Fluorinating agent and fluorination method

Abstract

Provided are a fluorinating agent that can be produced using a simple method, and a fluorination method that uses a fluorinating agent that can be produced using a simple method. The present disclosure provides a fluorinating agent that comprises a fluorine-containing compound and fluoride ions.

Description

Fluorinating agent and fluorination method

[0001] The present disclosure relates to fluorinating agents and methods.

[0002] Potassium fluoride (KF) is known as a fluorinating agent for organic chlorides, etc. Potassium fluoride is usually synthesized by the reaction of HF with KOH and processed into a fine powder by spray drying (see, for example, Non-Patent Document 1).

[0003] "2019 Edition: 17019 Chemical Products," Chemical Daily, 2019, p. 187

[0004] Potassium fluoride, which has been known as a fluorinating agent, has a problem in that it requires the use of a strong acid and a strong base and further requires the production of a fine powder by a spray drying method, making the production process complicated.

[0005] An object of the present disclosure is to provide a fluorinating agent that can be produced by a simple method, and a fluorination method using the fluorinating agent that can be produced by a simple method.

[0006] The present disclosure (1) is a fluorinating agent containing a fluorine-containing compound and a fluoride ion.

[0007] The present disclosure (2) is a fluorinating agent according to the present disclosure (1) that is solid at 25°C.

[0008] The present disclosure (3) is directed to a method for preparing a fluoride ion-containing compound, wherein the counter ion of the fluoride ion is an alkali metal, an alkaline earth metal, or NR １ ４ (R １ may be the same or different, and are H or an organic group having 1 to 10 carbon atoms).

[0009] The present disclosure (4) is a fluorinating agent in any combination with any of the present disclosures (1) to (3), which further contains a base.

[0010] The present disclosure (5) is the fluorinating agent according to the present disclosure (4), wherein the base is solid at 25°C.

[0011] The present disclosure (6) is the fluorinating agent according to the present disclosure (4) or (5), wherein the pKa of the base is 8 to 40.

[0012] The present disclosure (7) is a method for preparing a compound in which the base is R １０ OM (in the formula, R １０ is H or an organic group having 1 to 10 carbon atoms, M is a metal or NR １ ４ (R １ may be the same or different and represent H or an organic group having 1 to 10 carbon atoms). The fluorinating agent is at least one selected from the group consisting of compounds represented by the formula (I) and metal carbonates, and any combination of the fluorinating agent with any of the compounds (4) to (6) of the present disclosure.

[0013] The present disclosure (8) is a fluorinating agent in any combination with any of the present disclosures (4) to (7), wherein the base is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, cesium hydroxide, cesium carbonate, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium t-butoxide, and potassium t-butoxide.

[0014] The present disclosure (9) is a fluorinating agent in any combination with any of the present disclosures (4) to (8), in which the content of the base is 0.1 to 70 mass%.

[0015] The present disclosure (10) is a fluorinating agent in any combination with any of the present disclosures (1) to (9), wherein the fluorine-containing compound is solid at 25°C.

[0016] The present disclosure (11) is a fluorinating agent in any combination with any of the present disclosures (1) to (10), in which the fluorine-containing compound is a fluorine-containing polymer.

[0017] The present disclosure (12) is a fluorinating agent in any combination with any of the present disclosures (1) to (11), wherein the fluorine-containing compound is a fluorine-containing polymer containing polymerization units based on at least one monomer selected from the group consisting of tetrafluoroethylene, difluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl ether), trifluoroethylene, and monofluoroethylene.

[0018] The present disclosure (13) is a fluorinating agent in any combination with any of the present disclosures (1) to (12), wherein the fluorine-containing compound is at least one selected from the group consisting of polytetrafluoroethylene, polyvinylidene fluoride, and polychlorotrifluoroethylene.

[0019] The present disclosure (14) is a fluorinating agent which is a composition obtained by mechanochemically treating a fluorine-containing compound and a base.

[0020] The present disclosure (15) is a fluorination method including a step of fluorinating an object using the fluorinating agent according to the present disclosure (14).

[0021] The present disclosure (16) is a fluorination method including a step of fluorinating an object using a fluorinating agent containing a fluorine-containing compound and fluoride ions.

[0022] The present disclosure (17) is the fluorination method according to the present disclosure (15) or (16), wherein the fluorinating agent is solid at 25°C.

[0023] The present disclosure (18) is the fluorination method according to the present disclosure (16) or (17), wherein the fluorine-containing compound is solid at 25°C.

[0024] The present disclosure (19) is a fluorination method in any combination with any of the present disclosures (16) to (18), in which the fluorine-containing compound is a fluorine-containing polymer.

[0025] The present disclosure (20) is a fluorination method in any combination with any of the present disclosures (16) to (19), wherein the fluorine-containing compound is a fluorine-containing polymer containing polymerization units based on at least one monomer selected from the group consisting of tetrafluoroethylene, difluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl ether), trifluoroethylene, and monofluoroethylene.

[0026] The present disclosure (21) is a fluorination method in any combination with any of the present disclosures (16) to (20), in which the fluorine-containing compound is at least one selected from the group consisting of polytetrafluoroethylene, polyvinylidene fluoride, and polychlorotrifluoroethylene.

[0027] The present disclosure (22) is directed to a method for preparing a fluoride ion-containing compound, wherein the counter ion of the fluoride ion is an alkali metal, an alkaline earth metal, or NR １ ４ (R １ may be the same or different, and are H or an organic group having 1 to 10 carbon atoms).

[0028] The present disclosure (23) is a fluorination method in any combination with any of the present disclosures (15) to (22), in which the fluorinating agent further contains a base.

[0029] Disclosure (24) is the fluorination method according to Disclosure (23), wherein the base is solid at 25°C.

[0030] The present disclosure (25) is directed to a compound in which the base is R １０ OM (in the formula, R １０ is H or an organic group having 1 to 10 carbon atoms, M is a metal or NR １ ４ (R １ may be the same or different and represent H or an organic group having 1 to 10 carbon atoms.) and metal carbonates.

[0031] The present disclosure (26) is a fluorination method in any combination with any of the present disclosures (23) to (25), in which the base is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, cesium hydroxide, cesium carbonate, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium t-butoxide, and potassium t-butoxide.

[0032] The present disclosure (27) is a fluorination method in any combination with any of the present disclosures (23) to (26), in which the content of the base relative to the fluorinating agent is 0.1 to 70 mass%.

[0033] The present disclosure (28) is a fluorination method in any combination with any of the present disclosures (16) to (27), in which the fluorinating agent is obtained by mechanochemically treating a fluorine-containing compound and a base.

[0034] The present disclosure (29) is a fluorination method in any combination with any of the present disclosures (15) to (28), further comprising a step of purifying the crude product obtained by fluorination to recover the fluorinated target substance.

[0035] The present disclosure (30) is a fluorination method in any combination with any of the present disclosures (15) to (29), in which the fluorination is carried out in a dry manner.

[0036] The present disclosure (31) is a fluorination method in any combination with any of the present disclosures (15) to (30), in which the fluorination is carried out by mechanochemically treating the fluorinating agent and the object.

[0037] The present disclosure (32) is a fluorination method in any combination with any of the present disclosures (15) to (31), in which the step of obtaining the fluorinating agent and the step of fluorination are carried out continuously.

[0038] The present disclosure (33) is a fluorination method in any combination with any of the present disclosures (15) to (32), in which the amount of the fluorinating agent used is 1.0 to 3.0 equivalents per equivalent of a group that can be substituted with a fluorine atom that the target substance has.

[0039] The present disclosure (34) is a fluorination method in any combination with any of the present disclosures (15) to (33), wherein the target substance is an organic compound having at least one atom selected from the group consisting of a chlorine atom and a bromine atom.

