USRE49222E1 - Fluorine-containing complex compound, and production method for fluorine-containing organic compound employing same - Google Patents

Fluorine-containing complex compound, and production method for fluorine-containing organic compound employing same Download PDF

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USRE49222E1
USRE49222E1 US16/668,703 US201416668703A USRE49222E US RE49222 E1 USRE49222 E1 US RE49222E1 US 201416668703 A US201416668703 A US 201416668703A US RE49222 E USRE49222 E US RE49222E
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fluorine
group
compound
thf
formula
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Kenji Adachi
Takashi Shibanuma
Takabumi Nagai
Sensuke Ogoshi
Masato Ohashi
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Daikin Industries Ltd
Osaka University NUC
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Daikin Industries Ltd
Osaka University NUC
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Definitions

  • the present invention relates to a fluorine-containing complex compound and a method for producing a fluorine-containing organic compound using the fluorine-containing complex compound.
  • Fluorine-containing organic compounds have very unique properties distinguished from other compounds and due to, for example, the energy scale of the C—F bond, the low polarization of the C—F bond, and the dipole moment of the C—F bond. Because of their unique properties, fluorine-containing organic compounds have a considerably wide range of applications, for example, in resin, rubber, coating compositions, film, water repellents, oil repellents, liquid crystals, dyes, physiologically active substances, and starting materials of these materials, depending on their structure and characteristics.
  • TFE structure compounds having an organic group at both terminals of their tetrafluoroethylene structure (—CF 2 —CF 2 —) (this structure may be may be referred to hereinafter as “TFE structure”; and these compounds may be may be referred to hereinafter as a “TFE compound”) have unique characteristics, and are thus useful as monomers for fluorine-containing polymers applied to fuel cells or as crystal liquid materials, for example.
  • Non-patent Literature 1 to 4 disclose methods for synthesizing these TFE compounds by fluorinating various compounds.
  • Non-patent Literature 5 and 6 disclose methods for synthesizing TEL compounds using a fluorine-containing copper compound, for example.
  • Non-patent Literature 1 to 4 are not so simple, and do not provide many varieties of TFE compounds.
  • none of the literature discloses the synthesis of a fluorine-containing compound having a different organic group at both terminals of the TEE structure.
  • Non-patent Literature 5 and 6 do not use tetrafluoroethylene as a starting material, and thus obtaining starting materials involves some difficulty.
  • the present invention is thus intended to provide a production method that can use tetrafluoroethylene as a starting material and that enables the synthesis of a variety of fluorine-containing compounds having organic groups at both terminals of their TFE structure.
  • the present inventors conducted extensive research and developed a novel fluorine-containing complex compound produced by using tetrafluoroethylene as a starting material.
  • the inventors also found that the use of the fluorine-containing complex compound enables the synthesis of various fluorine-containing compounds having an organic group at both terminals of their TFE structure and completed the invention.
  • the present invention includes the following subject matter.
  • a fluorine-containing complex compound comprising
  • R 1 is as defined in Item 1, or an ester thereof, or a salt thereof, with
  • R 1 is as defined in Item 1; and R 2 represents an organic group
  • R 2 is as defined above; and X represents a halogen atom.
  • R a2L (—R a2S ) ma2 indicates R a2L substituted with ma2 R a2S ;
  • R a1S and R a2S are the same or different, and each represents independently in each occurrence a polymerizable group
  • ma1 and ma2 are the same or different, and each represents an integer of 0 or more, and the sum of ma1 and ma2 is 1 or more;
  • R a1L and R a2L are the same or different, and each represents an aromatic group optionally having, in addition to ma1 R a1S or ma2 R a2S , at least one substituent selected from the group consisting of fluoro group, perfluoro organic group, and pentafluorosulfanyl.
  • R a1S and R a2S are the same or different, and each represents independently in each occurrence acyl optionally substituted with at least one halogen atom;
  • ma1 and ma2 are the same or different, and each represents an integer of 0 or more, and the sum of ma1 and ma2 is 1 or more;
  • R a1L and R a2L are the same or different, and each represents (1) an aromatic group optionally having, in addition to ma1 R a1S or ma2 R a2S , at least one substituent selected from the group consisting of fluoro group, perfluoro organic group, and pentafluorosulfanyl, or (2) a bond with the proviso that R a1L and R a2L are not a bond at the same time.
