Fluorine-containing aromatic compound production method, fluorine-containing benzotriazole salt production method, aromatic fluoroether compound, and composition

Abstract

The present disclosure provides a fluorine-containing aromatic compound production method.　This fluorine-containing aromatic compound production method comprises a step for reacting an N-fluoroalkoxy compound and an aromatic compound in the presence of an oxidation-reduction catalyst to obtain a product. The N-fluoroalkoxy compound is a compound having an N-ORf moiety (Rf represents a fluoroalkyl group having 3 or more carbon atoms). The product includes at least one fluorine-containing aromatic compound selected from the group consisting of aromatic fluoroether compounds (E1) having an -ORf moiety, and aromatic compounds (E2) having an -Rf' moiety (Rf' represents a fluoroalkyl group obtained by removing one carbon atom from Rf).

Description

Method for producing fluorine-containing aromatic compounds, method for producing fluorine-containing benzotriazole salts, aromatic fluoroether compounds and compositions

[0001] The present invention relates to a method for producing fluorine-containing aromatic compounds, a method for producing fluorine-containing benzotriazole salts, aromatic fluoroether compounds, and compositions.

[0002] Compounds having a perfluoroalkoxy group on the aromatic ring are useful as pharmaceutical and agrochemical compounds.

[0003] Various methods for synthesizing such compounds have been investigated. For example, Non-Patent Document 1 discloses a method for synthesizing a compound having a perfluoroalkoxy group on an aromatic ring by irradiating an aromatic compound and a benzotriazole compound with active energy rays in the presence of a Ru catalyst.

[0004] Angew. Chem. Int. Ed. 2018,57,13795

[0005] This disclosure aims to provide a method for producing fluorine-containing aromatic compounds.

[0006] This disclosure includes the configurations described in the following sections.

[0007] Item 1 A method for producing a fluorine-containing aromatic compound, comprising the step of reacting an N-fluoroalkoxy compound and an aromatic compound in the presence of a redox catalyst to obtain a product, wherein the N-fluoroalkoxy compound is a compound having an N-ORf moiety (Rf represents a fluoroalkyl group with three or more carbon atoms), and the product comprises at least one fluorine-containing aromatic compound selected from the group consisting of an aromatic fluoroether compound having an -ORf moiety (E1) and an aromatic compound having an -Rf' moiety (Rf' represents a fluoroalkyl group obtained by removing one carbon atom from Rf) (E2).

[0008] Item 2 The manufacturing method according to Item 1, wherein the product is obtained by irradiating with an active energy ray in the above step.

[0009] Item 3. The production method according to Item 1 or 2, wherein the fluorine-containing aromatic compound contains both the aromatic fluoroether compound (E1) and the aromatic compound (E2).

[0010] Item 4. The production method according to any one of Items 1 to 3, wherein the redox catalyst is a metal catalyst.

[0011] Item 5. The production method according to Item 4, wherein the metal catalyst is a compound containing Ru.

[0012] Item 6. A benzotriazole compound having an Rf moiety (Rf represents a fluoroalkyl group having 3 or more carbon atoms) and an alkylating agent represented by the following formula (4): R

[0016] , １０ , , １３ , １２ , , １２ , １０ , １０ , １２ , １１ , ９ , １１ ,

[0015] , ９ , , １３ , １１ , ９ —X (4) (In formula (4), X represents a leaving group, and R １３ represents an alkyl group which may have a substituent). The method includes a step of obtaining a benzotriazole salt having an Rf moiety by reacting the benzotriazole compound having an Rf moiety with the alkylating agent. The benzotriazole compound having an Rf moiety is an N-fluoroalkoxy compound represented by the following general formula (3c-1)

[0013]

[0014] (In formula (3c-1), Rf represents a fluoroalkyl group having 3 or more carbon atoms, and R ９ , R １０ , R １１ , and R １２ each independently represent hydrogen or a monovalent group). The benzotriazole salt having an Rf moiety is represented by the following general formula (3'c)

[0015]

[0016] (In formula (3'c), Rf, R ９ , R １０ , R １１ , and R １２ have the same meanings as Rf, R ９ , R １０ , R １１ , and R １２ in formula (3c-1), and X and R １３ have the same meanings as X and R １３ in formula (4).A method for producing a fluorine-containing benzotriazole salt, which is equivalent to ( ).

[0017] Item 7 A composition comprising an aromatic fluoroether compound (E1) having an -ORf moiety (where Rf represents a fluoroalkyl group with three or more carbon atoms), and an aromatic compound (E2) having an -Rf' moiety (where Rf' represents a fluoroalkyl group obtained by removing one carbon atom from Rf).

[0018] Item 8 The composition according to item 7, wherein the aromatic fluoroether compound (E1) is contained in an amount of 15 to 95 mol% relative to the total amount of the aromatic fluoroether compound (E1) and the aromatic compound (E2).

[0019] Term 9 -ORf １ Aromatic fluoroether compounds having a moiety, Rf １ (CF ２ ) ｎ CFX １ CF ２ X ２ (n is a number between 3 and 20, X １ and X ２ Aromatic fluoroether compounds that are monovalent groups (which are the same or different halo groups).

[0020] Item 10 Rf １ The aromatic fluoroether compound according to item 9, wherein is a chlorofluoroalkyl group having three or more carbon atoms and having two chloro groups.

[0021] The method for producing fluorine-containing aromatic compounds according to this disclosure allows for the selective synthesis of at least one of a compound having a fluoroalkoxy group with 3 or more carbon atoms in the aromatic ring and a compound having an alkyl group with 2 or more carbon atoms in the aromatic ring.

[0022] While the method disclosed in Non-Patent Document 1 mentioned above only disclosed compounds having a perfluoromethoxy group with one carbon atom in the aromatic ring, the present inventors diligently conducted research to synthesize aromatic compounds having a fluoroalkoxy group with two or more carbon atoms. As a result, the present inventors have discovered a new synthetic method that can selectively synthesize at least one of compounds having a fluoroalkoxy group with three or more carbon atoms in the aromatic ring and compounds having an alkyl group with two or more carbon atoms in the aromatic ring.

[0023] In other words, the present disclosure aims to provide a novel synthetic method that can selectively synthesize at least one of a compound having a fluoroalkoxy group with three or more carbon atoms in an aromatic ring, or a compound having an alkyl group with two or more carbon atoms in an aromatic ring.

[0024] Specifically, the above objective is achieved by employing a process in which a product is obtained by reacting a predetermined N-fluoroalkoxy compound with an aromatic compound in the presence of a redox catalyst.

[0025] Embodiments of the present invention will be described in detail below. In this specification, the expressions "containing" and "including" include the concepts of "containing," "including," "substantially consisting of," and "consisting only of."

[0026] In the numerical ranges described stepwise in this specification, the upper or lower limit of a numerical range in one step can be arbitrarily combined with the upper or lower limit of a numerical range in another step. In the numerical ranges described in this specification, the upper or lower limit of a numerical range may be replaced with values ​​shown in the examples or values ​​that can be uniquely derived from the examples. Furthermore, in this specification, numbers connected by "~" mean a numerical range that includes the numbers before and after "~" as the lower and upper limits.

