Fluorinating agent and fluorination method

Abstract

To provide 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.SOLUTION: The present disclosure provides a fluorinating agent that comprises a fluorine-containing compound and fluoride ions.SELECTED DRAWING: None

Description

[Technical Field]

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

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

[0003] [Non-Patent Document 1] "2019 Edition: 17019 Chemical Products," Chemical Daily, 2019, p. 187 Summary of the Invention [Problem to be solved by the invention]

[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. [Means for solving the problem]

[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 producing 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 contain at least one selected from the group consisting of 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) further containing 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 base has a pKa of 8 to 40.

[0012] The present disclosure (7) is directed to a method 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 a compound represented by (I) and a metal carbonate, and any combination of the fluorinating agent according to any of the present disclosures (4) to (6).

[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 that 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) provides 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 contain at least one selected from the group consisting of H or an organic group having 1 to 10 carbon atoms), in any combination with any of the present disclosures (16) to (21).

[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 method for treating a hydroxyl group comprising administering to a subject a hydroxyl group having 10OM (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). In the fluorination method according to the present disclosure (23) or (24), the compound is at least one selected from the group consisting of a compound represented by the formula (I) and a metal carbonate.

[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 and recovering 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 by a dry method.

[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 performed 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 in the target substance.

[0039] The present disclosure (34) is a fluorination method in any combination with any of the present disclosures (15) to (33), in which 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. [Effects of the Invention]

[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. DETAILED DESCRIPTION OF THE INVENTION

[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 the fluorinating agent (1) of the present disclosure). The fluorinating agent (1) of the present disclosure has the above-mentioned configuration and 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 prevents the component from adhering even when absorbing moisture, and allows the component to maintain a powdery state, so that 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 a compound having a fluorine atom, 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. The fluorine-containing compound is preferably a solid at 25° C. in view of easier handling.

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

[0045] The fluorine-containing polymer preferably contains polymerized 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, further preferably contains polymerization units based on at least one monomer selected from the group consisting of TFE, VdF and CTFE, still 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 CF2=CFCF2-O-Rf copolymers, ... 1 (Rf 1 is a monomer represented by 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): CH2=CFRf 2 (1) (In the formula, Rf 2 is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms)

[0050] The fluoropolymer is preferably at least one selected from the group consisting of fluororesins and fluororubbers, more preferably at least one selected from the group consisting of PTFE, FEP, PFA, PVdF, PCTFE and fluororubbers, even more preferably at least one selected from the group consisting of PTFE, PVdF and PCTFE, still more preferably at least one selected from the group consisting of PTFE and PVdF, and particularly preferably PVdF. The fluorine-containing polymer is also preferably a perhalogen resin, more preferably at least one selected from the group consisting of a perfluororesin and PCTFE, even more preferably at least one selected from the group consisting of PTFE, PFA, FEP and PCTFE, and even more preferably at least one selected from the group consisting of PTFE, PFA and FEP. The fluorine-containing polymer is preferably at least one selected from the group consisting of perfluororesins and polydifluoroethylene, and more preferably at least one selected from the group consisting of PTFE and polydifluoroethylene.

[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 represented by the following general formula (I): Y-(CF2) x1 -(CH2) y1 -A (I) (In the formula, Y represents H or F, x1 represents an integer of 4 or more, y1 represents an integer of 0 to 3, and A represents -SO3M I or -COOM I indicates M I represents H, NH4, Li, Na, Mg, Al, K or Ca), and a compound (I) represented by the following general formula (II): F-(CF2) X2 O(CFXCF2O) y2 -CFX-A (II) (In the formula, x2 represents an integer of 1 or more, y2 represents an integer of 0 to 10, X represents F or CF3, and A represents -SO3M II or -COOM II indicates M II represents H, NH4, Li, Na, Mg, Al, K or Ca.

