Method for producing fluoroether

Abstract

The present disclosure provides a method for producing a fluoroether, with which it is possible to easily produce fluoroethers having various structures.　A method for producing a fluoroether according to the present disclosure comprises a step 1 for obtaining a fluoroether by reacting an alkene represented by formula (1): CR1R2=CX1X2 (wherein X1 and X2 may be the same as or different from each other and each represent a hydrogen atom or a halogen atom; and R1 and R2 may be the same as or different from each other and each represent a hydrogen atom, an aryl group or alkyl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a fluoroalkyl group which may have a substituent, a halogen atom, or a group represented by R-(CH2)n- (wherein R is an aryl group which may have a substituent; and n is an integer of 3 or more)) with an N-fluoroalkoxy compound in the presence of an oxidation-reduction catalyst and a nucleophilic agent.

Description

Method for producing fluoroether

[0001] The present invention relates to a method for producing fluoroether.

[0002] Fluoroether is a compound used as a pharmaceutical compound, a solvent, a refrigerant, a medical and agricultural chemical, and a functional material, and various methods for producing fluoroether have been proposed.

[0003] For example, Patent Document 1 discloses a method for producing fluoroether by reacting hypofluorite with tetrafluoroethylene.

[0004] U.S. Patent No. 4,032,566

[0005] An object of the present disclosure is to provide a method for producing fluoroether that can easily produce fluoroethers having various structures.

[0006] The present disclosure includes the configurations described in the following items.

[0007] Item 1 The following general formula (1) CR <​​​​​​​​​​​​​​​​​​​​​​​​​​​​R represents the same or different fluorine atom or fluoroalkyl group, ３ R represents a group containing an aryl group or fluoroalkyl group which may have a substituent, ４ R indicates a group containing a -N=N bond. ３ and R ４ Step 1 comprises reacting an N-fluoroalkoxy compound represented by (which may bond to each other with the nitrogen atom to which they are bonded to form a saturated or unsaturated ring) with a redox catalyst and a nucleophile in the presence of a fluoroether, wherein the fluoroether is represented by the following general formula (10)

[0010] (In equation (10), R １ , R ２ , X １ , X ２ , R ｆ１ , and R ｆ２ A method for producing fluoroethers, represented by (where is the same as above, and Y represents a monovalent group based on the nucleophile).

[0011] Item 2: The method for producing a fluoroether according to Item 1, wherein the reaction is carried out by irradiating with an active energy ray in step 1.

[0012] Item 3: The method for producing a fluoroether according to item 1 or 2, wherein the oxidation-reduction catalyst is a metal catalyst.

[0013] Item 4 The method for producing a fluoroether according to any one of items 1 to 3, wherein the oxidation-reduction catalyst is at least one selected from the group consisting of ruthenium catalysts and iridium catalysts.

[0014] Item 5 A method for producing a fluoroether according to any one of items 1 to 4, wherein an inorganic salt or an organic acid is added to step 1 and the reaction is carried out.

[0015] Item 6: A method for producing a fluoroether according to any one of items 1 to 5, wherein the N-fluoroalkoxy compound is a compound containing a nitrogen-containing heterocycle.

[0016] Item 7 A method for producing a fluoroether according to any one of items 1 to 6, wherein the reaction in step 1 is carried out in the presence of an organic solvent.

[0017] Item 8 The method for producing a fluoroether according to any one of items 1 to 7, wherein the nucleophile is a compound having a lone pair of electrons.

[0018] Item 9 The following general formula (3)

[0019]

[0020] (In formula (3), R ５ R is an aromatic ring which may have one or more substituents, or R ８ -CH = CH - (R ８ R represents an aromatic ring which may have one or more substituents. ｆ３ R represents a perfluoroalkyl group having 1 to 6 carbon atoms. ６ Y represents a hydrogen atom or a fluorine atom. １ is -NH(C=O)-R ７ (R ７ R is represented by an alkyl group (which may have substituents), an alkoxy group, a halogen atom (Cl, Br, I), or a hydroxyl group, provided that among the compounds represented by formula (3), ５ C ６ H ５ , Y １ OH, R ６ F, R ｆ３ C ２ F ５ The compound is R ５ C ６ H ５ , Y １ OH, R ６ F, R ｆ３ ga CF ３ Fluoroether compounds, excluding those compounds.

[0021] Item 10 The following general formula (4)

[0022]

[0023] (In formula (4), Y ２ is -NH(C=O)-R ９ (R ９ R represents an alkyl group which may have substituents), bromine, or iodine. ｆ４A fluoroether compound represented by (where represents a perfluoroalkyl group having 1 to 6 carbon atoms).

[0024] According to the method for producing fluoroethers of this disclosure, fluoroethers having various structures can be easily produced.

[0025] This shows the reaction scheme, products, and yields for the reactions carried out in Examples 1a, 1b, 1c, and 1d. This shows the reaction scheme, products, and yields for the reactions carried out in Example 2. This shows the structure of the starting material (alkene) used in the reaction carried out in Example 2. This shows the reaction scheme, products, and yields for the reactions carried out in Example 3. This shows the reaction scheme, products, and yields for the reactions carried out in Examples 4a to 4e. This shows the reaction scheme, products, and yields for the reactions carried out in Example 5. This shows the reaction scheme, products, and yields for the reactions carried out in Example 6. This shows the reaction scheme, products, and yields for each of the 7 examples.

[0026] The method disclosed in Patent Document 1, mentioned above, has the problem that the starting materials must be compounds that can decompose in air or with moisture, making them difficult to handle, and that the structure of the resulting fluoroether is limited. The present inventors have diligently conducted research to easily produce fluoroethers with various structures.

[0027] This disclosure has been made in view of the above, and aims to provide a novel method for producing fluoroethers having various structures that can be easily manufactured. Specifically, this objective is achieved by reacting a specific alkene with an N-fluoroalkoxy compound in the presence of a redox catalyst and a nucleophile.

[0028] 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."

[0029] 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.

[0030] 1. Method for producing fluoroether The method for producing fluoroether of the present invention is as follows: General formula (1) CR １ R ２ = CX １ X ２ Alkenes represented by (1) and the following general formula (2)

[0031]

[0032] The process includes step 1, in which an N-fluoroalkoxy compound represented by the formula is reacted with a redox catalyst and a nucleophile to obtain a fluoroether. Here, the fluoroether is represented by the following general formula (10).

[0033]

[0034] In the above formula (1), X １ and X ２ R represents the same or different hydrogen or halogen atoms. １ and R ２ These are the same or different hydrogen atoms, optionally substituted aryl groups, optionally substituted alkyl groups, optionally substituted alkenyl groups, optionally substituted alkynyl groups, optionally substituted fluoroalkyl groups, halogen atoms, or R-(CH ２ ) ｎ This represents a group represented by - (where R is an aryl group which may have substituents, and n is an integer of 3 or more).

[0035] In the above formula (2), R ｆ１ and R ｆ２R represents the same or different fluorine atom or fluoroalkyl group, ３ R represents a group containing an optionally substituted aryl group or an optionally substituted alkyl group, ４ R indicates a group containing a -N=N bond. ３ and R ４ These may bond with each other, along with the nitrogen atom to which they are bonded, to form a saturated or unsaturated ring.

[0036] In the above formula (10), R １ , R ２ , X １ and X ２ R in formula (1) above １ , R ２ , X １ and X ２ It is synonymous with R ｆ１ , and R ｆ２ R in formula (2) above is ｆ１ , and R ｆ２ This is synonymous. Y represents a monovalent group based on the nucleophile.

[0037] According to the method for producing fluoroethers of this disclosure, various fluoroethers having different structures can be easily produced by appropriately selecting the type of alkene and / or N-fluoroalkoxy compound. In particular, the method for producing fluoroethers of this disclosure selects alkene and / or N-fluoroalkoxy compounds that have not been used conventionally, thereby enabling the production of novel fluoroethers.