[0027] 1. Method for Producing Fluorine-Containing Aromatic Compounds The method for producing fluorine-containing aromatic compounds according to this disclosure includes a step of obtaining a product by reacting an N-fluoroalkoxy compound with an aromatic compound in the presence of a redox catalyst. Hereinafter, this step will be referred to as "Step 1".

[0028] In step 1, the N-fluoroalkoxy compound is a compound having an N-ORf moiety (where Rf represents a fluoroalkyl group with three or more carbon atoms).

[0029] In step 1, the product includes at least one fluorine-containing aromatic compound selected from the group consisting of an aromatic fluoroether compound having an -ORf moiety (E1) and an aromatic compound having an -Rf' moiety (Rf' represents a fluoroalkyl group obtained by removing one carbon atom from Rf) (E2). Hereinafter, "aromatic fluoroether compound having an -ORf moiety (E1)" may be simply abbreviated as compound (E1), and "aromatic compound having an -Rf' moiety (Rf' represents a fluoroalkyl group obtained by removing one carbon atom from Rf) (E2)" may be simply abbreviated as compound (E2).

[0030] (N-fluoroalkoxy compound) The N-fluoroalkoxy compound used in step 1 is a compound having an N-ORf moiety (Rf represents a fluoroalkyl group with three or more carbon atoms).

[0031] Examples of Rf include fluoroalkyl groups having 3 to 20 carbon atoms, preferably fluoroalkyl groups having 3 to 16 carbon atoms, more preferably fluoroalkyl groups having 3 to 12 carbon atoms, even more preferably fluoroalkyl groups having 3 to 10 carbon atoms, even more preferably fluoroalkyl groups having 3 to 8 carbon atoms, and particularly preferably fluoroalkyl groups having 3 to 6 carbon atoms. The fluoroalkyl group is preferably a perfluoroalkyl group. Furthermore, Rf may be a fluoroalkyl group containing chlorine. Examples of fluoroalkyl groups containing chlorine include CF ２ ClCFClCF ２ CF ２ Examples are given.

[0032] Rf may be linear or branched.

[0033] The N-fluoroalkoxy compound used in step 1 is preferably a compound represented by the following formula (3'c). That is, the N-fluoroalkoxy compound used in step 1 is preferably a benzotriazole salt represented by the following formula (3'c). In this case, the manufacturing method of the present disclosure facilitates the selective synthesis of at least one of the compounds (E1) and (E2).

[0034]

[0035] In equation (3'c), Rf, R ９ , R １０ , R １１ , and, R １２ Each of these represents the same or different hydrogen or monovalent group. Also, in formula (3'c), X represents a leaving group, and R １３ This indicates an alkyl group which may have substituents.

[0036] In formula (3'c) above, the monovalent group can be a halo group (F, Cl, Br, I); a nitro group; a cyano group; an oxo group; a thioxo group; a sulfo group; a sulfamoyl group; a sulfinamoyl group; a sulfenamoyl group; an alkoxy group; an amino group; a hydroxyl group; and an organic group, or a group that encompasses each of these groups.

[0037] The aforementioned organic group can be any of the various hydrocarbon groups. In this specification, "hydrocarbon group" can include, for example, alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, aralkyl groups, and combinations thereof. The hydrocarbon group may have, for example, 1 to 30 carbon atoms, preferably 20 or fewer, more preferably 15 or fewer, even more preferably 10 or fewer, particularly preferably 6 or fewer, and may also have 4 or fewer carbon atoms.

[0038] Furthermore, the organic group may be a haloalkyl group. In this specification, "haloalkyl group" means an alkyl group in which at least one hydrogen atom is substituted with a halogen atom. The number of halogen atoms in a "haloalkyl group" can be one or more (e.g., 1 to 3, 1 to 6, 1 to 12, or the maximum number that can be substituted from 1). For example, a haloalkyl group may have 1 to 30 carbon atoms, 1 to 20 carbon atoms, 6 to 20 carbon atoms, 1 to 20 carbon atoms, 1 to 15 carbon atoms, 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, 1 to 3 carbon atoms, 6 carbon atoms, 5 carbon atoms, 4 carbon atoms, 3 carbon atoms, 2 carbon atoms, or 1 carbon atom.

[0039] Examples of the haloalkyl groups mentioned above include fluoroalkyl groups, i.e., alkyl groups in which at least one hydrogen atom is substituted with a fluorine atom. The number of fluorine atoms in a "fluoroalkyl group" can be one or more (e.g., 1 to 3, 1 to 6, 1 to 12, or the maximum number that can be substituted from 1). A "fluoroalkyl group" can be, for example, a fluoroalkyl group having 1 to 30 carbon atoms, 1 to 20 carbon atoms, 6 to 20 carbon atoms, 1 to 20 carbon atoms, 1 to 15 carbon atoms, 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, 1 to 3 carbon atoms, 6 carbon atoms, 5 carbon atoms, 4 carbon atoms, 3 carbon atoms, 2 carbon atoms, or 1 carbon atom. A "fluoroalkyl group" includes perfluoroalkyl groups.

[0040] Specifically, "fluoroalkyl groups" include, for example, fluoromethyl groups, difluoromethyl groups, and trifluoromethyl groups (CF ３ -), 2,2,2-trifluoroethyl group, pentafluoroethyl group (C ２ F ５ -), tetrafluoropropyl group (e.g., HCF ２ CF ２ CH ２ -), hexafluoropropyl group (e.g., (CF ３ ) ２ CH-), nonafluorobutyl group, octafluoropentyl group (e.g., HCF) ２ CF ２ CF ２ CF ２ CH ２Examples include -), and tridecafluorohexyl groups.

[0041] In formula (3'c) above, the leaving group (X) is not particularly limited and a wide range of known leaving groups can be listed, for example, halogen atoms or halide ions such as Cl, I, Br, OMs group (where Ms is a mesyl group), OTs group (where Ts is a tosyl group), OTf group (where Tf is a trifluoromethanesulfonyl group; i.e., the OTf group means a triflat anion), NTf ２ The group (Tf is a trifluoromethylsulfonyl group, i.e., NTf) ２ The group refers to the bis(trifluoromethanesulfonyl)imide ion, BF ４ Group, BAr ４ group (Ar is an aryl group), SbF ６ , ClO ４ Base, PF ６ The basis is cited.

[0042] In the above formula (3'c), R １３ For example, it is an alkyl group having 1 to 30 carbon atoms, preferably 20 or less, more preferably 10 or less, even more preferably 5 or less, and particularly preferably 3 or less. １３ If the compound has substituents, these substituents can be synonymous with the monovalent group mentioned above.

