい。  [0044] The compound (2) is particularly preferably the compound (211) preferred by the compound (21).
第 1の好ま 、態様にぉ 、ては、化合物（3a)と化合物（2)またはその塩とを電極反 応させて、下記化合物（lla)、下記化合物（12a)、および下記化合物（13a)から選ば れるいずれか 1種の化合物を得る態様が挙げられる。化合物（12a)の立体配置はシ ス型であってもトランス型であってもよ！/、。 In a first preferred embodiment, the compound (3 a ) and the compound (2) or a salt thereof are electrode-reacted to produce the following compound (ll a ), the following compound (12 a ), and the following compound: An embodiment of obtaining any one compound selected from ( 13a ) is mentioned. The configuration of compound ( 12a ) may be either cis or trans! /.
[0045] [化 14]  [0045] [Chemical 14]
Figure imgf000014_0001
Figure imgf000014_0001
(11a) (12a) (13a) (11 a ) (12 a ) (13 a )
第 1の好ましい態様において、 Xaが基 (A)、カルボキシル基、シァノ基、または塩素 原子である化合物（3a)を用いた場合には、化合物（12a)と化合物（13a)が高選択率 に得られるため、化合物（12a)または化合物（13a)を得るのが好ましい。また、 Xaが水 素原子である化合物（3a)を用いた場合には化合物（1 la)が高選択率に得られるた め、化合物（lla)を得るのが好ましい。 [0046] 電極反応における、化合物（2)と化合物（2)の塩との総量に対する化合物（3a)の 量 ίま、 0. 4〜1. 0倍モノレカ好ましく、 0. 5〜0. 8倍モノレ力特に好まし!/、。 In the first preferred embodiment, when the compound (3 a ) in which X a is a group (A), a carboxyl group, a cyano group, or a chlorine atom is used, the compound (12 a ) and the compound (13 a ) are Since the compound can be obtained with high selectivity, it is preferable to obtain the compound (12 a ) or the compound (13 a ). In addition, when the compound (3 a ) in which X a is a hydrogen atom is used, the compound (1 l a ) can be obtained with high selectivity. Therefore, it is preferable to obtain the compound (ll a ). [0046] In the electrode reaction, the amount of the compound (3 a ) relative to the total amount of the compound (2) and the salt of the compound (2) is preferably 0.4 to 1.0 times monoreca, preferably 0.5 to 0.8. Double monore power is especially preferred!
電極反応における電流密度は、反応制御と反応効率の観点から、 0. 01〜5. OA Zcm2が好ましぐ 0. 05〜2. 5AZcm2がより好ましぐ 0. 1〜1. OAZcm2が特に 好ましい。電極反応における電流の総通電量は、化合物（2)、化合物（2)の塩、およ び化合物（3a)の総量に対して、 0. 1〜5. OFZmolが好ましぐ 0. 2〜2. 5F/mol 力 り好ましぐ 0. 3〜1. OFZmolが特に好ましい。 The current density in the electrode reaction, from the viewpoint of reaction control and reaction efficiency, 0. 01~5. OA Zcm 2 is preferably tool 0. 05~2. 5AZcm 2 more preferably tool 0. 1~1. OAZcm 2 Is particularly preferred. The total current amount of the current in the electrode reaction, the compound (2), a salt of the compound (2), relative to the total amount of and the compound (3 a), 0. 1~5. OFZmol is preferred instrument 0.2 ˜2.5 F / mol force, more preferably 0.3 to 1. OFZmol is particularly preferred.
電極反応における、反応温度、反応圧力、溶媒の有無、反応器の種類、および、 陽極と陰極の種類は、前記の条件を適用するのが好ましい。  The above conditions are preferably applied to the reaction temperature, reaction pressure, presence / absence of solvent, type of reactor, and type of anode and cathode in the electrode reaction.
[0047] 第 1の好ましい態様において、化合物（lla)、化合物（12a)、または化合物（13a)が 効率よく生成する理由は、必ずしも明確ではないが、それぞれ下記の理由によると考 えられる。 In the first preferred embodiment, the reason why the compound (ll a ), the compound (12 a ), or the compound (13 a ) is efficiently produced is not necessarily clear, but is considered to be due to the following reasons, respectively. It is done.
すなわち化合物（lla)が生成する理由としては、電極反応により、化合物（2)また はその塩力もラジカル（21)が生成し、つぎにラジカル（21)が化合物（3a)にラジカル付 加反応して下記ラジカル（1Ίが生成し、さらに 2個のラジカル（I31)がラジカルカップ リング反応したためと考えられる。 That is, the reason why the compound (ll a ) is generated is that the electrode ( 1 ) generates a radical (2 1 ) due to the electrode reaction, and then the radical (2 1 ) is converted into a radical (2 a) into the compound (3 a ). This is thought to be because the following radical (1Ί was generated by the addition reaction, and two radicals (I 31 ) were further radical-coupled.
[0048] [化 15] (1ar)[0048] [Chemical 15] (1 ar )
Figure imgf000015_0001
Figure imgf000015_0001
化合物（12a)が生成する理由としては、ラジカル（lai)のプロトンが脱離したためと 考えられる。 The reason why the compound (12 a ) is produced is considered to be that the proton of the radical (l ai ) has been eliminated.
[0049] 化合物（13a)が生成する理由としては、ラジカル（lai)とプロトンがラジカルカツプリ ング反応したためと考えられる。 The reason [0049] compound is (13 a) generates, protons and radical (l ai) is considered due to a radical Katsu pre ing reaction.
第 1の好ま 、態様は、化合物（3al)と化合物（21)またはその塩とを電極反応させ る、下記化合物（llal)、下記化合物（12al)、および下記化合物（13al)から選ばれる いずれか 1種の化合物の製造方法であるのが好ましい。化合物（12al)の立体配置 はシス型であってもトランス型であってもよ!/、。 [0050] [化 16] xa1 In a first preferred embodiment, the following compound (ll al ), the following compound (12 al ), and the following compound (13 al ) are prepared by subjecting the compound (3 al ) and the compound (21) or a salt thereof to an electrode reaction. Preferably, it is a method for producing any one selected compound. The configuration of the compound (12 al ) may be cis or trans! /. [0050] [Chemical 16] x a1
Ya1-C- Ya1 - C—
Figure imgf000016_0001
Y a1 -C- Y a1 -C—
Figure imgf000016_0001
特に Xalを炭素数 1〜10のアルキル基とした場合には、化合物（12al)と化合物（13 al)が高選択率に得られる。よって、この場合には化合物（12al)または化合物（13al) を得るのが好ましい。また、特に xalを水素原子とした場合には、化合物（i ial)が高 選択率に得られる。よって、この場合には化合物（i ial)を得るのが好ましい。 In particular, when the X al was an alkyl group having 1 to 10 carbon atoms, compound (12 al) and the compound (13 a l) is obtained in high selectivity. Therefore, in this case, it is preferable to obtain the compound (12 al ) or the compound (13 al ). Further, especially when the x al hydrogen atom, the compound (ii al) is obtained in high selectivity. Therefore, in this case, it is preferable to obtain the compound (ii al ).
[0051] 第 1の好ましい態様は、式 ΟΧ^Ο ίΟΐΙ ΟΖ1) =CHで表される化合物（31)と化合物 [0051] A first preferred embodiment is a compound (3 1 ) and a compound represented by the formula ΟΧ ^ Ο ίΟΐΙ ΟΖ 1 ) = CH
2  2
(211)またはその塩とを電極反応させる、下記化合物（11 、下記化合物（12 、お よび下記化合物（131)から選ばれるいずれか 1種の化合物の製造方法であるのが特 に好ましい。化合物（121)の立体配置はシス型であってもトランス型であってもよい。 (211) or a salt thereof is particularly preferably a method for producing any one compound selected from the following compounds (11, the following compounds (12), and the following compounds (13 1 ). The configuration of the compound (12 1 ) may be cis or trans.