[0040] According to the present disclosure, it is possible to provide a fluorinating agent that can be produced by a simple method, and a fluorination method using the fluorinating agent that can be produced by a simple method.

[0041] The present disclosure will be specifically described below.

[0042] The present disclosure relates to a fluorinating agent containing a fluorine-containing compound and a fluoride ion (hereinafter also referred to as fluorinating agent (1) of the present disclosure). Because the fluorinating agent (1) of the present disclosure has the above-described configuration, it can be produced by a simple method. Furthermore, the presence of a fluorine-containing compound with low hygroscopicity around a component having a fluoride ion suppresses adhesion of the component even when absorbing moisture, allowing the component to maintain a powdery state. Therefore, the fluorinating agent (1) of the present disclosure has excellent handleability even when left in the air.

[0043] The fluorine-containing compound in the fluorinating agent (1) of the present disclosure may be any compound having a fluorine atom, and may be a compound having a fluorine atom bonded to a carbon atom, and is preferably an organic compound having a fluorine atom bonded to a carbon atom. In addition, the fluorine-containing compound is preferably a solid at 25° C. in terms of being easier to handle.

[0044] The fluorine-containing compound is preferably a fluorine-containing polymer compound, more preferably a fluorine-containing polymer.

[0045] The fluoropolymer preferably contains polymerization units based on at least one monomer selected from the group consisting of tetrafluoroethylene [TFE], difluoroethylene, chlorotrifluoroethylene [CTFE], hexafluoropropylene [HFP], perfluoro(alkyl vinyl ether) [PAVE], trifluoroethylene, and monofluoroethylene. Examples of the difluoroethylene include vinylidene fluoride [VdF] and 1,2-difluoroethylene. The fluoropolymer more preferably contains polymerization units based on at least one monomer selected from the group consisting of TFE, difluoroethylene, and CTFE, even more preferably contains polymerization units based on at least one monomer selected from the group consisting of TFE, VdF, and CTFE, even more preferably contains polymerization units based on at least one monomer selected from the group consisting of TFE and VdF, and particularly preferably contains polymerization units based on VdF.

[0046] The fluorine-containing polymer may be a fluororesin or a fluororubber.

[0047] Examples of the fluororesin include polytetrafluoroethylene [PTFE], tetrafluoroethylene [TFE] / perfluoro(alkyl vinyl ether) [PAVE] copolymer [PFA], TFE / hexafluoropropylene [HFP] copolymer [FEP], ethylene [Et] / TFE copolymer [ETFE], Et / TFE / HFP copolymer [EFEP], polychlorotrifluoroethylene [PCTFE], chlorotrifluoroethylene [CTFE] / TFE copolymer, CTFE / TFE / PAVE copolymer, Examples of the perfluoroalkyl allyl ether include CF3 / CTFE copolymer, polyvinyl fluoride [PVF], polyvinylidene fluoride [PVdF], vinylidene fluoride [VdF] / TFE copolymer, VdF / HFP copolymer, VdF / TFE / HFP copolymer, VdF / HFP / (meth)acrylic acid copolymer, VdF / CTFE copolymer, VdF / pentafluoropropylene copolymer, VdF / PAVE / TFE copolymer, TFE / perfluoroalkyl allyl ether copolymer, etc., and these can be used alone or in combination. ２ =CFCF ２ -O-Rf １ (Rf １ is a perfluoroalkyl group having 1 to 5 carbon atoms).

[0048] Examples of the fluororubber include vinylidene fluoride [VdF]-based fluororubbers, tetrafluoroethylene [TFE] / propylene [Pr]-based fluororubbers, TFE / Pr / VdF-based fluororubbers, ethylene [Et] / hexafluoropropylene [HFP]-based fluororubbers, Et / HFP / VdF-based fluororubbers, Et / HFP / TFE-based fluororubbers, fluorosilicone-based fluororubbers, and fluorophosphazene-based fluororubbers, and these may be used alone or in combination.

[0049] Examples of the VdF-based fluororubbers include VdF / HFP copolymer, VdF / TFE / HFP copolymer, VdF / chlorotrifluoroethylene [CTFE] copolymer, VdF / CTFE / TFE copolymer, VdF / perfluoro(alkyl vinyl ether) [PAVE] copolymer, VdF / TFE / PAVE copolymer, VdF / HFP / PAVE copolymer, VdF / HFP / TFE / PAVE copolymer, VdF / TFE / Pr copolymer, VdF / Et / HFP copolymer, and VdF / copolymer of a fluorine-containing monomer represented by the following formula (1): Formula (1): CH ２ = CFRf ２ (1) (wherein, Rf ２ represents a linear or branched fluoroalkyl group having 1 to 12 carbon atoms)

[0050] As the fluorine-containing polymer, at least one selected from the group consisting of fluororesin and fluororubber is preferred, at least one selected from the group consisting of PTFE, FEP, PFA, PVdF, PCTFE and fluororubber is more preferred, at least one selected from the group consisting of PTFE, PVdF and PCTFE is even more preferred, at least one selected from the group consisting of PTFE and PVdF is even more preferred, PVdF is particularly preferred.In addition, as the fluorine-containing polymer, perhalogen resin is also preferred, at least one selected from the group consisting of perfluororesin and PCTFE is more preferred, at least one selected from the group consisting of PTFE, PFA, FEP and PCTFE is even more preferred, at least one selected from the group consisting of PTFE, PFA and FEP is even more preferred.In addition, as the fluorine-containing polymer, at least one selected from the group consisting of perfluororesin and polydifluoroethylene is also preferred, at least one selected from the group consisting of PTFE and polydifluoroethylene is more preferred.

[0051] The fluorine-containing compound does not have to be a polymer, and may be a fluorine-containing low molecular weight compound, as long as it is solid at 25° C. The fluorine-containing low molecular weight compound is a compound represented by the following general formula (I): Y—(CF ２ ) ｘ１ - (CH ２ )ｙ１ -A (I) (wherein Y represents H or F, x1 represents an integer of 4 or more, y1 represents an integer of 0 to 3, and A represents -SO ３ M Ｉ or -COOM Ｉ indicates M Ｉ is H, NH ４ , Li, Na, Mg, Al, K or Ca), and a compound (I) represented by the following general formula (II): F—(CF ２ ) Ｘ２ O(CFXCF ２ O) ｙ２ -CFX-A (II) (wherein x2 represents an integer of 1 or more, y2 represents an integer of 0 to 10, and X represents F or CF ３ A represents -SO ３ M ＩＩ or -COOM ＩＩ indicates M ＩＩ is H, NH ４ , Li, Na, Mg, Al, K or Ca.

[0052] Examples of the compound (I) include fluorocarboxylic acids and salts thereof, preferably perfluorocarboxylic acids and salts thereof, such as perfluorooctanoic acid and salts thereof (collectively referred to as "PFOA"). Examples of salts include ammonium salts and sodium salts, with ammonium salts being preferred, such as ammonium perfluorooctanoic acid (particularly referred to as "APFO"). Examples of the compound (I) also include fluorosulfonic acids and salts thereof, preferably perfluorosulfonic acids and salts thereof, such as perfluorooctanesulfonic acid and salts thereof (collectively referred to as "PFOS"). Examples of salts include ammonium salts and sodium salts. Examples of the compound (II) include perfluoroethercarboxylic acids and salts thereof, such as 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(trifluoromethoxy)propoxy]-propanoic acid.

[0053] The fluorine-containing low molecular weight compound may be adsorbed onto an adsorbent. In this embodiment, the fluorinating agent (1) of the present disclosure may include a solid in which the fluorine-containing low molecular weight compound is adsorbed onto an adsorbent. The adsorbent is not limited as long as it is a solid that can adsorb the fluorine-containing low molecular weight compound, but is preferably at least one selected from the group consisting of activated carbon, silica gel, clay, metal-organic framework (MOF), and zeolite.