[0043] In terms of high reactivity and the ability to increase the yield of compound (E1) and / or compound (E2) produced in step 1, the benzotriazole salt represented by formula (3'c) is preferably a benzotriazole salt having an electron-withdrawing group as a substituent, and preferably NO ２ , or CF ３ A benzotriazole salt having a group, more preferably NO ２ , and CF ３ A benzotriazole salt having a group, and more preferably, in formula (3'c) R ９ NO ２ , R １０ Hydrogen, R １１ ga CF ３ , R １２ is hydrogen, R １３CH ３ X is a benzotriazole salt in which X is an OTf group (triflat anion). Such compounds are derivatives of 1-hydroxybenzotriazole salts.

[0044] The method for producing the N-fluoroalkoxy compound used in Step 1 is not particularly limited. For example, the N-fluoroalkoxy compound used in Step 1 can be produced by a production method comprising a step of reacting a compound represented by the following general formula (3c-1) with an alkylating agent. Hereinafter, such a step will be referred to as "Step 2".

[0045]

[0046] In equation (3c-1), Rf, R ９ , R １０ , R １１ , and, R １２ These are Rf and R in formula (3'c) above, respectively. ９ , R １０ , R １１ , and, R １２ It is synonymous with [the above].

[0047] The alkylating agent is given by the following general formula (4) R １３ —X (4) can be expressed as.

[0048] In equation (4), X and R １３ In equation (3'c), X and R １３ It is synonymous with [the above].

[0049] R １３ ―Specific examples of X include methyl methanesulfonate and methyl trifluoromethanesulfonate (R １３ Examples include compounds in which X is a methyl group and X is an OTf group (triflat anion), methyl p-toluenesulfonate, methyl 4-nitrobenzenesulfonate, methyl 2-nitrobenzenesulfonate, etc.

[0050] In step 2, the reaction conditions between the N-fluoroalkoxy compound represented by formula (3c-1) and the alkylating agent are not particularly limited. For example, the reaction temperature can be 0 to 100°C. The reaction time can be appropriately set according to the reaction temperature, for example, 1 to 120 hours.

[0051] In step 2, the amounts of N-fluoroalkoxy compound and alkylating agent used are not particularly limited; for example, the amount of alkylating agent used can be 1 to 5 moles per mole of N-fluoroalkoxy compound.

[0052] In step 2, the reaction between the N-fluoroalkoxy compound and the alkylating agent may be carried out in a solvent. The solvent is not particularly limited, and examples include the solvents that can be used in step 1 described above. The reaction between the N-fluoroalkoxy compound and the alkylating agent may be carried out under pressure, atmospheric pressure, or reduced pressure. Furthermore, the reaction in step 2 may be a continuous reaction or a batch reaction.

[0053] The reaction between the N-fluoroalkoxy compound and the alkylating agent in step 2 yields the benzotriazole salt represented by formula (3'c).

[0054] (Aromatic Compounds) The aromatic compounds used in step 1 are not particularly limited, and for example, compounds having an aryl group can be broadly listed. The aryl group can be monocyclic, dicyclic, tricyclic, or tetracyclic. Unless otherwise specified, the "aryl group" can be a C6-C18 aryl group. Examples of "aryl groups" include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthuryl.

[0055] The aryl group may also be a heteroaryl group. Examples of "heteroaryl groups" can include monocyclic aromatic heterocyclic groups (e.g., 5- or 6-membered monocyclic aromatic heterocyclic groups). Examples of "5 or 6-membered monocyclic aromatic heterocyclic groups" include pyrrolyl (e.g., 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl), furyl (e.g., 2-furyl, 3-furyl), thienyl (e.g., 2-thienyl, 3-thienyl), pyrazolyl (e.g., 1-pyrrolyl, 3-pyrrolyl, 4-pyrrolyl), imidazolyl (e.g., 1-imidazolyl, 2-imidazolyl, 4-imidazolyl), isoxazolyl (e.g., 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl), oxazolyl (e.g., 2-oxazolyl, 4-oxazolyl, 5-oxazolyl), isothiazolyl (e.g., 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl), thiazolyl This can include compounds such as thiazolyl (e.g., 2-thiazolyl, 4-thiazolyl, 5-thiazolyl), triazolyl (e.g., 1,2,3-triazole-4-yl, 1,2,4-triazole-3-yl), oxadiazolyl (e.g., 1,2,4-oxadiazole-3-yl, 1,2,4-oxadiazole-5-yl), thiadiazolyl (e.g., 1,2,4-thiadiazole-3-yl, 1,2,4-thiadiazole-5-yl), tetrazolyl, pyridyl (e.g., 2-pyridyl, 3-pyridyl, 4-pyridyl), pyridadinyl (e.g., 3-pyridazinyl, 4-pyridazinyl), pyrimidinyl (e.g., 2-pyridazinyl, 4-pyridazinyl, 5-pyridazinyl), pyrazinyl, etc.

[0056] The aromatic compound used in step 1 may have substituents. Such substituents are synonymous with the monovalent group described above. The aromatic compound used in step 1 may have, together with or in place of, such a -CORa group or a -COORa group. Ra is an organic group, and is synonymous with the organic group in the monovalent group described above. The organic group is preferably a hydrocarbon group, for example, an alkyl group having 1 to 30 carbon atoms, preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, and particularly preferably 6 or less. Examples of aromatic compounds used in step 1 include benzene or benzene having the substituents described above.

[0057] (Redox Catalyst) The redox catalyst used in step 1 is not particularly limited, and a wide range of known redox catalysts can be mentioned. Examples of redox catalysts include known metal catalysts, and among these, it is preferable that the metal catalyst is a compound containing Ru or Ir. Examples of compounds containing Ru include tris(2,2'-bipyridine)ruthenium(II)bis(hexafluorophosphate), tris(1,10-phenanthroline)ruthenium(II)bis(hexafluorophosphate), and tris(1,10-phenanthroline)ruthenium(II) dichloride monohydrate. Examples of Ir-containing compounds include (4,4'-di-tert-butyl-2,2'-bipyridine)bis[(2-pyridinyl)phenyl]iridium(III) hexafluorophosphate, tris(2-phenylpyridinate)iridium(III), and [5,5'-bis(trifluoromethyl)-2,2'-bipyridine-κ]. ２ N １ , N １´ ] [bis[3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-κN]phenyl-κC １ Examples include iridium hexafluorophosphate.

[0058] (Step 1) In Step 1, the method of reacting the N-fluoroalkoxy compound (for example, the benzotriazole salt represented by formula (3'c)) with the aromatic compound in the presence of a redox catalyst is not particularly limited. For example, the reaction temperature can be -20 to 80°C. The reaction time can be appropriately set according to the reaction temperature, for example, 5 minutes to 24 hours.