  • R a2L (—R a2S ) ma2 indicates R a2L substituted with ma2 R a2S ;
  • R a1S represents independently in each occurrence 1,3-dioxo-1,3-dihydroisobenzofuran-5-yl optionally having at least one substituent selected from the group consisting of fluoro group, perfluoro organic group, and pentafluorosulfanyl;
  • R a2S represents independently in each occurrence
  • ma1 represents an integer of 1 or more
  • ma2 represents an integer of 0 or more
  • R a1L and R a2L are the same or different, and each represents (1) an aromatic group optionally having, in addition to ma1 R a1S or ma2 R a2S , at least one substituent selected from the group consisting of fluoro group, perfluoro organic group, and pentafluorosulfanyl, or a bond with the proviso that when R a2S is (2) amino, (3) carboxy, or (4) halogenocarbonyl, R a2L is (1) an aromatic group optionally having, in addition to R a2S , at least one substituent selected from the group consisting of fluoro group, perfluoro organic group, and pentafluorosulfanyl.
  • R a2L (—R a2S ) ma2 indicates R a2L substituted with ma2 R a2S ;
  • R a1S and R a2S are the same or different, and each represents independently in each occurrence fluoro group, perfluoro organic group, or pentafluorosulfanyl;
  • ma1 and ma2 are the same or different, and each represents an integer of 0 or more, and the sum of ma1 and ma2 is 1 or more;
  • R a1L and R a2L are the same or different, and each represents an aromatic group optionally having, in addition to ma1 R a1S or ma2 R a2S , at least one alkoxy group.
  • R a1S represents a polymerizable group
  • R a2S represents (1) carboxy or its precursor group, or (2) sulfo, or its precursor group;
  • ma1 represents an integer of 0 or more
  • R a1L represents an aromatic group optionally having, in addition to ma1 R a1S , at least one substituent selected from the group consisting of fluoro group, perfluoro organic group, and pentafluorosulfanyl.
  • the fluorine-containing complex compound according to the present invention can be synthesized by using tetrafluoroethylene as a starting material and enables the synthesis of various TFE compounds (in particular, TFE compounds having a different organic group at both terminals of their TFE structure).
  • halogen atom examples include fluorine, chlorine, bromine, and iodine.
  • organic group refers to a group formed by removing one hydrogen atom from an organic compound.
  • organic groups include the following:
  • perfluoro organic group refers to an organic group in which all of the hydrogen atoms attached to carbon atoms are substituted with fluorine atoms.
  • the perfluoro organic group may contain ether oxygen.
  • perfluoro organic groups include perfluoroalkyl (e.g., trifluoromethyl) and perfluoropolyether.
  • the perfluoro organic group for example, has a carbon number of 1 to 8, such as trifluoromethyl.
  • perfluoro organic group may sometimes be denoted by the symbol “Rf.”
  • acyl encompasses “acryloyl,” “alkanoyl,” and “aroyl.”
  • aromatic group encompasses “aryl,” and “heteroaryl.”
  • heterocyclic group encompasses “non-aromatic heterocyclic group,” and “heteroaryl.”
  • alkyl examples include linear or branched alkyl having a carbon number of 1 to 10, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, and hexyl.
  • alkenyl examples include linear or branched alkenyl having a carbon number of 2 to 10, such as vinyl, 1-propen-1-yl, 2-propen-1-yl, isopropenyl, 2-buten-1-yl, 4-penten-1-yl, and 5-hexen-1-yl.
  • alkynyl examples include linear or branched alkynyl having a carbon number of 2 to 10, such as ethynyl, 1-propyn-1-yl, 2-propyn-1-yl, 4-pentyn-1-yl, and 5-hexyn-1-yl.
  • cycloalkyl examples include cycloalkyl having a carbon number 3 to 10, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.
  • cycloalkenyl examples include cycloalkenyl having a carbon number of 3 to 10, such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and cycloheptenyl.
  • cycloalkadienyl examples include cycloalkadienyl having a carbon number of 4 to 10, such as cyclobutadienyl, cyclopentadienyl, cyclohexadienyl, cycloheptadienyl, cyclooctadienyl, cyclononadienyl, and cyclodecadienyl.
  • alkoxy examples include linear or branched alkoxy having a carbon number of 1 to 10, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, pentyloxy, and hexyloxy.
  • alkanoyl refers to a group represented by formula: R—CO— wherein R represents alkyl.
  • aryl may be monocyclic, dicyclic, tricyclic, or tetracyclic.
  • aryl may be aryl having a carbon number of 6 to 18.
  • aryl examples include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl.
  • aralkyl examples include benzyl, phenethyl, diphenylmethyl, 1-naphthyl methyl, 2-naphthyl methyl, 2,2-diphenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 2-biphenylylmethyl, 3-biphenylylmethyl, and 4-biphenylylmethyl.
  • aroyl refers to a group represented by formula: R—CO— wherein R represents aryl.
  • non-aromatic heterocyclic group may be monocyclic, dicyclic, tricyclic, or tetracyclic.
