WO2008035677A1 - Novel chlorofluorosulfonimide and method for producing the same - Google Patents

Novel chlorofluorosulfonimide and method for producing the same Download PDF

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WO2008035677A1
WO2008035677A1 PCT/JP2007/068096 JP2007068096W WO2008035677A1 WO 2008035677 A1 WO2008035677 A1 WO 2008035677A1 JP 2007068096 W JP2007068096 W JP 2007068096W WO 2008035677 A1 WO2008035677 A1 WO 2008035677A1
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compound
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group
carbon atoms
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PCT/JP2007/068096
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Masao Iwaya
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Asahi Glass Company, Limited
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/323—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/10—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms
    • C07D211/14—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms with hydrocarbon or substituted hydrocarbon radicals attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C07D213/20—Quaternary compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C07D215/10—Quaternary compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/08—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/12—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

Definitions

  • the present invention relates to novel chlorofluorosulfonimides and a method for producing the same.
  • Patent Document 1 Perfluoroalkanesulfonyl imide and its salt are known (see Patent Document 1).
  • the specific salt of bis (perfluoroalkanesulfurimide) is known to form an ionic liquid, and its application to various uses has been attempted.
  • CI—CF—SO NH is known as a black mouth fluoroalkanesulfonamide.
  • Patent Document 1 Japanese Patent Publication No. 11 512563
  • Non-patent document 1 Synthesis 1979, 972- 975
  • perfluorosulfonimide bis (perfluoroalkanesulfonyl) imide having a chlorine atom.
  • perfluorosulfonimide bis (perfluoroalkanesulfonyl) imide
  • the present invention provides the following inventions.
  • n An integer from i to 4.
  • R F a perfluoroalkyl group having 1 to 6 carbon atoms or a group represented by the formula Q F — C1.
  • Q F a perfluoroalkylene group having 1 to 6 carbon atoms.
  • n An integer from i to 4.
  • Q F a perfluoroalkylene group having 1 to 6 carbon atoms.
  • n is 1
  • M is an alkali metal ion, ammonium ion, or phosphonium ion
  • Q F is a difluoromethylene group 2> Compound described in 1.
  • n An integer from i to 4.
  • R F a perfluoroalkyl group having 1 to 6 carbon atoms or a group represented by the formula Q F — C1.
  • Q F a perfluoroalkylene group having 1 to 6 carbon atoms.
  • R F a perfluoroalkyl group having 1 to 6 carbon atoms or a group represented by the formula Q F — C1.
  • Q F a perfluoroalkylene group having 1 to 6 carbon atoms.
  • a compound represented by the following formula (3) and a compound represented by the following formula (31) are reacted with ammonia in the presence of an amine compound, and further reacted with a protonic acid.
  • a method for producing the compound represented by (2) is reacted with ammonia in the presence of an amine compound, and further reacted with a protonic acid.
  • R F a perfluoroalkyl group having 1 to 6 carbon atoms or a group represented by the formula Q F — C1.
  • Q F a perfluoroalkylene group having 1 to 6 carbon atoms.
  • a chemically stable electrolyte made of a low-volatile and flame-retardant ionic compound is provided. Furthermore, a novel ionic liquid is provided by selecting the cation species of the ionic compound of the present invention.
  • a compound represented by the formula (1) is referred to as a compound (1).
  • the symbols in the groups are as defined above unless otherwise specified.
  • the present invention provides the following compound (1).
  • Compound (1) is a salt of n-valent cation [M] n + and n monovalent anions [R F — SO —N-SO Q F — C1] _ It is.
  • n in compound (1) is 1.
  • n + in compound (1) is preferably a monovalent cation (hereinafter also referred to as the same).
  • the alkali metal ion is particularly preferably a lithium ion, preferably a lithium ion, a sodium ion or a potassium ion.
  • ammonium ion is not particularly limited, and may be [NH] +.
  • the organic ammonium ion may be a non-cyclic organic ammonium ion or a cyclic organic ammonium ion.
  • the number of carbon atoms in the organic ammonium ion is preferably 1300 and particularly preferably 120.
  • An acyclic organic ammonium ion is an ion represented by the formula [N (R A )] + (where R A is
  • the four R A may be the same or different.
  • one OC (O) or one C (O) O is inserted between the carbon atom and carbon atom bond! /, Or even! / ⁇ .
  • R A is an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, an n propyl group, is o Propyl, n-butyl, iso-butyl or tert-butyl are particularly preferred.
  • the cyclic organic ammonium ion is preferably an organic compound having a ring structure containing a positively charged nitrogen atom, and is an imidazolium, a virazolium, a pyradium, a pyridinium, a pyridazinium, a pyrimidinium, a pyrrolidinium, a piperidinium, a quinolinium, or Triadium is particularly preferred.
  • a carbon atom forming a ring of the cyclic organic ammonium ion may be bonded to a C 16 alkyl group, a fluorine atom, or a C 16 fluoroalkyl group.
  • Imidazolium is the following ion (im-1), virazolium is the following ion (pi-1), pyradium is the following ion (pi-2), and pyridinium is the following ion (py-1).
  • Pyridazinium is the following ion (py—2)
  • pyrimidinium is the following ion (py—3)
  • pyrrolidinium is the following ion (pr—1)
  • piperidinium is the following ion (pp—1)
  • triazolium is the following ion (tr-l) ) Or the following ions (tr 2) are preferred! / '
  • zi to z 17 are each independently methyl having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
  • the group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group or tert-butyl group is particularly preferred.
  • R F of the compound (1) is preferably a group represented by the formula —Q F —C1. That is, the compound (1)
  • Q F is preferably a difluoromethylene group (one CF—).
  • the following compound (11 1) is particularly preferable, and the following compound (11 1) is particularly preferable!
  • Specific examples of the compound (1) include the following compounds.
  • n 2 is the following compound ( 11-2 ) ([M 2 ] 2+ represents a divalent cation; the same shall apply hereinafter), and n Compound (1) when n is 3 is the following compound ( 11-3 ) ([M 3 ] 3+ represents a trivalent cation; the same shall apply hereinafter), and when n is 4, 1) is the following compound (1-4) ([M 4 ] 4+ represents a tetravalent cation; the same shall apply hereinafter).
  • [M 2 ] 2+ include calcium ions, magnesium ions, and copper (II) ions.
  • [M 3 ] 3+ include aluminum (III) ions.
  • the compound (1) can be produced by reacting the following compound (2) with a compound represented by the formula [M] n + ([OH] — (hereinafter also referred to as hydroxide).
  • X n-fold mole of hydroxide it is preferable to use (1.00-2.00) X n-fold mole of hydroxide with respect to compound (2). (1.0.5-1.50) X n It is particularly preferred to use double moles.
  • the temperature in the reaction is preferably 0 to 200 ° C, 40 to 40, and particularly preferably 120 ° C.
  • the pressure in the reaction is not particularly limited. The reaction may be carried out in the presence of a solvent or in the absence of a solvent.
  • hydroxide examples include lithium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetraptylammonium hydroxide, 1-ethylyl hydroxide 3-methylimidazolium hydroxide.
  • R F of the compound (2) is preferably a group represented by the formula: Q F — C1.
  • Q F is preferably a difluoromethylene group (—CF—).
  • the compound (2) is preferably the following compound (21).
  • Compound (2) is a novel compound. Provided is a method for producing a compound (2) in which the following compound (3) and the following compound (31) are reacted with ammonia in the presence of an amine compound and further reacted with a protonic acid.
  • the temperature in the reaction is preferably 20 to + 200 ° C force S, and more preferably +10 to + 80 ° C.
  • the pressure in the reaction is not particularly limited.
  • the reaction may be carried out in the presence of a solvent or in the absence of a solvent.
  • the reaction may be performed in the presence of a solvent or may be performed in the absence of a solvent.
  • the solvent is not particularly limited as long as it is inert to the reaction substrate! /.
  • R F of the compound (3) is preferably a group represented by the formula —Q F —C1 (that is, the compound (3) is preferably the compound (31)).
  • Q F prefers a difluoromethylene group (one CF—)
  • the amine compound is a compound represented by the formula (R B ) N (where R B is an alkyl having 1 to 6 carbon atoms.
  • the protonic acid is particularly preferably concentrated sulfuric acid, preferably hydrochloric acid, nitric acid or sulfuric acid.
  • the compound (1) of the present invention is a novel compound. The present inventors have found that the compound (1) forms a chemically stable ionic liquid in a wide temperature range (one 70 ° C. to + 300 ° C.). Furthermore, it has been found that the compound (1) is a compound having a high boiling point, low volatility, excellent compatibility with other compounds and excellent conductivity.
  • the present invention provides a composition comprising compound (1) as an active ingredient.
  • the composition of the present invention may be a composition comprising the compound (1) and another compound, which may be a composition comprising the compound (1).
  • the composition of the present invention preferably contains 1 to 100% by mass of the compound (1).
  • the composition of the present invention contains other compounds, it preferably contains more than 0 to 99% by mass of the other compounds.
  • the other compound may be a liquid compound or a solid compound. Further, the other compound may be an organic compound or an inorganic compound.
  • the composition of the present invention when used as an electrolyte for a lithium secondary battery, it is preferable that the composition contains a compound (1) in which [M] n + is a lithium ion! /.