[0038] (Alkene) In step 1, an alkene represented by formula (1) is used as the raw material. １ and X ２ Examples of halogen atoms in this compound include fluorine, chlorine, bromine, and iodine atoms, with fluorine being the most preferred.

[0039] In the above formula (1), X １ and X ２ It is preferable that X is the same or different hydrogen or fluorine atom. Therefore, in formula (1), X １ and X２ Preferably, one atom is hydrogen and the other is a fluorine atom, both atoms are hydrogen, or both atoms are fluorine atoms. In this case, the raw materials are advantageous in that they are less likely to decompose in air or moisture, and are easy to handle.

[0040] In the above formula (1), R １ and R ２ As mentioned above, these are the same or different hydrogen, optionally substituted aryl group, optionally substituted alkyl group, optionally substituted alkenyl group, optionally substituted alkynyl group, optionally substituted fluoroalkyl group, halogen atom (i.e., fluorine atom, chlorine atom, bromine atom, iodine atom), or R-(CH ２ ) ｎ This represents a group represented by - (where R is an aryl group which may have substituents, and n is an integer of 3 or more).

[0041] Herein, in this specification, "aryl group" can be monocyclic, dicyclic, tricyclic, or tetracyclic. Unless otherwise specified, "aryl group" can be an aryl group having 6 to 18 carbon atoms. Examples of "aryl groups" include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthuryl.

[0042] 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.

[0043] In this specification, examples of "alkyl group" can include linear, branched, or cyclic alkyl groups such as methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, cyclobutyl, isobutyl, sec-butyl, tert-butyl, pentyl, cyclopentyl, isopentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, and docosyl.

[0044] In this specification, examples of the "alkenyl group" can include linear, branched or cyclic alkenyl groups having 2 to 10 carbon atoms such as vinyl, 1-propen-1-yl, 2-propen-1-yl, isopropenyl, 2-buten-1-yl, 4-penten-1-yl, and 5-hexen-1-yl.

[0045] In this specification, examples of the "alkynyl group" can include linear, branched or cyclic alkynyl groups having 2 to 10 carbon atoms such as ethynyl, 1-propyn-1-yl, 2-propyn-1-yl, 4-pentyn-1-yl, 5-hexyn-1-yl.

[0046] In this specification, the "fluoroalkyl group" is an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. The number of fluorine atoms in the "fluoroalkyl group" can be 1 or more (e.g., 1 to 3, 1 to 6, 1 to 12, 1 to the maximum number that can be substituted). In this specification, the 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. Note that the "fluoroalkyl group" includes a perfluoroalkyl group (an alkyl group in which all hydrogen atoms are substituted with fluorine atoms).

[0047] Specific examples of the "fluoroalkyl group" include, for example, fluoromethyl group, difluoromethyl group, trifluoromethyl group (CF ３ -), 2,2,2-trifluoroethyl group, pentafluoroethyl group (C ２ F[[ID=:14]] 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 CH２ Examples include -), and tridecafluorohexyl groups.

[0048] In the above formula (1), R - (CH ２ ) ｎ The group represented by - is an aryl group in which n is an integer of 3 or more, and R may have substituents.

[0049] The above R-(CH ２ ) ｎ - In this case, the upper limit of n is not particularly limited; for example, n is 30 or less, preferably 20 or less, more preferably 16 or less, even more preferably 12 or less, even more preferably 8 or less, and especially preferably 6 or less.

[0050] The above R-(CH ２ ) ｎ -In this specification, R is an aryl group which may have substituents, and the aryl group is synonymous with the aryl group as defined herein as described above. R-(CH ２ ) ｎ A concrete example of this is C ６ H ５ - (CH ２ ) ３ - are some examples.

[0051] In this specification, substituents include halo groups (F, Cl, Br, I); nitro groups; cyano groups; oxo groups; thioxo groups; sulfo groups; sulfamoyl groups; sulfinamoyl groups; sulfenamoyl groups; and organic groups, or groups that encompass each of these groups.

[0052] The aforementioned organic group can be any of the various hydrocarbon groups. In this specification, "hydrocarbon group" can include, for example, the alkyl, alkenyl, and alkynyl groups mentioned above, as well as 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.

[0053] 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 (F, Cl, Br, I). 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. An example of the haloalkyl group is the fluoroalkyl group described above.

[0054] Other examples of the aforementioned organic group include R ａ -O-R ａ -COO- R ａ -OCO- can be listed.

[0055] Here R ａ Examples include the hydrocarbon group, the haloalkyl group, and a group having a phenylene group. A group having a phenylene group is "-C ６ H ４ Examples of groups having a '-' include alkyl groups having a phenylene group, N-SO ２ -C ６ H ４ Groups having - are examples. N-SO ２ -C ６ H ４ In this case, the aforementioned alkyl group may be bonded to the N atom. In this case, if one alkyl group is bonded to the N atom, a hydrogen atom may also be bonded to the N atom, and two alkyl groups may be bonded to the N atom.

[0056] The above R ａ -O-, R ａ -COO-, and R ａ An example of -OCO- is CF ３ -O-, C ６ H ５ -COO-, CH ３In addition to -OCO-, other examples of groups can be found that are represented by the following formulas (9a) or (9b).

[0057]

[0058] As an example of an alkene represented by formula (1), R １ and R ２ Examples of compounds in which one side is hydrogen and the other side is an optionally substituted aryl group include a phenyl group, a halogen-substituted phenyl group, an alkyl-substituted phenyl group, and so on. Also, as an example of an alkene represented by formula (1), R １ and R ２ Examples of compounds in which one part is hydrogen and the other part is an optionally substituted alkenyl group include, for example, C ６ H ５ -CH = CH-. Of course, R １ and R ２ Both of these groups may be other than hydrogen.

[0059] In step 1, one or more alkenes can be used as starting materials.

[0060] (N-fluoroalkoxy compound) In step 1, an N-fluoroalkoxy compound represented by formula (2) is used as a raw material. In step 1, one or more N-fluoroalkoxy compounds can be used.

[0061] In equation (2), R ３ R represents a group containing an optionally substituted aryl group or an optionally substituted alkyl group, in which case the substituent and aryl group are defined as above. ４ R represents a group containing a -N=N bond. In equation (2), R ３ and R ４ These may bond with each other, along with the nitrogen atom to which they are bonded, to form a saturated or unsaturated ring.

[0062] In equation (2), R ｆ１ and R ｆ２These are identical or different fluorine atoms or fluoroalkyl groups. Fluoroalkyl groups have the same meaning as the aforementioned "fluoroalkyl groups". R ｆ１ and R ｆ２ The fluoroalkyl group used is preferably a perfluoroalkyl group. Specific examples of perfluoroalkyl groups include, for example, a fluoromethyl group, a difluoromethyl group, and a trifluoromethyl group (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 ２ Examples include -), and perfluoroalkyl groups such as tridecafluorohexyl groups.

[0063] R ｆ１ and R ｆ２ One of the elements may be a fluorine atom and the other a fluoroalkyl group, both may be fluorine atoms, or both may be fluoroalkyl groups.

[0064] The compound represented by formula (2) is preferably a compound containing a nitrogen-containing heterocycle. In this case, the raw material is advantageous in that it is less likely to decompose in air or moisture and is easy to handle. An example of such a compound is the N-fluoroalkoxy compound represented by the following formula (2a).

[0065]

[0066] In equation (2a), Rf is CF(R ｆ１ ) (Caution ｆ２ ) indicates R ｆ１ and R ｆ２ R in equation (2) ｆ１ and Rｆ２ These are synonymous with each other.

[0067] The compound represented by formula (2a) is, in formula (2), R ３ is a group containing an aryl group, R ４ is a group containing a -N=N bond, and R ３ and R ４ These are examples of how these elements bond to each other along with the nitrogen atom to which they bind.