[0054] The fluoropolymer may be one which has been once heated to or above its melting point, or may be one which has been molded and then pulverized. From the viewpoint of reactivity in the production method described below, the smaller the particle size, the better.

[0055] The content of the fluorine-containing compound relative to the fluorinating agent (1) of the present disclosure is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, and is preferably 90% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less, even more preferably 50% by mass or less, even more preferably 30% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 1% by mass or less. The lower the content of the fluorine-containing compound, the better.

[0056] The fluorinating agent (1) of the present disclosure is preferably substantially free of fluorine-containing organic compounds. "Substantially free of fluorine-containing organic compounds" means that the content of organic fluorine relative to the fluorinating agent (1) of the present disclosure is 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.1% by mass or less. The lower limit is not particularly limited, and may be 0% by mass or even 0.0001% by mass. The content of organic fluorine in the fluorinating agent is measured by combustion ion chromatography. Incidentally, organic fluorine means fluorine bonded to carbon.

[0057] The fluorinating agent (1) of the present disclosure contains fluoride ions. The content of the fluoride ions relative to the fluorinating agent is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, even more preferably 3.0% by mass or more, and particularly preferably 5.0% by mass or more, and is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, particularly preferably 15% by mass or less, and may be 10% by mass or less.

[0058] The fluorinating agent (1) of the present disclosure typically contains a counterion along with a fluoride ion. The counterion may be a metal or a NR １ ４ (R １ may be the same or different, and preferably contain at least one selected from the group consisting of H or an organic group having 1 to 10 carbon atoms. These may be contained as cations. Examples of the metal include monovalent and divalent metals, such as alkali metals (Group 1) or alkaline earth metals (Group 2), and specific examples include Na, K, Li, Cs, and Ca. Of these, alkali metals are preferred, with Na, K, and Cs being more preferred, and K being even more preferred. NR １ ４ is ammonium (unsubstituted or substituted ammonium), and the four R １ may be the same or different. １is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms.

[0059] The counter ions include alkali metals, alkaline earth metals, and NR １ ４ (R １ may be the same or different, and may contain at least one selected from the group consisting of H or an organic group having 1 to 10 carbon atoms), more preferably contain at least one selected from the group consisting of alkali metals and alkaline earth metals, even more preferably contain an alkali metal, still more preferably contain at least one selected from the group consisting of Na, K, and Cs, and particularly preferably contain K.

[0060] The content of the counter ions is preferably an amount that balances the charge of the fluoride ions.

[0061] The fluorinating agent (1) of the present disclosure may include a compound having a fluoride ion, or may include a compound having a fluoride ion and a counter ion. Examples of the compound include metal fluorides and ammonium fluoride, with metal fluorides being preferred, alkali metal fluorides being more preferred, and potassium fluoride being even more preferred.

[0062] The fluorinating agent (1) of the present disclosure preferably further contains a base. A fluorinating agent containing a fluorine-containing compound and a base can be produced by mechanochemical treatment of the fluorine-containing compound and the base, and therefore can be produced by a simpler method.

[0063] The base is a basic compound, preferably a strongly basic compound, and is preferably a solid at 25°C for ease of handling.

[0064] In order to enable the production of the fluorinating agent using a general-purpose apparatus, the base preferably has a pKa (acid dissociation constant in water at 25°C) of 40 or less, more preferably 35 or less, and even more preferably 20 or less, and preferably 8 or more, more preferably 9 or more, even more preferably 12 or more, and even more preferably 15 or more. The pKa is measured by neutralization titration.

[0065] The base may be an inorganic base or an organic base, but is preferably an organic base in that the fluorinating agent can be produced using a general-purpose apparatus.

[0066] The base is a metal and NR １ ４ (R １ may be the same or different, and preferably contain at least one selected from the group consisting of H or an organic group having 1 to 10 carbon atoms. These may be contained as cations. １ ４ The base includes those mentioned above. The base includes alkali metals, alkaline earth metals, and NR １ ４ (R １ may be the same or different, and may contain at least one selected from the group consisting of H or an organic group having 1 to 10 carbon atoms), more preferably contain at least one selected from the group consisting of alkali metals and alkaline earth metals, even more preferably contain an alkali metal, still more preferably contain at least one selected from the group consisting of Na and K, and particularly preferably contain K.

[0067] The base may be R １０ OM (in the formula, R １０ is H or an organic group having 1 to 10 carbon atoms, M is a metal or NR １ ４ (R １ may be the same or different and represent H or an organic group having 1 to 10 carbon atoms). Examples of the compounds represented by the formula (R) include compounds represented by the formula (R), metal carbonates, metal acetates, cyclic amines, polyamines, etc. １０The number of carbon atoms in the organic group R is preferably 2 or more, more preferably 3 or more, and is preferably 8 or less, more preferably 6 or less. １０ is preferably H or an alkyl group having a carbon number within the above range, more preferably an alkyl group having a carbon number within the above range, and further preferably a methyl group, an ethyl group, or a t-butyl group. １ ４ Examples of M include those mentioned above. M is preferably a metal, more preferably an alkali metal or alkaline earth metal, even more preferably an alkali metal, even more preferably Na or K, and particularly preferably K. The metal of the metal carbonate is preferably an alkali metal or alkaline earth metal, even more preferably an alkali metal, even more preferably Na, K or Cs, and particularly preferably Cs. The metal of the metal acetate is preferably an alkali metal or alkaline earth metal, even more preferably an alkali metal, even more preferably Na or K, and particularly preferably K. Examples of the cyclic amine include 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) and derivatives thereof. Examples of the polyamine include polyethyleneimine.

[0068] As the base, R １０ At least one selected from the group consisting of compounds represented by R 0M and metal carbonates is preferred, and in that case, the fluorinating agent can be more easily produced using a general-purpose apparatus. １０ R in OM １０is an organic group having 1 to 10 carbon atoms, more preferably a metal alkoxide, even more preferably an alkali metal alkoxide, even more preferably at least one selected from the group consisting of alkali metal methoxides, alkali metal ethoxides, and alkali metal t-butoxides, and particularly preferably at least one selected from the group consisting of sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium t-butoxide, and potassium t-butoxide. The base is also preferably at least one selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, and alkali metal alkoxides, and more preferably at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, cesium hydroxide, cesium carbonate, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium t-butoxide, and potassium t-butoxide.

[0069] The content of the base relative to the fluorinating agent (1) of the present disclosure is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, even more preferably 50% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less. When the amount of the base is within the above range, decomposition of the substrate can be prevented when the fluorinating agent is used in the fluorination step, which is preferable from the viewpoint of yield.

[0070] The fluorinating agent (1) of the present disclosure preferably contains a compound having a structure obtained by defluorinating the fluorine-containing compound. The compound may have a structure obtained by defluorinating at least some of the fluorine atoms of the fluorine-containing compound. When the fluorinating agent (1) of the present disclosure contains a base, the compound may have a structure obtained by defluorinating at least some of the fluorine atoms of the fluorine-containing compound, which is derived from the base, for example, R １０ O-(R １０is the same as above) (for example, a hydroxy group or an alkoxy group, preferably an alkoxy group). A fluorinating agent containing a compound having the above structure can be produced by a simpler method, namely, decomposition (defluorination) of a fluorine-containing compound. Whether a fluorinating agent contains a compound having the above structure can be confirmed by removing components other than the fluorine-containing compound from the fluorinating agent by washing or the like, and then analyzing the fluorinating agent by XPS, FT-IR, solid-state NMR or the like, and by measuring the carbon and fluorine contents before and after the reaction by elemental analysis.