  • the composition of the present invention when used as an electrolytic solution for an electric double layer capacitor, the composition preferably contains a compound (1) in which [M] n + is an organic ammonium ion or phosphonium ion and an organic carbonate. .
  • the composition for the lithium secondary battery and the electric double layer capacitor preferably contains 40 to 80% by mass of the compound (1) and 20 to 60% by mass of the organic carbonate.
  • the carbonate is preferably ethylene carbonate, propylene power carbonate, butylene carbonate, dimethylol carbonate, or methino ethino carbonate.
  • the composition of the present invention when used as an antistatic agent, contains a compound (1) in which [M] n + is a lithium ion, an organic ammonium ion, or a phosphonium ion. It is preferable to include.
  • composition of the present invention may be used in various forms according to the application.
  • the composition of the present invention may be used alone or in combination with other materials.
  • composition of the present invention alone includes an electrolytic solution for an electrochemical device (lithium).
  • Um Secondary battery electrolyte, electric double layer capacitor electrolyte, fuel cell electrolyte, etc. Solvent (solvent for chemical reaction, solvent for extraction, solvent for electrolytic bath, etc.), heat medium, optical resolution agent, lubricant, gas detector for gas sensor, temperature sensor for temperature sensor, gas absorbent, chemical ( Skin absorption accelerators, enzyme coating agents, etc.) and immersion liquids in immersion exposure methods.
  • the composition of the present invention is particularly useful as an electrolyte for an electrochemical device, a solvent, or a heat medium from the viewpoint of its physical properties (low volatility, high compatibility, high conductivity, flame retardancy, etc.).
  • composition of the present invention with other materials include electrochemical device members (lithium secondary battery members, electric double layer capacitor members, fuel cell members, etc.), antistatic agents, and dispersants. It is done.
  • composition of the present invention examples include a carrier obtained by impregnating a porous carrier with the composition of the present invention, and another composition of the present invention.
  • examples thereof include composite materials obtained by kneading or adding to materials.
  • porous carrier examples include porous carbon materials (activated carbon and the like), porous inorganic materials (inorganic glass, silica gel, ceramics and the like), and porous resins.
  • the carrier is a carrier to which the physical properties (low volatility, high compatibility, high conductivity, flame retardancy, etc.) of the composition of the present invention are imparted, and is particularly useful as a member for an electrochemical device.
  • composite material examples include carbon materials (carbon nanotubes, fullerenes, diamonds, etc.), thermoplastic resins (fluorinated resins, polychlorinated bur resin, cellulose, polyolefin resins).
  • a composite material in which the other material is a carbon material can be a composite carbon material with improved flowability and excellent workability.
  • a composite material in which the other material is a thermoplastic resin is a composite material imparted with low volatility, high compatibility, high conductivity, and flame retardancy. It is useful as an optically anisotropic film, a conductive film, an antistatic film, a photoelectric conversion element, an actuator element, and a photosensitive element.
  • a photoreactor made of quartz, equipped with a high-pressure mercury lamp (output: 300 watts) was provided with a light source cooling jacket in an internal volume of 1 U. Distilled water at 60 ° C was circulated through the light source cooling jacket. In addition, a condenser with 30 ° C cooling water was installed at the gas outlet of the photoreactor, followed by a 78 ° C trap (made of SUS316, for collecting the product gas). Content volume 500mL).
  • CF (SO F) (COC1) 65g was charged into the photoreactor, and the photoreactor internal temperature was 80 ° C, 10:00.
  • Photoreaction was carried out by light irradiation. After completion of the reaction, Compound (3 1 ) (32 g) was obtained as a trap fraction. In addition, FO SCF CF SO F (8.4 g) was recovered in the photoreactor.
  • Example 2 The liquid (89.3 g) obtained in Example 1 and concentrated sulfuric acid (320 g) were charged into a flask (internal volume 500 mL) connected to an ice-cooled receiver (internal volume 300 mL). A 78 ° C glass trap was connected to the end of the receiver.
  • the compound of the present invention comprises a solvent (chemical reaction solvent, extraction solvent, electrolytic bath solvent, etc.), heat medium, optical resolution agent, lubricant, gas sensor gas detection agent, temperature sensor temperature sensitive agent, gas absorption.
  • Agent drug (percutaneous absorption enhancer, enzyme coating agent, etc.), immersion liquid in immersion exposure method, electrolyte for electrochemical devices (electrolyte for secondary battery, electrolyte for electric double layer capacitor, fuel cell) Electrolytes, etc.), electrochemical device members (secondary battery members, electric double layer capacitor members, fuel cell members, etc.), display element members, optical anisotropic films, conductive films, antistatic films, photoelectric conversion elements It is a useful compound for applications such as an actuator element and a photosensitive element. It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2006-256838 filed on September 22, 2006 are hereby incorporated herein by reference. It is something that is incorporated.

Abstract

Disclosed are novel chlorofluorosulfonimides and methods for producing such chlorofluorosulfonimides. Specifically disclosed are a compound (1) represented by the following formula: [M]n+([RF-SO2-N-SO2-QF-Cl]-)n; a compound (2) represented by the following formula: RF-SO2-NH-SO2-QF-Cl; a method for producing the compound (1) by reacting the compound (2) with [M]n+([OH]-)n; and a method for producing the compound (2) by reacting RF-SO2F and Cl-QF-SO2F with ammonia in the presence of an amine compound and then further reacting them with a protonic acid. In this connection, [M]n+ represents an n-valent cation; n represents an integer of 1-4; RF represents a perfluoroalkyl group having 1-6 carbon atoms or -QF-Cl; and QF represents a perfluoroalkylene group having 1-6 carbon atoms.

Description

明 細 書  Specification
新規なクロ口フルォロスルホンイミド類およびその製造方法  Novel black-mouthed fluorosulfonimides and process for producing the same
技術分野  Technical field
[0001] 本発明は、新規なクロ口フルォロスルホンイミド類およびその製造方法に関する。  [0001] The present invention relates to novel chlorofluorosulfonimides and a method for producing the same.
背景技術  Background art
[0002] スルホンイミド基（一SO -NH- SO一）を有するフルォロスルホンイミド類としては  [0002] As fluorosulfonimides having a sulfonimide group (one SO 2 —NH—SO 1),
2 2  twenty two
、 CF SO -NH- SO -CF、 CF CF SO— NH— SO— CF CF等のビス , CF SO -NH- SO -CF, CF CF SO- NH- SO- CF CF, etc.
3 2 2 3 3 2 2 2 2 33 2 2 3 3 2 2 2 2 3
(ペルフルォロアルカンスルホニル)イミド、その塩が知られている（特許文献 1など参 照。）。また、前記ビス（ペルフルォロアルカンスルホュル)イミドの特定塩は、イオン性 液体を形成することが知られており、種々の用途へ応用が試みられている。 (Perfluoroalkanesulfonyl) imide and its salt are known (see Patent Document 1). In addition, the specific salt of bis (perfluoroalkanesulfurimide) is known to form an ionic liquid, and its application to various uses has been attempted.
[0003] 一方、クロ口フルォロアルカンスルホンアミドとしては、 CI— CF - SO NHが知ら  On the other hand, CI—CF—SO NH is known as a black mouth fluoroalkanesulfonamide.
2 2 2 れている（非特許文献 1参照。）。 C1-CF SO NHに関しては、沸点と蒸気圧と  2 2 2 (see Non-Patent Document 1). For C1-CF SO NH, the boiling point and vapor pressure
2 2 2  2 2 2
が知られるにとどまる。  Remains to be known.
[0004] 特許文献 1 :特表平 11 512563号公報 [0004] Patent Document 1: Japanese Patent Publication No. 11 512563
非特許文献 1： Synthesis 1979, 972- 975  Non-patent document 1: Synthesis 1979, 972- 975
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0005] 本発明者らは、塩素原子を有するビス（ペルフルォロアルカンスルホニル)イミド（以 ノレ)イミド（以下、ペルフルォロスルホンイミド類ともいう。）に比較して、沸点が高く低 揮発性であると考えた。そして、鋭意検討の結果、新規なクロ口フルォロスルホンイミ ド類を見いだし、さらにクロ口フルォロスルホンイミドの塩が安定な電解質を形成しうる ことを見いだした。 [0005] The present inventors have a higher boiling point than bis (perfluoroalkanesulfonyl) imide (hereinafter referred to as perfluorosulfonimide) having a chlorine atom. Considered low volatility. As a result of intensive studies, the inventors have found novel chlorofluorosulfonimides and found that salts of chlorofluorosulfonimide can form stable electrolytes.
課題を解決するための手段  Means for solving the problem
[0006] すなわち、本発明は下記発明を提供する。 That is, the present invention provides the following inventions.
< 1 > 下式（1)で表される化合物。  <1> A compound represented by the following formula (1).
[M]n+ ( [RF- SO N— SO— QF— CI]— ) (1) ただし、式中の記号は下記の意味を示す。 [M] n + ([R F -SO N— SO— Q F — CI] —) (1) However, the symbol in a formula shows the following meaning.
[M]n+:n価の陽イオン。 [M] n + : n-valent cation.
n:i〜4の整数。  n: An integer from i to 4.