[0052] The compound (I) includes fluorocarboxylic acids and their salts, preferably perfluorocarboxylic acids and their salts, such as perfluorooctanoic acid and its salts (collectively referred to as "PFOA"). Examples of the salts include ammonium salts and sodium salts, and preferably ammonium salts, such as ammonium perfluorooctanoate (particularly referred to as "APFO"). Compound (I) also includes fluorosulfonic acid and its salts, preferably perfluorosulfonic acid and its salts, such as perfluorooctanesulfonic acid and its salts (collectively referred to as "PFOS"). Examples of the 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 contain 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 capable of adsorbing 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 content of the fluorine-containing compound is preferably as small as possible.

[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 0.0001% by mass. The content of organic fluorine in the fluorinating agent is measured by combustion ion chromatography. The organic fluorine refers to fluorine bonded to carbon.

[0057] The fluorinating agent (1) of the present disclosure contains fluoride ions. The content of 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, and 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 the fluoride ion. The counterion may be a metal or 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) and alkaline earth metals (Group 2), and specific examples include Na, K, Li, Cs, Ca, etc. Among 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 1may be the same or different. R 1 is 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 more preferably contain at least one selected from the group consisting of H or an organic group having 1 to 10 carbon atoms, even 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, even 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 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. The base 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, more preferably 12 or more, and even more preferably 15 or more. The pKa is determined 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. The above metals and NR 1 Examples of 4 include those mentioned above. The bases include alkali metals, alkaline earth metals, and NR 1 4(R 1 may be the same or different, and more preferably contain at least one selected from the group consisting of H or an organic group having 1 to 10 carbon atoms, even 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, even more preferably contain at least one selected from the group consisting of Na and K, and particularly preferably contain K.

[0067] The bases include 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 compound represented by (), metal carbonates, metal acetates, cyclic amines, polyamines, etc. R 10 The 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 even more preferably a methyl group, an ethyl group, or a t-butyl group. M metal and NR 1 Examples of 4 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, 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, 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 OM and metal carbonates is preferred, and in that this makes it easier to produce the fluorinating agent using a general-purpose device, 10 R in OM 10is an organic group having 1 to 10 carbon atoms, a metal alkoxide is more preferable, an alkali metal alkoxide is even more preferable, at least one selected from the group consisting of an alkali metal methoxide, an alkali metal ethoxide, and an alkali metal t-butoxide is even more preferable, and at least one selected from the group consisting of sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium t-butoxide, and potassium t-butoxide is particularly preferable. The base is 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 above 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 above-mentioned fluorine-containing compound. The compound may have a structure obtained by defluorinating at least some of the fluorine atoms in the above-mentioned fluorine-containing compound. When the fluorinating agent (1) of the present disclosure contains a base, the compound is a fluorine-containing compound in which at least some of the fluorine atoms have a structure derived from the base, such as a structure represented by the formula: R 10 O-(R 10 is 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 the 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 the range that does not impair the effect, such as 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 polyaminobismaleimide; 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 polymers may be non-fluorinated polymers.

[0074] The content of the other components 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, relative to the fluorinating agent, 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 maximum particle size of the fluorinating agent (1) of the present disclosure that can be confirmed when observed with a microscope such as a video microscope is 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. The fluorinating agent having a maximum particle size within the above range does not form agglomerates and is 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 known methods 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 produce a fluorinating agent that is substantially free of fluorine-containing organic compounds. It is also preferable that the fluorinating agent (1) of the present disclosure is one obtained by mechanochemically treating a fluorine-containing compound and a base and that is substantially free of fluorine-containing organic compounds. The production method (2) will be described in detail below.