  • non-aromatic heterocyclic group may be, for example, a non-aromatic heterocyclic group containing, in addition to carbon, 1 to 4 heteroatoms selected from oxygen, sulfur, and nitrogen as an annular atom.
  • non-aromatic heterocyclic group may be saturated or unsaturated.
  • non-aromatic heterocyclic group examples include tetrahydrofuryl, oxazolidinyl, imidazolinyl (e.g., 1-imidazolinyl, 2-imidazolinyl, and 4-imidazolinyl), aziridinyl (e.g., 1-aziridinyl and 2-aziridinyl), azetidinyl (e.g., 1-azetidinyl and 2-azetidinyl), pyrrolidinyl (e.g., 1-pyrrolidinyl, 2-pyrrolidinyl, and 3-pyrrolidinyl), piperidinyl (e.g., 1-piperidinyl, 2-piperidinyl, and 3-piperidinyl), azepanyl (e.g., 1-azepanyl, 2-azepanyl, 3-azepanyl, and 4-azepanyl),
  • imidazolinyl e.g
  • heteroaryl may be, for example, a monocyclic-, dicyclic-, tricyclic-, or tetracyclic-, 5 to 18-membered heteroaryl.
  • heteroaryl may be, for example, heteroaryl containing, in addition to carbon, 1 to 4 heteroatoms selected from oxygen, sulfur, and nitrogen as an annular atom.
  • the heteroaryl may have a carbon number of, for example, 3 to 17.
  • heteroaryl encompasses “monocyclic heteroaryl” and “aromatic fused heterocyclic group.”
  • examples of “monocyclic heteroaryl” include pyrrolyl (e.g., 1-pyrrolyl, 2-pyrrolyl, and 3-pyrrolyl), furyl (e.g., 2-furyl and 3-furyl), thienyl (e.g., 2-thienyl and 3-thienyl), pyrazolyl (e.g., 1-pyrazolyl, 3-pyrazolyl, and 4-pyrazolyl), imidazolyl (e.g., 1-imidazolyl, 2-imidazolyl, and 4-imidazolyl), isooxazolyl (e.g., 3-isooxazolyl, 4-isooxazolyl, and 5-isooxazolyl), oxazolyl (e.g., 2-oxazolyl, 4-oxazolyl, and 5-oxazolyl), isothiazolyl (e.g., 3-isothiazolyl, 4-isothiazolyl, 4-isothiazo
  • examples of “aromatic fused heterocyclic group” include isoindolyl (e.g., 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, and 7-isoindolyl), indolyl (e.g., 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, and 7-indolyl), benzo[b]furanyl (e.g., 2-benzo[b]furanyl, 3-benzo[b]furanyl, 4-benzo[b]furanyl, 5-benzo[b]furanyl, 6-benzo[b]furanyl, and 7-benzo[b]furanyl), benzo[c]furanyl (e.g., 1-isoindolyl, 2-
  • fluorine-containing complex compound (1) comprises
  • Fluorine-containing complex compound (1) preferably consists of fluorine-containing organic metal compound (1a) and at least one ligand (1b).
  • the metal represented by M 1 forms a coordinate bond with at least one ligand (1b).
  • M 1 is preferably copper (preferably, copper(I)).
  • R 1 is preferably
  • examples of the substituent for the “aryl optionally having at least one substituent” include divalent groups, such as carbonyloxycarbonyl (—CO—O—CO—).
  • the divalent group forms a fused ring (e.g., 1,3-dioxo-1,3-dihydroisobenzofuran) with one benzene ring in aryl.
  • examples of a “polymerizable group” include:
  • alkenyl optionally substituted with at least one halogen atom e.g., vinyl optionally substituted with at least one halogen atom
  • (f) (meta)acryloyl optionally substituted with at least one halogen atom e.g., methacryloyl, acryloyl, 2-fluoroacryloyl, and 2-chloroacryloyl.
  • R 1 is more preferably
  • pyridine ring-containing compounds examples include phenanthroline (e.g., 1,10-phenanthroline), 2,2′-bipyridyl, pyridine, methyl pyridine, and lutidine (e.g., 2,6-lutidine).
  • phenanthroline e.g., 1,10-phenanthroline
  • 2,2′-bipyridyl 2,2′-bipyridyl
  • pyridine e.g., 1,10-phenanthroline
  • 2,2′-bipyridyl examples include 2,2′-bipyridyl, pyridine, methyl pyridine, and lutidine (e.g., 2,6-lutidine).
  • the “phosphine,” stated as ligand (1b), are preferably trialkylphosphine and triarylphosphine.
  • Specific examples of trialkylphosphines include tri(C 3-20 alkyl)phosphines, such as tricyclohexylphosphine, triisopropylphosphine, tri-t-butylphosphine, trihexylphosphine, triadamantylphosphine, tricyclopentylphosphine, di-t-butylmethylphosphine, tribicyclo[2,2,2]octylphosphine, and trinorbornylphosphine.