RF:炭素数 1〜6のペルフルォロアルキル基または式 QF— C1で表される基。 R F : a perfluoroalkyl group having 1 to 6 carbon atoms or a group represented by the formula Q F — C1.
QF:炭素数 1〜6のペルフルォロアルキレン基。 Q F : a perfluoroalkylene group having 1 to 6 carbon atoms.
[0007] <2> 下式（11)で表される化合物。 [0007] <2> A compound represented by the following formula (11):
[M]n+([Cl-QF-SO -N-SO— QF— C1]— ) (11) [M] n + ([Cl-Q F -SO -N-SO— Q F — C1] —) (11)
2 2 n  2 2 n
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.
[M]n+:n価の陽イオン。 [M] n + : n-valent cation.
n:i〜4の整数。  n: An integer from i to 4.
QF:炭素数 1〜6のペルフルォロアルキレン基。 Q F : a perfluoroalkylene group having 1 to 6 carbon atoms.
[0008] <3> 前記式（11)において、 nが 1であり、 Mがアルカリ金属イオン、アンモニゥム イオン、又はホスホニゥムイオンであり、かつ QFがジフルォロメチレン基である上記く 2〉に記載の化合物。 <3> In the above formula (11), n is 1, M is an alkali metal ion, ammonium ion, or phosphonium ion, and Q F is a difluoromethylene group 2> Compound described in 1.
<4> 下式（2)で表される化合物と式 [M]n+([OH]— ) で表される化合物とを反 応させる下式（1)で表される化合物の製造方法。 <4> A process for producing a compound represented by the following formula (1), wherein a compound represented by the following formula (2) and a compound represented by the formula [M] n + ([OH] —) are reacted.
RF-SO -NH-SO -QF-C1 (2) R F -SO -NH-SO -Q F -C1 (2)
2 2  twenty two
[M]n+([RF— SO— N— SO— QF— CI]— ) (1) [M] n + ([R F — SO— N— SO— Q F — CI] —) (1)
2 2 n  2 2 n
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.
[M]n+:n価の陽イオン。 [M] n + : n-valent cation.
n:i〜4の整数。  n: An integer from i to 4.
RF:炭素数 1〜6のペルフルォロアルキル基または式 QF— C1で表される基。 R F : a perfluoroalkyl group having 1 to 6 carbon atoms or a group represented by the formula Q F — C1.
QF:炭素数 1〜6のペルフルォロアルキレン基。 Q F : a perfluoroalkylene group having 1 to 6 carbon atoms.
[0009] <5> 下式（2)で表される化合物。 [0009] <5> A compound represented by the following formula (2).
RF-SO -NH-SO -QF-C1 (2) R F -SO -NH-SO -Q F -C1 (2)
2 2  twenty two
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.
RF:炭素数 1〜6のペルフルォロアルキル基または式 QF— C1で表される基。 R F : a perfluoroalkyl group having 1 to 6 carbon atoms or a group represented by the formula Q F — C1.
QF:炭素数 1〜6のペルフルォロアルキレン基。 [0010] < 6 > 下式（21)で表される化合物。 Q F : a perfluoroalkylene group having 1 to 6 carbon atoms. [0010] <6> A compound represented by the following formula (21).
Cl-QF- SO -NH- SO -QF-C1 (21) Cl-Q F -SO -NH- SO -Q F -C1 (21)
2 2  twenty two
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.
QF :炭素数 1〜6のペルフルォロアルキレン基。 Q F : a perfluoroalkylene group having 1 to 6 carbon atoms.
[0011] < 7 > 下式（3)で表される化合物および下式（31)で表される化合物を、アミン化 合物の存在下にアンモニアと反応させ、さらにプロトン酸と反応させる下式（2)で表さ れる化合物の製造方法。 <7> A compound represented by the following formula (3) and a compound represented by the following formula (31) are reacted with ammonia in the presence of an amine compound, and further reacted with a protonic acid. A method for producing the compound represented by (2).
RF— SO F (3) R F — SO F (3)
2  2
Cl-QF- SO F (31) Cl-Q F -SO F (31)
2  2
RF- SO -NH- SO -QF-C1 (2) R F -SO -NH- SO -Q F -C1 (2)
2 2  twenty two
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.
RF :炭素数 1〜6のペルフルォロアルキル基または式 QF— C1で表される基。 R F : a perfluoroalkyl group having 1 to 6 carbon atoms or a group represented by the formula Q F — C1.
QF :炭素数 1〜6のペルフルォロアルキレン基。 Q F : a perfluoroalkylene group having 1 to 6 carbon atoms.
発明の効果  The invention's effect
[0012] 本発明によれば、化学的に安定な、低揮発性かつ難燃性のイオン性化合物からな る電解質が提供される。さらに、本発明のイオン性化合物のカチオン種を選択するこ とにより、新規なイオン性液体が提供される。  [0012] According to the present invention, a chemically stable electrolyte made of a low-volatile and flame-retardant ionic compound is provided. Furthermore, a novel ionic liquid is provided by selecting the cation species of the ionic compound of the present invention.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0013] 本明細書においては、式（1)で表される化合物を化合物（1)と記す。他の式で表さ れる化合物も同様に記す。また、基中の記号は特に記載しない限り前記と同義であ In the present specification, a compound represented by the formula (1) is referred to as a compound (1). The same applies to compounds represented by other formulas. The symbols in the groups are as defined above unless otherwise specified.
[0014] 本発明は、下記化合物（1)を提供する。 [0014] The present invention provides the following compound (1).
[M]n+ ( [RF- SO N— SO— QF— CI]— ) (1) [M] n + ([R F -SO N— SO— Q F — CI] —) (1)
2 2 n  2 2 n
[0015] 化合物（1)は、 n価の陽イオンである [M]n+と、 n個の 1価の陰イオンである [RF— S O -N- SO QF— C1] _との塩である。 [0015] Compound (1) is a salt of n-valent cation [M] n + and n monovalent anions [R F — SO —N-SO Q F — C1] _ It is.
2 2  twenty two
[0016] 化合物（1)の nは 1であるのが好ましぐ化合物（1)の [M]n+は 1価の陽イオン（以 下、 ともいう。以下同様。）が好ましい。 [0016] It is preferable that n in compound (1) is 1. [M] n + in compound (1) is preferably a monovalent cation (hereinafter also referred to as the same).
—は、アルカリ金属イオン、アンモニゥムイオンまたはホスホニゥムイオンが好ま しぐアルカリ金属イオンまたはアンモニゥムイオンが特に好ましい。 — Is preferably alkali metal ion, ammonium ion or phosphonium ion Particularly preferred are alkali metal ions or ammonium ions.
[0017] アルカリ金属イオンは、リチウムイオン、ナトリウムイオンまたはカリウムイオンが好ま しぐリチウムイオンが特に好ましい。 [0017] The alkali metal ion is particularly preferably a lithium ion, preferably a lithium ion, a sodium ion or a potassium ion.
[0018] アンモニゥムイオンは、特に限定されず、 [NH ] +であってもよぐ有機アンモニゥム [0018] The ammonium ion is not particularly limited, and may be [NH] +.
4  Four
イオンであってもよい。  It may be an ion.
有機アンモニゥムイオンは、非環状有機アンモニゥムイオンであってもよぐ環状有 機アンモニゥムイオンであってもよい。有機アンモニゥムイオンの炭素数は、 1 30カ 好ましく、 1 20が特に好ましい。  The organic ammonium ion may be a non-cyclic organic ammonium ion or a cyclic organic ammonium ion. The number of carbon atoms in the organic ammonium ion is preferably 1300 and particularly preferably 120.
[0019] 非環状有機アンモニゥムイオンは、式 [N (RA) ] +で表されるイオン (ただし、 RAは [0019] An acyclic organic ammonium ion is an ion represented by the formula [N (R A )] + (where R A is
4  Four
炭素数;!〜 10の 1価炭化水素基または炭素数;!〜 10の 1価ハロゲン化炭化水素基 を示す。）が好ましい。 4個の RAは、同一であってもよぐ異なっていてもよい。また、 R A中に炭素原子 炭素原子結合が存在する場合、該炭素原子 炭素原子結合間に は一 O C (O) または一 C (O) O が揷入されて!/、てもよ!/ヽ。 A monovalent hydrocarbon group of carbon number;! To 10 or a monovalent halogenated hydrocarbon group of carbon number; ) Is preferred. The four R A may be the same or different. In addition, when a carbon atom-carbon atom bond exists in RA, one OC (O) or one C (O) O is inserted between the carbon atom and carbon atom bond! /, Or even! / ヽ.
[0020] RAは、炭素数 1 10のアルキル基、炭素数 1 10のフルォロアルキル基が好まし ぐ炭素数 1 6のアルキル基がより好ましぐメチル基、ェチル基、 n プロピル基、 is o プロピル基、 n ブチル基、 iso ブチル基または tert ブチル基が特に好まし い。 [0020] R A is an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, an n propyl group, is o Propyl, n-butyl, iso-butyl or tert-butyl are particularly preferred.