[0079] The amount of the base used in the mechanochemical treatment is preferably 0.01 equivalents or more relative to 1 equivalent (molar equivalent) of the fluorine-containing compound, more preferably 0.05 equivalents or more, and even more preferably 0.10 equivalents or more, 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 the production method (2), the mechanochemical treatment can be carried out with a relatively small amount of base. The small amount of base has the advantage that decomposition of the substrate can be prevented when the above-mentioned fluorinating agent is used in the fluorination step. When the fluorine-containing compound is a fluorine-containing polymer, the equivalent weight 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, and shaking, thereby activating the reactant and imparting structural change, phase transition, reactivity, adsorption, catalytic activity, and the like. The mechanochemical treatment method is not particularly limited, and examples thereof include a compressive 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 capable of applying mechanical energy by the above-mentioned method, and known pulverizers and mixers can be used. For example, pulverizers such as ball mills, rod mills, jet mills, vibration mills, and SAG mills; grinders such as rotary stone mills and crushers; (horizontal axis rotation) container rotation type mixers such as horizontal cylindrical, V-type, double cone, square cube, S-type, and continuous V-type; (baffle blade equipped) container rotation type mixers such as horizontal cylindrical, V-type, double cone, and ball mill types; (rotation vibration) container rotation type mixers such as rocking type and cross rotary type; (horizontal axis) container rotation type mixers such as ribbon type, paddle type, single shaft rotor type, and bag 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; (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; 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 performed using a planetary mill, but is preferably performed without one. While planetary mills are capable of applying high energy, they also generate a large amount of wear debris. For example, Figure 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 a planetary mill and the amount of wear debris generated by the mill, indicating that a certain amount of wear debris is generated by a planetary mill. If the reaction composition is to be used as a fluorinating agent, it is preferable that it does not contain impurities. By performing mechanochemical treatment without using a planetary mill and under conditions that are less likely to generate wear debris, a composition suitable for use as a fluorinating agent can be obtained. Furthermore, methods using general-purpose equipment such as a ball mill rather than a planetary mill have the advantage of being easier to commercialize. In particular, when the base is an organic base, it is preferable not to use a planetary mill.

[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 duration of 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 also be carried out in the presence of a small amount of solvent, if necessary. The presence of a small amount of solvent may sometimes facilitate 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] As the solvent for the mechanochemical treatment, organic solvents such as ethers, nitriles, esters, aromatics, hydrocarbons, alcohols, and halogens are preferred. 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 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) is 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 is obtained by a specific treatment and therefore has excellent properties as a fluorinating agent.

[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 0.0001% by mass. The content of organic fluorine in the composition is measured by combustion ion chromatography. The organic fluorine refers to 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) that includes a step of fluorinating an object using a fluorine-containing compound and a fluorinating agent that contains fluoride ions. The fluorination method (1) of the present disclosure has the above-mentioned features, and therefore, fluorination can be carried out 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 having fluoride ions suppresses adhesion of the component even when absorbing moisture, and the fluorinating agent can maintain a powdery state, so that fluorination can be carried out 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] As the fluorinating agent used in the fluorination method (1) of the present disclosure, the same fluorinating agent as the above-mentioned fluorinating agent (1) of the present disclosure can be used. The fluorinating agent used in the fluorination method (2) of the present disclosure is the above-described fluorinating agent (2) of the present disclosure.

[0102] The substance to be fluorinated may have a group that can be substituted with a fluorine atom. The substance 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 organic group preferably has 1 or more carbon atoms, more preferably 2 or more carbon atoms, and preferably 10 or less, more preferably 7 or less carbon atoms. The organic group may be an alkenyl group, an alkynyl group, an OSO2R 2 (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 can be set to 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 in the target substance. In calculating the equivalent weight 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, such as 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 to carry out the fluorination by mechanochemical treatment of the fluorinating agent and the object. When the fluorination is carried out by a dry method, it is particularly preferable to employ mechanochemical treatment. The 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 step of fluorination by mechanochemical treatment. The specific implementation method is not limited, but 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] By the above fluorination, 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) is obtained.