[0059] In step 1, the N-fluoroalkoxy compound (for example, the benzotriazole salt represented by formula (3'c)) and the aromatic compound can be irradiated with active energy rays as needed. That is, the product can also be obtained in step 1 by irradiating with active energy rays. This allows the reaction between the N-fluoroalkoxy compound and the aromatic compound to proceed rapidly under mild conditions. Examples of active energy rays include blue LEDs, ultraviolet rays, electron beams, visible light, X-rays, and ion beams, among which blue LEDs, ultraviolet rays, or visible light are preferred in terms of versatility. There are no particular restrictions on the light source, but for example, white fluorescent lamps, LEDs (white, blue, etc.), halogen lamps, incandescent bulbs, mercury lamps, and ordinary ambient light (sunlight) can be used.

[0060] The amounts of N-fluoroalkoxy compound and aromatic compound used in step 1 are not particularly limited. For example, the amount of aromatic compound used per mole of N-fluoroalkoxy compound can be 0.7 to 200 moles, preferably 1 mole or more, more preferably 3 moles or more, even more preferably 5 moles or more, preferably 150 moles or less, more preferably 120 moles or less, even more preferably 100 moles or less, and particularly preferably 80 moles or less.

[0061] In step 1, the amount of redox catalyst used is not particularly limited, and is, for example, 0.1 to 20 mol%, preferably 0.3 to 15 mol%, relative to the N-fluoroalkoxy compound used in step 1 (for example, the benzotriazole salt represented by formula (3'c)).

[0062] In step 1, the reaction between the N-fluoroalkoxy compound and the aromatic compound can also be carried out in a solvent. The solvent is not particularly limited and examples include hydrocarbon solvents such as benzene, toluene, and xylene; ketone solvents such as acetone, methyl ethyl ketone, and isophorone; alcohol solvents such as tert-butyl alcohol, benzyl alcohol, phenoxyethanol, phenylpropylene glycol, and hexafluoro-2-propanol; halogenated hydrocarbon solvents such as methylene chloride and chloroform; ether solvents such as 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane, and anisole; ester solvents such as ethyl acetate, propyl acetate, ethyl carbitol acetate, and butyl carbitol acetate; amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide; carbonate solvents such as dimethyl carbonate, diethyl carbonate, and propylene carbonate; nitrile solvents such as acetonitrile; and nitro solvents such as nitromethane. The solvent may be a mixed solvent, for example, a mixed solvent containing two or more organic solvents, or a mixed solvent containing an organic solvent and water.

[0063] The amount of solvent used is not particularly limited. For example, per 1 mmol of N-fluoroalkoxy compound used in the reaction of step 1, the amount of solvent can be, for example, 0.005 mmol / L or more, 0.01 mmol / L or more, or 0.05 mmol / L or more. The amount of solvent used can be 8 mmol / L or less, 4 mmol / L or less, 2 mmol / L or less, or 1 mmol / L or less per 1 mmol of N-fluoroalkoxy compound. The amount of solvent used can be appropriately changed depending on the type of solvent. For example, it may be in the range of 0.005 to 4 mmol / L, 0.01 to 2 mmol / L, or 0.05 to 1 mmol / L.

[0064] The reaction in step 1 may be carried out under pressure, atmospheric pressure, or reduced pressure. Furthermore, the reaction in step 1 may be a continuous reaction or a batch reaction.

[0065] (Product of Step 1) The product obtained in Step 1 includes at least one fluorine-containing aromatic compound selected from the group consisting of an aromatic fluoroether compound having an -ORf moiety (i.e., compound (E1)) and an aromatic compound having an -Rf' moiety (Rf' represents a fluoroalkyl group obtained by removing one carbon atom from Rf) (i.e., compound (E2)).

[0066] Compound (E1) has a structure in which an ORf moiety (i.e., an -ORf group) is bonded to the aromatic compound used in step 1. If the aromatic compound is monocyclic, at least one ORf moiety is bonded to one aromatic ring, preferably one ORf moiety is bonded to one aromatic ring. If the aromatic compound is polycyclic with two or more rings, at least one ORf moiety may be bonded to only one aromatic ring, or at least one ORf moiety may be bonded to multiple aromatic rings.

[0067] On the other hand, compound (E2) has a structure in which an Rf' moiety (i.e., a -Rf' group) is attached to the aromatic compound used in step 1. If the aromatic compound is monocyclic, at least one Rf' moiety is attached to one aromatic ring, preferably one Rf' moiety is attached to one aromatic ring. If the aromatic compound is polycyclic with two or more rings, at least one Rf' moiety may be attached to only one aromatic ring, or at least one Rf' moiety may be attached to multiple aromatic rings.

[0068] Here, Rf' represents a fluoroalkyl group obtained by subtracting one carbon atom from Rf; that is, if Rf has n carbon atoms, then Rf' has n-1 carbon atoms.

[0069] The product obtained in step 1 may contain both the aromatic fluoroether compound (E1) and the aromatic compound (E2). Furthermore, the product obtained in step 1 may contain compound E1 but not compound E2, or it may not contain compound E1 but contain compound E2.

[0070] The proportions of compound (E1) and compound (E2) in the product obtained in step 1 can be adjusted according to the reaction conditions in step 1. For example, the proportions of compound (E1) and compound (E2) in the product can be adjusted by adjusting various reaction conditions such as the number of carbon atoms in Rf in the benzotriazole salt represented by formula (3'c), the reaction concentration (amount of solvent used), the amount of redox catalyst used, and the illuminance and output of the active energy rays.

[0071] To elaborate on specific examples, for instance, increasing the number of carbon atoms in Rf (e.g., to 6 or more) makes it easier to produce compound E2 in the reaction of step 1 (i.e., the selectivity of compound E2 is high), and lowering the reaction concentration (the concentration of the N-fluoroalkoxy compound and aromatic compound relative to the solvent) also increases the selectivity of compound E2. Furthermore, increasing the amount of redox catalyst used in the reaction of step 1 increases the selectivity of compound E1. In this way, depending on the reaction conditions, it is possible to selectively synthesize at least one of a compound having a fluoroalkoxy group with 3 or more carbon atoms in the aromatic ring and a compound having an alkyl group with 2 or more carbon atoms in the aromatic ring.

[0072] The fluorine-containing aromatic compound produced in step 1 may consist only of compound (E1) and compound (E2), or it may contain compounds other than compound (E1) and compound (E2). The product obtained in step 1 contains a total of 30 mol% or more of compound (E1) and compound (E2), preferably 50 mol% or more, more preferably 60 mol% or more, even more preferably 70 mol% or more, and particularly preferably 80 mol% or more.

[0073] In the fluorine-containing aromatic compound produced in step 1, the proportions of compound (E1) and compound (E2) are not particularly limited, but it is preferable that the proportion of compound (E1) is greater than that of compound (E2) (i.e., it is preferable that compound (E1) is selectively obtained). In this case, the fluorine-containing aromatic compound (product) produced in step 1 tends to have improved functions such as hydrophobicity, durability, metabolic stability, pharmacological activity, and pesticide activity. While we do not necessarily want to limit the interpretation of the reason why such functions are expressed, one reason is presumed to be due to the electrical and / or steric effects caused by the presence of an oxygen atom between the perfluoroalkyl group and aromatic ring in compound (E1) (the aromatic fluoroether compound).