  • triarylphosphines include tri(monocyclic aryl)phosphines, such as triphenylphosphine, trimesitylphosphine, and tri(o-tolyl)phosphine. Of these, triphenylphosphine, tricyclohexylphosphine, and tri-t-butylphosphine are preferable.
  • Ligand (1b) is preferably a bidentate ligand.
  • Preferable example include 1,10-phenanthroline.
  • the coordination number of ligand (1b) bound to fluorine-containing organic metal compound (1a) varies depending on the oxidation number of metal M 1 and the number of coordinating atoms of ligand (1b), but is preferably 1 to 3.
  • the fluorine-containing complex compound according to the present invention can be produced by, for example, the production method described below.
  • a method for producing the fluorine-containing complex compound according to the present invention comprises step A of reacting
  • organic boron compound (2) examples include boronic acid represented by formula (2-1), esters thereof, and salts thereof: R 1 —BY 2 (2-1) wherein
  • R 1 is as defined above;
  • Y represents independently hydroxy or alkoxy
  • two alkoxy groups represented by Y may be crosslinked to each other.
  • alkoxy represented by Y examples include C 1-6 alkoxy.
  • organic boron compound (2) is a boronic acid.
  • organic boron compound (2) is a boronic acid ester.
  • Organic boron compound (2) can be produced by a known method or a method according to the known method, and is also commercially available.
  • halides of metal compound (3) include fluorides, chlorides, bromides, and iodides of metal compound (3).
  • the alkoxy moiety of alkoxide in metal compound (3) is preferably a group represented by formula: RO— wherein R is linear or branched alkyl having a carbon number of 1 to 10, more preferably quaternary alkoxy, and further more preferably tert-butoxy.
  • the aryloxy moiety of phenoxide in metal compound (3) is preferably a group represented by formula: RO— wherein R is optionally substituted aryl having a carbon number of 6 to 10, and more preferably phenoxy.
  • the alkylthio moiety of thioalkoxide in metal compound (3) is preferably a group represented by formula: RS— wherein R is linear or branched alkyl having a carbon number of 1 to 10.
  • the arylthio moiety of thiophenoxide in metal compound (3) is preferably a group represented by formula: RO— wherein R is optionally substituted aryl having a carbon number of 6 to 10, and more preferably phenylsulfanyl.
  • Metal compound (3) is preferably alkoxide in which the alkoxy moiety is quaternary alkoxy, and more preferably tert-butoxide.
  • Metal compound (3) can be produced by a known method or a method according to the known method, and is also commercially available.
  • Ligand (1b) described for the fluorine-containing complex compound mentioned above is used as ligand (1b).
  • ligand (1b) in the fluorine-containing complex compound and a starting material compound corresponding to this ligand (1b) are both referred to as “ligand (1b)”. Both ligands (1b) are distinguished depending on the context.
  • Ligand (1b) can be produced by a known method or a method according to the known method, and is also commercially available.
  • step A can be performed by mixing organic boron compound (2), metal compound (3), ligand (1b ), and tetrafluoroethylene (which may be hereinafter abbreviated as “TFE”).
  • the mixing can be performed, for example, by introducing TFE gas into a solution or a suspension of organic boron compound (2), metal compound (3), and ligand (1b).
  • solvents for the solution or suspension include diethylether, 1,4-dioxane, acetonitrile, ethyl acetate, ethyl formate, toluene, dimethyl sulfoxide, dimethylformamide, hexane, tetrahydrofuran, and mixtures thereof.
  • the amount of the solvent is typically within the range of 0.5 to 500 parts by weight, preferably 1 to 100 parts by weight, and more preferably 2.5 to 50 parts by weight per part by weight of organic boron compound (2).
  • the amount of metal compound (3) is typically within the range of 0.2 to 10 moles, preferably 0.5 to 5 moles, and more preferably 0.8 to 2 moles per mole of organic boron compound (2).
  • the amount of ligand (1b) is typically within the range of 0.2 to 10 moles, preferably 0.5 to 5 moles, and more preferably 0.8 to 2 moles per mole of organic boron compound (2).
  • the amount of TFE is typically within the range of 0.5 moles to an excessive amount, preferably 0.8 to 50 moles, and more preferably 1 to 10 moles per mole of organic boron compound (2).
  • Step A is performed at a temperature within the range of typically ⁇ 20 to 200° C., preferably 0 to 150° C., and more preferably 20 to 100° C.
  • the reaction time of step A is within the range of typically 1 minute to 10 days, preferably 5 minutes to 3 days, and more preferably 10 minutes to 1 day.