[0052] [化 17] [0052] [Chemical 17]
Z OiO)C-Z OiO) C-
Z 0(0)C-
Figure imgf000016_0002
Z 0 (0) C-
Figure imgf000016_0002
(111) (121) (131) 特に X1をメチル基とした場合には、化合物（121)と化合物（131)が高選択率に得ら れる。よって、この場合には化合物（121)または化合物（131)を得るのが好ましい。ま た、特に X1を水素原子とした場合には、化合物（I I1)が高選択率に得られる。よって 、この場合には化合物（111)を得るのが好ま 、。 (11 1 ) (12 1 ) (13 1 ) Especially when X 1 is a methyl group, the compound (12 1 ) and the compound (13 1 ) can be obtained with high selectivity. Therefore, in this case, it is preferable to obtain the compound (12 1 ) or the compound (13 1 ). In particular, when X 1 is a hydrogen atom, compound (II 1 ) can be obtained with high selectivity. Therefore, in this case, it is preferable to obtain the compound (11 1 ).
[0053] 化合物（I I1)は、 2個のフルォロスルホ-ル基と 2個の式 C (0) OZ1で表される基 を有する特徴ある新規ィ匕合物である。化合物（I I1)は、フルォロモノマーの原料、界 面活性剤等の機能性材料として有用である。化合物（I I1)の具体例としては下記化 合物が挙げられる。 The compound (II 1 ) is a characteristic novel compound having two fluorosulfol groups and two groups represented by the formula C (0) OZ 1 . The compound (II 1 ) is useful as a functional material such as a raw material for fluoromonomers and a surfactant. Specific examples of the compound (II 1 ) include the following compounds.
[0054] [化 18] HO(0)C— CH-CH2CF2S02F HO(0)C -CH -CH2CF(CF3)S02F H0(0)C-CH-CH2CF2SO2F HO(0)C -CH -CH2CF(CF3)S02F [0054] [Chemical 18] HO (0) C— CH-CH 2 CF 2 S0 2 F HO (0) C -CH -CH 2 CF (CF 3 ) S0 2 F H0 (0) C-CH-CH 2 CF 2 SO 2 F HO ( 0) C -CH -CH 2 CF (CF 3 ) S0 2 F
CH30(0)C— CH - CH2CF2S02F CH30(0)C -CH -CH2CF(CF3)S02F CH 3 0 (0) C— CH-CH 2 CF 2 S0 2 F CH 3 0 (0) C -CH -CH 2 CF (CF 3 ) S0 2 F
CH30(0)C— CH— CH2CF2S02F CH30(0)C— CH - CH2CF(CF3)S02F CH 3 0 (0) C— CH— CH 2 CF 2 S0 2 F CH 3 0 (0) C— CH-CH 2 CF (CF 3 ) S0 2 F
CH3 CH3 CH 3 CH 3
HO(0)C一 C— CH2CF2S02F HO(0)C一 C— CH2CF(CF3)S02FHO (0) C 1 C— CH 2 CF 2 S0 2 F HO (0) C 1 C— CH 2 CF (CF 3 ) S0 2 F
HO(0)C— C— CH2CF2S02F HO(0)C一 C— CH2CF(CF3)S02F HO (0) C— C— CH 2 CF 2 S0 2 F HO (0) C One C— CH 2 CF (CF 3 ) S0 2 F
CH3 CH3 CH 3 CH 3
CH3 CH3 CH 3 CH 3
CH30(0)C一 C— CH2CF2S02F CH30(0)C -C— CH2CF(CF3)S02F CH 3 0 (0) C One C— CH 2 CF 2 S0 2 F CH 3 0 (0) C -C— CH 2 CF (CF 3 ) S0 2 F
CH30(0)C一 C— CH2CF2S02F CH30(0)C— C— CH2CF(CF3)S02F CH 3 0 (0) C One C— CH 2 CF 2 S0 2 F CH 3 0 (0) C— C— CH 2 CF (CF 3 ) S0 2 F
CH3 CH3 化合物（121)は、フルォロスルホ-ル基と式 C (O) OZ1で表される基を有する特 徴ある構造の新規なエチレン性ィ匕合物である。化合物（121)は、フルォロモノマー、 界面活性剤等の機能性材料等として有用である。化合物（121)の具体例としては下 記化合物が挙げられる。 The CH 3 CH 3 compound (12 1 ) is a novel ethylenic compound having a characteristic structure having a fluorosulfol group and a group represented by the formula C (O) OZ 1 . The compound (12 1 ) is useful as a functional material such as a fluoromonomer or a surfactant. Specific examples of the compound (12 1 ) include the following compounds.
[0055] [化 19] [0055] [Chemical 19]
Figure imgf000017_0001
Figure imgf000017_0001
化合物（131)は、フルォロスルホ-ル基と式 C (O) OZ1で表される基を有する特 徴ある構造の新規化合物である。化合物（131)は、フルォロモノマーの原料、界面活 性剤等の機能性材料として有用である。化合物（131)の具体例としては下記化合物 が挙げられる。 The compound (13 1 ) is a novel compound having a characteristic structure having a fluorosulfol group and a group represented by the formula C (O) OZ 1 . The compound (13 1 ) is useful as a functional material such as a raw material for fluoromonomers and a surfactant. Specific examples of the compound (13 1 ) include the following compounds.
[0056] [化 20]
Figure imgf000018_0001
[0056] [Chemical 20]
Figure imgf000018_0001
本発明の第 2の好ましい態様としては、式 CFYb=CHZbで表される化合物（3b)と、 化合物（2)またはその塩とを電極反応させる態様が挙げられる。 A second preferred embodiment of the present invention includes an embodiment in which the compound (3 b ) represented by the formula CFY b = CHZ b is reacted with the compound (2) or a salt thereof.
[0057] 化合物（3b)における Ybは、反応収率の観点から、基 (A)またはカルボキシル基が 好ましぐアルキル基、アルコキシカルボ-ル基、またはアルキルカルボ-ルォキシ基 であって、炭素数 1〜10の基 (Ab)もしくはカルボキシル基が特に好ましぐメトキシカ ルポ二ル基、ヒドロキシメチル基またはカルボキシ基が最も好まし 、。 [0057] Y b in the compound (3 b ) is an alkyl group, an alkoxy carbo yl group, or an alkyl carbo oxy group in which the group (A) or the carboxyl group is preferable from the viewpoint of the reaction yield, A methoxycarbonyl group, a hydroxymethyl group or a carboxy group is most preferred, and a group having 1 to 10 carbon atoms (A b ) or a carboxyl group is particularly preferred.
[0058] 基 (Ab)中にフッ素原子を含んで 、てもよ 、炭素数 2以上のアルキル基部分が存在 し該アルキル基中の炭素原子 炭素原子結合間に、 O 、 一 C(O)—、 一 C(O) 0—、または一 OC(O)—が挿入されている場合、挿入される基の数は、 1〜4個が好 ましぐ 1個が特に好ましい。前記アルキル基中の炭素原子 炭素原子結合間にこ れらの基が挿入された場合、基 (Abl)の炭素数は、 2〜10が好ましぐ 2〜8が特に好 ましい。 [0058] The group (A b ) may contain a fluorine atom, but there may be an alkyl group part having 2 or more carbon atoms, and a carbon atom in the alkyl group may be bonded with an O 1 or a C (O ) —, 1 C (O) 0—, or 1 OC (O) — is inserted, the number of inserted groups is preferably 1 to 4, and particularly preferably 1. When these groups are inserted between carbon atoms in carbon atoms in the alkyl group, the number of carbon atoms in the group (A bl ) is preferably from 2 to 10, and particularly preferably from 2 to 8.