[0071] The fluorinating agent (1) of the present disclosure may contain other components within a range that does not impair the effect. Examples of such other components include general fillers, polymers, and the above-mentioned adsorbents.

[0072] Examples of the common filler include inorganic fillers such as glass fiber, glass beads, carbon fiber, spherical carbon, carbon black, graphite, silica, alumina, mica, silicon carbide, boron nitride, aluminum nitride, titanium oxide, bismuth oxide, cobalt oxide, magnesium oxide, molybdenum disulfide, bronze, gold, silver, copper, nickel, aluminum fluoride, carbon fluoride, and carbon black.

[0073] Examples of the common polymers include polyolefin resins such as polyethylene and polypropylene; polyamide [PA] resins such as nylon 6, nylon 11, nylon 12, nylon 46, nylon 66, nylon 610, nylon 612, and nylon MXD6; polyesters such as polyethylene terephthalate [PET], polybutylene terephthalate [PBT], polyarylate, aromatic polyesters (including liquid crystal polyesters), and polycarbonate [PC]; polyacetal [POM] resins; polyether resins such as polyphenylene oxide [PPO], modified polyphenylene ether, and polyether ether ketone [PEEK]; polyamide imide [PAI] resins such as polyamino bismaleimide; polysulfone resins such as polysulfone [PSF] and polyethersulfone [PES]; vinyl polymers such as ABS resin and poly 4-methylpentene-1 (TPX resin), as well as polyphenylene sulfide [PPS], polyketone sulfide, polyetherimide, polyimide [PI], and epoxy resins. The nylon MXD6 is a crystalline polycondensate obtained from metaxylenediamine (MXD) and adipic acid. The general polymer may be a non-fluorine-containing polymer.

[0074] The content of the other components, relative to the fluorinating agent, may be 50% by mass or less, preferably 30% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, and may be 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, or 1% by mass or more.

[0075] The fluorinating agent (1) of the present disclosure is preferably a solid at 25° C. and is preferably a powder, in view of ease of handling.

[0076] The fluorinating agent (1) of the present disclosure has a maximum particle size that can be confirmed when observed with a microscope such as a video microscope of preferably 7 mm or less, more preferably 6 mm or less, even more preferably 5 mm or less, and particularly preferably 4 mm or less, and is preferably 10 μm or more, more preferably 100 μm or more, even more preferably 300 μm or more, and particularly preferably 500 μm or more. Fluorinating agents having a maximum particle size within the above range are not agglomerated and are easy to handle.

[0077] The fluorinating agent (1) of the present disclosure can be produced, for example, by mixing a fluorine-containing compound, a compound having a fluoride ion, and, if necessary, a base (hereinafter also referred to as production method (1)). The mixing method is not particularly limited, and any known method can be used.

[0078] When the fluorinating agent (1) of the present disclosure contains a base, it can also be produced by mechanochemically treating a fluorine-containing compound and a base (hereinafter also referred to as production method (2)). From the viewpoint of producing it in a simpler manner, production method (2) is preferred. That is, the fluorinating agent (1) of the present disclosure is preferably one obtained by mechanochemically treating a fluorine-containing compound and a base. Furthermore, the mechanochemical treatment can also make it a fluorinating agent that is substantially free of fluorine-containing organic compounds. The fluorinating agent (1) of the present disclosure is also preferably one obtained by mechanochemically treating a fluorine-containing compound and a base and that is substantially free of fluorine-containing organic compounds. Hereinafter, production method (2) will be described in detail.

[0079] The amount of the base used in the mechanochemical treatment is preferably 0.01 equivalents or more, more preferably 0.05 equivalents or more, and even more preferably 0.10 equivalents or more, relative to 1 equivalent (molar equivalent) of the fluorine-containing compound, and is preferably 10 equivalents or less, more preferably 8 equivalents or less, even more preferably 5 equivalents or less, even more preferably 3 equivalents or less, even more preferably 1 equivalent or less, and particularly preferably 0.8 equivalents or less. In production method (2), the mechanochemical treatment can be carried out with a relatively small amount of base. When the amount of base is small, there is an advantage that decomposition of the substrate can be prevented when the fluorinating agent is used in the fluorination step. When the fluorine-containing compound is a fluorine-containing polymer, the equivalent is calculated based on the monomers constituting the fluorine-containing polymer.

[0080] The mechanochemical treatment is a treatment method in which mechanical energy is applied to a reactant (preferably a solid reactant) by methods such as shearing, compression, stretching, grinding, friction, kneading, mixing, dispersing, crushing, shaking, etc., to activate the reactant and impart structural change, phase transition, reactivity, adsorptivity, catalytic activity, etc. The method of mechanochemical treatment is not particularly limited, and examples include a compression shear treatment method, an impact treatment method, and a mixed shear friction method, with the impact treatment method being preferred.

[0081] The apparatus for carrying out the mechanochemical treatment is not particularly limited as long as it is an apparatus that can apply mechanical energy by the above-mentioned method, and known pulverizers and mixers can be used. For example, pulverizers such as a ball mill, rod mill, jet mill, vibration mill, SAG mill, etc.; attritors such as a rotary stone mill, crusher, etc.; (horizontal axis rotation) container rotation type mixers such as a horizontal cylindrical type, V type, double cone type, square cube type, S type, and continuous V type; (baffle blade equipped) container rotation type mixers such as a horizontal cylindrical type, V type, double cone type, and ball mill type; (rotation vibration) container rotation type mixers such as a rocking type and cross rotary type; (horizontal axis) container rotation type mixers such as a ribbon type, paddle type, single shaft rotor type, and bug mill type. (rotating) fixed vessel type mixers; (vertical axis rotating) fixed vessel type mixers such as ribbon type, screw type, planetary type, turbine type, high speed fluid type, rotating disk type and Mahler type; (vibrating) fixed vessel type mixers such as vibration mill type and sieve type; (fluidization) fluid motion type mixers such as heterogeneous fluidized bed, swirling fluidized bed, type with riser and Jot pump type; (gravity) fluid motion type mixers such as gravity type and static mixer; and kneaders such as twin-screw kneaders, single-screw kneaders, mixers, roll mills, etc.

[0082] The apparatus for carrying out the mechanochemical treatment is preferably an apparatus using balls, more preferably a ball mill. A ball mill (excluding planetary ball mills) is preferred because it can be produced using a more general-purpose apparatus. This form is particularly suitable when the base is an organic base.

[0083] The mechanochemical treatment can be carried out using a planetary mill, but is preferably carried out without a planetary mill. While a planetary mill is a device that can impart high energy, it also generates a large amount of wear powder derived from the device. For example, Fig. 3 in J. Soc. Powder Technol., Japan, 44, 186-190 (2007) [https: / / www. jstage. jst. go. jp / article / sptj1978 / 44 / 3 / 44_3_186 / _pdf / -char / ja] describes the relationship between the rotation speed of the planetary mill and the amount of wear powder generated from the device, and shows that a certain amount of wear powder is generated by the planetary mill. When the composition after the reaction is used as a fluorinating agent, it is preferable that it does not contain impurities. By performing mechanochemical treatment without using a planetary mill under conditions that are less likely to generate wear particles from the equipment, a composition suitable for a fluorinating agent can be obtained. Furthermore, methods that use general-purpose equipment such as a ball mill rather than a planetary mill also have the advantage of being easily industrialized. It is particularly preferable not to use a planetary mill when the base is an organic base.

[0084] The temperature of the mechanochemical treatment is preferably 5°C or higher, more preferably 10°C or higher, even more preferably 15°C or higher, even more preferably 20°C or higher, and is preferably 300°C or lower, more preferably 250°C or lower, even more preferably 200°C or lower, even more preferably 160°C or lower.