[0068] In equation (2a), R ９ , R １０ , R １１ , and, R １２ Each of these is either the same or different hydrogen or monovalent group. Here, a monovalent group can mean the substituents mentioned above. Therefore, the monovalent group in formula (2a) can be the aforementioned hydrocarbon group or haloalkyl group, which are organic groups, and can also be a halo group; nitro group; cyano group; oxo group; thioxo group; sulfo group; sulfamoyl group; sulfinamoyl group; sulfenamoyl group; alkoxy group; amino group; hydroxyl group. The monovalent group is preferably an electron-withdrawing group, more preferably a nitro group and a trifluoromethyl group, and even more preferably R ９ NO ２ , R １０ Hydrogen, R １１ ga CF ３ , R １２ This is hydrogen. Note that in equation (2a), R ９ , R １０ , R １１ , and, R １２ When is hydrogen, the compound represented by formula (2a) is 1-hydroxybenzotriazole. As an example of the compound represented by formula (2a), R ９ NO ２ , R １０ is hydrogen, R １１ ga CF ３ , R １２ Examples of compounds in which hydrogen is present are given.

[0069] In the compound represented by formula (2a), R ｆ１ and R ｆ２One of the elements may be a fluorine atom and the other a fluoroalkyl group, both may be fluorine atoms, or both may be fluoroalkyl groups.

[0070] The method for producing the N-fluoroalkoxy compound represented by formula (2a) will be described later.

[0071] Other examples of compounds represented by formula (2) include N-fluoroalkoxy compounds represented by the following formula (2a').

[0072]

[0073] The N-fluoroalkoxy compound used in step 1 is preferably in the form of a salt, and more preferably has a benzotriazole salt skeleton. An example of such an N-fluoroalkoxy compound is the compound represented by the following formula (2b) (hereinafter sometimes referred to as a benzotriazole salt).

[0074]

[0075] In equation (2b), Rf is equivalent to Rf in equation (2a).

[0076] In equation (2b), R ９ , R １０ , R １１ , and, R １２ These are R in equation (2a), respectively. ９ , R １０ , R １１ , and, R １２ This is equivalent to: X indicates a leaving group, and R １３ represents an alkyl group which may have substituents, specifically X and R in formula (4) below. １３ It is synonymous with [the above].

[0077] In the benzotriazole salt represented by formula (2b), for example, R ９ NO ２ , R １０ is hydrogen, R １１ ga CF ３ , R １２ is hydrogen, R １３ Examples of compounds in which the group is a methyl group are given.

[0078] The method for producing the benzotriazole salt is not particularly limited. For example, the benzotriazole salt represented by formula (2b) is produced by combining the N-fluoroalkoxy compound represented by formula (2a) with the following formula (4) R １３ It can be obtained by reaction with an alkylating agent represented by -X (4).

[0079] In formula (4), X represents a leaving group, and R １３ This indicates an alkyl group which may have substituents.

[0080] The leaving group (X) is not particularly limited and can be broadly described as any known leaving group, 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 One example is the group (trifluoromethylsulfonylimide).

[0081] In equation (4), R １３ For example, the carbon number is 1 or more and 30 or less, preferably 20 or less, more preferably 10 or less, even more preferably 5 or less, and particularly preferably 3 or less. １３ If the group is a methyl group, the alkylating agent becomes a methylating agent. １３ If is an alkyl group which may have substituents, the substituent is synonymous with the substituent defined above.

[0082] R １３ ―Specific examples of X include methyl trifluoromethanesulfonate (R １３ Examples include compounds in which X is a methyl group and X is an OTf group (triflat anion).

[0083] The reaction conditions between the N-fluoroalkoxy compound represented by formula (2a) and the alkylating agent are not particularly limited. For example, the reaction temperature can be 25 to 100°C. The reaction time can be appropriately set according to the reaction temperature, for example, 1 to 60 hours. The amounts of the N-fluoroalkoxy compound and alkylating agent used are also not particularly limited; for example, the amount of alkylating agent used can be 1 to 5 moles per mole of N-fluoroalkoxy compound.

[0084] The reaction between the N-fluoroalkoxy compound and the alkylating agent can also 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 may be carried out under pressure, atmospheric pressure, or reduced pressure. The reaction may also be carried out in a continuous or batch manner.

[0085] The method for producing the N-fluoroalkoxy compound represented by formula (2a) is not particularly limited. For example, in the presence of an oxidizing agent, the N-hydroxy compound and the following general formula (5) RbSO ２ A desired N-fluoroalkoxy compound can be obtained by a step of reacting it with a sulfinic acid compound represented by formula (5) (wherein Rb is a fluoroalkyl group having 1 or more carbon atoms, and M is an alkali metal or alkaline earth metal) to obtain an N-fluoroalkoxy compound. Hereinafter, this step will be referred to as "step a".

[0086] The type of oxidizing agent used in step a is not particularly limited, and for example, a wide range of known inorganic oxidizing agents can be used. In terms of the rapid reaction and the ability to obtain N-fluoroalkoxy compounds in high yield, the inorganic oxidizing agent is preferably a compound containing a metal.

[0087] The inorganic oxidizing agent is preferably in a solid state under atmospheric pressure and at a temperature of 25°C. In this case, the reaction carried out in step a can be easily performed, and the yield of the N-fluoroalkoxy compound produced in step a can be increased.

[0088] The inorganic oxidizing agent can be a wide range of compounds containing various metals. Examples of such metals include cerium, iron, manganese, chromium, and copper. Cerium is more preferable as the metal because it is highly reactive and can increase the yield of the N-fluoroalkoxy compound produced in step a. That is, the inorganic oxidizing agent used in step a is more preferably a compound containing cerium.

[0089] In step a, the amount of inorganic oxidizing agent used can be 0.1 equivalents or more and 5 equivalents or less relative to the N-hydroxy compound, and the yield is more easily improved in the order of 0.5, 0.8, 1.0, 1.5, 2.0, and 3.0.

[0090] The cerium-containing compound is not particularly limited as long as it can function as an inorganic oxidizing agent, and for example, a wide range of known cerium-containing compounds can be mentioned. Among these, the cerium-containing compound is preferably ammonium hexanitratocerium(IV)ate. When the inorganic oxidizing agent is ammonium hexanitratocerium(IV)ate, the yield of the N-fluoroalkoxy compound produced in step a can be made particularly high.

[0091] The inorganic oxidizing agent used in step a may be just one type, or it may be two or more different types. The inorganic oxidizing agent used in step a can be obtained by a known manufacturing method, or it can be obtained from a commercially available product.

[0092] Examples of N-hydroxy compounds used in step a include compounds represented by the following general formula (2').

[0093]

[0094] In the above formula (2'), R ３ and R ４ R in equation (2) ３ and R ４ These are synonymous with each other.

[0095] As an example of a compound represented by formula (2'), the compound represented by the following formula (2'-1) can be given.

[0096]

[0097] The compound represented by formula (2'-1) has R in formula (2'). ３ is a group containing an aryl group, R ４ is a group containing a -N=N bond, and R ３ and R ４ These are examples of how these elements bond to each other along with the nitrogen atom to which they bind.

[0098] In equation (2'-1), R ９ , R １０ , R １１ , and, R １２ These are R in equation (2a), respectively. ９ , R １０ , R １１ , and, R １２ This is synonymous with the above. In terms of being able to increase the yield of the N-fluoroalkoxy compound, an electron-withdrawing group is preferable, more preferably a nitro group and a trifluoromethyl group, and even more preferably R ９ NO ２ , R １０ is hydrogen, R １１ ga CF ３ , R １２ is hydrogen. Note that in equation (2'-1), R ９ , R １０ , R １１ , and, R １２ When is hydrogen, the compound represented by formula (2'-1) is 1-hydroxybenzotriazole. An example of a compound represented by formula (2'-1) is R ９ NO ２ , R １０ is hydrogen, R １１ ga CF ３ , R １２ Examples of compounds in which hydrogen is present are given.