[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. [Example]

[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 - ) and base content measurement It was measured 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. Measurements were then carried out using a Tosoh IC-8100ST 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. Fluoropolymer A-1: ​​PVdF (VdF homopolymer, manufactured by BLD Pharmatech Ltd.), powder Fluoropolymer A-2: PTFE (TFE homopolymer, 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·H2O (inorganic base, pKa=15) Base B-6: Cs2CO3 (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 of the constituent monomer VdF (64.03)), 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 at room temperature (25°C) and 30 Hz for 60 minutes. After 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 solid (powder) at 25° C. and contained fluororesin A-1, <59% by mass of base B-1, and 1.8% by 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 ions K in the base B-1 were 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 (1280 mg, 20 mmol, calculated based on the molecular weight of the constituent monomer VdF (64.03)), 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 at room temperature (25°C) and 30 Hz for 30 minutes. After 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 solid (powder) at 25° C. and contained fluororesin A-1, base B-1, and 2.9 mass % of fluoride ions. The counter ion of the fluoride ion is K. The yield of KF is shown in Table 1.

[0121] Example 3 The 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 resulting composition was 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 ion is K. The yield of KF is shown in Table 1.

[0122] Example 4 The 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 (1200 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 (the internal temperature was estimated to be approximately 150°C) with a heat gun. The resulting composition was 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 ion is K. The yield of KF is shown in Table 1.

[0123] Example 5 The 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 with a heat gun (the internal temperature was estimated to be approximately 100°C). The resulting composition was a solid (powder) at 25° C. and contained fluororesin A-3, base B-1, and 2.0 mass % of fluoride ions. The counter ion of the fluoride ion is K. The yield of KF is shown in Table 1.

[0124] Example 6 The 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 resulting composition was solid (powder) at 25° C. and contained fluororesin A-1, <1.7% by mass of base B-2, and 9.1% by mass of fluoride ions. The counter ion of the fluoride ion is K. The yield of KF is shown in Table 1.

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

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

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

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

[0129] Example 11 The 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 resulting composition was a solid (powder) at 25° C. and contained the fluororesin A-1, the base B-7, and 5.2 mass % of fluoride ions. The counter ion of the fluoride ion is K. The yield of KF is shown in Table 1.

[0130] Example 12 The 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 resulting composition was 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 ion is Na. The yield of NaF is shown in Table 1.

[0131] [Table 1]

[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 by F NMR to be 52%.

[0133] Reference example 1 p-Toluoyl Fluoride was obtained in a 55% yield 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.

[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 dried by heating at 120°C in advance, 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] The fluorinating agent of the present disclosure has been found to have excellent atmospheric storage stability and ease of handling compared to KF, which is a conventionally known fluorinating agent.

[0137] Example 14 To a glass reaction vessel equipped with a magnetic stir bar, the composition obtained in Example 3 (0.3 mmol, 1.5 eq.), the sulfonyl chloride (R-SOCl, 0.2 mmol, 1.0 eq.) shown in Table 2, distilled water (2.0 eq., 0.4 mmol), and acetone (0.2 M) were added as a solvent. After stirring the reaction mixture 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 obtain the corresponding sulfonyl fluoride (R-SOF). The yields of the resulting sulfonyl fluorides (Entry 9, 10, and 11) were calculated as follows: 19 The yields were calculated using F NMR with 4-fluoroanisole as the internal standard. All other yields are isolated yields.) are shown in Table 2.

[0138] [Table 2]

[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 a 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 yields of the obtained acyl fluorides (isolation yields) are shown in Table 3.

[0140] [Table 3]

[0141] Example 16 A glass reaction vessel was charged with the composition obtained in Example 3 (2.0 eq., 0.4 mmol), the bromide (R-Br, 0.2 mmol, 1.0 eq.) shown in Table 4, 18-crown-6-ether (1.0 eq.), HO (18 μL, 5.0 eq.), and anhydrous tBuOH (0.8 mL). 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. Purification was carried out using silica gel column chromatography to obtain the corresponding fluoride (RF). The yields (isolation yields) of the resulting fluorides are shown in Table 4.