[0085] When the mechanochemical treatment is carried out using a ball mill (excluding planetary ball mills), the shaking conditions can be determined depending on the apparatus and ball used. For example, when treatment is carried out using a jar of about 1 to 20 mL and one stainless steel ball of about 1 to 15 mm in diameter, shaking can be carried out under conditions of preferably 100 rpm or more, more preferably 300 rpm or more, even more preferably 500 rpm or more, and preferably 1800 rpm or less, more preferably 1600 rpm or less, even more preferably 1500 rpm or less.

[0086] When the mechanochemical treatment is carried out using a ball mill (excluding planetary ball mills), the time for the mechanochemical treatment is preferably 5 minutes or more, more preferably 10 minutes or more, and even more preferably 20 minutes or more, and is preferably 500 minutes or less, more preferably 300 minutes or less, even more preferably 200 minutes or less, and even more preferably 100 minutes or less.

[0087] The mechanochemical treatment may be carried out in any atmosphere, for example, in air, in an inert gas, in vacuum, etc. From the viewpoint of low cost, it is preferably carried out in air.

[0088] The mechanochemical treatment can be carried out in the absence of a solvent, but may be carried out in the presence of a small amount of solvent, if necessary. The presence of a small amount of solvent may sometimes promote mixing of the components. The amount of the solvent used is preferably 0.001 μl / mg or more, more preferably 0.01 μl / mg or more, and more preferably 0.05 μl / mg or more, based on the total mass of the fluorine-containing compound and the base, and is preferably 3.0 μl / mg or less, more preferably 1.0 μl / mg or less, and even more preferably 0.5 μl / mg or less.

[0089] The solvent used in the mechanochemical treatment is preferably an organic solvent such as an ether, nitrile, ester, aromatic, hydrocarbon, alcohol, or halogen-based solvent. Examples of the organic solvent include esters such as methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, and tert-butyl acetate; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aliphatic hydrocarbons such as hexane, cyclohexane, octane, nonane, decane, undecane, dodecane, and mineral spirits; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; alcohols such as methanol, ethanol, tert-butanol, isopropanol, and ethylene glycol monoalkyl ether; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; nitriles such as acetonitrile and propionitrile; amides such as dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide; halogenated hydrocarbons such as dichloromethane, dichloroethane, and chloroform; and mixtures thereof. Of these, cyclic ethers are preferred as the solvent.

[0090] The mechanochemical treatment is also preferably carried out in a dry manner, which means that the amount of liquid in the reaction system is 5% by mass or less, preferably 1% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.01% by mass or less.

[0091] The mechanochemical treatment can cause the fluorine-containing compound to react, which may be a reaction that produces fluoride ions, and is preferably a defluorination reaction.

[0092] By the mechanochemical treatment, a composition containing a fluorine-containing compound, a base, and fluoride ions (and counter ions) can be obtained, and this composition can be used as is as the fluorinating agent (1) of the present disclosure.

[0093] The present disclosure also relates to a fluorinating agent (hereinafter also referred to as fluorinating agent (2) of the present disclosure) which is a composition obtained by mechanochemically treating a fluorine-containing compound and a base. The fluorinating agent (2) of the present disclosure has excellent properties as a fluorinating agent because it is obtained by a specific treatment.

[0094] Examples of the fluorine-containing compound and base in the fluorinating agent (2) of the present disclosure include the same fluorine-containing compound and base as those described in the fluorinating agent (1) of the present disclosure, and preferred embodiments are also the same.

[0095] The mechanochemical treatment for the fluorinating agent (2) of the present disclosure may be the same as the production method (2) described for the fluorinating agent (1) of the present disclosure, and the preferred embodiments are also the same.

[0096] The fluorinating agent (2) of the present disclosure is preferably substantially free of fluorine-containing organic compounds. "Substantially free of fluorine-containing organic compounds" means that the content of organic fluorine relative to the fluorinating agent (2) of the present disclosure is 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.1% by mass or less. The lower limit is not particularly limited, and may be 0% by mass or even 0.0001% by mass. The content of organic fluorine in the composition is measured by combustion ion chromatography. Incidentally, organic fluorine means fluorine bonded to carbon.

[0097] The fluorinating agents (1) and (2) of the present disclosure can be used to produce various compounds having fluorine atoms, and are particularly suitable for producing fluorine-containing organic compounds. Furthermore, the fluorinating agents (1) and (2) of the present disclosure can be suitably used as fluorinating agents in the fluorination method of the present disclosure described below.

[0098] The present disclosure also relates to a fluorination method (hereinafter also referred to as fluorination method (1) of the present disclosure) including a step of fluorinating an object using a fluorinating agent containing a fluorine-containing compound and fluoride ions. Because the fluorination method (1) of the present disclosure has the above-described configuration, fluorination can be performed using a fluorinating agent that can be produced by a simple method. Furthermore, the presence of a fluorine-containing compound with low hygroscopicity around a component containing fluoride ions suppresses adhesion of the component even when absorbing moisture, allowing the fluorinating agent to maintain a powdery state. This allows fluorination to be performed using a fluorinating agent that is easy to handle even when left in the air.

[0099] The present disclosure also relates to a fluorination method (hereinafter also referred to as the fluorination method (2) of the present disclosure) that includes a step of fluorinating an object using the fluorinating agent (2) of the present disclosure. The fluorination method (2) of the present disclosure can achieve a good fluorination reaction by using a fluorinating agent obtained by a specific treatment.

[0100] In this specification, the fluorination methods (1) and (2) of the present disclosure are also collectively referred to as the "fluorination method of the present disclosure."

[0101] The fluorinating agent used in the fluorination method (1) of the present disclosure may be the same as the fluorinating agent (1) of the present disclosure described above. The fluorinating agent used in the fluorination method (2) of the present disclosure is the fluorinating agent (2) of the present disclosure described above.

[0102] The substance to be fluorinated may have a group that can be substituted with a fluorine atom. The substance to be fluorinated is preferably a compound having at least one group that can nucleophilically react with a fluorine atom, and more preferably an organic compound having at least one group that can nucleophilically react with a fluorine atom.

[0103] Examples of the group capable of nucleophilically reacting with a fluorine atom include a chlorine atom, a bromine atom, an iodine atom, a hydrogen atom, a hydroxy group, and an organic group. The number of carbon atoms in the organic group is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 7 or less. Examples of the organic group include an alkenyl group, an alkynyl group, an OSO group, and the like. ２ R２ (R ２ is an organic group having 1 to 10 carbon atoms), a carboxy group, etc. The group capable of nucleophilically reacting with a fluorine atom is preferably at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom, and a hydroxy group, more preferably at least one selected from the group consisting of a chlorine atom, a bromine atom, and a hydroxy group, even more preferably at least one selected from the group consisting of a chlorine atom and a bromine atom, and even more preferably a chlorine atom.

[0104] The fluorination can be carried out by contacting the target substance with the fluorinating agent. The contacting method is not limited, and known methods can be used.

[0105] The amount of the fluorinating agent used in the fluorination is preferably 1.0 equivalent or more, more preferably 1.3 equivalents or more, even more preferably 2.0 equivalents or more, and preferably 10 equivalents or less, more preferably 5.0 equivalents or less, even more preferably 3.0 equivalents or less, relative to 1 equivalent of the group that can be substituted with a fluorine atom possessed by the target substance. In calculating the equivalent of the fluorinating agent, the molecular weight of the fluorinating agent is calculated by the following formula, where M1 is the molecular weight of the fluorine-containing compound (or its constituent monomer in the case of a polymer), M2 is the molecular weight of the base, and x:1 is the equivalent ratio of the two in the fluorinating agent (fluorine-containing compound:base). Molecular weight of fluorinating agent = xM1 + M2

[0106] The fluorination is preferably carried out in the presence of a solvent. Examples of the solvent include water, an organic solvent, or a mixture thereof. Examples of the organic solvent include esters such as methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, and tert-butyl acetate; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aliphatic hydrocarbons such as hexane, cyclohexane, octane, nonane, decane, undecane, dodecane, and mineral spirits; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; alcohols such as methanol, ethanol, tert-butanol, isopropanol, and ethylene glycol monoalkyl ether; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; nitriles such as acetonitrile and propionitrile; amides such as dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide; halogenated hydrocarbons such as dichloromethane, dichloroethane, and chloroform, and mixtures thereof.