[0074] In the product produced in step 1, the content of compound (E1) (the aromatic fluoroether compound) can be 70 mol% or more, preferably 80 mol% or more, more preferably 85 mol% or more, and even more preferably 90 mol% or more.

[0075] The product obtained in the reaction of step 1 may also contain compounds other than the fluorine-containing aromatic compound. The product obtained in the reaction of step 1 contains 30 mol% or more of the fluorine-containing aromatic compound (i.e., the sum of compound (E1) and compound (E2)), preferably 50 mol% or more, more preferably 60 mol% or more, even more preferably 70 mol% or more, and particularly preferably 80 mol% or more.

[0076] The product obtained in step 1 can be subjected to appropriate methods to remove solvents and other substances, thereby obtaining a fluorine-containing aromatic compound containing compound E1 and / or compound E2, for example, as a solid. The solid thus collected can be purified, dried, or otherwise processed using appropriate methods to obtain the target compound E1 and / or compound E2 with high purity.

[0077] The method for producing a fluoroether compound according to this disclosure may consist only of step 1, or it may include other steps besides step 1.

[0078] The method for producing fluorine-containing aromatic compounds, including step 1, allows for the synthesis of fluorine-containing aromatic compounds containing compound (E1) and / or compound (E2) by a simple method. In particular, by adjusting the reaction conditions, one or both of compound (E1) and compound (E2) can be selectively synthesized. That is, the method for producing fluorine-containing aromatic compounds, including step 1, allows for the selective synthesis of at least one of a compound having a fluoroalkoxy group with 3 or more carbon atoms in the aromatic ring and a compound having an alkyl group with 2 or more carbon atoms in the aromatic ring.

[0079] While we do not necessarily want a restrictive interpretation, it is presumed that in the reaction of step 1, one or both of two types of radicals, the RfO radical and the Rf radical, are generated, thereby selectively synthesizing one or both of compounds (E1) and (E2).

[0080] 2. Method for Producing Fluorine-Containing Benzotriazole Salts This disclosure includes a method for producing fluorine-containing benzotriazole salts. The method for producing fluorine-containing benzotriazole salts according to this disclosure includes the step of obtaining a benzotriazole salt having an Rf moiety by reacting a benzotriazole compound having an Rf moiety (where Rf represents a fluoroalkyl group with 3 or more carbon atoms) with an alkylating agent represented by formula (4), wherein the benzotriazole compound having an Rf moiety is an N-fluoroalkoxy compound represented by the general formula (3c-1), and the benzotriazole salt having an Rf moiety is a compound represented by the general formula (3'c).

[0081] In other words, the steps of the method for producing a fluorine-containing benzotriazole salt according to this disclosure are the same as "Step 2" described above.

[0082] The benzotriazole compound having an Rf moiety used in the method for producing the fluorine-containing benzotriazole salt of this disclosure, i.e., the N-fluoroalkoxy compound represented by the general formula (3c-1), can be produced by reaction with an N-hydroxy compound and a sulfinic acid compound in the presence of an oxidizing agent.

[0083] The sulfinic acid compound is represented by the following general formula (1): RfSO ２ M (1) (In formula (1), Rf is a fluoroalkyl group having 3 or more carbon atoms, and M is an alkali metal or an alkaline earth metal). Examples of the compound represented by formula (1) can be given. In formula (1), it has the same meaning as Rf in formula (3´c). M is preferably sodium. Examples of the sulfinic acid compound include CF ３ CF ２ CF ２ SO ２ Na and the like.

[0084] The type of the oxidizing agent is not particularly limited. For example, known oxidizing agents can be widely used. In terms of the reaction proceeding rapidly and obtaining the N-fluoroalkoxy compound in a high yield, it is preferable that the oxidizing agent includes an inorganic oxidizing agent. The inorganic oxidizing agent here is, for example, a compound containing a metal. The inorganic oxidizing agent is preferably other than a compound containing copper.

[0085] The inorganic oxidizing agent is preferably in a solid state under atmospheric pressure and at a 25°C atmosphere. The inorganic oxidizing agent can widely include compounds containing various metals other than copper. Such metals can include, for example, cerium, iron, manganese, chromium, copper, etc., and more preferably it is cerium.

[0086] The compound containing cerium is not particularly limited as long as it can exhibit the function as an oxidizing agent. For example, known compounds containing cerium can be widely included. Among them, the compound containing cerium is preferably ammonium hexanitratocerium(IV). When the inorganic oxidizing agent is ammonium hexanitratocerium(IV), the synthesis of the benzotriazole compound having an Rf moiety becomes easier.

[0087] Examples of the N-hydroxy compound include compounds represented by the following formula (2a-3).

[0088]

[0089] In formula (2a-3), R ９ , R １０ , R１１ and R １２ are each the same or different and are hydrogen or a monovalent group, and in particular, R in the formula (3´c) ９ , R １０ , R １１ and R １２ are synonymous.

[0090] Examples of the N-hydroxy compound are preferably benzotriazole salts having an electron-withdrawing group as a substituent, and preferably NO ２ or a benzotriazole salt having a CF ３ group, more preferably a benzotriazole salt having NO ２ and CF ３ groups, and even more preferably a compound in which R ９ is NO ２ , R １０ is hydrogen, R １１ is CF ３ , R １２ is hydrogen in the formula (2a-3). In the formula (2a-3), when R ９ , R １０ , R １１ and R １２ are hydrogen, the compound represented by the formula (2a-3) is 1-hydroxybenzotriazole.

[0091] The N-hydroxy compound can be obtained by a known production method or can also be obtained from commercially available products.

[0092] By reacting the N-hydroxy compound with the sulfinic acid compound in the presence of the oxidizing agent, the N-fluoroalkoxy compound (benzotriazole compound having an Rf moiety) used in Step 2 can be obtained.

[0093] In the reaction between the N-hydroxy compound and the sulfinic acid compound, a solvent can also be used. The type of the solvent is not particularly limited, and for example, the solvents that can be used in Step 1 described above can be exemplified.

[0094] The method of reaction between the N-hydroxy compound and the sulfinic acid compound is not particularly limited. For example, the reaction can be carried out by placing the N-hydroxy compound, the sulfinic acid compound, the oxidizing agent, and a solvent as needed into a suitable reaction vessel and stirring. The reaction can be carried out under an inert gas atmosphere such as argon as needed.

[0095] The reaction temperature is not particularly limited and can be selected from, for example, a range of -20 to 100°C. The reaction time can be set appropriately according to the reaction temperature, for example, in the range of 1 minute to 48 hours, preferably in the range of 3 minutes to 24 hours, and more preferably in the range of 5 minutes to 12 hours.

[0096] The amount of oxidizing agent used is not particularly limited. For example, the amount of oxidizing agent used per mole of sulfinic acid compound is preferably 1 mole or more, more preferably 2 moles or more, even more preferably 4 moles or more, and preferably 10 moles or less, more preferably 8 moles or less, and even more preferably 5 moles or less.