[0021] 環状有機アンモユウムイオンは、正荷電した窒素原子を含む環構造を有する有機 力チ才ンが好ましく、イミダゾリゥム、ビラゾリゥム、ピラジュゥム、ピリジニゥム、ピリダジ 二ゥム、ピリミジニゥム、ピロリジニゥム、ピペリジニゥム、キノリニゥムまたはトリアジユウ ムが特に好ましい。また、環状有機アンモニゥムイオンの環を形成する炭素原子には 、炭素数 1 6のアルキル基、フッ素原子または炭素数 1 6のフルォロアルキル基が 結合していてもよい。  [0021] The cyclic organic ammonium ion is preferably an organic compound having a ring structure containing a positively charged nitrogen atom, and is an imidazolium, a virazolium, a pyradium, a pyridinium, a pyridazinium, a pyrimidinium, a pyrrolidinium, a piperidinium, a quinolinium, or Triadium is particularly preferred. In addition, a carbon atom forming a ring of the cyclic organic ammonium ion may be bonded to a C 16 alkyl group, a fluorine atom, or a C 16 fluoroalkyl group.
[0022] イミダゾリゥムは下記イオン（im— 1)であり、ビラゾリゥムは下記イオン（pi— 1)であり 、ピラジュゥムは下記イオン (pi— 2)であり、ピリジニゥムは下記イオン (py— 1)であり 、ピリダジニゥムは下記イオン (py— 2)であり、ピリミジニゥムは下記イオン (py— 3)で あり、ピロリジニゥムは下記イオン (pr— 1)であり、ピペリジニゥムは下記イオン (pp— 1 )であり、キノリニゥムは下記イオン（qu—l)であり、トリアゾリゥムは下記イオン (tr—l )または下記イオン (tr 2)であるのが、それぞれ好まし!/ ' [0022] Imidazolium is the following ion (im-1), virazolium is the following ion (pi-1), pyradium is the following ion (pi-2), and pyridinium is the following ion (py-1). , Pyridazinium is the following ion (py—2), pyrimidinium is the following ion (py—3), pyrrolidinium is the following ion (pr—1), piperidinium is the following ion (pp—1), quinolinium Is the following ion (qu-l), and triazolium is the following ion (tr-l) ) Or the following ions (tr 2) are preferred! / '
[0023] [化 1] [0023] [Chemical 1]
Figure imgf000006_0001
Figure imgf000006_0001
[0024] ただし、式中の記号は下記の意味を示す（以下同様。）。  However, the symbols in the formulas have the following meanings (the same applies hereinafter).
z z2、 z3、 z4、 z5、 z6、 z7、 z8、 z9、 z10、 zu、 z12、 z13、 z14、 z15、 z16および z17はzz 2 , z 3 , z 4 , z 5 , z 6 , z 7 , z 8 , z 9 , z 10 , z u , z 12 , z 13 , z 14 , z 15 , z 16 and z 17
、それぞれ独立に、炭素数 1〜20の 1価炭化水素基または炭素数 1〜20の 1価フッ 素化炭化水素基を示す。 Each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms.
また、 zi〜z17中に炭素原子 炭素原子結合が存在する場合、該炭素原子 炭素 原子結合間には O 、 一 C (O) または C (O) O が揷入されて!/、てもよ!/、。 Also, if there is a carbon atom carbon atom bond in Zi～z 17, is between the carbon carbon atom bonded O, and mono C (O) or C (O) O is揷入! /, Even Yo! /
[0025] zi〜z17は、それぞれ独立に、炭素数 1〜； 10のアルキル基または炭素数 1〜； 10の フルォロアルキル基が好ましぐ炭素数 1〜6のアルキル基がより好ましぐメチル基、 ェチル基、 n プロピル基、 iso プロピル基、 n ブチル基、 iso ブチル基または t ert ブチル基が特に好ましい。 [0025] zi to z 17 are each independently methyl having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. The group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group or tert-butyl group is particularly preferred.
[0026] 化合物（1)の RFは、式— QF— C1で表される基が好ましい。すなわち、化合物（1)の [0026] R F of the compound (1) is preferably a group represented by the formula —Q F —C1. That is, the compound (1)
1価の陰イオン部分 [R— SO -N- SO - -QF— C1]—は [C1 Q SO -N- SOThe monovalent anion moiety [R—SO—N—SO——Q F — C1] —has [C1 Q SO —N—SO
— GT— Cl] _が好ましい。 QFは、ジフルォロメチレン基（一CF―)が好ましい。— GT—Cl] _ is preferred. Q F is preferably a difluoromethylene group (one CF—).
2 2 twenty two
[0027] 化合物（1)は、下記化合物（11)が好ましぐ下記化合物（11 1)が特に好まし!/ '  [0027] As the compound (1), the following compound (11 1) is particularly preferable, and the following compound (11 1) is particularly preferable!
[M]n+ ( [Cl-Qr - SO N— SO— Q -C1]— ) (11) [M1] + [Cl-QF-SO -N-SO— QF— CI]— (11— 1) [M] n + ([Cl-Q r -SO N— SO— Q -C1] —) (11) [M 1 ] + [Cl-Q F -SO -N-SO— Q F — CI] — (11— 1)
2 2  twenty two
[0028] 化合物（1)の具体例としては、下記化合物が挙げられる。  [0028] Specific examples of the compound (1) include the following compounds.
[0029] [化 2] [0029] [Chemical 2]
|Lij [ Cl-CF2-S02-N-S02-CF2-Cl NH4 J [ C1-CF2-S02-N-S02-CF2-CI | | Lij [Cl-CF 2 -S0 2 -N-S0 2 -CF 2 -Cl NH 4 J [C1-CF 2 -S0 2 -N-S0 2 -CF 2 -CI |
[N(CH3)4 ] +| CI-CF2-S02-N-S02-CF2-CI ] [ N(CH2CH3)4j [ CI-CF2-S02-N-S02-CF2-CI ] [N (CH 3 ) 4 ] + | CI-CF 2 -S0 2 -N-S0 2 -CF 2 -CI] [N (CH 2 CH 3 ) 4 j [CI-CF 2 -S0 2 -N-S0 2 -CF 2 -CI]
Figure imgf000007_0001
Figure imgf000007_0001
[0030] なお、 nが 2である場合の化合物（1)は下記化合物（1一 2) ([M2]2+は 2価の陽ィォ ンを示す。以下同様。）であり、 nが 3である場合の化合物（1)は下記化合物（1一 3) ( [M3]3+は 3価の陽イオンを示す。以下同様。）であり、 nが 4である場合の化合物（1) は下記化合物（1—4) ([M4]4+は 4価の陽イオンを示す。以下同様。）である。 [0030] The compound (1) in the case where n is 2 is the following compound ( 11-2 ) ([M 2 ] 2+ represents a divalent cation; the same shall apply hereinafter), and n Compound (1) when n is 3 is the following compound ( 11-3 ) ([M 3 ] 3+ represents a trivalent cation; the same shall apply hereinafter), and when n is 4, 1) is the following compound (1-4) ([M 4 ] 4+ represents a tetravalent cation; the same shall apply hereinafter).
[M2]2+([RF-SO -N-SO -QF-C1]") (1-2) [M 2 ] 2+ ([R F -SO -N-SO -Q F -C1] ") (1-2)
2 2 2  2 2 2
[M3]3+([RF-SO -N-SO— QF— CI]— ) (1— 3) [M 3 ] 3+ ([R F -SO -N-SO— Q F — CI] —) (1— 3)
2 2 3  2 2 3
[M4]4+([RF-SO -N-SO— QF— CI]— ) (1—4) [M 4 ] 4+ ([R F -SO -N-SO— Q F — CI] —) (1-4)
2 2 4  2 2 4
[0031] [M2]2+の具体例としては、カルシウムイオン、マグネシウムイオン、銅（II)イオンが 挙げられる。 [0031] Specific examples of [M 2 ] 2+ include calcium ions, magnesium ions, and copper (II) ions.
[M3]3+の具体例としては、アルミニウム（III)イオンが挙げられる。 [0032] 化合物（1)は、下記化合物（2)と式 [M]n+ ( [OH]— で表される化合物（以下、水 酸化物ともいう。）を反応させることにより製造できる。 Specific examples of [M 3 ] 3+ include aluminum (III) ions. The compound (1) can be produced by reacting the following compound (2) with a compound represented by the formula [M] n + ([OH] — (hereinafter also referred to as hydroxide).
RF- SO -NH- SO -QF-C1 (2) R F -SO -NH- SO -Q F -C1 (2)
2 2  twenty two
[0033] 前記反応においては、化合物（2)に対して水酸化物の（1. 00-2. 00) X n倍モル を用いるのが好ましぐ (1. 05-1. 50) X n倍モルを用いるのが特に好ましい。前記 反応における温度は、 0〜200°Cが好ましぐ 40〜； 120°Cが特に好ましい。前記反応 における圧力は、特に限定されない。前記反応は、溶媒の存在下に行ってもよぐ溶 媒の不存在下に行ってもょレ、。  [0033] In the above reaction, it is preferable to use (1.00-2.00) X n-fold mole of hydroxide with respect to compound (2). (1.0.5-1.50) X n It is particularly preferred to use double moles. The temperature in the reaction is preferably 0 to 200 ° C, 40 to 40, and particularly preferably 120 ° C. The pressure in the reaction is not particularly limited. The reaction may be carried out in the presence of a solvent or in the absence of a solvent.