[0107] The fluorination temperature is preferably 5°C or higher, more preferably 10°C or higher, even more preferably 15°C or higher, and even more preferably 20°C or higher, and is preferably 200°C or lower, more preferably 150°C or lower, even more preferably 100°C or lower, and even more preferably 50°C or lower.

[0108] The fluorination time is preferably 5 minutes or more, more preferably 10 minutes or more, and even more preferably 20 minutes or more, and is preferably 50 hours or less, more preferably 30 hours or less, even more preferably 20 hours or less, and even more preferably 15 hours or less.

[0109] It is also preferable to carry out the above-mentioned fluorination in a dry system. It has been found that the fluorination reaction proceeds even in a dry system when the above-mentioned fluorinating agent is used. Carrying out the fluorination in a dry system means that the amount of liquid in the fluorination reaction system is 5% by mass or less, preferably 1% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.01% by mass or less.

[0110] It is also preferable that the fluorination is carried out by mechanochemically treating the fluorinating agent and the object. When the fluorination is carried out in a dry system, it is particularly preferable to employ mechanochemical treatment. Conditions for the mechanochemical treatment of the fluorinating agent and the object can be the same as those described in the method (2) for producing a fluorinating agent of the present disclosure.

[0111] It is also preferable to carry out the step of obtaining the fluorinating agent and the step of fluorination continuously. In this embodiment, it is preferable to carry out both steps in the same reaction vessel, and it is also preferable to carry out the step of fluorination after the step of obtaining the fluorinating agent without isolating or purifying the product. It is also preferable to carry out the fluorination step by mechanochemical treatment. Although the specific implementation method is not limited, for example, it is preferable that after the step of obtaining the fluorinating agent is completed, the object to be fluorinated is charged into the same reaction vessel without removing the contents of the reaction vessel, and the fluorination reaction is carried out.

[0112] The fluorination yields a crude product containing a fluorinated target substance (a compound in which a group that can be substituted with a fluorine atom has been substituted with a fluorine atom).

[0113] The fluorination method of the present disclosure also preferably includes a step of purifying the crude product obtained by fluorination to recover the fluorinated target substance. The purification method is not particularly limited, and any known method can be used.

[0114] The fluorination method of the present disclosure can be used to produce various compounds having fluorine atoms, and can be particularly suitably used to produce fluorine-containing organic compounds.

[0115] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

[0116] The present disclosure will now be described in more detail with reference to examples, but the present disclosure is not limited to these examples.

[0117] <Fluoride ions (F) after reaction －Measurement of the content of methyl methacrylate and base> Measurement was performed by ion chromatography. After the reaction, the mixture was filtered using distilled water to remove the liquid, and the residue was diluted with distilled water. Measurement was performed using an IC-8100ST manufactured by Tosoh Corporation equipped with a column (TSKgel (registered trademark) SuperIC-Anion HS) at an oven temperature of 40°C and a flow rate of 1.50 mL / min.

[0118] In the examples and reference examples, the following materials (all solid at 25°C) were used: Fluororesin A-1: ​​PVdF (VdF homopolymer, manufactured by BLD Pharmatech Ltd.), powder Fluororesin A-2: PTFE (TFE homopolymer, manufactured by Kitamura Co., Ltd., KTL-2N) Fluororesin A-3: PCTFE (CTFE homopolymer, manufactured by Sigma-Aldrich), powder Base B-1: tBuOK (organic base, pKa = 17) Base B-2: KOMe (organic base, pKa = 16) Base B-3: KOEt (organic base, pKa = 17) Base B-4: tBuONa (organic base, pKa = 17) Base B-5: CsOH.H ２ O (inorganic base, pKa = 15) Base B-6: Cs ２ CO ３ (inorganic base, pKa = 10) Base B-7: KOH (inorganic base, pKa = 14.7) Base B-8: NaOH (inorganic base, pKa = 13)

[0119] Example 1 A 10 mL stainless steel jar was charged with a stainless steel ball (10 mm), 0.5 eq. (equivalent) of fluororesin A-1 (128 mg, 2.0 mmol, calculated based on the molecular weight (64.03) of the constituent monomer VdF), 1.0 eq. of base B-1 (449 mg, 4.0 mmol), and anhydrous THF (0.5 μL / mg of fluororesin). The jar was closed and placed in a ball mill (Retsch Mixer Mill MM 400). Mechanochemical treatment using the ball mill was carried out for 60 minutes at room temperature (25°C) and 30 Hz. Upon completion, the jar was opened, washed with water, and concentrated in vacuo. The resulting composition (reaction mixture) was diluted with water and analyzed by ion chromatography. The resulting composition was a solid (powder) at 25°C and contained fluororesin A-1, <59 mass% of base B-1, and 1.8 mass% of fluoride ions. The counter ion of the fluoride ion is K. The yield of KF is shown in Table 1. The yield was calculated assuming that the case in which all of the counter ion K of the base B-1 was converted to KF was 100%.

[0120] Example 2 A 10 mL stainless steel jar was charged with a stainless steel ball (10 mm), 5.0 eq. (equivalent) of fluororesin A-1 (1,280 mg, 20 mmol, calculated based on the molecular weight (64.03) of the constituent monomer VdF), and 1.0 eq. of base B-1 (449 mg, 4.0 mmol). The jar was closed and placed in a ball mill (Retsch Mixer Mill MM 400). Mechanochemical treatment using the ball mill was carried out for 30 minutes at room temperature (25°C) and 30 Hz. Upon completion, the jar was opened, washed with water, and concentrated in vacuo. The resulting composition (reaction mixture) was diluted with water and analyzed by ion chromatography. The resulting composition was a solid (powder) at 25°C and contained fluororesin A-1, base B-1, and 2.9% by mass of fluoride ions. The counter ion for the fluoride ions was K. The yield of KF is shown in Table 1.

[0121] Example 3 A mechanochemical treatment was carried out in the same manner as in Example 1, except that the amount of fluororesin A-1 was changed to 3.0 eq. The obtained composition was a solid (powder) at 25°C and contained fluororesin A-1, <7.3 mass% of base B-1, and 7.7 mass% of fluoride ions. The counter ion of the fluoride ions was K. The yield of KF is shown in Table 1.

[0122] Example 4 A mechanochemical treatment was carried out in the same manner as in Example 1, except that 0.5 eq. of fluororesin A-1 was changed to 1.0 eq. of fluororesin A-2 (1,200 mg, 12.0 mmol, calculated based on the molecular weight of the constituent monomer TFE (100.02)), and the outer surface of the reaction vessel was heated to 300°C (internal temperature estimated to be approximately 150°C) with a heat gun. The obtained composition was a solid (powder) at 25°C and contained fluororesin A-2, base B-1, and 4.2 mass% of fluoride ions. The counter ion of the fluoride ions was K. The yield of KF is shown in Table 1.