  • the obtained fluorine-containing complex compound (1) of the present invention may be used, as it is, for the fluorine-containing compound described below, or may further be purified by a known purification method, such as solvent extraction, desiccation, filtration, distillation, concentration, recrystallization, sublimation, column chromatography, and combinations thereof.
  • the method for producing a fluorine-containing compound according to the present invention produces by using the fluorine-containing complex compound of the present invention described above, a fluorine-containing compound represented by formula (4) (which may be may be referred to hereinafter as “fluorine-containing compound (4)”): R 2 —CF 2 —CF 2 —R 1 (4) wherein
  • R 1 is as defined above;
  • R 2 represents an organic group.
  • the production method comprises step B of reacting
  • R 2 is as defined above;
  • X represents a halogen atom
  • R 1 is as defined for the “fluorine-containing complex compound.”
  • X is preferably iodine.
  • R 2 is preferably
  • R 2 may be the same as or different from R 1 .
  • step B can be performed by mixing fluorine-containing complex compound (1) of the present invention with halogen compound (5).
  • the mixing can be performed, for example, by adding halogen compound (5) to a suspension of fluorine-containing complex compound (1) in a solvent.
  • solvents for the suspension include diethylether, 1,4-dioxane, acetonitrile, ethyl acetate, ethyl formate, toluene, dimethyl sulfoxide, dimethylformamide, hexane, tetrahydrofuran, and mixtures thereof.
  • the amount of the solvent is typically within the range of 0.5 to 500 parts by weight, preferably 1 to 100 parts by weight, and more preferably 2.5 to 50 parts by weight per part by weight of fluorine-containing complex compound (1).
  • the amount of halogen compound (5) is typically within the range of 0.2 to 10 moles, preferably 0.5 to 5 moles, and more preferably 0.8 to 2 moles per mole of fluorine-containing complex compound (1).
  • Step B is performed at a temperature typically within the range of ⁇ 20 to 200° C., preferably 0 to 150° C., and more preferably 20 to 100° C.
  • the reaction time of step B is typically within the range of 1 minute to 10 days, preferably 5 minutes to 3 days, and more preferably 10 minutes to 1 day.
  • Step B may be performed in one pod with step A.
  • step A and step B can be performed in one pod by, for example, mixing organic boron compound (2), metal compound (3), ligand (1b), halogen compound (5), and TFE.
  • a known technique such as acylation and alkylation, may be applied to fluorine-containing compound (4) obtained by the production method described above or its intermediate to introduce or replace one or more substituents, thereby producing fluorine-containing compound (4).
  • Fluorine-containing compound (4) obtained by the production method of the present invention can be used as, for example, monomers for fluorine-containing polymers used in fuel cell materials, and liquid crystal materials.
  • Fluorine-containing compound (4) obtained by the production method may be used, as it is, as monomers for fluorine-containing polymers used in heat-resistant polymers, fuel cell materials, and the like, and liquid crystal materials. If desired, fluorine-containing compound (4) may be further purified by a known purification method, such as solvent extraction, desiccation, filtration, distillation, concentration, recrystallization, sublimation, column chromatography, and combinations thereof.
  • Fluorine-containing compound (4) encompasses novel compounds represented by the following formulae (4-1), (4-2), (4-3), (4-4), and (4-5).
  • Fluorine-containing compound represented by formula (4-1) (which may be may be referred to hereinafter as “fluorine-containing compound (4-1)”): (R a1S —) ma1 R a1L —CF 2 —CF 2 —R a2L (—R a2S ) ma2 (4-1) wherein
  • R a2L (—R a2S ) ma2 indicates R a2L substituted with ma2 R a2S ;
  • R a1S and R a2S are the same or different, and each represents independently in each occurrence a polymerizable group
  • ma1 and ma2 are the same or different, and each represents an integer of 0 or more, and the sum of ma1 and ma2 is 1 or more;
  • R a1L and R a2L are the same or different, and each represents an aromatic group optionally having, in addition to ma1 R a1S or ma2 R a2S , at least one substituent selected from the group consisting of fluoro group, perfluoro organic group (preferably C 1-8 perfluoro organic group, and more preferably trifluoromethyl), and pentafluorosulfanyl.
  • R a1L and R a2L are preferably the same or different, and are phenyl optionally having, in addition to ma1 R a1S or ma2 R a2S , at least one substituent selected from the group consisting of fluoro group, perfluoro organic group (preferably C 1-8 perfluoro organic group, and more preferably trifluoromethyl), and pentafluorosulfanyl.
  • fluorine-containing compound (4-1) Of fluorine-containing compound (4-1), the following compounds are preferable.
  • TMS represents trimethylsilyl
  • R represents independently hydrogen, methyl, chlorine, or fluorine.