[0059] Ybの好ましい態様としては、一 C(0)OCH、 一 CH OH、 一 CH OC(0)CH、 -[0059] Preferred embodiments of Y b include one C (0) OCH, one CH OH, one CH OC (0) CH,-
3 2 2 33 2 2 3
C(O) OH等が挙げられる。 C (O) OH etc. are mentioned.
化合物（3b)における Zbは、水素原子またはフッ素原子が好ましい。 Z b in the compound (3 b ) is preferably a hydrogen atom or a fluorine atom.
化合物（3b)は、式 CFYbl = CHZblで表される化合物（3bl)が好ましい。 化合物（3b)の具体例としては、 CF(C(0)OH) =CH、 CF(C(0)OCH ) =CH The compound (3 b ) is preferably a compound (3 bl ) represented by the formula CFY bl = CHZ bl . Specific examples of the compound (3 b ) include CF (C (0) OH) = CH, CF (C (0) OCH) = CH
2 3 2 2 3 2
、 CF(CH OH) =CHF、 CF(CH OC(0)CH ) =CHF、 CF(CH C(0)OCH ) , CF (CH OH) = CHF, CF (CH OC (0) CH) = CHF, CF (CH C (0) OCH)
2 2 3 2 3 2 2 3 2 3
= CHF等が挙げられる。 = CHF etc. are mentioned.
[0060] 化合物（3b)は、 oc フルォロエチレン類であって化合物（3b)中の炭素原子 炭素 原子 2重結合は低活性であることから電極反応しないと考えられた。したがって、化 合物（3b)が電極反応することは予想外の効果であり、さらに該電極反応において化 合物（14b)が高選択率に生成することは特に予想外の効果であった。 [0061] 化合物（2)は、化合物（21)がより好ましぐ化合物（211)が特に好ましい。 [0060] The compound (3 b ) was oc fluoroethylenes, and the carbon atom in the compound (3 b ) had a low activity, so it was considered that no electrode reaction occurred. Therefore, it is an unexpected effect that the compound (3 b ) undergoes an electrode reaction, and the formation of the compound (14 b ) at a high selectivity in the electrode reaction is a particularly unexpected effect. It was. [0061] Compound (2) is particularly preferably compound (211), more preferably compound (21).
第 2の好ま 、態様にぉ 、ては、化合物（3b)と化合物（2)またはその塩とを電極反 応させて、下記化合物（l lb)、下記化合物（12b)、および下記化合物（14b)から選ば れるいずれか 1種の化合物を得る。化合物（12a)の立体配置はシス型であってもトラ ンス型であってもよい。 In a second preferred embodiment, the compound (3 b ) and the compound (2) or a salt thereof are electrode-reacted to produce the following compound (ll b ), the following compound (12 b ), and the following compound. Any one compound selected from ( 14b ) is obtained. The configuration of the compound ( 12a ) may be cis type or trans type.
[0062] [化 21]  [0062] [Chemical 21]
Yb-C-CHZbQ(S02F)m Y b -C-CHZ b Q (S0 2 F) m
Yb— C-CHZbQ(S02F)m bQ(S02F)m Y b — C-CHZ b Q (S0 2 F) m b Q (S0 2 F) m
Figure imgf000019_0001
Figure imgf000019_0001
(11 b) (12b) (14b) (11 b ) (12 b ) (14 b )
第 2の好ましい態様において、化合物（14b)が高選択率に得られるため、化合物（1 4b)を得るのが好ましい。 In a second preferred embodiment, since the compound (14 b) is obtained in high selectivity, preferably to obtain a compound (1 4 b).
[0063] 電極反応における、化合物（2)と化合物（2)との塩の総量に対する化合物（3b)の 量 ίま、 0. 25〜0. 5倍モノレ力好ましく、 0. 3〜0. 4倍モノレ力特に好まし!/、。 [0063] In the electrode reaction, the amount of the compound (3 b ) relative to the total amount of the salt of the compound (2) and the compound (2) is preferably 0.25 to 0.5 times the monoreaction power, preferably 0.3 to 0. 4 times monore power is especially preferred!
電極反応における電流密度は、反応制御と反応効率の観点から、 0. 01〜5. OA /cm2が好ましぐ 0. 1〜1. OA/cm2が特に好ましい。電極反応における電流の総 通電量は、化合物（2)、化合物（2)の塩、および化合物（3b)の総量に対して、 0. 1 〜5. OFZmolが好ましぐ 0. 2〜2. 5FZmolがより好ましぐ 0. 3〜1. OFZmolが 特に好ましい。 The current density in the electrode reaction is preferably 0.01 to 5. OA / cm 2 from the viewpoint of reaction control and reaction efficiency, and particularly preferably 0.1 to 1. OA / cm 2 . The total amount of electric current in the electrode reaction is preferably 0.1 to 5. OFZmol with respect to the total amount of compound (2), salt of compound (2) and compound (3 b ). 5FZmol is more preferred 0.3 to 1. OFZmol is particularly preferred.
電極反応における、反応温度、反応圧力、溶媒の有無、反応器の種類、および、 陽極と陰極の種類は、前記の条件を適用するのが好ましい。  The above conditions are preferably applied to the reaction temperature, reaction pressure, presence / absence of solvent, type of reactor, and type of anode and cathode in the electrode reaction.
本発明の製造方法において、化合物（l lb)、化合物（12b)、または化合物（14b)が 効率よく生成する理由は、必ずしも明確ではないが、それぞれ下記の理由によると考 えられる。 In the production method of the present invention, the reason why the compound (ll b ), the compound (12 b ), or the compound (14 b ) is efficiently produced is not necessarily clear, but is considered to be due to the following reasons, respectively.
[0064] 化合物（14b)が生成する理由としては、電極反応により、ラジカル（2 が生成し、つ ぎにラジカル（21)が化合物（3b)にラジカル付加反応して下記ラジカル（lbl)が生成し 、さらにラジカル（21)とラジカル（lbl)がラジカルカップリング反応したためと考えられ る。 [0065] [化 22] vb ^C— CHZbQ(S02F)m 化合物（ 12b)が生成する理由としては、ラジカル ( lbr)のプロトンが脱離したためと 考えられる。 [0064] The reason why the compound (14 b ) is formed is that the radical (2 is generated by the electrode reaction, and then the radical (2 1 ) undergoes a radical addition reaction to the compound (3 b ) and the following radical (1 This is thought to be because bl ) was generated and radical (2 1 ) and radical (l bl ) were further subjected to radical coupling reaction. [0065] [Chemical Formula 22] v b ^ C— CHZ b Q (S0 2 F) m It is considered that the compound (12 b ) is formed because the proton of the radical (l br ) is eliminated.
[0066] 化合物（l lb)が生成する理由としては、 2個のラジカル（lbl")がラジカルカップリング 反応したためと考えられる。 [0066] The reason why the compound (ll b ) is produced is considered to be that two radicals (l bl ") have undergone radical coupling reaction.