[0123] Example 5 A mechanochemical treatment was carried out in the same manner as in Example 4, except that 1.0 eq. of fluororesin A-2 was changed to 3.0 eq. of fluororesin A-3, the reaction time was changed to 180 minutes, and the outer surface of the reaction vessel was heated to 200°C (the internal temperature was estimated to be about 100°C) with a heat gun. The obtained composition was a solid (powder) at 25°C and contained fluororesin A-3, base B-1, and 2.0 mass% fluoride ions. The counter ion of the fluoride ions was K. The yield of KF is shown in Table 1.

[0124] Example 6 A mechanochemical treatment was carried out in the same manner as in Example 1, except that the amount of fluororesin A-1 was changed to 2.0 eq. and the base was changed to B-2 (1.0 eq.). The obtained composition was a solid (powder) at 25°C and contained fluororesin A-1, <1.7 mass% of base B-2, and 9.1 mass% of fluoride ions. The counter ion of the fluoride ions was K. The yield of KF is shown in Table 1.

[0125] Example 7 A mechanochemical treatment was carried out in the same manner as in Example 6, except that the base was changed to B-3. The obtained composition was a solid (powder) at 25°C and contained fluororesin A-1, base B-3, and 8.8 mass% of fluoride ions. The counter ion of the fluoride ions was K. The yield of KF is shown in Table 1.

[0126] Example 8 A mechanochemical treatment was carried out in the same manner as in Example 6, except that the base was changed to B-4. The obtained composition was a solid (powder) at 25°C and contained fluororesin A-1, base B-4, and 8.1 mass% of fluoride ions. The counter ion of the fluoride ions was Na. The yield of NaF is shown in Table 1.

[0127] Example 9 A mechanochemical treatment was carried out in the same manner as in Example 6, except that the base was changed to B-5. The obtained composition was a solid (powder) at 25°C and contained fluororesin A-1, base B-5, and 8.0 mass% of fluoride ions. The counter ion of the fluoride ions was Cs. The yield of CsF is shown in Table 1.

[0128] Example 10 A mechanochemical treatment was carried out in the same manner as in Example 6, except that the base was changed to B-6. The obtained composition was a solid (powder) at 25°C and contained fluororesin A-1, base B-6, and 0.2 mass% of fluoride ions. The counter ion of the fluoride ions was Cs. The yield of CsF is shown in Table 1.

[0129] Example 11 A mechanochemical treatment was carried out in the same manner as in Example 1, except that the amount of fluororesin A-1 was changed to 3.0 eq. and base B-1 was changed to base B-7. The obtained composition was a solid (powder) at 25°C and contained fluororesin A-1, base B-7, and 5.2 mass% of fluoride ions. The counter ion of the fluoride ions was K. The yield of KF is shown in Table 1.

[0130] Example 12 A mechanochemical treatment was carried out in the same manner as in Example 1, except that the amount of fluororesin A-1 was changed to 3.0 eq. and base B-1 was changed to base B-8. The obtained composition was a solid (powder) at 25°C and contained fluororesin A-1, base B-8, and 1.9 mass% of fluoride ions. The counter ion of the fluoride ions was Na. The yield of NaF is shown in Table 1.

[0131]

[0132] Example 13 Nitrogen gas was sealed into an oven-dried vial equipped with a magnetic stir bar. Next, the composition obtained in Example 2 (172.94 mg, 0.4 mmol, 2.0 eq.), ethyl acetate (1 mL), and p-toluoyl chloride (26.43 μL, 0.2 mmol, 1.0 eq.) were added sequentially. The mixture was stirred in the vial under a nitrogen gas atmosphere at room temperature (25°C) for 12 hours. The yield of the obtained p-toluoyl fluoride was determined using 4-fluoroanisole as an internal standard. １９ It was determined to be 52% by F NMR.

[0133] Reference Example 1 p-Toluoyl fluoride was obtained in the same manner as in Example 4, except that 1.5 eq. of KF obtained by spray drying was used instead of the composition obtained in Example 2. The yield was 55%.

[0134] It has been found that by using the fluorinating agent of the present disclosure, fluorination proceeds with efficiency comparable to that of KF, which is conventionally known as a fluorinating agent.

[0135] Reference Example 2 The sample obtained in Example 3, which had been previously dried by heating at 120°C, and KF produced by spray drying were left in the air for 5 hours, and their states after leaving were observed. The KF produced by spray drying deliquesced and solidified, and could not maintain its powdery state, impairing its handleability as KF. On the other hand, the sample obtained in Example 3 maintained its powdery state, maintained its handleability, and was in a state where it could be used as a fluorinating agent as it was.

[0136] It has been found that the fluorinating agent of the present disclosure has excellent atmospheric storage stability and handling properties compared to KF, which is a conventionally known fluorinating agent.

[0137] Example 14 In a glass reaction vessel equipped with a magnetic stir bar, the composition obtained in Example 3 (0.3 mmol, 1.5 eq.), sulfonyl chloride (R—SO ) shown in Table 2, and ２ Cl, 0.2 mmol, 1.0 eq.), distilled water (2.0 eq., 0.4 mmol), and acetone (0.2 M) as solvent were added. After stirring the reaction at room temperature for 30 minutes, the resulting suspension or crude product was filtered through a plug of silica eluted with EtOAc to remove insoluble by-products, and the solvent was removed by concentration under reduced pressure to give the corresponding sulfonyl fluoride (R-SO ２ The yields of the obtained sulfonyl fluorides (Entries 9, 10 and 11) were １９ The yields were calculated using F NMR with 4-fluoroanisole as an internal standard. The remaining yields are isolated yields.) are shown in Table 2.

[0138]

[0139] Example 15 Nitrogen gas was sealed into an oven-dried vial equipped with a magnetic stir bar. Next, the composition obtained in Example 2 (0.2 mmol, 1.5 eq.), dry ethyl acetate (1 mL), and the acyl chloride (R-COCl, 0.2 mmol, 1.0 eq.) shown in Table 3 were sequentially added. The mixture was stirred in the vial under a nitrogen gas atmosphere at room temperature (25°C) for 12 hours. Isolation and purification were carried out using silica gel column chromatography to obtain the corresponding acyl fluoride (R-COF). The yield (isolation yield) of the obtained acyl fluoride is shown in Table 3.

[0140]

[0141] Example 16 In a glass reaction vessel, the composition obtained in Example 3 (2.0 eq., 0.4 mmol), a bromide shown in Table 4 (R—Br, 0.2 mmol, 1.0 eq.), 18-crown-6-ether (1.0 eq.), H ２0 (18 μL, 5.0 eq.) and anhydrous tBuOH (0.8 mL) were added. After stirring at 100°C for the time shown in Table 4, the resulting suspension was cooled to room temperature, filtered with EtOAc to remove insoluble by-products, and concentrated under reduced pressure to remove the solvent. Isolation and purification were carried out using silica gel column chromatography to obtain the corresponding fluoride (R-F). The yields of the obtained fluorides (isolation yields) are shown in Table 4.

[0142]

[0143] Example 17 A 1.5 mL stainless steel jar was charged with a stainless steel ball (5 mm), the composition obtained in Example 3 (1.5 eq., 0.3 mmol), and a sulfonyl chloride (R—SO ) shown in Table 5. ２ Cl, 0.2 mmol, 1.0 eq.) was added. The jar was closed and placed in a ball mill (Retsch Mixer Mill MM 400). Mechanochemical treatment using the ball mill was carried out for 5 minutes at room temperature (25°C) at 30 Hz. After completion, the jar was opened, washed with ethyl acetate, and concentrated in vacuo to give the corresponding sulfonyl fluoride (R-SO ２ The yields of the obtained sulfonyl fluorides (Entry 1 is the yield measured by gas chromatography (GC) using mesitylene as an internal standard; the others are isolated yields) are shown in Table 5.