  • the compound represented by formula (4-1-a-3) in the following scheme can be produced by conducting step A and step B described above to thereby produce the compound represented by formula (4-1-a-1) in the scheme and reacting the compound represented by formula (4-1-a-1) with the compound represented by formula (4-1-a-2) as described in the scheme.
  • the compounds represented by formula (4-1-a-1) and formula (4-1-b-1) can be produced by conducting step A and step B, the compounds can also be produced by preparing an intermediate in accordance with step A and step B using a starting material having its hydroxy protected by a known protective group and then deprotecting the protective group by a known method.
  • known protective groups include trialkylsilyl, alkyl, alkoxyalkyl, benzyl, and acyl.
  • Me represents methyl
  • the compound represented by formula (4-1-c-2) in the following scheme can be produced by conducting step A and step B to thereby produce the compound represented by formula (4-1-c-1) in the scheme and epoxidizing the compound represented by formula (4-1-c-1) using a hydrogen peroxide solution or meta-chloroperbenzoic acid (MCPBA).
  • MCPBA meta-chloroperbenzoic acid
  • step A can be produced by conducting step A using an organic boron compound containing trifluorovinyl produced by the method disclosed in WO2012/121345. Thereafter, step B may be performed using a halide containing a predetermined functional group.
  • Fluorine-containing compound represented by formula (4-2) (which may be may be referred to hereinafter as “fluorine-containing compound (4-2)”): (R a1S —) ma1 R a1L —CF 2 —CF 2 —R a2L (—R a2S ) ma2 (4-2) wherein
  • R a1S and R a2S are the same or different, and each represents independently in each occurrence acyl optionally substituted with at least one halogen atom;
  • ma1 and ma2 are the same or different, and each represents an integer of 0 or more, and the sum of ma1 and ma2 is 1 or more;
  • R a1L and R a2L are the same or different, and each represents (1) an aromatic group optionally having, in addition to ma1 R a1S or ma2 R a2S , at least one substituent selected from the group consisting of fluoro group, perfluoro organic group (preferably C 1-8 perfluoro organic group, and more preferably trifluoromethyl), and pentafluorosulfanyl, or (2) a bond with the proviso that R a1L and R a2L are not a bond at the same time.
  • R a1L or R a2L is a bond
  • ma1 or ma2 is 1
  • R a1L or R a2L directly bonds to —CF 2 —CF 2 —.
  • R a1L and R a2L are preferably the same or different, and each represents (1) phenyl optionally having, in addition to ma1 R a1S or ma2 R a2S , at least one substituent selected from the group consisting of fluoro group, perfluoro organic group (preferably C 1-8 perfluoro organic group, and more preferably trifluoromethyl), and pentafluorosulfanyl, or (2) a bond.
  • fluorine-containing compound (4-2) the following compounds are preferable.
  • R represents hydrogen, methyl, chlorine, or fluorine.
  • fluorine-containing compound represented by formula (4-3) (R a1S —) ma1 R a1L —CF 2 —CF 2 —R a2L (—R a2S ) ma2 (4-3) wherein
  • R a2L (—R a2S ) ma2 indicates R a2L substituted with ma2 R a2S ;
  • R a1S represents independently in each occurrence 1,3-dioxo-1,3-dihydroisobenzofuran-5-yl optionally having at least one substituent selected from the group consisting of fluoro group, perfluoro organic group (preferably C 1-8 perfluoro organic group, and more preferably trifluoromethyl), and pentafluorosulfanyl;
  • R a2S represents independently in each occurrence
  • ma1 represents an integer of 1 or more
  • ma2 represents an integer of 0 or more (preferably an integer of 1 or more);
  • R a1L and R a2L are the same or different, and each represents (1) an aromatic group optionally having, in addition to ma1 R a1S or ma2 R a2S , at least one substituent selected from the group consisting of fluoro group, perfluoro organic group (preferably C 1-8 perfluoro organic group, and more preferably trifluoromethyl), and pentafluorosulfanyl, or (2) a bond with the proviso that when R a2S is (2) amino, (3) carboxy, or (4) halogenocarbonyl, R a2L is (1) an aromatic group optionally having, in addition to R a2S , at least one substituent selected from the group consisting of fluoro group, perfluoro organic group (preferably C 1-8 perfluoro organic group, and more preferably trifluoromethyl), and pentafluorosulfanyl.
  • R a1L and R a2L are preferably the same or different, and each represents (1) phenyl optionally having, in addition to ma1 R a1S or ma2 R a2S , at least one substituent selected from the group consisting of fluoro group, perfluoro organic group (preferably C 1-8 perfluoro organic group, and more preferably trifluoromethyl), and pentafluorosulfanyl, or (2) a bond.