[0142] [Table 4]

[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 the sulfonyl chloride (R-SOCl, 0.2 mmol, 1.0 eq.) shown in Table 5. 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 5 minutes. After completion, the jar was opened, washed with ethyl acetate, and concentrated in vacuo to obtain the corresponding sulfonyl fluoride (R-SOF). The yields of the obtained sulfonyl fluorides (Entry 1 is the yield measured by gas chromatography (GC) using mesitylene as an internal standard; the other entries are isolated yields) are shown in Table 5.

[0144] [Table 5]

[0145] Example 18 A 1.5 mL stainless steel jar was charged with a 5 mm stainless steel ball, 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 sulfonyl chloride (R-SO2Cl, 0.2 mmol, 1.0 eq.) shown in Table 6 was added to the mixture. The jar was closed, and mechanochemical treatment using the ball mill was carried out at room temperature (25°C) and 30 Hz for 5 minutes. After completion, the jar was opened, washed with ethyl acetate, and concentrated in vacuo. The yield of the target sulfonyl fluoride (R-SO2F) was determined using hexafluorobenzene as an internal standard. 19 The results were measured by F NMR and are shown in Table 6.

[0146] [Table 6]

[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 added to 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. 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 the 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. The mass (X mg) was measured, and the mass increase rate was calculated using the following formula, which was 20%. Growth rate (%) = (X-298) / 298 x 100 The mass increase rate of the composition obtained in Example 1 was similarly determined and was found to be 12%.

Claims

1. A fluorinating agent containing a fluorine-containing compound and a fluoride ion.

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

3. The counter ions of the fluoride ions are selected from alkali metals, alkaline earth metals, and 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 claim 1 or 2, further comprising a base.

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

6. 5. The fluorinating agent according to claim 4, 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.

8. 5. The fluorinating agent according to claim 4, 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. 5. The fluorinating agent according to claim 4, wherein the content of the base is 0.1 to 70% by mass.

10. 3. The fluorinating agent according to claim 1, wherein the fluorine-containing compound is solid at 25°C.

11. 3. The fluorinating agent according to claim 1, wherein the fluorine-containing compound is a fluorine-containing polymer.

12. 3. The fluorinating agent according to claim 1 or 2, 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.

13. 3. The fluorinating agent according to claim 1, 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 fluorinating agent containing a fluorine-containing compound and fluoride ions.

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

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

19. 17. The fluorination method according to claim 16, wherein the fluorine-containing compound is a fluorine-containing polymer.

20. The fluorination method according to claim 16, 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.

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

22. The counter ions of the fluoride ions are selected from alkali metals, alkaline earth metals, and 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. 17. The fluorination method according to claim 15 or 16, wherein the fluorinating agent further comprises a base.

24. 24. The fluorination process according to 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, 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 claim 23, 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 claim 23, wherein the content of the base relative to the fluorinating agent is 0.1 to 70% by mass.

28. 17. The fluorination method according to claim 16, wherein the fluorinating agent is obtained by mechanochemically treating a fluorine-containing compound with a base.

29. 17. The fluorination method according to claim 15 or 16, further comprising the step of purifying the crude product obtained by the fluorination and recovering the fluorinated target substance.

30. 17. The fluorination method according to claim 15 or 16, wherein the fluorination is carried out in a dry manner.

31. 17. The fluorination method according to claim 15 or 16, wherein the fluorination is carried out by mechanochemically treating the fluorinating agent and the object.

32. 17. The fluorination method according to claim 15 or 16, wherein the step of obtaining the fluorinating agent and the step of fluorination are carried out continuously.

33. 17. The fluorination method according to claim 15, wherein the amount of the fluorinating agent used is 1.0 to 3.0 equivalents per equivalent of the group that can be substituted with a fluorine atom contained in the target substance.

34. 17. The fluorination method according to claim 15, 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.

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