[0097] The amount of N-hydroxy compound used is not particularly limited. For example, the amount of sulfinic acid compound used per mole of sulfinic acid compound is preferably 0.5 moles or more, more preferably 1.0 mole or more, even more preferably 1.5 moles or more, and also preferably 10 moles or less, more preferably 8 moles or less, and even more preferably 5 moles or less.

[0098] The reaction between the N-hydroxy compound and the sulfinic acid compound may be carried out under pressure, atmospheric pressure, or reduced pressure. The reaction may also be carried out in a continuous or batch manner.

[0099] The product obtained in the above reaction can be removed from the solvent by an appropriate method, thereby obtaining a product containing an N-fluoroalkoxy compound (a benzotriazole compound having an Rf moiety) as, for example, a solid.

[0100] 3. Compositions This disclosure encompasses compositions. Examples of compositions include the following composition 1: Composition 1; comprising an aromatic fluoroether compound (E1) having an -ORf moiety (Rf represents a fluoroalkyl group with three or more carbon atoms), and an aromatic compound (E2) having an -Rf' moiety (Rf' represents a fluoroalkyl group obtained by removing one carbon atom from Rf).

[0101] In composition 1, the aromatic fluoroether compound (E1) having an -ORf moiety (Rf represents a fluoroalkyl group with three or more carbon atoms) is the aforementioned compound (E1), and the aromatic compound (E2) having an -Rf' moiety (Rf' represents a fluoroalkyl group obtained by removing one carbon atom from Rf) is the aforementioned compound (E2). That is, one embodiment of the composition of the present disclosure is a composition comprising compound (E1) and compound (E2). Such composition 1 can be obtained, for example, by a manufacturing method comprising step 1, and is, for example, a product obtained by step 1.

[0102] In composition 1, the content ratio of compound (E1) (the aromatic fluoroether compound (E1)) and compound (E2) (the aromatic compound (E2)) is not particularly limited. For example, in a fluorine-containing aromatic compound, compound (E1) is present in an amount of 15 to 95 mol%. It is preferable that composition 1 contains a higher amount of compound (E1) (i.e., it is preferable that compound (E1) is selectively obtained). In this case, because an oxygen atom is present between the perfluoroalkyl group and the aromatic ring of compound (E1) (the aromatic fluoroether compound), electrical and / or steric effects can be brought about to improve the functions of the composition, such as hydrophobicity, durability, metabolic stability, pharmacological activity, and pesticide activity. Therefore, the content ratio of compound (E1) relative to the total amount of compound (E1) and compound (E2) can be 70 mol% or more, preferably 80 mol% or more, more preferably 85 mol% or more, and even more preferably 90 mol% or more.

[0103] Composition 1 may consist only of compound (E1) and compound (E2), or it may contain components other than compound (E1) and compound (E2). Composition 1 contains compound (E1) and compound (E2) in amounts of 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more.

[0104] 4. Aromatic Fluoroether Compounds This disclosure includes aromatic fluoroether compounds. Such aromatic fluoroether compounds are -ORf １ Aromatic fluoroether compounds having a moiety, Rf １ (CF ２ ) ｎ CFX １ CF ２ X ２ It is a monovalent group represented by Rf. １ In this, n is, for example, 3 to 20, preferably 3 to 16, more preferably 3 to 12, even more preferably 3 to 10, even more preferably 3 to 8, and particularly preferably 3 to 6. １ and X ２ Rf is the same or different halo group, which is I, Br, or Cl, preferably Br or Cl, more preferably Cl. １ One example is a chlorofluoroalkyl group having three or more carbon atoms and two chloro groups, and more specifically, CF ２ ClCFClCF ２ CF ２ Examples include the following.

[0105] As an aromatic fluoroether compound in this disclosure, in compound E1 described above, Rf is Rf １ Examples of such compounds are given.

[0106] The aromatic fluoroether compounds of this disclosure can be obtained, for example, by a manufacturing method comprising step 1 described above. Specifically, in formula (3'c), Rf is Rf １ This can be obtained by reacting an N-fluoroalkoxy compound with the aromatic compound in the presence of the redox catalyst. The reaction method can be the same as in step 1.

[0107] For example, as an N-fluoroalkoxy compound represented by formula (3'c), Rf is CF ２ ClCFClCF ２ CF ２ , R ９ NO ２ , R １０ Hydrogen, R １１ ga CF ３ , R １２ If a compound in which hydrogen is used and benzene is used as the aromatic compound when step 1 is carried out, the resulting aromatic fluoroether compound is CF ２ ClCFClCF ２ CF ２ -C ６ H ５ That is the case.

[0108] In specifying the inventions contained herein, the components (properties, structures, functions, etc.) described in each embodiment of this disclosure may be combined in any way. That is, this disclosure encompasses all subject matter consisting of any combination of the combinatable components described herein.

[0109] The present invention will be described more specifically below with reference to examples, but the present invention is not limited to the embodiments of these examples.

[0110] (Example 1a) As an N-fluoroalkoxy compound, in formula (3'c) above, Rf is C ３ F ７ , R ９ NO ２ , R １０ Hydrogen, R １１ ga CF ３ , R １２ is hydrogen, R １３ CH ３ A benzotriazole salt was prepared in which X is an OTf group (triflat anion). This benzotriazole salt was mixed with benzene as an aromatic compound and tris(2,2'-bipyridine)ruthenium(II)bis(hexafluorophosphate)((Ru(bpy)) as a redox catalyst. ３ (PF ６ ) ２The raw material solution obtained by adding )) to the solvent acetonitrile was irradiated with active energy rays at room temperature (25°C) for 1 hour (Step 1). In this reaction, the molar ratio of benzotriazole salt to benzene (benzotriazole salt:benzene) was set to 1:10, and Ru(bpy) ３ (PF ６ ) ２ The benzotriazole salt was used in an amount of 1 mol%, and the active energy beam was a Kessil blue LED (power consumption 40 W, maximum wavelength 456 nm). The concentration of the starting materials (N-fluoroalkoxy compound and aromatic compound) in the solvent was 0.1 M. The reaction in step 1 produced C ６ H ５ -OC ３ F ７ (Compound (E1)) is 70 mol%, C ６ H ５ -C ２ F ５ A product containing 30 mol% of compound (E2) was obtained in 50% yield.

[0111] (Example 1b) Only the Rf of the benzotriazole salt is C ４ F ９ The reaction in step 1 was carried out in the same manner as in Example 1a, except that it was changed to C. ６ H ５ -OC ４ F ９ (Compound (E1)) is 17 mol%, C ６ H ５ -C ３ F ７ A product containing 83 mol% of compound (E2) was obtained in 70% yield.

[0112] (Example 1c) Only the Rf of the benzotriazole salt is C ６ F １３ The reaction in step 1 was carried out in the same manner as in Example 1a, except that it was changed to C. ６ H ５ -OC ６ F １３ (Compound (E1)) is not included, C ６ H ５ -C ５ F １１A product containing 100 mol% of compound (E2) was obtained in 75% yield.