[0034] 水酸化物の具体例としては、水酸化リチウム、水酸化アンモユウム、水酸化テトラメ チルアンモニゥム、水酸化テトラエチルアンモニゥム、水酸化テトラプチルアンモニム ゥム、水酸化 1ーェチルー 3—メチルイミダゾリゥム、水酸化- 1ーメチルー 3—プロ ピルイミダゾリゥム、水酸化 1 , 2—ジメチルー 3—ブチルイミダゾリゥム、水酸化 1 ーェチルー 2—メチルビラゾリゥム、水酸化 1 メチルー 2—プロピルビラゾリゥム、 水酸化 1 メチルピリジニゥム、水酸化 1一へキシルピリジニゥム、水酸化 1 ブチルピリジニゥム、水酸化 1 ェチルピリジニゥム、水酸化 1 プロピル 3— メチルピリジニゥム、水酸化 1ーェチルー 1 メチルピロリジニゥム、水酸化 1ーメ チルー 1 プロピルピロリジニゥム、水酸化 1ーェチルー 1ーメチルビペリジニゥム、 水酸化 1ーメチルー 1 プロピルピぺリジユウム、水酸化 1ーメチルー 2—プロピ ノレ 1 , 2, 4—トリアゾリゥム、水酸ィ匕ー 1ーェチノレー 2—メチノレー 1 , 2, 4—トリアゾリ ゥム、水酸化ー1 プロピルー2—メチルー 1 , 2, 3—トリアゾリゥム、水酸化ー1ーェ チルー 2—メチルー 1 , 2, 3—トリアゾリゥム、水酸化ー1 メチルピリダジニゥム、水 酸化— 1—へキシルピリダジニゥム、水酸化— 1—ブチルピリダジニゥム、水酸化— 1 ェチルピリダジニゥム、水酸化 1 プロピル 3—メチルピリダジニゥム、水酸化 —1—メチルピリミジニゥム、水酸化— 1—へキシルピリミジニゥム、水酸化— 1—ブチ ルピリミジニゥム、水酸化 1 ェチルピリミジニゥム、水酸化 1 プロピルー3—メ チルピリミジニゥム、水酸化— 1—メチルビラジュゥム、水酸化— 1—へキシルビラジュ ゥム、水酸化 1ーブチルビラジュゥム、水酸化 1ーェチルビラジュゥム、水酸化 1 プロピル 3ーメチルビラジュゥム、水酸化 1ーェチルキノリニゥム、又は水酸 化 1ーェチルー 4ーメチルキノリニゥムが挙げられる。水酸化物は、水和物を使用し てもよい。 [0034] Specific examples of the hydroxide include lithium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetraptylammonium hydroxide, 1-ethylyl hydroxide 3-methylimidazolium hydroxide. 1-Methyl hydroxide 3-Propyrimazole, 1,2-Dimethyl-3-butylimidazolium hydroxide, 1-Ethyl hydroxide 2-Methylvirazolium, 1-Methyl-2-propylvirazol hydroxide 1-hydroxypyridinium hydroxide, 1-hexylpyridinium hydroxide, 1-butylpyridinium hydroxide, 1-ethylpyridinium hydroxide, 1-propylpyridinium hydroxide, 1-propyl3-hydroxymethylhydroxide Dinium, 1-hydroxyl methyl hydroxide 1-methylpyrrolidinium, 1-methylhydroxyl-1-propylpyrrolidinium, 1-ethylpyrrolidone 1-methylbiperidinium 1-Methyl-1 propylpiperidinium hydroxide, 1-methyl-2-propylene 1,2-, 4-triazolium, hydroxide 1-ethylinole 2-methinole 1,2,4-triazolium, hydroxide-1 Propyl-2-methyl-1,2,3-triazolium, hydroxide-1 etheryl 2-methyl-1,2,3-triazolium, hydroxide-1 methylpyridazinium, hydroxanized 1-hexylpyrida Dinium, hydroxylated—1-butylpyridazinium, hydroxylated—1-ethylpyridazinium, hydroxylated 1-propyl 3-methylpyridazinium, hydroxylated—1-methylpyrimidine Hydroxyl, 1-Hexylpyrimidinium, Hydroxyl-1-Butylpyrimidinium, Hydroxyl 1 Ethylpyrimidinium, Hydroxyl 1 Propyl-3-Methylpyrimidinium, Hydroxylation 1- To methyl villajume, hydroxylation—1— Shirubiraju © beam, hydroxide -1-butyl Villa Juu-time, hydroxide 1 over E chill Villa Juu-time, hydroxide 1-propyl 3-methyl villanium, 1-hydroxyquinolinium hydroxide, or 1-ethyl 4-methylquinolinium hydroxide. As the hydroxide, a hydrate may be used.
[0035] 化合物（2)の RFは、式一 QF— C1で表される基が好ましい。 QFは、ジフルォロメチレ ン基（― CF―)が好ましい。 [0035] R F of the compound (2) is preferably a group represented by the formula: Q F — C1. Q F is preferably a difluoromethylene group (—CF—).
2  2
化合物（2)は、下記化合物（21)が好ましい。  The compound (2) is preferably the following compound (21).
Cl-QF- SO -NH- SO -QF-C1 (21) Cl-Q F -SO -NH- SO -Q F -C1 (21)
2 2  twenty two
[0036] 化合物（2)は、新規化合物である。下記化合物（3)および下記化合物（31)をアミ ン化合物の存在下にアンモニアと反応させ、さらにプロトン酸と反応させる化合物（2) の製造方法を提供する。  [0036] Compound (2) is a novel compound. Provided is a method for producing a compound (2) in which the following compound (3) and the following compound (31) are reacted with ammonia in the presence of an amine compound and further reacted with a protonic acid.
RF— SO F (3) R F — SO F (3)
2  2
Cl-QF- SO F (31) Cl-Q F -SO F (31)
[0037] 化合物（3)および下記化合物（31)とアンモニアの反応にお!/、ては、化合物（3)と 化合物（31)の総量に対して、 1. 0〜； 1. 5倍モルのアンモニアを用いるのが好ましい [0037] In the reaction of the compound (3) and the following compound (31) with ammonia! /, 1.0 to 1.5 times the total amount of the compound (3) and the compound (31) It is preferable to use ammonia
〇 Yes
[0038] 前記反応における温度は、 20〜 + 200°C力 S好ましく、 + 10〜 + 80°Cが特に好 ましい。前記反応における圧力は、特に限定されない。前記反応は、溶媒の存在下 に行ってもよぐ溶媒の不存在下に行ってもよい。前記反応は、溶媒の存在下に行つ てもよく、溶媒の不存在下に行ってもよい。溶媒は、反応基質に対して不活性な溶媒 であれば特に限定されな!/、。  [0038] The temperature in the reaction is preferably 20 to + 200 ° C force S, and more preferably +10 to + 80 ° C. The pressure in the reaction is not particularly limited. The reaction may be carried out in the presence of a solvent or in the absence of a solvent. The reaction may be performed in the presence of a solvent or may be performed in the absence of a solvent. The solvent is not particularly limited as long as it is inert to the reaction substrate! /.
[0039] 化合物（3)の RFは、式— QF—C1で表される基が好ましい（すなわち、化合物（3)は 化合物（31)であるのが好ましい。）。 QFは、ジフルォロメチレン基（一 CF—）が好ま [0039] R F of the compound (3) is preferably a group represented by the formula —Q F —C1 (that is, the compound (3) is preferably the compound (31)). Q F prefers a difluoromethylene group (one CF—)
2  2
しい。  That's right.
[0040] ァミン化合物は、式 (RB) Nで表される化合物（ただし、 RBは炭素数 1〜6のアルキ [0040] The amine compound is a compound represented by the formula (R B ) N (where R B is an alkyl having 1 to 6 carbon atoms.
3  Three
ル基であり、 3個の RBは同一であってもよく異なっていてもよい。）が好ましぐ N (CH A group, the three R B may be different may be the same. ) Is preferred N (CH
3 Three
) 、 N (CH CH ) 、 N (CH CH CH ) 、 N (CH ) (CH CH ) または N (CH ) (C), N (CH CH), N (CH CH CH), N (CH) (CH CH) or N (CH) (C
3 2 3 3 2 2 3 3 3 2 3 2 3 23 2 3 3 2 2 3 3 3 2 3 2 3 2
H CH )が特に好ましい。 H 2 CH 3) is particularly preferred.
2 3  twenty three
[0041] プロトン酸は、塩酸、硝酸または硫酸が好ましぐ濃硫酸が特に好ましい。 [0042] 本発明の化合物（1)は、新規化合物である。本発明者らは、化合物（1)が、広い温 度範囲（一 70°C〜 + 300°C)において、化学的に安定なイオン性液体を形成するこ とを見いだした。さらに、化合物（1)は、沸点が高く低揮発性で、他の化合物と高い 相溶性を有する導電性に優れた化合物であるとの知見を得た。 [0041] The protonic acid is particularly preferably concentrated sulfuric acid, preferably hydrochloric acid, nitric acid or sulfuric acid. [0042] The compound (1) of the present invention is a novel compound. The present inventors have found that the compound (1) forms a chemically stable ionic liquid in a wide temperature range (one 70 ° C. to + 300 ° C.). Furthermore, it has been found that the compound (1) is a compound having a high boiling point, low volatility, excellent compatibility with other compounds and excellent conductivity.