[0099] The N-hydroxy compound used in step a may be just one type, or it may be two or more different types. The N-hydroxy compound used in step a can be obtained by known manufacturing methods, or it can be obtained from a commercially available product.

[0100] In step a, the N-hydroxy compound is reacted with the sulfinic acid compound represented by formula (5) in the presence of the oxidizing agent. This yields an N-fluoroalkoxy compound.

[0101] In formula (5), Rb is exemplified by, for example, a fluoroalkyl group having 1 to 20 carbon atoms, preferably a fluoroalkyl group having 1 to 16 carbon atoms, more preferably a fluoroalkyl group having 1 to 12 carbon atoms, and even more preferably a fluoroalkyl group having 1 to 10 carbon atoms. Examples of fluoroalkyl groups include a fluoromethyl group, a difluoromethyl group, and a trifluoromethyl group (CF ３ -), 2,2,2-trifluoroethyl group, pentafluoroethyl group (C ２ F ５ -), CF ２ HCFH-, CF (CF ２ H) ２ -, tetrafluoropropyl group (e.g., HCF) ２ CF ２ CH ２ -), hexafluoropropyl group (e.g., (CF ３ ) ２ CH-), CF ２ HCFHCFH-, CF ２ HCFHCFHCFH, CF ２ HCFHCFHCFHCFH, CFH ２ CFH-, CFH ２ CFHCFH-, CFH ２ CFHCFHCFH, CFH ２ CFHCFHCFHCFH-, nonafluorobutyl group, octafluoropentyl group (e.g., HCF ２ CF ２ CF ２ CF ２ CH ２ Examples include -), and the tridecafluorohexyl group. The sulfinic acid compound represented by formula (5) is CF ３ SO ２ Examples include sodium (Na).

[0102] In formula (5), Rb is preferably a perfluoroalkyl group. Alternatively, Rb may be a chlorine-containing fluoroalkyl group. Examples of chlorine-containing fluoroalkyl groups include CF ２ ClCFClCF ２ CF ２ Examples are given.

[0103] In formula (5), Rb may be linear or branched.

[0104] The reaction in step a may be carried out either in the absence of a solvent or in the presence of a solvent, but it is preferable to carry it out in the presence of a solvent.

[0105] The type of solvent is not particularly limited and includes, for example, 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 also 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.

[0106] The amount of solvent used is not particularly limited, and for example, per 1 mmol of the sulfinic acid compound represented by formula (5) used in the reaction of step a, it may be, for example, 2 mL or more, 3 mL or more, 4 mL or more, 5 mL or more, or 6 mL or more. The amount of solvent used may be, for example, 60 mL or less, 50 mL or less, 40 mL or less, 30 mL or less, or 20 mL or less per 1 mmol of the compound represented by formula (5). The amount of solvent used may be, for example, in the range of 2 to 60 mL or in the range of 5 to 50 mL per 1 mmol of the sulfinic acid compound.

[0107] In step a, the reaction method is not particularly limited. For example, the reaction can be carried out by adding the N-hydroxy compound, the sulfinic acid compound, the oxidizing agent, and a solvent used as needed to a suitable reaction vessel and stirring. The reaction can be carried out under an inert gas atmosphere such as argon as needed.

[0108] 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.

[0109] The amount of oxidizing agent used in step a is not particularly limited. In order to facilitate the reaction in step a and increase the yield of the N-fluoroalkoxy compound produced in step a, the amount of oxidizing agent used per mole of sulfinic acid compound can be 0.4 moles or more, or 0.8 moles or more, preferably 1 mole or more, more preferably 1.5 moles or more, even more preferably 2.0 moles or more, particularly preferably 3.0 moles or more, and also preferably 10 moles or less, more preferably 8 moles or less, even more preferably 5 moles or less, and particularly preferably 3 moles or less.

[0110] The amount of the N-hydroxy compound used in step a is not particularly limited. In order to facilitate the reaction in step a and increase the yield of the N-fluoroalkoxy compound produced in step a, the amount of the sulfinic acid compound used per mole of the N-hydroxy compound can be 0.4 moles or more, or 0.8 moles or more, preferably 1 mole or more, more preferably 1.2 moles or more, even more preferably 1.5 moles or more, preferably 10 moles or less, more preferably 8 moles or less, even more preferably 6 moles or less, and particularly preferably 4 moles or less.

[0111] The reaction may be carried out under pressure, atmospheric pressure, or reduced pressure. Furthermore, the reaction may be continuous or in batch mode.

[0112] The product obtained in step a can be desoldered by an appropriate method, thereby obtaining a product containing the N-fluoroalkoxy compound, for example, as a solid. The solid thus collected can be purified, dried, or otherwise treated by an appropriate method to obtain the target N-fluoroalkoxy compound with high purity. The above reaction produces a product containing the target N-fluoroalkoxy compound.

[0113] The method for producing an N-fluoroalkoxy compound may consist only of step a, or it may include other steps besides step a.

[0114] (Redox Catalyst) A redox catalyst is used in the reaction carried out in step 1. The type of such redox catalyst is not particularly limited, and for example, a wide range of known redox catalysts can be used.

[0115] Examples of oxidation-reduction catalysts include organic photo-oxidation-reduction catalysts and metal catalysts. Examples of organic photo-oxidation-reduction catalysts include 1,2,3,5-tetrakis(carbazole-9-yl)-4,6-dicyanobenzene, 2,3,4-tri(9H-carbazole-9-yl)-5-chloroisophthalonitrile, 2,4,6-tris(diphenylamino)-5-fluoroisophthalonitrile, 9,10-dicyanoanthracene, 9-methicyl-10-methylacridinium perchlorate, 10-phenylphenothiazine, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, and tetrabromofluorescein.

[0116] Because the reaction proceeds easily and the target product can be obtained in high yield, the redox catalyst is preferably a metal catalyst. Here, a metal catalyst can mean an elemental metal or a compound (including complexes) containing a metal.

[0117] In particular, the oxidation-reduction catalyst is more preferably at least one selected from the group consisting of ruthenium catalysts and iridium catalysts. In this case, the target product can be obtained in a particularly high yield.

[0118] Ruthenium catalysts and iridium catalysts may contain ligands, such as bipyridine, 4,4'-di-tert-butylbipyridine, 4,7-dimethyl-1,10-phenanthroline, and 3,4,7,8-tetramethyl-1,10-phenanthroline.

[0119] An example of a ruthenium catalyst is tris(2,2'-bipyridine)ruthenium(II) hexafluorophosphate (Ru(bpy) ３ (PF ６ ) ２ Examples include (4,4'-di-tert-butyl-2,2'-bipyridine)bis[(2-pyridinyl)phenyl]iridium(III) hexafluorophosphate, tris(1,10-phenanthroline)ruthenium(II) bis(hexafluorophosphate), and tris(1,10-phenanthroline)ruthenium(II) dichloride monohydrate.

[0120] Examples of iridium catalysts 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.

[0121] In step 1, the amount of the redox catalyst used is not particularly limited, and is, for example, 0.1 to 20 mol%, preferably 0.3 to 15 mol%, and more preferably 0.5 to 10 mol%, relative to the N-fluoroalkoxy compound used in step 1.

[0122] In step 1, one or more oxidation-reduction catalysts can be used.

[0123] (Nucleophile) A nucleophile is used in the reaction carried out in step 1. The type of such nucleophile is not particularly limited, and for example, a wide range of known nucleophiles can be used.

[0124] The nucleophile is preferably a compound having a lone pair of electrons. In this case, the reaction in step 1 proceeds more easily, and the target product can be obtained in a higher yield. From this viewpoint, examples of the nucleophile include compounds having an N atom, compounds having an OH group, compounds having S, compounds containing an alkoxy, and ammonium halide salts.