[0067] 第 2の好ましい態様は、化合物（3bl)と、化合物（21)またはその塩とを電極反応さ せる下記化合物（l lbl)、下記化合物（12bl)、および下記化合物（14bl)から選ばれ るいずれか 1種の化合物の製造方法であるのが好ましい。化合物（12bl)の立体配置 はシス型であってもトランス型であってもよい。該製造方法においては化合物（14bl) が高選択率に得られるため化合物（14bl)を得るのが好ましい。 [0067] In a second preferred embodiment, the following compound (ll bl ), the following compound (12 bl ), and the following compound (14 bl ) are prepared by subjecting the compound (3 bl ) to the compound (21) or a salt thereof. The method for producing any one compound selected from (1) is preferred. The configuration of the compound (12 bl ) may be cis or trans. In the production method, the compound (14 bl ) is preferably obtained because the compound (14 bl ) can be obtained with high selectivity.
[0068] [化 23]  [0068] [Chemical 23]
Yb1 -Y b1-
Yb1-
Figure imgf000020_0001
Y b1-
Figure imgf000020_0001
(11 b1) (12 1) (14b1) 第 2の好ましい態様は、式 ΟΡ ^ ίΟΐΙ ΟΖ1) =CH (Z1は、水素原子またはメチル基 (11 b1 ) (12 1 ) (14 b1 ) In a second preferred embodiment, the formula ΟΡ ^ ίΟΐΙ ΟΖ 1 ) = CH (Z 1 represents a hydrogen atom or a methyl group
2  2
)で表される化合物（32)と、化合物（211)またはその塩とを電極反応させる下記化合 物（112)、下記化合物（122)、および下記化合物（142)から選ばれるいずれか 1種の 化合物の製造方法であるのが特に好ましい。化合物（122)の立体配置はシス型であ つてもトランス型であってもよい。該製造方法においては化合物（142)が高選択率に 得られるため、化合物（142)を得るのが好ましい。 ) And the following compound (11 2 ), the following compound (12 2 ), and the following compound (14 2 ), wherein the compound (3 2 ) and the compound (211) or a salt thereof are subjected to electrode reaction It is particularly preferable that the method is a method for producing one kind of compound. The configuration of the compound (12 2 ) may be cis or trans. In the production method, since the compound (14 2 ) can be obtained with high selectivity, it is preferable to obtain the compound (14 2 ).
[0069] [化 24] [0069] [Chemical 24]
Ϊ10(0)C-Ϊ 1 0 (0) C-
∑10{0)C— 2CFR , S02F∑ 1 0 {0) C— 2 CFR, S0 2 F
Figure imgf000020_0002
Figure imgf000020_0002
(11 ) (12") (142) 化合物（l l2)は、フルォロスルホ-ル基と式 ο ίοΐι οζ1で表される基を有する特 徴ある構造の新規な含フッ素化合物である。化合物（I I2)は、フルォロモノマーの原 料、界面活性剤等の機能性材料として有用である。 (11) (12 ") (14 2 ) The compound (ll 2 ) is a novel fluorine-containing compound having a characteristic structure having a fluorosulfol group and a group represented by the formula ο ίοΐι οζ 1 . The compound (II 2 ) is useful as a functional material such as a raw material for fluoromonomers and a surfactant.
化合物（I I2)の具体例としては、下記の化合物が挙げられる。 Specific examples of the compound (II 2 ) include the following compounds.
[0070] [化 25] [0070] [Chemical 25]
HO(0)C-CF-CH2CF2S02F CH30(0》C— CF— CH2CF2S02F HO (0) C-CF-CH 2 CF 2 S0 2 F CH 3 0 (0) C— CF— CH 2 CF 2 S0 2 F
HO(0)C-CF-CH2CF2S02F CH30{0)C-CF-CH2C F2S02F HO (0) C-CF-CH 2 CF 2 S0 2 F CH 3 0 (0) C-CF-CH 2 CF 2 S0 2 F
HO{0)C-CF-CH2CF(CF3)S02F CH30(0)C_CF_CH2CF(CF3)S02F HO {0) C-CF-CH 2 CF (CF 3 ) S0 2 F CH 3 0 (0) C_CF_CH 2 CF (CF 3 ) S0 2 F
HO(0)C-CF-CH2CF(CF3)S02F CH30(0)C— CF_CH2CF(CF3)S02F 化合物（122)は、フルォロスルホ-ル基と式 C (O) OZ1で表される基を有する特 徴ある構造の新規なエチレン性の含フッ素化合物である。化合物（122)は、フルォロ モノマー、界面活性剤等の機能性材料等として有用である。化合物（122)の具体例 としては、下記の化合物が挙げられる。 HO (0) C-CF-CH 2 CF (CF 3 ) S0 2 F CH 3 0 (0) C — CF_CH 2 CF (CF 3 ) S0 2 F The compound (12 2 ) has a fluorosulfol group and the formula C (O) A novel ethylenic fluorine-containing compound having a characteristic structure having a group represented by OZ 1 . The compound (12 2 ) is useful as a functional material such as a fluoromonomer or a surfactant. Specific examples of the compound (12 2 ) include the following compounds.
[0071] [化 26] [0071] [Chemical 26]
CF(C(0>OH)c=CHCF2S02F CF(C(0)OCH3)=C HCF2S02F CF (C (0> OH) c = CHCF 2 S0 2 F CF (C (0) OCH 3 ) = C HCF 2 S0 2 F
CF(C(0)OH)=CHCF(CF3)S02F CF(C(0)OCH3)=CHCF(CF3)S02F 化合物（142)は、 2個のフルォロスルホ-ル基と 1個の式 Ο ίΟΐΙ ΟΖ1で表される基 を有する特徴ある新規ィ匕合物である。化合物（142)は、フルォロモノマーの原料、界 面活性剤等の機能性材料として有用である。化合物（142)の具体例としては、下記 の化合物が挙げられる。 CF (C (0) OH) = CHCF (CF 3 ) S0 2 F CF (C (0) OCH 3 ) = CHCF (CF 3 ) S0 2 F Compound (14 2 ) has two fluorosulfol groups and It is a unique novel compound having a group represented by one formula (1). The compound (14 2 ) is useful as a functional material such as a raw material for fluoromonomers and a surfactant. Specific examples of the compound (14 2 ) include the following compounds.
[0072] [化 27] [0072] [Chemical 27]
C(0)OH C(0)OCH3 C(0)OH C(0)OCH3 C (0) OH C (0) OCH 3 C (0) OH C (0) OCH 3
CF— CH2CF2S02F CF— CH2CF2S02F ,CF— CH2CF《CF3)S。2F ノ CF— CH2CF(CF3)S02F CF2S02F CF2S02F CF(CF3)S02F CF(CF3)S02F 実施例 CF—CH 2 CF 2 S 0 2 F CF—CH 2 CF 2 S 0 2 F, CF—CH 2 CF << CF 3 ) S. 2F No CF—CH 2 CF (CF 3 ) S0 2 F CF 2 S0 2 F CF 2 S0 2 F CF (CF 3 ) S0 2 F CF (CF 3 ) S0 2 F
[0073] 以下に実施例を挙げて本発明を具体的に説明するが、本発明はこれらによって限 定されない。ガスクロマトグラフィは GCと、ガスクロマトグラフィ質量分析法は GC— M Sと、電子イオン化質量分析法は EI— MSと、化学イオン化質量分析法は CI MSと 、 GCのピーク面積比より求めた収率は GC収率と、ミリファラデーは mFと、記す。 [0073] The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. GC for gas chromatography and GC-M for gas chromatography mass spectrometry S, EI—MS for electron ionization mass spectrometry, CI MS for chemical ionization mass spectrometry, GC yield for the yield determined from the peak area ratio of GC, and mF for millifaradaic.