[0043] 本発明は、化合物（1)を有効成分とする組成物を提供する。本発明の組成物は、 化合物（ 1 )からなる組成物であつてもよぐ化合物（ 1 )と他の化合物を含む組成物で あってもよい。本発明の組成物は、化合物（1)の 1〜； 100質量％を含むのが好ましい 。本発明の組成物が、他の化合物を含む場合には、他の化合物の 0超〜 99質量％ を含むのが好ましい。他の化合物は、液状の化合物であってもよぐ固体状の化合物 であってもよい。また、他の化合物は、有機化合物であってもよく無機化合物であつ てもよい。  [0043] The present invention provides a composition comprising compound (1) as an active ingredient. The composition of the present invention may be a composition comprising the compound (1) and another compound, which may be a composition comprising the compound (1). The composition of the present invention preferably contains 1 to 100% by mass of the compound (1). When the composition of the present invention contains other compounds, it preferably contains more than 0 to 99% by mass of the other compounds. The other compound may be a liquid compound or a solid compound. Further, the other compound may be an organic compound or an inorganic compound.
[0044] 本発明の組成物における化合物（1)の種類と、他の化合物の種類と、その配合量 とは、本発明の組成物の用途にしたがって、適宜変更される。  [0044] The type of the compound (1) in the composition of the present invention, the types of the other compounds, and the blending amount thereof are appropriately changed according to the use of the composition of the present invention.
たとえば、本発明の組成物をリチウム 2次電池用電解液として使用する場合、組成 物は [M]n+がリチウムイオンである化合物（1)を含むのが好まし!/、。 For example, when the composition of the present invention is used as an electrolyte for a lithium secondary battery, it is preferable that the composition contains a compound (1) in which [M] n + is a lithium ion! /.
本発明の組成物を電気二重層キャパシタ用電解液として使用する場合、組成物は 、 [M]n+が有機アンモニゥムイオンまたはホスホニゥムイオンである化合物（1)と有機 カーボネートとを含むのが好ましい。リチウム 2次電池用及び電気二重層キャパシタ 用の組成物は、化合物（1)の 40〜80質量％を含み、かつ有機カーボネートの 20〜 60質量％を含むのが好ましい。カーボネートは、エチレンカーボネート、プロピレン力 ーボネート、ブチレンカーボネート、ジメチノレカーボネート、またはメチノレエチノレカー ボネートが好ましい。 When the composition of the present invention is used as an electrolytic solution for an electric double layer capacitor, the composition preferably contains a compound (1) in which [M] n + is an organic ammonium ion or phosphonium ion and an organic carbonate. . The composition for the lithium secondary battery and the electric double layer capacitor preferably contains 40 to 80% by mass of the compound (1) and 20 to 60% by mass of the organic carbonate. The carbonate is preferably ethylene carbonate, propylene power carbonate, butylene carbonate, dimethylol carbonate, or methino ethino carbonate.
[0045] 本発明の組成物を帯電防止剤として使用する場合には、本発明の組成物は、 [M] n+がリチウムイオン、有機アンモニゥムイオンまたはホスホニゥムイオンである化合物（ 1)を含むのが好ましい。 [0045] When the composition of the present invention is used as an antistatic agent, the composition of the present invention contains a compound (1) in which [M] n + is a lithium ion, an organic ammonium ion, or a phosphonium ion. It is preferable to include.
[0046] また、本発明の組成物は、用途にしたがって種々の形態で使用されうる。本発明の 組成物は、単独で使用してもよぐ他の材料と組み合わせて使用してもよい。  [0046] The composition of the present invention may be used in various forms according to the application. The composition of the present invention may be used alone or in combination with other materials.
[0047] 本発明の組成物を単独で使用する用途としては、電気化学デバイス用電解液（リチ ゥム 2次電池用電解液、電気二重層キャパシタ用電解液、燃料電池用電解質等。）、 溶媒 (化学反応用溶媒、抽出用溶媒、電解浴用溶媒等。）、熱媒体、光学分割剤、 潤滑剤、ガスセンサー用ガス検出剤、温度センサー用感温剤、ガス吸収剤、薬剤（経 皮吸収促進剤、酵素コーティング剤等。）、液浸露光方法における液浸液が挙げられ る。本発明の組成物は、その物性 (低揮発性、高相溶性、高導電性、難燃性等。）の 観点から、電気化学デバイス用電解質、溶媒、または熱媒体として特に有用である。 [0047] The use of the composition of the present invention alone includes an electrolytic solution for an electrochemical device (lithium). Um Secondary battery electrolyte, electric double layer capacitor electrolyte, fuel cell electrolyte, etc. ), Solvent (solvent for chemical reaction, solvent for extraction, solvent for electrolytic bath, etc.), heat medium, optical resolution agent, lubricant, gas detector for gas sensor, temperature sensor for temperature sensor, gas absorbent, chemical ( Skin absorption accelerators, enzyme coating agents, etc.) and immersion liquids in immersion exposure methods. The composition of the present invention is particularly useful as an electrolyte for an electrochemical device, a solvent, or a heat medium from the viewpoint of its physical properties (low volatility, high compatibility, high conductivity, flame retardancy, etc.).
[0048] 本発明の組成物を他の材料と組み合わせる用途としては、電気化学デバイス部材（ リチウム 2次電池部材、電気二重層キャパシタ部材、燃料電池部材等。）、帯電防止 剤、分散剤が挙げられる。  [0048] Applications for combining the composition of the present invention with other materials include electrochemical device members (lithium secondary battery members, electric double layer capacitor members, fuel cell members, etc.), antistatic agents, and dispersants. It is done.
[0049] 本発明の組成物と他の材料を組み合わせて得た物品の具体例としては、本発明の 組成物を多孔性担体に含浸して得られた担体、本発明の組成物を他の材料に混練 または添加して得られた複合材料等が挙げられる。  [0049] Specific examples of articles obtained by combining the composition of the present invention with other materials include a carrier obtained by impregnating a porous carrier with the composition of the present invention, and another composition of the present invention. Examples thereof include composite materials obtained by kneading or adding to materials.
[0050] 前記多孔性担体の具体例としては、多孔性炭素材料 (活性炭等。 )、多孔性無機材 料 (無機ガラス、シリカゲル、セラミックス等。）、多孔性樹脂が挙げられる。前記担体 は、本発明の組成物の物性 (低揮発性、高相溶性、高導電性、難燃性等。）が付与さ れた担体であり、電気化学デバイス用部材として特に有用である。  [0050] Specific examples of the porous carrier include porous carbon materials (activated carbon and the like), porous inorganic materials (inorganic glass, silica gel, ceramics and the like), and porous resins. The carrier is a carrier to which the physical properties (low volatility, high compatibility, high conductivity, flame retardancy, etc.) of the composition of the present invention are imparted, and is particularly useful as a member for an electrochemical device.
[0051] 前記複合材料における他の材料の具体例としては、炭素材料 (カーボンナノチュー ブ、フラーレン、ダイヤモンド等。）、熱可塑性樹脂 (含フッ素樹脂、ポリ塩化ビュル樹 脂、セルロース、ポリオレフイン系樹脂（ポリエチレン、ポリプロピレン、ポリ酢酸ビュル 等。 )、スチレン系樹脂（ポリスチレン、 ABS等。 )、ポリエステル系樹脂（ポリエチレン テレフタレート、ポリブチレンテレフタレート等。）、（メタ）アクリル系樹脂（ポリアクリレ ート、ポリメチルメタタリレート等。）、ポリアミド系樹脂（ナイロン 6、ナイロン 66、ナイ口 ン MXD6等。）、ポリカーボネート系樹脂（ビスフエノール Aポリカーボネート等。）、ポ リエーテル系樹脂（ポリフエ二レンエーテル、ポリアセタール等。）が挙げられる。  [0051] Specific examples of other materials in the composite material include carbon materials (carbon nanotubes, fullerenes, diamonds, etc.), thermoplastic resins (fluorinated resins, polychlorinated bur resin, cellulose, polyolefin resins). (Polyethylene, polypropylene, poly (butyl acetate), etc.), styrene resins (polystyrene, ABS, etc.), polyester resins (polyethylene terephthalate, polybutylene terephthalate, etc.), (meth) acrylic resins (polyacrylate, polymethyl) Metatalylate, etc.), polyamide resins (nylon 6, nylon 66, nay MXN6, etc.), polycarbonate resins (bisphenol A polycarbonate, etc.), polyether resins (polyphenylene ether, polyacetal, etc.). ).
[0052] 他の材料が炭素材料である複合材料は、流動性が改善された、加工性に優れる複 合炭素材料となりうる。  [0052] A composite material in which the other material is a carbon material can be a composite carbon material with improved flowability and excellent workability.