[0125] As for compounds containing an N atom, R ７ -C≡N(R ７This is an alkyl group which may have substituents. Such substituents and alkyl groups are as defined above. Examples include nitrile compounds represented by the above definition, pyridine compounds such as pyridine, 2,6-di-tert-butylpyridine, 4-acetylpyridine, N,N-dimethylaminopyridine, and 2-cyanopyridine; nitrogen-containing aromatic compounds such as N-methylimidazole, pyrimidine, 2-methylpyrazine, 3-methylpyridazine, and 1,10-phenanthroline; N-oxide compounds such as 4-methoxypyridine-N-oxide; aliphatic amine compounds such as triethylamine and 1,4-diazabicyclo[2.2.2]octane; and ammonium salts such as N-alkyl-substituted ammonium salts. The alkyl group of N-alkyl-substituted ammonium salts such as tetrabutylammonium salt has 1 to 20 or fewer carbon atoms, preferably 2 to 10, more preferably 3 to 8, and examples of salts include halogen ions such as fluoride ions and bromide ions.

[0126] Examples of compounds containing an OH group include water, as well as alcohol compounds such as methanol and ethanol.

[0127] Examples of compounds containing alkoxy include methanol, ethanol, isopropyl alcohol, and butyl alcohol.

[0128] Examples of halogen-containing compounds include tetrabutylammonium bromide, tetraethylammonium bromide, tetraethylammonium bromide, tetraethylammonium iodide, and tetraethylammonium chloride.

[0129] Typical nucleophiles include acetonitrile (R ７ Examples include nitrile compounds in which the methyl group is present, water, methanol, tetrabutylammonium bromide, and tetrabutylammonium fluoride.

[0130] If the alkene is a compound that does not have an aryl group, it is preferable to use a nitrile compound such as acetonitrile as the nucleophile. Also, if the alkene is a compound that has an aryl group but does not have an alkenyl group, it is preferable to use a nitrile compound such as acetonitrile as the nucleophile. If the alkene is a compound that has both an aryl group and an alkenyl group, the nucleophile can be a wide range of compounds having an N atom and compounds having an OH group as described above.

[0131] The nucleophile used in step 1 may be one or more types.

[0132] In step 1, the amount of nucleophile used is not particularly limited, and is, for example, 0.1 to 10 equivalents, preferably 0.5 to 7 equivalents, relative to the N-fluoroalkoxy compound used in step 1.

[0133] (Step 1) In Step 1, an alkene is reacted with an N-fluoroalkoxy compound in the presence of the aforementioned redox catalyst and nucleophile to obtain a fluoroether.

[0134] In the manufacturing method of this disclosure, it is preferable to carry out the reaction by irradiating with an active energy ray in step 1. That is, the reaction between the alkene and the N-fluoroalkoxy compound can be carried out by irradiating with active energy. In this case, the reaction between the alkene and the N-fluoroalkoxy compound proceeds easily, and step 1 can be carried out simply. Examples of active energy rays include ultraviolet rays, electron beams, visible light, X-rays, and ion beams, among which ultraviolet rays, electron beams, or visible light are preferred from the viewpoint of versatility, and ultraviolet rays and visible light are particularly preferred. Examples of light sources for ultraviolet rays and visible light can be used, such as blue LEDs, ultraviolet LEDs, chemical lamps, high-pressure mercury lamps, low-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arcs, xenon arcs, electrodeless ultraviolet lamps, etc.

[0135] In the manufacturing method of this disclosure, it is also preferable to add an inorganic salt or an organic acid to step 1 and carry out the reaction. That is, the reaction between the alkene and the N-fluoroalkoxy compound can be carried out in the presence of an inorganic salt or an organic acid. In this case, the reaction between the alkene and the N-fluoroalkoxy compound proceeds more easily, and step 1 can be carried out simply.

[0136] The type of inorganic salt is not particularly limited and includes, for example, carbonates, bicarbonates, phosphates, acetates, nitrates, sulfates, and borates. The type of salt in phosphates is also not particularly limited and includes, for example, alkali metals such as sodium, as well as alkaline earth metals and ammonium salts. Other examples of inorganic salts include metal salts such as copper(II) chloride, copper(II) bromide, copper(II) iodide, zinc chloride, nickel chloride, silver chloride, and gold chloride.

[0137] The type of organic acid is not particularly limited, and examples include bis(trifluoromethanesulfonyl)imide, p-toluenesulfonic acid, trifluoromethanesulfonic acid, methanesulfonic acid, benzenesulfonic acid, trifluoroacetic acid, and the like.

[0138] When using an inorganic salt or organic acid in step 1, the amount used is not particularly limited. For example, the amount of inorganic salt used can be 0.1 equivalents or more and 5 equivalents or less relative to the N-fluoroalkoxy compound, and is preferably 0.1 to 10 equivalents, and more preferably 0.5 to 5 equivalents. Similarly, the amount of organic salt used can be 0.1 equivalents or more and 5 equivalents or less relative to the N-fluoroalkoxy compound, and is preferably 0.1 to 10 equivalents, and more preferably 0.5 to 5 equivalents.

[0139] In step 1, the reaction can be carried out in the presence of an organic solvent. The type of organic solvent is not particularly limited and includes, for example, 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 organic 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.

[0140] When an organic solvent is used in step 1, the amount used is not particularly limited. For example, the amount of organic solvent used can be 0.1 to 100 mL per 1 mmol of N-hydroxy compound, preferably 0.2 to 20 mL, and more preferably 0.25 to 12.5 mL.

[0141] In step 1, the reaction method is not particularly limited. For example, the reaction can be carried out by placing the N-hydroxy compound and alkene, the nucleophile and redox catalyst, and, if necessary, an inorganic salt, organic salt solvent, organic solvent, etc., into a suitable reaction vessel and irradiating it with active energy rays. The reaction can be carried out under an inert gas atmosphere such as nitrogen or argon, if necessary.

[0142] The reaction temperature is not particularly limited and can be selected from, for example, a range of -20 to 100°C. The reaction time (or irradiation time if active energy rays are irradiated) can be set appropriately according to the reaction temperature, for example, within a range of 1 minute to 48 hours, preferably within a range of 3 minutes to 24 hours, and more preferably within a range of 5 minutes to 12 hours.

[0143] The above reaction yields a product containing the fluoroether represented by formula (10). In formula (10), Y is a monovalent group based on the nucleophile (i.e., a group derived from the nucleophile). For example, Y is -NH(C=O)-R ７ (R ７ R is an alkyl group (which may have substituents), an alkoxy group, a halogen atom (Cl, Br, I), or a hydroxyl group. ７ In (an alkyl group which may have substituents), the substituents and alkyl groups are as defined above. ７ For example, a methyl group is one such group.

[0144] In the reaction of step 1, in addition to the fluoroether represented by formula (10), other fluoroethers may also be produced. For example, a compound obtained by removing one carbon atom from the fluoroether represented by formula (10) may be produced in the reaction of step 1. Specifically, in formula (10), R ｆ１ or R ｆ２ One of them is C ｎ F ２ｎ＋１ And, if the other is fluorine, R ｆ１ or R ｆ２ One of them is C ｎ－１ F ２ｎ＋１ A fluoroether a is produced. However, if n is 1, the fluoroether a is not produced, and preferably when n is 2 or more, and more preferably when n is 3 or more, the fluoroether a is produced.

[0145] The product obtained in step 1 can be subjected to appropriate methods to remove solvents and other substances, thereby obtaining a product containing fluoroether, for example, as a solid. The solid thus collected can then be purified, dried, or otherwise processed using appropriate methods to obtain the target fluoroether with high purity.

[0146] The method for producing a fluoroether according to this disclosure may consist only of step 1, or it may include other steps besides step 1.