[0113] (Example 2a) The reaction in step 1 was carried out in the same manner as in Example 1a, except that the concentration of the raw materials (N-fluoroalkoxy compound and aromatic compound) in the solvent was changed to 1 M. As a result of the reaction in step 1, C ６ H ５ -OC ３ F ７ (Compound (E1)) is 93 mol%, C ６ H ５ -C ２ F ５ A product containing 7 mol% of compound (E2) was obtained in a yield of 68%.

[0114] (Example 2b) Only the Rf of the benzotriazole salt is C ４ F ９ The reaction in step 1 was carried out in the same manner as in Example 2a, except that it was changed to C. ６ H ５ -OC ４ F ９ (Compound (E1)) is 72 mol%, C ６ H ５ -C ３ F ７ A product containing 8 mol% of compound (E2) was obtained in 69% yield.

[0115] (Example 2c) Only the Rf of the benzotriazole salt is C ５ F １１ The reaction in step 1 was carried out in the same manner as in Example 2a, except that it was changed to C. ６ H ５ -OC ５ F １１ (Compound (E1)) is 61 mol%, C ６ H ５ -C ４ F ９ A product containing 39 mol% of compound (E2) was obtained in a yield of 69%.

[0116] (Example 2d) Only the Rf of the benzotriazole salt is C ６ F １３The reaction in step 1 was carried out in the same manner as in Example 2a, except that it was changed to C. ６ H ５ -OC ６ F １３ (Compound (E1)) is 64 mol%, C ６ H ５ -C ５ F １１ A product containing 36 mol% of compound (E2) was obtained in a yield of 66%.

[0117] (Example 2e) Only the Rf of the benzotriazole salt is used in CF ２ ClCFClCF ２ CF ２ The reaction in step 1 was carried out in the same manner as in Example 2a, except that it was changed to CF. ２ ClCFClCF ２ CF ２ O-C ６ H ５ (Compound (E1)) is 69 mol%, CF ２ ClCFClCF ２ -C ６ H ５ A product containing 31 mol% of compound (E2) was obtained in 54% yield.

[0118] (Example 3a) Ru(bpy) ３ (PF ６ ) ２ Use in an amount of 2 mol% relative to the benzotriazole salt, and use only the Rf of the benzotriazole salt as C ６ F １３ The reaction in step 1 was carried out in the same manner as in Example 1a, except that it was changed to C. ６ H ５ -OC ６ F １３ (Compound (E1)) is 69 mol%, C ６ H ５ -C ５ F １１ A product containing 31 mol% of compound (E2) was obtained in 59% yield.

[0119] (Example 3b) The reaction in step 1 was carried out in the same manner as in Example 3a, except that the solvent was changed to acetone. As a result of the reaction in step 1, C６ H ５ -OC ６ F １３ (Compound (E1)) is 64 mol%, C ６ H ５ -C ５ F １１ A product containing 36 mol% of compound (E2) was obtained in 70% yield.

[0120] (Example 3c) The reaction in step 1 was carried out in the same manner as in Example 3a, except that the solvent was changed to nitromethane. As a result of the reaction in step 1, C ６ H ５ -OC ６ F １３ (Compound (E1)) is 59 mol%, C ６ H ５ -C ５ F １１ A product containing 41 mol% of compound (E2) was obtained in a yield of 61%.

[0121] (Example 3d) The reaction in step 1 was carried out in the same manner as in Example 3a, except that the solvent was changed to trifluoroethanol. As a result of the reaction in step 1, C ６ H ５ -OC ６ F １３ (Compound (E1)) is 54 mol%, C ６ H ５ -C ５ F １１ A product containing 46 mol% of compound (E2) was obtained in 26% yield.

[0122] (Example 3e) The reaction in step 1 was carried out in the same manner as in Example 3a, except that the solvent was changed to benzene. As a result of the reaction in step 1, C ６ H ５ -OC ６ F １３ (Compound (E1)) is 24 mol%, C ６ H ５ -C ５ F １１ A product containing 76 mol% of compound (E2) was obtained in 49% yield.

[0123] (Example 4a) Ru(bpy) ３ (PF ６ )２ Use 5 mol% of the benzotriazole salt, and use only the Rf of the benzotriazole salt as C ６ F １３ The reaction in step 1 was carried out in the same manner as in Example 1a, except that it was changed to C. ６ H ５ -OC ６ F １３ (Compound (E1)) is 73 mol%, C ６ H ５ -C ５ F １１ A product containing 26 mol% of compound (E2) was obtained in 70% yield.

[0124] (Example 4b) The reaction in step 1 was carried out in the same manner as in Example 4a, except that the amount of raw materials used was changed to 10 times. As a result of the reaction in step 1, C ６ H ５ -OC ６ F １３ (Compound (E1)) is 62 mol%, C ６ H ５ -C ５ F １１ A product containing 38 mol% of compound (E2) was obtained in 74% yield.

[0125] (Example 4c) The reaction in step 1 was carried out in the same manner as in Example 4a, except that the activation energy ray was changed to irradiation with a 1W blue LED. As a result of the reaction in step 1, C ６ H ５ -OC ６ F １３ (Compound (E1)) is 69 mol%, C ６ H ５ -C ５ F １１ A product containing 31 mol% of compound (E2) was obtained in a yield of 68%.

[0126] (Example 5a) Ru(bpy) ３ (PF ６ ) ２ The reaction in step 1 was carried out in the same manner as in Example 4a, except that the amount used was changed to 0.1 mol% relative to the benzotriazole salt. As a result of the reaction in step 1, C ６ H ５ -OC６ F １３ (Compound (E1)) is 50 mol%, C ６ H ５ -C ５ F １１ A product containing 50 mol% of compound (E2) was obtained in 44% yield.

[0127] (Example 5b) Ru(bpy) ３ (PF ６ ) ２ The reaction in step 1 was carried out in the same manner as in Example 4a, except that the amount used was changed to 0.5 mol% relative to the benzotriazole salt. As a result of the reaction in step 1, C ６ H ５ -OC ６ F １３ (Compound (E1)) is 65 mol%, C ６ H ５ -C ５ F １１ A product containing 35 mol% of compound (E2) was obtained in a yield of 62%.

[0128] (Example 5c) Ru(bpy) ３ (PF ６ ) ２ The reaction in step 1 was carried out in the same manner as in Example 4a, except that the amount used was changed to 1 mol% relative to the benzotriazole salt. As a result of the reaction in step 1, C ６ H ５ -OC ６ F １３ (Compound (E1)) is 62 mol%, C ６ H ５ -C ５ F １１ A product containing 38 mol% of compound (E2) was obtained in a yield of 68%.