他の材料が熱可塑性樹脂である複合材料は、低揮発性、高相溶性、高導電性、お よび難燃性が付与された複合材料であり、電気化学デバイス部材、表示素子用部材 、光学異方性フィルム、導電性フィルム、帯電防止性フィルム、光電変換素子、ァク チユエータ素子、感光素子として有用である。 A composite material in which the other material is a thermoplastic resin is a composite material imparted with low volatility, high compatibility, high conductivity, and flame retardancy. It is useful as an optically anisotropic film, a conductive film, an antistatic film, a photoelectric conversion element, an actuator element, and a photosensitive element.
実施例  Example
[0053] 本発明を、実施例によって具体的に説明するが、本発明はこれらに限定されない。  [0053] The present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.
[0054] <参考例 1〉 CF C1SO F ;化合物（31)の製造例 <Reference Example 1> CF C1SO F; Production Example of Compound (3 1 )
2 2  twenty two
真空に引いたオートクレーブ（ノヽステロイ製、内容積 500mUに、テトラフルォロェ タンサルトン（テトラフルォロェタン 1 , 2 スルトン）（900g)を仕込んだ。つぎに、ォ 一トクレーブ内温 20°C以下にて、オートクレーブに水（89. Og)を吸引させて添加し た。添加終了後、オートクレープ内温 25°Cにて、オートクレープ内を 12時間撹拌した 。つづいて、オートクレーブ内の副生 HFを留去した後に、オートクレーブ内容物を蒸 留精製して CF (SO F) (COOH) (863g)を得た。  An autoclave that was evacuated (manufactured by North Steloy, with an internal volume of 500 mU and tetrafluoroethane sultone (tetrafluoroethane 1, 2 sultone) (900 g) was charged. Water (89. Og) was sucked into the autoclave and added.After the addition was completed, the autoclave was stirred for 12 hours at an internal temperature of 25 ° C. Subsequently, the by-product HF in the autoclave was distilled off. After leaving, the autoclave contents were purified by distillation to obtain CF (SOF) (COOH) (863 g).
2 2  twenty two
[0055] 4つ口フラスコ（ガラス製、内容積 2Uに、 PCI (625g)を仕込み、 CF (SO F) (C  [0055] Four-necked flask (made of glass, internal volume 2U, charged with PCI (625g), CF (SO F) (C
5 2 2  5 2 2
OOH) (534g)をフラスコを氷冷撹拌しながら 2時間かけて滴下した。滴下終了後、 2 5°Cにてフラスコ内を 12時間撹拌した後に、フラスコ内容物を蒸留精製して CF (SO  OOH) (534 g) was added dropwise over 2 hours while stirring the flask with ice. After completion of dropping, the flask was stirred at 25 ° C for 12 hours, and the flask contents were purified by distillation to obtain CF (SO
2 2
F) (COC1) (481g)を得た。 F) (COC1) (481 g) was obtained.
2  2
[0056] 高圧水銀灯（出力 300ワット)を備えた光反応器 (石英製、内容積 1Uに光源冷却 用ジャケットを設置した。光源冷却用ジャケットには、 60°Cの蒸留水を流通させた。ま た、光反応器のガス出口には 30°Cの冷却水を流通させたコンデンサーを設置した。 さらに、その先には生成ガスを捕集するための一 78°Cのトラップ（SUS316製、内容 積 500mL)を設置した。  [0056] A photoreactor (made of quartz, equipped with a high-pressure mercury lamp (output: 300 watts) was provided with a light source cooling jacket in an internal volume of 1 U. Distilled water at 60 ° C was circulated through the light source cooling jacket. In addition, a condenser with 30 ° C cooling water was installed at the gas outlet of the photoreactor, followed by a 78 ° C trap (made of SUS316, for collecting the product gas). Content volume 500mL).
[0057] 光反応器に、 CF (SO F) (COC1) (65g)を仕込み、光反応器内温 80°Cにて 10時  [0057] CF (SO F) (COC1) (65g) was charged into the photoreactor, and the photoreactor internal temperature was 80 ° C, 10:00.
2 2  twenty two
間光照射して光反応を行った。反応終了後、トラップの留分として化合物（31) (32g) を得た。また光反応器中に FO SCF CF SO F (8. 4g)を回収した。 Photoreaction was carried out by light irradiation. After completion of the reaction, Compound (3 1 ) (32 g) was obtained as a trap fraction. In addition, FO SCF CF SO F (8.4 g) was recovered in the photoreactor.
2 2 2 2  2 2 2 2
[0058] く例 1〉 [NH ] + [CF C1SO N— S〇 CF CI] ；化合物（1N)の製造例 [0058] Example 1> [NH] + [CF C1SO N— S〇 CF CI]; Production Example of Compound (1 N )
4 2 2 2 2  4 2 2 2 2
オートクレーブ（ノ、ステロイ製、内容積 500mL)に、 CH CI (200mL)と N (CH C  In an autoclave (NO, STELLOY, inner volume 500mL), CH CI (200mL) and N (CH C
2 2 2 2 2 2
H ) (55. 5g)を仕込み、オートクレーブ内温一 78。Cにて CF C1SO F (90. 6g)をH) (55. 5g) was charged and the autoclave inside temperature was 78. CF C1SO F (90.6 g) in C
3 3 2 2 3 3 2 2
手早く仕込み、すぐにオートクレープを密閉した。つぎに、オートクレープ内温 40 °Cにて、マスフローコントローラを用い、 NHガス（9. 34g)を一定量ずつ 2時間かけ てオートクレープに導入した。その後、オートクレープ内を 12時間撹拌した。 Prepared quickly and immediately sealed the autoclave. Next, using a mass flow controller at an autoclave internal temperature of 40 ° C, NH gas (9.34 g) was added in a fixed amount over 2 hours. And introduced into the autoclave. Thereafter, the inside of the autoclave was stirred for 12 hours.
[0059] オートクレーブ内雰囲気をパージし、オートクレーブ内を窒素ガスで 2時間バブリン グした後に、クリーム色でスラリー状のオートクレープ内容物を回収して、ろ過した。得 られたろ液を濃縮し、さらに真空乾燥して粘調な液体 (99. 7g)を得た。前記液体を19 F— NMR(283MHz、溶媒： CD CN,内部標準： CFC1 )で分析した結果、 δ (ρρ [0059] The atmosphere in the autoclave was purged and the inside of the autoclave was bubbled with nitrogen gas for 2 hours, and then the creamy slurry autoclave contents were collected and filtered. The obtained filtrate was concentrated and further dried under vacuum to obtain a viscous liquid (99.7 g). As a result of analyzing the liquid by 19 F—NMR (283 MHz, solvent: CD CN, internal standard: CFC1), δ (ρρ
3 3  3 3
m)： - 63. 0 (s、 4F)であり、化合物（1N) (純度約 50%)の生成を確認した。 m): −63.0 (s, 4F), and formation of the compound (1 N ) (purity about 50%) was confirmed.
[0060] <例 2〉 [CF C1SO -NH- SO CF C1]；化合物（1H)の製造例 [0060] <Example 2> [CF C1SO -NH-SO CF C1]; Production Example of Compound (1 H )
2 2 2 2  2 2 2 2
氷冷した受器（内容積 300mL)を連結したフラスコ（内容積 500mL)に、例 1で得 た液体（89. 3g)と濃硫酸（320g)を仕込んだ。なお、受器の先には 78°Cのガラス トラップを連結した。  The liquid (89.3 g) obtained in Example 1 and concentrated sulfuric acid (320 g) were charged into a flask (internal volume 500 mL) connected to an ice-cooled receiver (internal volume 300 mL). A 78 ° C glass trap was connected to the end of the receiver.
[0061] フラスコを加熱しフラスコ内温 100°Cにてフラスコ内を真空ポンプで減圧すると、受 器に白色結晶が留出しはじめた（なお、フラスコと受器をつなぐガラス配管は、固結に よる閉塞を回避するために 50°C以上に加熱した。）。さらに、白色結晶の留出が停止 するまでフラスコ内温を 120°Cに加熱した。加熱終了後、受器に留出した白色結晶（ 65. 4g)を回収して、 19F— NMR(283MHz、溶媒： CD CN,内部標準： CFC1 )で [0061] When the flask was heated and the inside of the flask was depressurized with a vacuum pump at a temperature of 100 ° C, white crystals began to distill into the receiver (note that the glass piping connecting the flask and the receiver was solidified). Heated to 50 ° C or higher to avoid obstruction due to this). Furthermore, the temperature inside the flask was heated to 120 ° C. until the distillation of white crystals stopped. After heating, white crystals (65.4 g) distilled in the receiver were collected and analyzed by 19 F-NMR (283 MHz, solvent: CD CN, internal standard: CFC1).
3 3 分析した結果、 δ (ppm)： - 63. 2 (s、 4F)であり、化合物（1H) (純度 70%。）の生成 を確認した。 3 3 As a result of analysis, it was found that δ (ppm) was −63.2 (s, 4F), and formation of compound (1 H ) (purity 70%) was confirmed.
[0062] <例 3〉 [Li] + [CF C1SO N— SO CF CI] ；化合物（1L)の製造例 [0062] <Example 3> [Li] + [CF C1SO N— SO CF CI]; Production Example of Compound (1 L )
2 2 2 2  2 2 2 2
氷冷下のフラスコ（内容積 50mUに、例 2で得た白色結晶（6. 2g)と水（30ml)を 仕込み、白色結晶を水に溶解させた。つぎに、フラスコ内容物が塩基性になるまで、 フラスコに LiOH'H 0 (1. 35g)を添カロした。  An ice-cooled flask (with an internal volume of 50 mU was charged with the white crystals (6.2 g) obtained in Example 2 and water (30 ml), and the white crystals were dissolved in water. Until this time, LiOH'H 0 (1.35 g) was added to the flask.