[0074] [例 1]化合物（liu)、化合物（1211)およびィ匕合物（1311)の製造例 [0074] [Example 1] Production example of compound (liu), compound (12 11 ) and compound (13 11 )
冷媒流通用ジャケットと底部に抜出バルブを備えた電槽 (ガラス製、内容積 50mL) に撹拌翼を設置し、 0°Cの冷媒を流通させた。また撹拌翼に干渉しないように、 2個の 白金網（縦 3cmX横 3cm、 80メッシュ）を陽極および負極として電槽内に設置した。 白金網は短絡を防止するためにポリエチレンメッシュの袋に入れて用いた。 CH =C  A stirring blade was installed in a battery tank (made of glass, internal volume 50 mL) equipped with a refrigerant distribution jacket and a discharge valve at the bottom, and 0 ° C refrigerant was circulated. Two platinum nets (length 3 cm x width 3 cm, 80 mesh) were installed in the battery case as anodes and anodes so as not to interfere with the stirring blades. The platinum mesh was used in a polyethylene mesh bag to prevent short circuit. CH = C
2 2
H(C(0)OCH ) (60mmol)、 CF (SO F) (C(O)OH) (90mmol)、非プロトン性 H (C (0) OCH) (60 mmol), CF (SO F) (C (O) OH) (90 mmol), aprotic
3 2 2  3 2 2
溶媒としてァセトニトリル（30mL)、および支持電解質としてイオン交換水 (5mL)を 電槽に入れた。  Acetonitrile (30 mL) as a solvent and ion-exchanged water (5 mL) as a supporting electrolyte were placed in a battery case.
[0075] つぎに撹拌翼を毎分 500回転させながら、 0.5Aの電流を総通電量が 90mFにな るまで電槽に通電して電極反応を行った。抜出バルブカゝら電槽内溶液を全量回収し 、 GC、 EI— MSおよび CI— MSにより分析した結果、下記化合物（II11) (GC収率 7 7%)、下記化合物（1211)および下記化合物（1311)の生成を確認した。 [0075] Next, while the stirring blade was rotated at 500 revolutions per minute, an electrode reaction was performed by applying a current of 0.5 A to the battery tank until the total energization amount reached 90 mF. The whole solution in the battery case was recovered from the extraction valve cover and analyzed by GC, EI-MS and CI-MS. As a result, the following compound (II 11 ) (GC yield 77%), the following compound (12 11 ) and Formation of the following compound (13 11 ) was confirmed.
[0076] 化合物（1111)の NMRデータを以下に示す。 [0076] The NMR data of the compound (11 11 ) are shown below.
'H-NMROOO.4MHZ, CDCl , Si(CH ) ) δ (ppm) :2.2〜2.8(m, 2Η),  'H-NMROOO.4MHZ, CDCl, Si (CH)) δ (ppm): 2.2 ~ 2.8 (m, 2Η),
3 3 4  3 3 4
3.0〜3.3(m, 4Η), 3.9(bs, 6H)。  3.0-3.3 (m, 4Η), 3.9 (bs, 6H).
19F-NMR(282.7MHz, CDCl , CFC1 ) δ (ppm) :+34. 7(2F), —98. 8 ( 1 9 F-NMR (282.7MHz, CDCl, CFC1) δ (ppm): +34.7 (2F), —98.8 (
3 3  3 3
4F)。  4F).
[0077] [化 28] [0077] [Chemical 28]
H H
CH30(0)C— C— CH2CF2S02F CH 3 0 (0) C— C— CH 2 CF 2 S0 2 F
CH30(0)C— C— CH2CF2S02F ,C=CH2CF2S02F ^CH— CH2CF2S02F CH 3 0 (0) C— C— CH 2 CF 2 S0 2 F, C = CH2CF 2 S0 2 F ^ CH— CH 2 CF 2 S0 2 F
H C(0)OCH3 C(0)OCH3 HC (0) OCH 3 C (0) OCH 3
(11") (12") (13")  (11 ") (12") (13 ")
[0078] [例 2]化合物（1112)、化合物（1212)およびィヒ合物（1312)の製造例 [0078] [Example 2] Production Example of Compound (11 12 ), Compound (12 12 ) and Ich Compound (13 12 )
CH =CH(C(0)OCH )のかわりに CH =C(CH ) (C(O)OCH )を用いる以外 Other than using CH = C (CH) (C (O) OCH) instead of CH = CH (C (0) OCH)
2 3 2 3 3 は例 1と同様にして電極反応を行って、下記化合物（1112)、下記化合物（1212) (GC 収率 37%)および下記化合物（1312) (GC収率 29%)を得た。 [0079] [化 29] 2 3 2 3 3 was subjected to an electrode reaction in the same manner as in Example 1, and the following compound (11 12 ), the following compound (12 12 ) (GC yield 37%) and the following compound (13 12 ) (GC yield 29 %). [0079] [Chemical 29]
CH30(0)C— CH 3 0 (0) C—
CH30(0)C— 2CF2S02FCH 3 0 (0) C— 2 CF 2 S0 2 F
Figure imgf000023_0001
Figure imgf000023_0001
(1212) (1312) (12 12 ) (13 12 )
[0080] [例 3]化合物（l r1)、化合物（121)および化合物（141)の製造例 [0080] [Example 3] Production Examples of Compound (lr 1 ), Compound (12 1 ) and Compound (14 1 )
冷媒流通用ジャケットと底部に抜出バルブを備えた電槽 (ガラス製、内容積 50mL) に撹拌翼を設置し、 0°Cの冷媒を流通させた。また撹拌翼に干渉しないように、 2個の 白金網（縦 3cmX横 3cm、 80メッシュ）を陽極および負極として電槽内に設置した。 白金網は短絡を防止するためにポリエチレンメッシュの袋に入れて用いた。 CH =C  A stirring blade was installed in a battery tank (made of glass, internal volume 50 mL) equipped with a refrigerant distribution jacket and a discharge valve at the bottom, and 0 ° C refrigerant was circulated. Two platinum nets (length 3 cm x width 3 cm, 80 mesh) were installed in the battery case as anodes and anodes so as not to interfere with the stirring blades. The platinum mesh was used in a polyethylene mesh bag to prevent short circuit. CH = C
2 2
F(C(0)OCH ) (10mmol)、 CF (SO F) (C(O)OH) (60mmol)、非プロトン性 F (C (0) OCH) (10 mmol), CF (SO F) (C (O) OH) (60 mmol), aprotic
3 2 2  3 2 2
溶媒としてァセトニトリル（30mL)、および支持電解質としてイオン交換水 (5mL)を 電槽に入れた。  Acetonitrile (30 mL) as a solvent and ion-exchanged water (5 mL) as a supporting electrolyte were placed in a battery case.
[0081] つぎに撹拌翼を毎分 500回転させながら、 0.8Aの電流を総通電量が 60mFにな るまで電槽に通電して電極反応を行った。抜出バルブカゝら電槽内溶液を全量回収し 、 GC、 EI— MS、および CI— MSにより分析した結果、下記化合物（II21) (GC収率 63. 3%)、下記化合物（1221) (GC収率 4. 8%)および下記化合物（1421) (GC収率 30.6%)の生成を確認した。 [0081] Next, while the stirring blade was rotated at 500 revolutions per minute, an electrode reaction was performed by applying a current of 0.8 A to the battery tank until the total energization amount reached 60 mF. The entire amount of the solution in the battery case was recovered from the extraction valve cover and analyzed by GC, EI-MS, and CI-MS. As a result, the following compound (II 21 ) (GC yield 63.3%), the following compound (12 21 ) (GC yield 4.8%) and the following compound (14 21 ) (GC yield 30.6%) were confirmed to be produced.
[0082] 化合物（1121)の NMRデータを以下に示す。 [0082] The NMR data of the compound (11 21 ) are shown below.