  • fluorine-containing compound (4-3) Of fluorine-containing compound (4-3), the following compounds are preferable.
  • a fluorine-containing compound represented by formula (4-4) (which may be may be referred to hereinafter as “fluorine-containing compound (4-4)”): (R a1S —) ma1 R a1L —CF 2 —CF 2 —R a2L (—R a2S ) ma2 (4-4) wherein
  • R a2L (—R a2S ) ma2 indicates R a2L substituted with ma2 R a2S ;
  • R a1S and R a2S are the same or different, and each represents independently in each occurrence fluoro group, perfluoro organic group (preferably C 1-8 perfluoro organic group, and more preferably trifluoromethyl), or pentafluorosulfanyl;
  • ma1 and ma2 are the same or different, and each represents an integer of 0 or more, and the sum of ma1 and ma2 is 1 or more;
  • R a1L and R a2L are the same or different, and each represents an aromatic group optionally having, in addition to ma1 R a1S or ma2 R a2S , at least one alkoxy group.
  • R a1L and R a2L are the same or different, and each represents phenyl or naphthyl optionally having, in addition to ma1 R a1S or ma2 R a2S , at least one alkoxy group.
  • fluorine-containing compound (4-4) the following compounds are preferable.
  • fluorine-containing compound represented by formula (4-5) (which may be may be referred to hereinafter as “fluorine-containing compound (4-5)”): (R a1S —) ma1 R a1L —CF 2 —CF 2 —R a2S (4-5) wherein
  • R a1S represents a polymerizable group
  • R a2S represents (1)carboxy or its precursor group, or (2) sulfo or its precursor group;
  • ma1 represents an integer of 0 or more (preferably an integer of 1 or more);
  • R a1L represents an aromatic group optionally having, in addition to ma1 R a1S , at least one substituent selected from the group consisting of fluoro group, perfluoro organic group (preferably C 1-8 perfluoro organic group, and more preferably trifluoromethyl), and pentafluorosulfanyl.
  • R a1L is preferably phenyl optionally having, in addition to ma1 R a1S , at least one substituent selected from the group consisting of fluoro group, perfluoro organic group (preferably C 1-8 perfluoro organic group, and more preferably trifluoromethyl), and pentafluorosulfanyl.
  • fluorine-containing compound (4-5) Of fluorine-containing compound (4-5), the following compounds are preferable.
  • a polyimide can be produced by reacting a diamine with fluorine-containing compound (4-3) in which one R a1S and one R a2S are 1,3-dioxo-1,3-dihydroisobenzofuran-5-yl optionally having at least one substituent selected from the group consisting of fluoro group, perfluoro organic group (preferably C 1-8 perfluoro organic group, and more preferably trifluoromethyl), and pentafluorosulfanyl (which may be may be referred to hereinafter as “fluorine-containing compound (4-3a)”).
  • the polyimide is a novel compound.
  • the polyimide contains structural unit A represented by the following formula:
  • ma1′ is (ma1)-1 and represents an integer of 0 or more,
  • ma2′ is (ma2)-1 and represents an integer of 0 or more
  • R a1L and R a2L are the same or different, and each represents an aromatic group or a single bond
  • R y represents a divalent organic group
  • the aromatic groups represented by R a1L and R a2L are the same as the aromatic groups represented by R a1L and R a2L in formula (4-3).
  • R a1L and R a2L are both preferably a single bond.
  • R y is a group formed by removing two amino groups from the diamine.
  • the diamine as used herein is represented by H 2 N—R y —NH 2 wherein R y represents a divalent organic group.
  • R y is preferably
  • X represents —O—, —NH—, —NPh-, —S—, —S( ⁇ O)—, —SO 2 —, —Rf— (preferably —CF 2 — or —CF 2 CF 2 —), or —Ar—, and
  • Ar represents arylene optionally having at least one substituent or biaryl optionally having at least one substituent.
  • R y more preferably represents arylene or biaryl, each optionally having at least one substituent, further more preferably biaryl optionally having at least one substituent, and still more preferably biphenyl optionally having at least one substituent.
  • substituents include fluoro group, perfluoro organic group (preferably C 1-8 perfluoro organic group, and more preferably trifluoromethyl), and pentafluorosulfanyl; more preferable examples include fluorine and perfluoro organic group (preferably C 1-8 perfluoro organic group, and more preferably trifluoromethyl); and further more preferable examples include trifluoromethyl.
  • R y is particularly preferably the following.
  • R y is particularly more preferably the following.
  • fluorine-containing compound (4-3a) include the following compounds.
  • fluorine-containing compound (4-3a) for use in the polyimide mentioned above may be one type, or a combination of two or more types.
  • the units A may be the same or different at each occurrence.