2  2
[0063] フラスコ内の水を留去した後に、フラスコ内容物（白色固体）をァセトニトリルに溶解 させて得られた溶液を、ろ過した。得られたろ液のァセトニトリルを留去して白色固体 を得た。前記白色固体を、ジォキサンとァセトニトリルの混合溶媒中で再結晶し、さら にシリカゲルカラムクロマトグラフィー精製 (展開溶媒 : 75体積％へキサンと 25体積％ 酢酸ェチルからなる混合溶媒。）して、 19F— NMR(283MHz、溶媒： CD CN,内部 [0063] After the water in the flask was distilled off, a solution obtained by dissolving the contents of the flask (white solid) in acetonitrile was filtered. The acetonitrile of the obtained filtrate was distilled off to obtain a white solid. The white solid was recrystallized in a mixed solvent of dioxane and acetonitrile, and further purified by silica gel column chromatography (developing solvent: a mixed solvent consisting of 75% by volume hexane and 25% by volume ethyl acetate), and 19 F. — NMR (283 MHz, solvent: CD CN, internal
3 標準： CFC1 )で分析した結果、 δ (ppm) : - 63. 2 (s、 4F)であり、高純度な化合物  3 Standard: Analysis by CFC1), δ (ppm):-63.2 (s, 4F), high purity compound
3  Three
(1L) (1. 36g)を得た。 産業上の利用可能性 (1 L ) (1.36 g) was obtained. Industrial applicability
本発明の化合物は、溶媒 (化学反応用溶媒、抽出用溶媒、電解浴用溶媒等。 )、熱 媒体、光学分割剤、潤滑剤、ガスセンサー用ガス検出剤、温度センサー用感温剤、 ガス吸収剤、薬剤（経皮吸収促進剤、酵素コーティング剤等。）、液浸露光方法にお ける液浸液、電気化学デバイス用電解質 (2次電池用電解質、電気二重層キャパシ タ用電解質、燃料電池用電解質等。 )、電気化学デバイス部材 (2次電池部材、電気 二重層キャパシタ部材、燃料電池部材等。）、表示素子用部材、光学異方フィルム、 導電フィルム、帯電防止性フィルム、光電変換素子、ァクチユエータ素子、感光素子 等の用途に有用な化合物である。 なお、 2006年 9月 22曰に出願された曰本特許出願 2006— 256838号の明細書 、特許請求の範囲、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、取り入れるものである。  The compound of the present invention comprises a solvent (chemical reaction solvent, extraction solvent, electrolytic bath solvent, etc.), heat medium, optical resolution agent, lubricant, gas sensor gas detection agent, temperature sensor temperature sensitive agent, gas absorption. Agent, drug (percutaneous absorption enhancer, enzyme coating agent, etc.), immersion liquid in immersion exposure method, electrolyte for electrochemical devices (electrolyte for secondary battery, electrolyte for electric double layer capacitor, fuel cell) Electrolytes, etc.), electrochemical device members (secondary battery members, electric double layer capacitor members, fuel cell members, etc.), display element members, optical anisotropic films, conductive films, antistatic films, photoelectric conversion elements It is a useful compound for applications such as an actuator element and a photosensitive element. It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2006-256838 filed on September 22, 2006 are hereby incorporated herein by reference. It is something that is incorporated.

Claims

請求の範囲 The scope of the claims
[1] 下式（1)で表される化合物。  [1] A compound represented by the following formula (1).
[M]n+([RF-SO N— SO— QF— CI]— ) (1) [M] n + ([R F -SO N— SO— Q F — CI] —) (1)
2 2 n  2 2 n
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.
[M]n+:n価の陽イオン。 [M] n + : n-valent cation.
n:i〜4の整数。  n: An integer from i to 4.
RF:炭素数 1〜6のペルフルォロアルキル基または式 QF— C1で表される基。 R F : a perfluoroalkyl group having 1 to 6 carbon atoms or a group represented by the formula Q F — C1.
QF:炭素数 1〜6のペルフルォロアルキレン基。 Q F : a perfluoroalkylene group having 1 to 6 carbon atoms.
[2] 下式（11)で表される化合物。 [2] A compound represented by the following formula (11):
[M]n+([Cl-QF-SO -N-SO— QF— C1]— ) (11) [M] n + ([Cl-Q F -SO -N-SO— Q F — C1] —) (11)
2 2 n  2 2 n
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.
[M]n+:n価の陽イオン [M] n + : n-valent cation
n:i〜4の整数。  n: An integer from i to 4.
QF:炭素数 1〜6のペルフルォロアルキレン基。 Q F : a perfluoroalkylene group having 1 to 6 carbon atoms.
[3] 前記式（11)において、 nが 1であり、 Mがアルカリ金属イオン、アンモニゥムイオン、 又はホスホニゥムイオンである請求項 2に記載の化合物。 [3] The compound according to claim 2, wherein in the formula (11), n is 1, and M is an alkali metal ion, an ammonium ion, or a phosphonium ion.
[4] 下式（2)で表される化合物と式 [M]n+([OH]_) で表される化合物とを反応させる 下式（1)で表される化合物の製造方法。 [4] A method for producing a compound represented by the following formula (1), comprising reacting a compound represented by the following formula (2) with a compound represented by the formula [M] n + ([OH] _).
RF-SO -NH-SO -QF-C1 (2) R F -SO -NH-SO -Q F -C1 (2)
2 2  twenty two
[M]n+([RF— SO— N— SO— QF— CI]— ) (1) [M] n + ([R F — SO— N— SO— Q F — CI] —) (1)
2 2 n  2 2 n
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.
[M]n+:n価の陽イオン。 [M] n + : n-valent cation.
n:i〜4の整数。  n: An integer from i to 4.
RF:炭素数 1〜6のペルフルォロアルキル基または式 QF— C1で表される基。 R F : a perfluoroalkyl group having 1 to 6 carbon atoms or a group represented by the formula Q F — C1.
QF:炭素数 1〜6のペルフルォロアルキレン基。 Q F : a perfluoroalkylene group having 1 to 6 carbon atoms.
[5] 下式 (2)で表される化合物。 [5] A compound represented by the following formula (2):
RF-SO -NH-SO -QF-C1 (2) R F -SO -NH-SO -Q F -C1 (2)
2 2  twenty two
ただし、式中の記号は下記の意味を示す。 RF:炭素数 1〜6のペルフルォロアルキル基または式 QF— CIで表される基。 However, the symbol in a formula shows the following meaning. R F : A perfluoroalkyl group having 1 to 6 carbon atoms or a group represented by the formula Q F — CI.
QF:炭素数 1〜6のペルフルォロアルキレン基。 Q F : a perfluoroalkylene group having 1 to 6 carbon atoms.
[6] 下式 (21)で表される化合物。 [6] A compound represented by the following formula (21):
Cl-QF-SO -NH-SO -QF-C1 (21) Cl-Q F -SO -NH-SO -Q F -C1 (21)
2 2  twenty two
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.
QF:炭素数 1〜6のペルフルォロアルキレン基。 Q F : a perfluoroalkylene group having 1 to 6 carbon atoms.
[7] 下式（3)で表される化合物および下式（31)で表される化合物を、ァミン化合物の 存在下にアンモニアと反応させ、さらにプロトン酸と反応させる下式（2)で表される化 合物の製造方法。 [7] A compound represented by the following formula (3) and a compound represented by the following formula (31) are reacted with ammonia in the presence of an amine compound, and further reacted with a protonic acid. A method for producing a compound.
RF— SO F (3) R F — SO F (3)
2  2
Cl-QF-SO F (31) Cl-Q F -SO F (31)
2  2
RF-SO -NH-SO -QF-C1 (2) R F -SO -NH-SO -Q F -C1 (2)
2 2  twenty two
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.
RF:炭素数 1〜6のペルフルォロアルキル基または式 QF— C1で表される基。 R F : a perfluoroalkyl group having 1 to 6 carbon atoms or a group represented by the formula Q F — C1.
QF:炭素数 1〜6のペルフルォロアルキレン基。 Q F : a perfluoroalkylene group having 1 to 6 carbon atoms.
PCT/JP2007/068096 2006-09-22 2007-09-18 Novel chlorofluorosulfonimide and method for producing the same WO2008035677A1 (en)

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EP2660196B1 (en) * 2011-03-03 2017-05-03 Nippon Soda Co., Ltd. Manufacturing method for fluorosulfonylimide ammonium salt
CA2826375C (en) 2011-03-03 2016-02-16 Nippon Soda Co., Ltd. Process for producing fluorine-containing sulfonylimide salt

Non-Patent Citations (1)

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Title
HU L-Q. ET AL.: "Synthesis of perhaloalkanesulfonyl halides and their sulfonamide derivatives", INORGANIC CHEMISTRY, vol. 32, no. 23, 1993, pages 5007 - 5010, XP000925887 *

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