'H-NMROOO.4MHZ, CDCl , Si(CH ) ) δ (ppm) :3.0〜3.5(m, 4Η),  'H-NMROOO.4MHZ, CDCl, Si (CH)) δ (ppm): 3.0-3.5 (m, 4Η),
3 3 4  3 3 4
3.9(bs, 6H)。  3.9 (bs, 6H).
19F-NMR(282.7MHz, CDCl , CFC1 ) δ (ppm) :+34.0(2F), —93.7〜 19 F-NMR (282.7MHz, CDCl, CFC1) δ (ppm): +34.0 (2F), —93.7〜
3 3  3 3
-99.8 (4F) , -171.6〜― 173.0(2F)。  -99.8 (4F), -171.6--173.0 (2F).
[0083] 化合物（1421)の NMRデータを以下に示す。 [0083] The NMR data of the compound (14 21 ) are shown below.
'H-NMROOO.4MHZ, CDCl , Si(CH ) ) δ (ppm) :3.4〜3.5(m, 2H),  'H-NMROOO.4MHZ, CDCl, Si (CH)) δ (ppm): 3.4 to 3.5 (m, 2H),
3 3 4  3 3 4
4.0(s, 3H)。  4.0 (s, 3H).
19F-NMR(282.7MHz, CDCl , CFC1 ) δ (ppm) : +45.9 (IF), +34.4( 19 F-NMR (282.7MHz, CDCl, CFC1) δ (ppm): +45.9 (IF), +34.4 (
3 3  3 3
IF), -95.5〜一 100.2(2F), —103.6〜一 105.6(2F), —175.5(1F)。 [化 30] IF), -95.5 to 1 100.2 (2F), —103.6 to 1 105.6 (2F), —175.5 (1F). [Chemical 30]
C(0)OCH3 C (0) OCH 3
CH30(0)C-CF— CH2CF2S02F ^CF CH2CF2SO2FCH 3 0 (0) C-CF— CH 2 CF 2 S0 2 F ^ CF CH2CF2SO2F
CH30(0)C— CF - CH2CF2S02F CF(C(0)OCH3^=CHCF2S02F CF2S02F CH 3 0 (0) C— CF-CH 2 CF 2 S0 2 F CF (C (0) OCH 3 ^ = CHCF 2 S0 2 F CF 2 S0 2 F
(1121) (1221) (1421) 産業上の利用可能性 (11 21 ) (12 21 ) (14 21 ) Industrial applicability
本発明の製造方法によれば、種々の構造の含フッ素化合物、特にフルォロスルホ -ル基を有する化合物を容易に製造できる。本発明の化合物は、フルォロモノマー の原料、フルォロモノマー、界面活性剤等の機能性材料として有用である。 なお、 2005年 11月 8曰に出願された曰本特許出願 2005— 323515号及び 2005 年 11月 10日に出願された日本特許出願 2005— 326309号の明細書、特許請求の 範囲、図面及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り 人れるものである。  According to the production method of the present invention, fluorine-containing compounds having various structures, particularly compounds having a fluorosulfol group can be easily produced. The compound of the present invention is useful as a functional material such as a raw material of a fluoromonomer, a fluoromonomer, and a surfactant. The specification, claims, drawings and abstract of Japanese Patent Application 2005-323515 filed on November 8, 2005 and Japanese Patent Application 2005-326309 filed on November 10, 2005 The entire contents of this document are hereby incorporated by reference and can be taken as the disclosure of the specification of the present invention.

Claims

請求の範囲 The scope of the claims
[1] 式 CXY=CHZで表される化合物（3)と、式 Q (SO F) (C (O) OH)で表される化  [1] Compound (3) represented by the formula CXY = CHZ and a compound represented by the formula Q (SO F) (C (O) OH)
2 m  2 m
合物（2)またはその塩とを電極反応させる、下式（11)で表される化合物、下式（12) で表される化合物、下式（ 13)で表される化合物および下式（14)で表される化合物 から選ばれる!/、ずれか 1種の化合物の製造方法。  A compound represented by the following formula (11), a compound represented by the following formula (12), a compound represented by the following formula (13), and a compound represented by the following formula (2) or a salt thereof: 14) A method for producing one compound selected from the compounds represented by 14)!
[化 1]  [Chemical 1]
X X
Y-C-CHZQ(SOzF)m X X X YC-CHZQ (SO z F) m XXX
I \ \ \ I \ \ \
Y-C-CHZQ(S02F)m /C=CZQ(S02F) CH— CHZQ(S02F)m Y— C-CHZQ(S02F)n X Y Y Q(S02F)m YC-CHZQ (S0 2 F) m / C = CZQ (S0 2 F) CH— CHZQ (S0 2 F) m Y— C-CHZQ (S0 2 F) n XYYQ (S0 2 F) m
(11) (12) (13) (14) 式中の記号は、下記の意味を示す。  (11) (12) (13) (14) The symbols in the formulas have the following meanings.
X、 Υ、 Ζ :それぞれ独立に、アルキル基、クロ口アルキル基、フルォロアルキル基、ヒ ドロキシアルキル基、アルコキシカルボ-ル基、フルォロアルコキシカルボ-ル基、ァ ルキルカルボニルォキシ基、またはフルォロアルキルカルボニルォキシ基であって、 炭素数 1〜： L0の基 (Α)、カルボキシル基、シァノ基、塩素原子、フッ素原子もしくは 水素原子。  X, Υ, and Ζ: each independently an alkyl group, a closed-mouth alkyl group, a fluoroalkyl group, a hydroxyalkyl group, an alkoxycarbonyl group, a fluoroalkoxycarbonyl group, an alkylcarbonyloxy group, or A fluoroalkylcarbonyloxy group, which is a group having 1 to C carbon atoms: L0 (Α), a carboxyl group, a cyano group, a chlorine atom, a fluorine atom or a hydrogen atom.
ただし、基 (Α)中にフッ素原子を含んでいてもよい炭素数 2以上のアルキル基部分 が存在する場合、該アルキル基中の炭素原子 炭素原子結合間には、式 Ο で 表される基、式 C (O)—で表される基、式 C (O) O で表される基、または式 oc(o)一で表される基が挿入されていてもよい。  However, when an alkyl group moiety having 2 or more carbon atoms which may contain a fluorine atom is present in the group (Α), a group represented by the formula Ο is present between the carbon atom and carbon atom bond in the alkyl group. A group represented by the formula C (O) —, a group represented by the formula C (O) 2 O 3, or a group represented by the formula oc (o) 1 may be inserted.
Q：炭素数 1〜10の（m+ 1)価のポリフルォロ飽和炭化水素基。  Q: (m + 1) -valent polyfluoro saturated hydrocarbon group having 1 to 10 carbon atoms.
ただし、 Q中の炭素原子 炭素原子結合間には、式 O で表される基が挿入さ れていてもよい。  However, a group represented by the formula O may be inserted between the carbon atom and the carbon atom bond in Q.
m: l、 2、または 3。  m: l, 2, or 3.
[2] 化合物（2)が、式 CR (SO F) (C (O) OH)で表される化合物（21)である請求  [2] The compound (2) is the compound (21) represented by the formula CR (SO F) (C (O) OH)
3-n 2 n  3-n 2 n
項 1に記載の製造方法。  Item 2. The manufacturing method according to Item 1.
式中の記号は、下記の意味を示す。  The symbols in the formula have the following meanings.
R:フッ素原子またはトリフルォロメチル基。 n: l、 2、または 3。 R: a fluorine atom or a trifluoromethyl group. n: l, 2, or 3.