  • fluorine-containing compound (4-3) wherein one R a1S and one R a2S are 3,4-dicarboxyphenyl with an acid anhydride, such as acetic anhydride, to obtain fluorine-containing compound (4-3a) (intramolecular dehydration condensation of two carboxyl groups).
  • an acid anhydride such as acetic anhydride
  • diamines examples include diamines typically used in the production of polyimides.
  • diamine examples include aliphatic diamines optionally having at least one fluorine atom, alicyclic diamines optionally having at least one fluorine atom, and aromatic diamines optionally having at least one fluorine atom.
  • aliphatic diamines as used herein are diamines having no annular moiety, and are preferably aliphatic diamines having a carbon number of 1 to 6.
  • alicyclic diamines as used herein are diamines having at least one non-aromatic ring as an annular moiety, and are preferably diamines having only at least one non-aromatic ring as an annular moiety.
  • aromatic diamines as used herein are diamines having at least one aromatic ring as an annular moiety, and are preferably diamines having only at least one aromatic ring as an annular moiety.
  • the diamine preferably has a carbon number of 1 to 30, and preferably 2 to 20.
  • the diamine is preferably an aromatic diamine optionally having at least one trifluoromethyl.
  • the diamine is preferably an aromatic diamine having a carbon number of 6 to 30, and preferably 6 to 20 with optionally at least one fluorine atom.
  • the diamine is more preferably an aromatic diamine optionally having at least one trifluoromethyl with a carbon number of 7 to 30, and preferably 7 to 20.
  • Preferable examples of the diamine include the following compound.
  • the diamine may be one type of diamine, or a combination of two or more types of diamines. In other words, the same or different structural units A may be repeated.
  • the polyimide mentioned above can be synthesized, for example, by a known synthesis method of polyimide, or a method according to the known method.
  • polyimides can be produced by, for example, a production method comprising step P1 of reacting fluorine-containing compound (4-3a) with a diamine to obtain polyamide acid, and step P2 of heating the polyamide acid to subject the polyamide acid to a ring-closing reaction.
  • the molar ratio of fluorine-containing compound (4-3a) to a diamine in step P1 is typically within the range of 55:45 to 45:55, preferably 52:48 to 48:52, and more preferably 51:49 to 49:51.
  • Step P1 is preferably performed in the presence of a polar solvent.
  • polar solvents include dimethylamino acetamide.
  • the polar solvents may be used singly or in a combination of two or more.
  • the reaction temperature in step P1 is typically 0 to 150° C., and preferably room temperature (25° C.) to 100° C.
  • the reaction time in step P1 is typically 2 to 24 hours, and preferably 2 to 12 hours.
  • the reaction in step P1 may be performed, for example, by stirring a solution of fluorine-containing compound (4-3a) and the diamine in a polar solvent.
  • the polar solvent is preferably evaporated from the obtained product under reduced pressure.
  • the reaction temperature (heating temperature) in step P2 is typically within the range of 20 to 300° C., and preferably 50 to 200° C.
  • the reaction time in step P2 is typically within the range of 1 to 48 hours, and preferably 2 to 24 hours.
  • R independently may represent alkyl or benzyl.
  • Examples 2-1 to 2-24 were performed using the complex compound: (phen)CuCF 2 CF 2 Ph prepared and isolated in Example 1 by the following method A and/or method B to thereby obtain the respective target fluorine-containing compounds.
  • a substrate was added to a suspension of (phen)CuCF 2 CF 2 Ph (1.2 eq) in 10 ml of THF under a nitrogen atmosphere and heated at 60° C. for a predetermined time period. The reaction mixture was then cooled to room temperature, and 10 ml of ether was added thereto, followed by filtration to remove the insoluble matter. The filtrate was concentrated and then purified by column chromatography, thereby giving the target product.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method B as described below.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method B as described below.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method B as described below.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method B as described below.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method B as described below.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method B as described below.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method B as described below.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method B as described below.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method A as described below.
  • the title compound was prepared by method B as described below.
  • Examples 3-1 to 3-11 were performed by stepwise synthesis in accordance with the following method C, thereby giving the respective target fluorine-containing compounds.
  • Example 4-1 the target fluorine-containing compound was obtained in one-step synthesis.
  • the Celite was washed with THF, and the liquid was combined with the THF solution obtained in advance, followed by concentration under reduced pressure.
  • the obtained concentrate was purified by column chromatography (SiO 2 , n-hexane), thereby giving 130.0 mg of the target product (compound 1) (yield 12%).
  • Compound 5 IR (KBr, cm ⁇ 1 ): 1770, 1718, 1700, 1685, 1628, 1560, 1542, 1509, 1489, 1419, 1335, 1259, 1224, 1170, 1119, 1053.
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