[0147] According to the method for producing fluoroethers of this disclosure, various fluoroethers having different structures can be easily produced by appropriately selecting the type of alkene and / or N-fluoroalkoxy compound. In particular, the method for producing fluoroethers of this disclosure selects alkene and / or N-fluoroalkoxy compounds that have not been used conventionally, thereby enabling the production of novel fluoroethers.

[0148] The fluoroethers obtained by the manufacturing method of this disclosure can be suitably used as solvents, refrigerants, pharmaceuticals and agrochemicals, functional materials, etc., and can be widely applied to various uses.

[0149] 2. Fluoroether

[0150] This disclosure includes compounds (fluoroether compounds) represented by the following general formula (3).

[0151]

[0152] In formula (3), R ５ R is an aromatic ring which may have one or more substituents, or R ８ -CH = CH - (R ８ R represents an aromatic ring which may have one or more substituents. ｆ３ R represents a perfluoroalkyl group having 1 to 6 carbon atoms. ６ Y represents a hydrogen atom or a fluorine atom. １ is -NH(C=O)-R ７ (R ７This represents an alkyl group (which may have substituents), an alkoxy group, a halogen atom (Cl, Br, I), or a hydroxyl group.

[0153] However, among the compounds represented by formula (3), R ５ C ６ H ５ , Y １ OH, R ６ F, R ｆ３ C ２ F ５ The compound is R ５ C ６ H ５ , Y １ OH, R ６ F, R ｆ３ ga CF ３ Compounds that are [specifically] shall be excluded.

[0154] In formula (3), R ５ and R ８ (An aromatic ring which may have one or more substituents) is, for example, an aryl group (R) which may have substituents in formula (1) above. １ or R ２ This is equivalent to ). In equation (3), R ７ In (an alkyl group which may have substituents), the substituents and alkyl groups are as defined above. ７ For example, a methyl group is one such group.

[0155] This disclosure includes compounds (fluoroether compounds) represented by the following general formula (4).

[0156]

[0157] In formula (4), Y ２ is -NH(C=O)-R ９ (R ９ R represents an alkyl group which may have substituents), bromine, or iodine. ｆ４ This represents a perfluoroalkyl group having 1 to 6 carbon atoms.

[0158] In formula (4), R ９ In (an alkyl group which may have substituents), the substituents and alkyl groups are as defined above.９ For example, a methyl group is one such group.

[0159] The fluoroether represented by formula (3) and the fluoroether represented by formula (4) can be obtained by the manufacturing method of the present disclosure described above. That is, the fluoroether represented by formula (3) and the fluoroether represented by formula (4) can be produced by selecting the corresponding alkene and utilizing step 1.

[0160] 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.

[0161] 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.

[0162] (Production Example 1) An N-fluoroalkoxy compound (benzotriazole salt) was synthesized by the following procedure. First, CF ３ SO ２ Na and a 1-hydroxybenzotriazole derivative (in formula (2'-1), R ９ NO ２ , R １０ is hydrogen, R １１ ga CF ３ , R １２ A compound in which hydrogen is present, ammonium hexanitratocerium(IV)ate (hereinafter abbreviated as CAN) as an inorganic oxidizing agent, and a mixed solvent of acetonitrile and water (acetonitrile:water = 4:1, v / v) were charged into the reactor. The reaction was carried out by stirring the reactor for 10 minutes while maintaining the reactor at room temperature (25°C) (step a). In this reaction, CF ３ SO ２ Molar ratio of Na to 1-hydroxybenzotriazole derivative (CF ３ SO ２ The ratio of Na (1-hydroxybenzotriazole derivative) to the solvent is 1:1.5, and 4 equivalents of the inorganic oxidizing agent are used. ３ SO ２The concentration of Na and the 1-hydroxybenzotriazole derivative was set to 0.1 M. The reaction in step a yielded the benzotriazole derivative (in formula (2a), R ９ NO ２ , R １０ is hydrogen, R １１ ga CF ３ , R １２ is hydrogen, Rf is CF ３ The compound (which is...) was obtained in a yield of 71%. １ 1H NMR and １９ The results of the F NMR were as follows: 1 H NMR (300 MHz, CDCl3)δ8.61 (s, 1H), 8.31 (s, 1H). 1 H NMR (300 MHz, CDCl3)δ-62.6 (s, 3F), -64.7 (s, 3F).

[0163] The benzotriazole derivative obtained as described above was reacted with methyl trifluoromethanesulfonate as an alkylating agent (methylating agent) in n-hexane at 50°C for 48 hours. In this reaction, the molar ratio of the benzotriazole derivative to the alkylating agent (N-fluoroalkoxy compound:alkylating agent) was 1:3, and the concentration of the starting materials (N-fluoroalkoxy compound and alkylating agent) relative to the solvent was 0.5 M. As a result of this reaction, the benzotriazole salt (in formula (2b), R ９ NO ２ , R １０ is hydrogen, R １１ ga CF ３ , R １２ is hydrogen, R １３ A compound in which Rf is a methyl group, Rf is a fluoromethyl group, and X is an OTf group was obtained in a yield of 91%. １ 1H NMR and １９ The results of the F NMR were as follows: 1 H NMR (300 MHz, CD3CN) δ 9.06 (s, 1F), 9.02 (s, 1F), 4.92 (s, 3F). 19F NMR (282 MHz, CD3CN) δ -60.9 (s, 3F), -77.2 (s, 3F), -80.8 (t, J = 2.0 Hz, 3F), -87.7 (d, J = 2.0 Hz, 2F).

[0164] (Production example 2) CF ３ SO ２ Instead of Na, C ２ F ５ SO ２ Except for the use of Na, the product was manufactured in the same manner as in Manufacturing Example 1 (step a), and the benzotriazole derivative (in formula (2a), R ９ NO ２ , R １０ is hydrogen, R １１ ga CF ３ , R １２ is hydrogen, Rf is C ２ F ５ A compound (which is R) was obtained in a yield of 51%. Using this benzotriazole derivative, a benzotriazole salt (in formula (2b), R) was prepared in the same manner as in Production Example 1 (step b). ９ NO ２ , R １０ is hydrogen, R １１ ga CF ３ , R １２ is hydrogen, R １３ Rf is a methyl group, and Rf is a fluoroethyl group (C ２ F ５ Compounds (where X is an OTf group) were obtained in 89% yield.

[0165] (Production example 3) CF ３ SO ２ Instead of Na, C ６ F １３ SO ２ Except for the use of Na, the product was manufactured in the same manner as in Manufacturing Example 1 (step a), and the benzotriazole derivative (in formula (2a), R ９ NO ２ , R １０ is hydrogen, R １１ ga CF ３ , R １２ is hydrogen, Rf is C ６ F １３A compound (which is R) was obtained in a yield of 58%. Using this benzotriazole derivative, a benzotriazole salt (in formula (2b), R) was obtained in the same manner as in Production Example 1 (step b). ９ NO ２ , R １０ is hydrogen, R １１ ga CF ３ , R １２ is hydrogen, R １３ Rf is a methyl group, and Rf is C ６ F １３ A compound (where X is an OTf group) was obtained in 83% yield.

[0166] (Example 1a) A fluoroether was prepared according to the reaction scheme shown in Figure 1. One equivalent of the N-fluoroalkoxy compound (benzotriazole salt) obtained in Production Example 1, five equivalents of 4-chlorostyrene, and tris(2,2'-bipyridine)ruthenium(II) hexafluorophosphate (Ru(bpy) ３ (PF ６ ) ２ Step 1 involved charging a reaction vessel with 0.5 mol% of the N-fluoroalkoxy compound, 1 equivalent of water, and dry acetonitrile as a nucleophile and organic solvent, and irradiating it with an active energy beam (blue LED (45W)) at room temperature (25°C) for 1 hour. This yielded the compound shown in Figure 1(a) in a yield of 39%.