[3] 式 CXaYa=CHで表される化合物（3a)と、式 Q (SO F) (C (O) OH)で表される [3] A compound represented by the formula CX a Y a = CH (3 a ) and a formula Q (SO F) (C (O) OH)
2 2 m  2 2 m
化合物（2)またはその塩とを電極反応させる、下式（l la)で表される化合物、下式（1 2a)で表される化合物、および下式（13a)で表される化合物力も選ばれるいずれか 1 種の化合物の製造方法。 A compound represented by the following formula (ll a ), a compound represented by the following formula (1 2 a ), and a compound represented by the following formula (13 a ), which are reacted with the compound (2) or a salt thereof. A method for producing any one compound in which force is also selected.
[化 2]  [Chemical 2]
Ya- χ气 Y a - χ gas
Ya— CH— CH2Q(S02F)m Y a — CH— CH 2 Q (S0 2 F) m
Figure imgf000026_0001
Figure imgf000026_0001
(11 ) (12d) (13a) 式中の記号は、下記の意味を示す。 (11) ( 12d ) ( 13a ) The symbols in the formula have the following meanings.
Xa、 Ya:それぞれ独立に、アルキル基、クロ口アルキル基、フルォロアルキル基、ヒド ロキシアルキル基、アルコキシカルボ-ル基、フルォロアルコキシカルボ-ル基、アル キルカルボ-ルォキシ基、またはフルォロアルキルカルボ-ルォキシ基であって、炭 素数 1〜： L0の基 (A)、カルボキシル基、シァノ基、塩素原子、もしくは水素原子。 ただし、基 (A)中にフッ素原子を含んでいてもよい炭素数 2以上のアルキル基部分 が存在する場合、該アルキル基中の炭素原子 炭素原子結合間には、式 O で 表される基、式 C (O)—で表される基、式 C (O) O で表される基、または式 oc(o)一で表される基が挿入されていてもよい。 X a , Y a : each independently an alkyl group, a closed alkyl group, a fluoroalkyl group, a hydroxyalkyl group, an alkoxy carbo group, a fluoro alkoxy carbo ol group, an alkyl carbo oxy group, or a fluoro It is a loalkylcarboxoxy group, which is a carbon number of 1 to: L0 group (A), carboxyl group, cyano group, chlorine atom, or hydrogen atom. However, when an alkyl group part having 2 or more carbon atoms that may contain a fluorine atom is present in the group (A), a group represented by the formula O is present between the carbon atom and carbon atom bond in the alkyl group. A group represented by the formula C (O) —, a group represented by the formula C (O) 2 O 3, or a group represented by the formula oc (o) 1 may be inserted.
Q：炭素数 1〜10の（m+ 1)価のポリフルォロ飽和炭化水素基。  Q: (m + 1) -valent polyfluoro saturated hydrocarbon group having 1 to 10 carbon atoms.
ただし、 Q中の炭素原子 炭素原子結合間には、式 O で表される基が挿入さ れていてもよい。  However, a group represented by the formula O may be inserted between the carbon atom and the carbon atom bond in Q.
m: l、 2、または 3。  m: l, 2, or 3.
[4] 化合物（3a)が、式 CXalYal = CHで表される化合物（3al)である請求項 3に記載の [4] Compound (3 a) is, according to claim 3, wherein the compound represented by the formula CX al Y al = CH (3 al)
2  2
製造方法。  Production method.
式中の記号は、下記の意味を示す。  The symbols in the formula have the following meanings.
xal:炭素数 1〜10のアルキル基または水素原子。 x al : an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.
Y31 :アルキル基、アルコキシカルボ-ル基、またはアルキルカルボ-ルォキシ基で あって、炭素数 1〜10の基 (Aa)もしくはカルボキシル基。 Y 31 : an alkyl group, an alkoxy carbo group, or an alkyl carbo oxy group And a group having 1 to 10 carbon atoms (A a ) or a carboxyl group.
ただし、基 (Aa)中に炭素数 2以上のアルキル基部分が存在する場合、該アルキル 基中の炭素原子-炭素原子結合間には、式— 0—で表される基、式— c (o)o で 表される基、または式 OC (O)—で表される基が挿入されていてもよい。 However, when an alkyl group having 2 or more carbon atoms is present in the group (A a ), a group represented by the formula —0—, a formula —c, is present between the carbon atom-carbon atom bonds in the alkyl group. (o) A group represented by o or a group represented by the formula OC (O) — may be inserted.
[5] 化合物（2)が、式 CR (SO F) (C (O) OH)で表される化合物（21)である請求 [5] The compound (2) is the compound (21) represented by the formula CR (SO F) (C (O) OH)
3-n 2 n  3-n 2 n
項 3または 4に記載の製造方法。  Item 5. The manufacturing method according to Item 3 or 4.
式中の記号は、下記の意味を示す。  The symbols in the formula have the following meanings.
R:フッ素原子またはトリフルォロメチル基。  R: a fluorine atom or a trifluoromethyl group.
n: l、 2、または 3。  n: l, 2, or 3.
[6] 式 CFYb=CHZbで表される化合物（3b)と、式 Q (SO F) (C (O) OH)で表される [6] A compound (3 b ) represented by the formula CFY b = CHZ b and a formula Q (SO F) (C (O) OH)
2 m  2 m
化合物（2)またはその塩とを電極反応させる、下式（l lb)で表される化合物、下式（1 2b)で表される化合物、および下式（ 14b)で表される化合物力 選ばれる 、ずれか 1 種の化合物の製造方法。 A compound represented by the following formula (ll b ), a compound represented by the following formula (1 2 b ), and a compound represented by the following formula (14 b ), which cause electrode reaction between the compound (2) or a salt thereof Force A method of producing one compound that is chosen.
[化 3]  [Chemical 3]
YB— C-CHZBQ(S02F)N Y B — C-CHZ B Q (S0 2 F) N
Y — C -CHZBQ(S02F)N Y — C -CHZ B Q (S0 2 F) N
Figure imgf000027_0001
Figure imgf000027_0001
(" (12 ) (1 式中の記号は、下記の意味を示す。  ("(12) (1 The symbols in the formula have the following meanings.
Yb、 zb:それぞれ独立に、アルキル基、クロ口アルキル基、フルォロアルキル基、ヒド ロキシアルキル基、アルコキシカルボ-ル基、フルォロアルコキシカルボ-ル基、アル キルカルボ-ルォキシ基、またはフルォロアルキルカルボ-ルォキシ基であって、炭 素数 1〜： L0の基 (A)、カルボキシル基、シァノ基、塩素原子、フッ素原子、もしくは水 素原子。 Y b , z b : each independently an alkyl group, a closed alkyl group, a fluoroalkyl group, a hydroxyalkyl group, an alkoxy carbo ol group, a fluoro alkoxy carbo ol group, an alkyl carbo oxy oxy group, or a fluoro It is a loalkylcarboxoxy group, which has a carbon number of 1 to: L0 group (A), a carboxyl group, a cyano group, a chlorine atom, a fluorine atom, or a hydrogen atom.
ただし、基 (A)中にフッ素原子を含んでいてもよい炭素数 2以上のアルキル基部分 が存在する場合、該アルキル基中の炭素原子 炭素原子結合間には、式 O で 表される基、式 C (O)—で表される基、式 C (O) O で表される基、または式 oc(o)一で表される基が挿入されていてもよい。 Q：炭素数 1〜10の（m+ 1)価のポリフルォロ飽和炭化水素基。 However, when an alkyl group part having 2 or more carbon atoms that may contain a fluorine atom is present in the group (A), a group represented by the formula O is present between the carbon atom and carbon atom bond in the alkyl group. A group represented by the formula C (O) —, a group represented by the formula C (O) 2 O 3, or a group represented by the formula oc (o) 1 may be inserted. Q: (m + 1) -valent polyfluoro saturated hydrocarbon group having 1 to 10 carbon atoms.