[0144]

[0145] Example 18 A 1.5 mL stainless steel jar was charged with a stainless steel ball (5 mm), 5.0 eq. of fluororesin A-1, and 1.1 eq. of base B-1. The jar was closed and placed in a ball mill (Retsch Mixer Mill MM 400). Mechanochemical treatment using the ball mill was carried out at room temperature (25°C) and 30 Hz for 60 minutes. After completion, the jar was opened, and the mixture was added with sulfonyl chloride (R—SO ) shown in Table 6. ２ Cl, 0.2 mmol, 1.0 eq.) was added. The jar was closed, and mechanochemical treatment was carried out using a ball mill at room temperature (25°C) at 30 Hz for 5 minutes. After completion, the jar was opened, washed with ethyl acetate, and concentrated in vacuo. The resulting target sulfonyl fluoride (R-SO ２The yield of F) was calculated using hexafluorobenzene as an internal standard. １９ The results are shown in Table 6.

[0146]

[0147] Example 19: The composition obtained in Example 3 (1.5 eq., 0.3 mmol), 1-bromooctane (1.0 eq., 0.2 mmol), water (18 μL, 5.0 eq.), and anhydrous tBuOH (0.8 mL) were placed in a glass reaction vessel. Fluorination was carried out in the same manner as in Example 13, except that the mixture was stirred at 100° C. for 10 hours. The yield of the fluoride was 74%.

[0148] Example 20 Fluorination was carried out in the same manner as in Example 13, except that 0.5 eq. of fluororesin A-1, 1.0 eq. of base B-1, and sulfonyl chloride were changed to p-toluenesulfonyl chloride. The fluorination yield was 1%.

[0149] Example 21 Fluorination was carried out in the same manner as in Example 20, except that 2.0 eq. of fluororesin A-1 was used instead. The fluorination yield was 90%.

[0150] Example 22 The composition obtained in Example 11 (1.5 eq., 0.3 mmol), p-toluenesulfonyl chloride (1.0 eq., 0.2 mmol), and water (8 μL, 2.0 eq.) were added. Fluorination was carried out in the same manner as in Example 13, except that the mixture was stirred at 25° C. for 30 minutes. The yield of fluoride was 58%.

[0151] Experimental Example 23 Commercially available KF (298 mg) was weighed in a glove box and stored in the atmosphere for 24 hours, after which its mass (X mg) was measured. The mass increase rate was calculated using the following formula, which was 20%: Increase rate (%) = (X - 298) / 298 × 100. The mass increase rate of the composition obtained in Example 1 was also calculated in the same manner, which was 12%.

Claims

1. Fluorinated compounds and fluorinating agents containing fluoride ions.

2. The fluorinating agent according to claim 1, which is solid at 25°C.

3. The counter ion of the fluoride ion is an alkali metal, an alkaline earth metal, or NR １ ４ (R １ and may be the same or different, and contain at least one selected from the group consisting of H or an organic group having 1 to 10 carbon atoms.

4. The fluorinating agent according to any one of claims 1 to 3, further comprising a base.

5. The fluorinating agent of claim 4, wherein said base is a solid at 25°C.

6. The fluorinating agent according to claim 4 or 5, wherein the base has a pKa of 8 to 40.

7. The base is R １０ OM (in the formula, R １０ is H or an organic group having 1 to 10 carbon atoms, M is a metal or NR １ ４ (R １ and may be the same or different and represent H or an organic group having 1 to 10 carbon atoms.) The fluorinating agent according to any one of claims 4 to 6, which is at least one selected from the group consisting of compounds represented by the formula (I) and metal carbonates.

8. The fluorinating agent according to any one of claims 4 to 7, wherein the base is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, cesium hydroxide, cesium carbonate, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium t-butoxide, and potassium t-butoxide.

9. The fluorinating agent according to any one of claims 4 to 8, wherein the content of the base is 0.1 to 70 mass %.

10. The fluorinating agent according to any one of claims 1 to 9, wherein the fluorine-containing compound is solid at 25°C.

11. The fluorinating agent according to any one of claims 1 to 10, wherein the fluorine-containing compound is a fluorine-containing polymer.

12. The fluorinating agent according to any one of claims 1 to 11, wherein the fluorine-containing compound is a fluorine-containing polymer containing polymerized units based on at least one monomer selected from the group consisting of tetrafluoroethylene, difluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl ether), trifluoroethylene, and monofluoroethylene.

13. The fluorinating agent according to any one of claims 1 to 12, wherein the fluorine-containing compound is at least one selected from the group consisting of polytetrafluoroethylene, polyvinylidene fluoride, and polychlorotrifluoroethylene.

14. A fluorinating agent which is a composition obtained by mechanochemically treating a fluorine-containing compound with a base.

15. A fluorination method comprising the step of fluorinating an object using the fluorinating agent according to claim 14.

16. A fluorination method comprising the step of fluorinating an object using a fluorine-containing compound and a fluorinating agent containing fluoride ions.

17. The fluorination method according to claim 15 or 16, wherein the fluorinating agent is solid at 25°C.

18. The fluorination method according to claim 16 or 17, wherein the fluorine-containing compound is solid at 25°C.

19. The fluorination method according to any one of claims 16 to 18, wherein the fluorine-containing compound is a fluorine-containing polymer.

20. The fluorination method according to any one of claims 16 to 19, wherein the fluorine-containing compound is a fluorine-containing polymer containing polymerized units based on at least one monomer selected from the group consisting of tetrafluoroethylene, difluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl ether), trifluoroethylene, and monofluoroethylene.

21. The fluorination method according to any one of claims 16 to 20, wherein the fluorine-containing compound is at least one member selected from the group consisting of polytetrafluoroethylene, polyvinylidene fluoride, and polychlorotrifluoroethylene.

22. The counter ion of the fluoride ion is an alkali metal, an alkaline earth metal, or NR １ ４ (R １ may be the same or different, and contain at least one selected from the group consisting of H or an organic group having 1 to 10 carbon atoms.

23. The fluorination method according to any one of claims 15 to 22, wherein the fluorinating agent further contains a base.

24. The fluorination process of claim 23, wherein the base is a solid at 25°C.

25. The base is R １０ OM (in the formula, R １０ is H or an organic group having 1 to 10 carbon atoms, M is a metal or NR １ ４ (R １ and may be the same or different and represent H or an organic group having 1 to 10 carbon atoms.) The fluorination method according to claim 23 or 24, wherein the fluorination group is at least one selected from the group consisting of compounds represented by the formula (I) and metal carbonates.

26. The fluorination method according to any one of claims 23 to 25, wherein the base is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, cesium hydroxide, cesium carbonate, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium t-butoxide, and potassium t-butoxide.

27. The fluorination method according to any one of claims 23 to 26, wherein the content of the base relative to the fluorinating agent is 0.1 to 70% by mass.

28. The fluorination method according to any one of claims 16 to 27, wherein the fluorinating agent is obtained by mechanochemically treating a fluorine-containing compound with a base.

29. The fluorination method according to any one of claims 15 to 28, further comprising the step of purifying the crude product obtained by fluorination and recovering the fluorinated target substance.

30. The fluorination method according to any one of claims 15 to 29, wherein the fluorination is carried out dry.

31. A fluorination method according to any one of claims 15 to 30, wherein the fluorination is carried out by mechanochemically treating the fluorinating agent and the object.

32. The fluorination method according to any one of claims 15 to 31, wherein the step of obtaining the fluorinating agent and the step of fluorination are carried out continuously.

33. A fluorination method according to any one of claims 15 to 32, wherein the amount of the fluorinating agent used is 1.0 to 3.0 equivalents per equivalent of a group that can be substituted with a fluorine atom possessed by the target substance.

34. A fluorination method according to any one of claims 15 to 33, wherein the target substance is an organic compound having at least one atom selected from the group consisting of chlorine atoms and bromine atoms.

Images