[0167] (Example 1b) 1 equivalent of the N-fluoroalkoxy compound (benzotriazole salt) obtained in Production Example 1, 5 equivalents of 4-chlorostyrene, and tris(2,2'-bipyridine)ruthenium(II) hexafluorophosphate (Ru(bpy) ３ (PF ６ ) ２ Step 1 involved charging a reaction vessel with 0.5 mol% of the N-fluoroalkoxy compound, 5 equivalents of methanol as a nucleophile, 1 equivalent of sodium phosphate as an inorganic salt, and dry acetone as an organic solvent. The vessel was then irradiated with an active energy beam (blue LED (45W)) at room temperature (25°C) for 1 hour. This yielded the compound shown in Figure 1(b) in a yield of 39%.

[0168] (Example 1c) 1 equivalent of the N-fluoroalkoxy compound (benzotriazole salt) obtained in Production Example 1, 5 equivalents of 4-chlorostyrene, and tris(2,2'-bipyridine)ruthenium(II) hexafluorophosphate (Ru(bpy) ３ (PF ６ ) ２ Step 1 involved charging a reaction vessel with 0.5 mol% of the N-fluoroalkoxy compound, 5 equivalents of tetrabutylammonium bromide (TBAB) as a nucleophile, and dry acetone as an organic solvent. The vessel was then irradiated with an active energy beam (blue LED (45W)) at room temperature (25°C) for 1 hour. This yielded the compound shown in Figure 1(c) in a yield of 47%.

[0169] (Example 1d) 1 equivalent of the N-fluoroalkoxy compound (benzotriazole salt) obtained in Production Example 1, 5 equivalents of 4-chlorostyrene, and tris(2,2'-bipyridine)ruthenium(II) hexafluorophosphate (Ru(bpy) ３ (PF ６ ) ２ ) is added in a 0.5 mol% ratio relative to the N-fluoroalkoxy compound, and tetrabutylammonium fluoride trihydrate (TBAF·3H) is added as a nucleophile. ２ O) Five equivalents of dry acetone as an organic solvent were placed in a reaction vessel, and the vessel was irradiated with active energy rays (blue LED (45W)) at room temperature (25°C) for 1 hour (Step 1). This yielded the compound shown in Figure 1(d) in a yield of 30%.

[0170] Figure 1 shows the reaction scheme, products, and yields carried out in Examples 1a, 1b, 1c, and 1d.

[0171] (Example 2) Each of the fluoroethers shown in Figure 2 was prepared (i.e., 27 different reactions were carried out to produce each fluoroether). Specifically, 1 equivalent of the N-fluoroalkoxy compound (benzotriazole salt) obtained in Production Example 1, 5 equivalents of a predetermined alkene, 2 equivalents of bis(trifluoromethanesulfonyl)imide as an organic acid, and tris(2,2'-bipyridine)ruthenium(II) hexafluorophosphate (Ru(bpy) ３ (PF６ ) ２ Step 1 involved charging a reaction vessel with 1 mol% of ) relative to the N-fluoroalkoxy compound, acetonitrile (0.1 M relative to the N-fluoroalkoxy compound) as a nucleophile, and 1 equivalent of water. The reaction was then irradiated with an active energy beam (blue LED (45W)) at room temperature (25°C) for 1 hour under a nitrogen atmosphere. This yielded each of the compounds shown in Figure 2 (19 types, 3aF to 3rF and 3uF) in the yields indicated in Figure 2. Furthermore, by changing the nucleophile from Step 1 to propanenitrile and deuterated acetonitrile, 3sF and 3tF were obtained in the yields indicated in Figure 2. Additionally, compounds 3aH to 3kH were obtained in the yields indicated in Figure 2 by following the procedure from Step 1, excluding the addition of bis(trifluoromethanesulfonyl)imide. The alkenes used in each reaction were as follows.

[0172] Figure 2 shows the reaction schemes, products, and yields for each reaction carried out in Example 2, while Figure 3 shows the starting materials. For example, "2aF" in Figure 3 is the starting material for obtaining "3aF" in Figure 2; that is, compounds whose two-letter alphabetical characters match in Figures 2 and 3 correspond to starting materials and products.

[0173] (Example 3) Each of the fluoroethers shown in Figure 4 was prepared (i.e., three different reactions were carried out to produce each fluoroether). Specifically, 1 equivalent of the N-fluoroalkoxy compound (benzotriazole salt) obtained in Production Example 1, 5 equivalents of a predetermined alkene, and tris(2,2'-bipyridine)ruthenium(II) hexafluorophosphate (Ru(bpy) ３ (PF ６ ) ２Step 1 involved charging a reaction vessel with 1 mol% of ) relative to the N-fluoroalkoxy compound, 1 equivalent of water as a nucleophile, and 0.1 M of acetone relative to the N-fluoroalkoxy compound as an organic solvent. The reaction vessel was then irradiated with an active energy beam (blue LED (45W)) at room temperature (25°C) for 1 hour under a nitrogen atmosphere. This yielded the compounds shown in Figure 4 (two types: 4aF and 4gF) in the yields indicated in Figure 4. Furthermore, by adding 1 equivalent of sodium phosphate to the conditions of Step 1, 4jH, shown in Figure 4, was obtained in the yield indicated in Figure 4. The alkenes used in each reaction were 2aF, 2gF, and 2jH, shown in Figure 3.

[0174] (Example 4a) A fluoroether was prepared according to the reaction scheme shown in Figure 5. One equivalent (0.05 mmol) of the N-fluoroalkoxy compound (benzotriazole salt) obtained in Production Example 1, five equivalents of 4-chlorostyrene, and tris(2,2'-bipyridine)ruthenium(II) hexafluorophosphate (Ru(bpy) ３ (PF ６ ) ２ Step 1 involved charging a reaction vessel with 1 mol% of the N-fluoroalkoxy compound, 1 equivalent of sodium phosphate as an inorganic salt, 1 equivalent of water, and 0.5 mL of acetone (0.1 M relative to the N-fluoroalkoxy compound) as an organic solvent, and irradiating it with an active energy beam (blue LED (45 W)) at room temperature (25°C) for 1 hour. This yielded the compounds shown in Figure 5(a) and / or (b).

[0175] (Example 4b) The compounds shown in Figure 5(a) and / or (b) were obtained in the same manner as in Example 4a, except that the N-fluoroalkoxy compound obtained in Production Example 2 was used instead of the N-fluoroalkoxy compound obtained in Production Example 1.

[0176] (Example 4c) The compound shown in Figure 5(a) and / or (b) was obtained in the same manner as in Example 4a, except that the N-fluoroalkoxy compound obtained in Production Example 3 was used instead of the N-fluoroalkoxy compound obtained in Production Example 1.

[0177] (Example 4d) The compound shown in Figure 5(a) and / or (b) was obtained in the same manner as in Example 4b, except that the amount of acetone used was changed to 0.05 mL (1 M relative to the N-fluoroalkoxy compound).

[0178] (Example 4e) The compound shown in Figure 5(a) and / or (b) was obtained in the same manner as in Example 4c, except that the amount of acetone used was changed to 0.05 mL (1 M relative to the N-fluoroalkoxy compound).

[0179] Table 1 shows the yields of the fluoroethers obtained in Examples 4a to 4e (compounds (a) and (b) in Figure 5).

[0180]

[0181] (Example 5) A fluoroether was prepared according to the reaction scheme shown in Figure 6. One equivalent (0.3 mmol) of the N-fluoroalkoxy compound (benzotriazole salt) obtained in Production Example 1, five equivalents of the difluoroalkene 2vF shown in Figure 6, two equivalents of bis(trifluoromethanesulfonyl)imide, and tris(2,2'-bipyridine)ruthenium(II) hexafluorophosphate (Ru(bpy) ３ (PF ６ ) ２ Step 1 involved charging a reaction vessel with 1 mol% of the N-fluoroalkoxy compound and 0.1 M acetonitrile and 1 equivalent of water as nucleophiles relative to the N-fluoroalkoxy compound, and irradiating it with an active energy beam (blue LED (45W)) at room temperature (25°C) for 1 hour under a nitrogen atmosphere. This produced compound 3vF shown in Figure 6. １９ F was obtained with an NMR yield of 40%.