ただし、 Q中の炭素原子 炭素原子結合間には、式 O で表される基が挿入さ れていてもよい。  However, a group represented by the formula O may be inserted between the carbon atom and the carbon atom bond in Q.
m: l、 2、または 3。  m: l, 2, or 3.
[7] 化合物（3b)が、式 CFYbl = CHZblで表される化合物（3bl)で表される化合物であ る請求項 6に記載の製造方法。 7. The production method according to claim 6, wherein the compound (3 b ) is a compound represented by the compound (3 bl ) represented by the formula CFY bl = CHZ bl .
式中の記号は、下記の意味を示す。  The symbols in the formula have the following meanings.
Ybl :アルキル基、アルコキシカルボ-ル基、またはアルキルカルボ-ルォキシ基で あって、炭素数 1〜10の基 (Ab)もしくはカルボキシル基。 Y bl : an alkyl group, an alkoxycarbo group, or an alkylcarboxoxy group, a group having 1 to 10 carbon atoms (A b ) or a carboxyl group.
ただし、基 (Ab)中に炭素数 2以上のアルキル基部分が存在する場合、該アルキル 基中の炭素原子-炭素原子結合間には、式— 0—で表される基、式— c(o)o で 表される基、または式 OC (O)—で表される基が挿入されていてもよい。 However, when an alkyl group having 2 or more carbon atoms is present in the group (A b ), a group represented by the formula —0—, a formula —c, is present between the carbon atom-carbon atom bonds in the alkyl group. (o) A group represented by o or a group represented by the formula OC (O) — may be inserted.
zbl：水素原子またはフッ素原子。 z bl : a hydrogen atom or a fluorine atom.
[8] 化合物（2)が、式 CR (SO F) (C (O) OH)で表される化合物（21)である請求 [8] The compound (2) is the compound (21) represented by the formula CR (SO F) (C (O) OH)
3-n 2 n  3-n 2 n
項 6または 7に記載の製造方法。  Item 8. The manufacturing method according to Item 6 or 7.
式中の記号は、下記の意味を示す。  The symbols in the formula have the following meanings.
R:フッ素原子またはトリフルォロメチル基。  R: a fluorine atom or a trifluoromethyl group.
n: l、 2、または 3。  n: l, 2, or 3.
[9] 下式（I I1)で表される化合物（ただし、 X1および Z1はそれぞれ独立に、水素原子ま たはメチル基を、 R1はフッ素原子またはトリフルォロメチル基を、示す。 ) o [9] A compound represented by the following formula (II 1 ) (where X 1 and Z 1 each independently represent a hydrogen atom or a methyl group, and R 1 represents a fluorine atom or a trifluoromethyl group) O)
[化 4]  [Chemical 4]
X，
Figure imgf000028_0001
X,
Figure imgf000028_0001
下式（I I2)で表される化合物（ただし、 Z1は水素原子またはメチル基を、 R1はフッ 素原子またはトリフルォロメチル基を、示す。 ) o Compound represented by the following formula (II 2 ) (wherein Z 1 represents a hydrogen atom or a methyl group, and R 1 represents a fluorine atom or a trifluoromethyl group.) O
[化 5]
Figure imgf000029_0001
[Chemical 5]
Figure imgf000029_0001
[11] 下式（121)で表される化合物（ただし、 X1および Z1はそれぞれ独立に、水素原子ま たはメチル基を、 R1はフッ素原子またはトリフルォロメチル基を、示す。 ) o [11] A compound represented by the following formula (12 1 ) (wherein X 1 and Z 1 each independently represent a hydrogen atom or a methyl group, and R 1 represents a fluorine atom or a trifluoromethyl group) O)
[化 6] [Chemical 6]
Figure imgf000029_0002
Figure imgf000029_0002
下式（122)で表される化合物（ただし、 Z1は水素原子またはメチル基を、 R1はフッ 素原子またはトリフルォロメチル基を、示す。 ) o Compound represented by the following formula (12 2 ) (wherein Z 1 represents a hydrogen atom or a methyl group, and R 1 represents a fluorine atom or a trifluoromethyl group.) O
[化 7] [Chemical 7]
Figure imgf000029_0003
Figure imgf000029_0003
下式（131)で表される化合物（ただし、 X1および Z1はそれぞれ独立に、水素原子ま たはメチル基を、 R1はフッ素原子またはトリフルォロメチル基を、示す。 ) o Compound represented by the following formula (13 1 ) (wherein, X 1 and Z 1 each independently represent a hydrogen atom or a methyl group, and R 1 represents a fluorine atom or a trifluoromethyl group.) O
[化 8] [Chemical 8]
Figure imgf000029_0004
Figure imgf000029_0004
下式（142)で表される化合物（ただし、 Z1は水素原子またはメチル基を、 R1はフッ 素原子またはトリフルォロメチル基を、示す。 ) o Compound represented by the following formula (14 2 ) (wherein Z 1 represents a hydrogen atom or a methyl group, and R 1 represents a fluorine atom or a trifluoromethyl group.) O
[化 9] [Chemical 9]
Figure imgf000029_0005
Figure imgf000029_0005
PCT/JP2006/322199 2005-11-08 2006-11-07 Process for production of compound having fluorosulfonyl group, and novel compound WO2007055212A1 (en)

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Citations (7)

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Publication number Priority date Publication date Assignee Title
JPS58213749A (en) * 1983-05-13 1983-12-12 Asahi Chem Ind Co Ltd Novel fluorinated carboxylic acid derivative and preparation thereof
JPH03243607A (en) * 1990-02-20 1991-10-30 Asahi Glass Co Ltd Production of ethylene-tetrafluoroethylene copolymer
JPH0433904A (en) * 1990-05-29 1992-02-05 Asahi Glass Co Ltd Production of tetrafluoroethylene-ethylene-based copolymer with high mechanical strength and elongation
JPH0672987A (en) * 1992-08-25 1994-03-15 Nippon Bayeragrochem Kk Production of methanesulfonyl fluoride derivative
JPH07150378A (en) * 1993-08-31 1995-06-13 Minnesota Mining & Mfg Co <3M> Preparation of fluorochemical
JPH08512095A (en) * 1993-06-30 1996-12-17 ミネソタ マイニング アンド マニュファクチャリング カンパニー Method for producing perfluoroalkanesulfonyl fluoride
WO2005003062A2 (en) * 2003-07-02 2005-01-13 Asahi Glass Co Ltd Process for production of fluorinated sulfonyl fluorides

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58213749A (en) * 1983-05-13 1983-12-12 Asahi Chem Ind Co Ltd Novel fluorinated carboxylic acid derivative and preparation thereof
JPH03243607A (en) * 1990-02-20 1991-10-30 Asahi Glass Co Ltd Production of ethylene-tetrafluoroethylene copolymer
JPH0433904A (en) * 1990-05-29 1992-02-05 Asahi Glass Co Ltd Production of tetrafluoroethylene-ethylene-based copolymer with high mechanical strength and elongation
JPH0672987A (en) * 1992-08-25 1994-03-15 Nippon Bayeragrochem Kk Production of methanesulfonyl fluoride derivative
JPH08512095A (en) * 1993-06-30 1996-12-17 ミネソタ マイニング アンド マニュファクチャリング カンパニー Method for producing perfluoroalkanesulfonyl fluoride
JPH07150378A (en) * 1993-08-31 1995-06-13 Minnesota Mining & Mfg Co <3M> Preparation of fluorochemical
WO2005003062A2 (en) * 2003-07-02 2005-01-13 Asahi Glass Co Ltd Process for production of fluorinated sulfonyl fluorides

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