[0129] (Example 5d) Ru(bpy) ３ (PF ６ ) ２ The reaction in step 1 was carried out in the same manner as in Example 4a, except that the amount used was changed to 2 mol% relative to the benzotriazole salt. As a result of the reaction in step 1, C ６ H ５ -OC ６ F １３ (Compound (E1)) is 69 mol%, C６ H ５ -C ５ F １１ A product containing 31 mol% of compound (E2) was obtained in 59% yield.

[0130] (Example 5e) Ru(bpy) ３ (PF ６ ) ２ The reaction in step 1 was carried out in the same manner as in Example 4a, except that the amount used was changed to 5 mol% relative to the benzotriazole salt. As a result of the reaction in step 1, C ６ H ５ -OC ６ F １３ (Compound (E1)) is 73 mol%, C ６ H ５ -C ５ F １１ A product containing 7 mol% of compound (E2) was obtained in 70% yield.

[0131] (Example 5f) Ru(bpy) ３ (PF ６ ) ２ The reaction in step 1 was carried out in the same manner as in Example 1a, except that the amount used was changed to 10 mol% relative to the benzotriazole salt. As a result of the reaction in step 1, C ６ H ５ -OC ６ F １３ (Compound (E1)) is 70 mol%, C ６ H ５ -C ５ F １１ A product containing 30 mol% of compound (E2) was obtained in a yield of 64%.

[0132] (Example 6a) The reaction in step 1 was carried out in the same manner as in Example 5e, except that the concentration of the raw materials (N-fluoroalkoxy compound and aromatic compound) relative to the solvent was changed to 2 M. As a result of the reaction in step 1, C ６ H ５ -OC ６ F １３ (Compound (E1)) is 77 mol%, C ６ H ５ -C ５ F １１A product containing 23 mol% of compound (E2) was obtained in 60% yield.

[0133] (Example 6b) The reaction in step 1 was carried out in the same manner as in Example 5e, except that the concentration of the raw materials (N-fluoroalkoxy compound and aromatic compound) in the solvent was changed to 0.5 M. As a result of the reaction in step 1, C ６ H ５ -OC ６ F １３ (Compound (E1)) is 60 mol%, C ６ H ５ -C ５ F １１ A product containing 40 mol% of compound (E2) was obtained in 60% yield.

[0134] (Example 6c) The reaction in step 1 was carried out in the same manner as in Example 5e, except that the concentration of the raw materials (N-fluoroalkoxy compound and aromatic compound) in the solvent was changed to 0.2 M. As a result of the reaction in step 1, C ６ H ５ -OC ６ F １３ (Compound (E1)) is 39 mol%, C ６ H ５ -C ５ F １１ A product containing 61 mol% of compound (E2) was obtained in 59% yield.

[0135] (Example 6d) The reaction in step 1 was carried out in the same manner as in Example 5e, except that the concentration of the raw materials (N-fluoroalkoxy compound and aromatic compound) in the solvent was changed to 0.1 M. As a result of the reaction in step 1, C ６ H ５ -OC ６ F １３ (Compound (E1)) is 25 mol%, C ６ H ５ -C ５ F １１ A product containing 75 mol% of compound (E2) was obtained in a yield of 68%.

[0136] (Example 6e) The reaction in step 1 was carried out in the same manner as in Example 5e, except that the concentration of the raw materials (N-fluoroalkoxy compound and aromatic compound) in the solvent was changed to 0.05 M. As a result of the reaction in step 1, C ６ H ５ -OC ６ F １３ (Compound (E1)) is 13 mol%, C ６ H ５ -C ５ F １１ A product containing 86 mol% of compound (E2) was obtained in 75% yield.

[0137] (Example 6f) The reaction in step 1 was carried out in the same manner as in Example 5c, except that the concentration of the raw materials (N-fluoroalkoxy compound and aromatic compound) in the solvent was changed to 0.1 M. As a result of the reaction in step 1, C ６ H ５ -OC ６ F １３ (Compound (E1)) is not included, C ６ H ５ -C ５ F １１ A product containing 100 mol% of compound (E2) was obtained in 75% yield.

Claims

1. A method for producing a fluorine-containing aromatic compound, comprising the step of reacting an N-fluoroalkoxy compound and an aromatic compound in the presence of a redox catalyst to obtain a product, wherein the N-fluoroalkoxy compound is a compound having an N-ORf moiety (Rf represents a fluoroalkyl group with three or more carbon atoms), and the product comprises at least one fluorine-containing aromatic compound selected from the group consisting of an aromatic fluoroether compound having an -ORf moiety (E1) and an aromatic compound having an -Rf' moiety (Rf' represents a fluoroalkyl group obtained by removing one carbon atom from Rf) (E2).

2. The manufacturing method according to claim 1, wherein the product is obtained by irradiating with an active energy ray in the above step.

3. The manufacturing method according to claim 1, wherein the fluorine-containing aromatic compound comprises both the aromatic fluoroether compound (E1) and the aromatic compound (E2).

4. The manufacturing method according to claim 1 or 2, wherein the oxidation-reduction catalyst is a metal catalyst.

5. The manufacturing method according to claim 4, wherein the metal catalyst is a compound containing Ru.

6. A step of obtaining a benzotriazole salt having an Rf moiety (where Rf represents a fluoroalkyl group having 3 or more carbon atoms) by reacting a benzotriazole compound having an Rf moiety with an alkylating agent represented by the following formula (4): R １３ ―X (4) (In formula (4), X represents a leaving group, and R １３ represents an alkyl group which may have a substituent). The method for producing a fluorine-containing benzotriazole salt represented by the following general formula (3´c) (where in formula (3´c), Rf, R (In formula (3c-1), Rf represents a fluoroalkyl group having 3 or more carbon atoms, and R ９ , R １０ , R １１ , and R １２ each independently represent hydrogen or a monovalent group) is an N-fluoroalkoxy compound represented by the following general formula (3c-1): (In formula (3´c), Rf, R ９ , R １０ , R １１ , and R １２ are synonymous with Rf, R ９ , R １０ , R １１ , and R １２ in formula (3c-1), and X and R １３ are synonymous with X and R １３ in formula (4)).

7. A composition comprising an aromatic fluoroether compound (E1) having an -ORf moiety (Rf represents a fluoroalkyl group with three or more carbon atoms), and an aromatic compound (E2) having an -Rf' moiety (Rf' represents a fluoroalkyl group obtained by removing one carbon atom from Rf).

8. The composition according to claim 7, wherein the aromatic fluoroether compound (E1) is contained in an amount of 70 mol% or more relative to the total amount of the aromatic fluoroether compound (E1) and the aromatic compound (E2).

9. -ORf １ Aromatic fluoroether compounds having a moiety, Rf １ (CF ２ ) ｎ CFX １ CF ２ X ２ (n is a number between 3 and 20, X １ and X ２ Aromatic fluoroether compounds that are monovalent groups (which are the same or different halo groups).

10. Rf １ The aromatic fluoroether compound according to claim 9, wherein is a chlorofluoroalkyl group with three or more carbon atoms and has two chloro groups.

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