[0182] (Example 6) A fluoroether was prepared according to the reaction scheme shown in Figure 7. One equivalent (0.05 mmol) of the N-fluoroalkoxy compound (benzotriazole salt) obtained in Production Example 2, five equivalents of 1-octene (2wH in Figure 7), and tris(2,2'-bipyridine)ruthenium(II) hexafluorophosphate (Ru(bpy) ３ (PF ６ )２ Step 1 involved charging a reaction vessel with 5 mol% of ) relative to the N-fluoroalkoxy compound, 20 mol% of copper(II) chloride relative to the N-fluoroalkoxy compound, and 0.1 M acetonitrile and 1 equivalent of water as nucleophiles relative to the N-fluoroalkoxy compound. The vessel was then irradiated with an active energy beam (blue LED (45W)) at room temperature (25°C) for 1 hour under a nitrogen atmosphere (Step 1). This resulted in the compound 3wF shown in Figure 7 being produced. １９ F was obtained with an NMR yield of 25%.

[0183] Example 7 (Example 7a) A fluoroether was prepared according to the reaction scheme shown in Figure 8. One equivalent (0.1 mmol) of the N-fluoroalkoxy compound (benzotriazole salt) obtained in Production Example 1, five equivalents of 4-chloro-β,β-difluorostyrene, and tris(2,2'-bipyridine)ruthenium(II) hexafluorophosphate (Ru(bpy) ３ (PF ６ ) ２ Step 1 involved charging a reaction vessel with 1 mol% of the N-fluoroalkoxy compound, 2 equivalents of bis(trifluoromethanesulfonyl)imide as an organic acid, and 0.1 M acetonitrile and 1 equivalent of water relative to the N-fluoroalkoxy compound as a nucleophile and organic solvent. The reaction vessel was then irradiated with an active energy beam (blue LED (45W)) at room temperature (25°C) for 1 hour under a nitrogen atmosphere. This yielded the compounds shown as 3aF and / or 4aF in Figure 8.

[0184] (Example 7b) The compound shown as 3aF and / or 4aF in Figure 8 was obtained in the same manner as in Example 7a, except that 2 equivalents of bis(trifluoromethanesulfonyl)imide were not added.

[0185] (Example 7c) The compound shown as 3aF and / or 4aF in Figure 8 was obtained in the same manner as in Example 7a, except that the N-fluoroalkoxy compound was changed to compound 1d shown in Figure 8 and 2 equivalents of bis(trifluoromethanesulfonyl)imide were not added.

[0186] (Example 7d) The compound shown as 3aF and / or 4aF in Figure 8 was obtained in the same manner as in Example 7a, except that bis(trifluoromethanesulfonyl)imide was replaced with trifluoromethanesulfonic acid.

[0187] (Example 7e) The compound shown as 3aF and / or 4aF in Figure 8 was obtained in the same manner as in Example 7a, except that the amount of 4-chloro-β,β-difluorostyrene added was changed to 1 equivalent.

[0188] (Example 7f) Tris(2,2'-bipyridine)ruthenium(II) hexafluorophosphate (Ru(bpy) ３ (PF ６ ) ２ ) to [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 The compounds shown as 3aF and / or 4aF in Figure 8 were obtained in the same manner as in Example 7a, except that iridium hexafluorophosphate was used instead.

[0189] (Example 7g) Tris(2,2'-bipyridine)ruthenium(II)hexafluorophosphate (Ru(bpy) ３ (PF ６ ) ２ The compound shown as 3aF and / or 4aF in Figure 8 was obtained in the same manner as in Example 7a, except that ) was changed to 1,2,3,5-tetrakis(carbazole-9-yl)-4,6-dicyanobenzene.

[0190] (Example 7h) The compound shown as 3aF and / or 4aF in Figure 8 was obtained in the same manner as in Example 7a, except that the amount of water added was changed to 50 equivalents.

[0191] (Example 7i) The compound shown as 3aF and / or 4aF in Figure 8 was obtained in the same manner as in Example 7a, except that the organic solvent was changed to acetone and 2 equivalents of bis(trifluoromethanesulfonyl)imide were not added.

[0192] (Comparative Example 1) Tris(2,2'-bipyridine)ruthenium(II)hexafluorophosphate (Ru(bpy) ３ (PF ６ ) ２ The compounds shown as 3aF and / or 4aF in Figure 8 were obtained in the same manner as in Example 7a, except that the additive () was not added.

Claims

1. The following general formula (1) CR １ R ２ =CX １ X ２ (1) (In formula (1), X １ and X ２ each independently represent a hydrogen atom or a halogen atom, and R １ and R ２ each independently represent a hydrogen atom, an aryl group optionally having a substituent, an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, an alkynyl group optionally having a substituent, a fluoroalkyl group optionally having a substituent, a halogen atom, or a group represented by R-(CH ２ ) ｎ - (where R represents an aryl group optionally having a substituent, and n is an integer of 3 or more)), and an alkene represented by the following general formula (2) (In formula (2), R ｆ１ and R ｆ２ each independently represent a fluorine atom or a fluoroalkyl group, R ３ represents a group containing an aryl group or an alkyl group optionally having a substituent, R ４ represents a group containing a -N=N- bond, and R[[ID=3i]] ３ and R ４ may be bonded to each other together with the nitrogen atom to which they are bonded to form a saturated or unsaturated ring)), and an N-fluoroalkoxy compound represented by the following general formula (10) (In formula (10), R １ , R ２ , X １ , X ２ , R ｆ１ , and R ｆ２ are as defined above, and Y represents a monovalent group based on the nucleophile.) A method for producing a fluoroether.

2. The method for producing a fluoroether according to claim 1, wherein the reaction is carried out by irradiating with an active energy ray in step 1.

3. The method for producing a fluoroether according to claim 1 or 2, wherein the oxidation-reduction catalyst is a metal catalyst.

4. The method for producing a fluoroether according to claim 1 or 2, wherein the oxidation-reduction catalyst is at least one selected from the group consisting of ruthenium catalysts and iridium catalysts.

5. A method for producing a fluoroether according to claim 1 or 2, wherein an inorganic salt or an organic acid is added to step 1 and the reaction is carried out.

6. The method for producing a fluoroether according to claim 1 or 2, wherein the N-fluoroalkoxy compound is a compound containing a nitrogen-containing heterocycle.

7. The method for producing a fluoroether according to claim 1 or 2, wherein the reaction in step 1 is carried out in the presence of an organic solvent.

8. The method for producing a fluoroether according to claim 1 or 2, wherein the nucleophile is a compound having a lone pair of electrons.

9. The following general formula (3) (In formula (3), R ５ R is an aromatic ring which may have one or more substituents, or R ８ -CH = CH - (R ８ R represents an aromatic ring which may have one or more substituents. ｆ３ R represents a perfluoroalkyl group having 1 to 6 carbon atoms. ６ Y represents a hydrogen atom or a fluorine atom. １ is -NH(C=O)-R ７ (R ７ R is represented by an alkyl group (which may have substituents), an alkoxy group, a halogen atom (Cl, Br, I), or a hydroxyl group, provided that among the compounds represented by formula (3), ５ C ６ H ５ , Y １ OH, R ６ F, R ｆ３ C ２ F ５ The compound is R ５ C ６ H ５ , Y １ OH, R ６ F, R ｆ３ ga CF ３ Fluoroether compounds, excluding those compounds.

10. The following general formula (4) (In formula (4), Y ２ is -NH(C=O)-R ９ (R ９ R represents an alkyl group which may have substituents), bromine, or iodine. ｆ４ A fluoroether compound represented by (where represents a perfluoroalkyl group having 1 to 6 carbon atoms).

Images