WO2021060276A1

WO2021060276A1 - Fluorinating agent and method for producing fluorine-containing compounds

Info

Publication number: WO2021060276A1
Application number: PCT/JP2020/035800
Authority: WO
Inventors: 岡添　隆; 雄一郎石橋; 京子野崎; 光介相川; 晶哉足立
Original assignee: Ａｇｃ株式会社; 国立大学法人東京大学
Priority date: 2019-09-24
Filing date: 2020-09-23
Publication date: 2021-04-01
Also published as: JPWO2021060276A1

Abstract

Provided, inter alia, is a fluorinating agent that can selectively produce a monofluorination product through preferential synthesis of the monofluorination product over a difluorination product, in a fluorination reaction in which a fluorine atom is introduced onto a carbon atom, of the carbon atoms constituting the C=C bond in a silyl enol ether compound, other than a carbon atom bonded to a silyl ether group. Also provided is a method for producing a fluorine-containing compound using this fluorinating agent.　The compound is represented by the following general formula (A1) (in the formula, R¹ is a possibly substituted C_6-14 aryl group and R² is a possibly substituted C_1-30 alkyl group (possibly having from 1-5 oxygen atoms in ether linkages between carbon atoms) or a possibly substituted aromatic group).

Description

Method for producing fluorinating agent and fluorine-containing compound

The present invention relates to a fluorinating agent that introduces a fluorine atom into an organic compound, and a method for producing a fluorine-containing compound obtained by using the fluorinating agent.

Fluorine atom has high electronegativity and is as small as hydrogen atom. Due to this feature, fluorine atoms can be stably bonded to many atoms, and organic compounds into which fluorine has been introduced tend to have improved heat resistance, chemical resistance, light resistance, water resistance, etc. than before the introduction. It is in. In particular, the carbon-fluorine bond has a short bond length, is rigid, and has a low polarizability. Due to this characteristic of the carbon-fluorine bond, the organic compound into which the carbon-fluorine bond is introduced has a reduced reactivity and an improved stability as a compound. Since useful organic compounds can be synthesized by fluorinating organic compounds, various fluorinating agents have been developed.

Examples of the fluorinating agent include N-fluorobenzenesulfonimide (NFSI). It has been reported that NFSI can introduce a fluorine atom into a carbon atom adjacent to a carbonyl group (Non-Patent Documents 1 and 2). When NFSI is used, not only a monofluorinated product in which one fluorine atom is introduced into a carbon atom adjacent to a carbonyl group but also a difluorinated product in which two fluorine atoms are introduced is synthesized. Therefore, the selectivity of the monofluorinated product is insufficient.

In addition, among the carbon atoms constituting the C = C bond of the silyl enol ether compound, N-fluoro-o is a fluorinating agent that introduces a fluorine atom into a carbon atom different from the carbon atom to which the silyl ether group is bonded. -Benzenedisulfonimide (NFOBS) (Non-Patent Document 3) and iodotoluene difluoride (ITDF) (Non-Patent Document 4) have been reported. However, NFOBS the raw material is difficult to obtain, also, it is necessary to use a CFCl ₃ is a CFC as a solvent during the feed synthesis, when the solvent using CHCl ₃ instead CFCl ₃ a is CFCl ₃ Is generated.

The present invention is used in a fluorination reaction in which a fluorine atom is introduced into a carbon atom different from the carbon atom to which the silyl ether group is bonded among the carbon atoms constituting the C = C bond with respect to the silyl enol ether compound. Provided are a fluorinating agent capable of selectively producing a monofluorinated product by synthesizing an atomized product with priority over a difluorinated product, and a method for producing a fluorine-containing compound using the fluorinated agent. The purpose is.

When a fluorinated amine compound protected with a carbonyl group or an oxycarbonyl group and an arylsulfonyl group is used as a fluorinating agent, the present inventors constitute a C = C bond of the silylenol ether compound. We found that a monofluorinated compound in which only one fluorine atom was introduced into the carbon atom of the above was more selectively produced than a difluorinated compound in which two fluorine atoms were introduced into the carbon atom. Completed the invention.

That is, the present invention is as follows.
[1] A compound represented by the following general formula (A1).

However, the group in the formula means the following.
R ¹ _{is a C 6-14} aryl group which may have a substituent and is a C 6-14 aryl group.
R ² _{has a C 1-30} alkyl group which may have a substituent (may have 1 to 5 ether-bonding oxygen atoms between carbon atoms) or a substituent. It is an aromatic group that may be present.

[2] R ¹ is a phenyl group which may have 1 to 3 substituents, and is a phenyl group.
R ² may have a C _1-10 alkyl group which may _{have a substituent, a C 6-14} aryl group which may have a substituent, or a nitrogen-containing heteroaryl which may have a substituent. The compound of the above [1], which is a group.
[3] R ¹ contains 1 to 3 substituents selected from the group consisting of C _1-6 alkyl group, C _1-6 alkyl group, C _{1-6 alkoxy group, halogen atom, and trihalomethyl group.} It is a phenyl group that may have
R ² may have a substituent C _1-6 alkyl group, may have a substituent C _1-10 alkoxy group, or may have a substituent C _6-14 aryl The compound of the above [1], which is a group.
[4] A fluorinating agent containing any of the compounds [1] to [3] as an active ingredient.

[5] Using a fluorinating agent containing any of the compounds [1] to [3] as an active ingredient, one fluorine atom is introduced into a substrate compound represented by the following general formula (A2). , A method for producing a fluorine-containing compound, which comprises producing a fluorine-containing compound represented by the following general formula (A3) or (A4).

However, the group in each formula means the following.
R ²¹ , R ²² and R ²³ are independently C _1-4 alkyl groups; R ²⁴ _{is a C 1-30} aliphatic hydrocarbon group which may have a hydrogen atom and a substituent. (It may have 1 to 5 ether-bonding oxygen atoms between carbon atoms), it may have a substituent, it may have a C _1-30 alkoxy group, or it may have a substituent. A good aromatic group; R ²⁵ _{is a C 1-30} aliphatic hydrocarbon group which may have a hydrogen atom, a substituent (having 1-5 ether-bonded oxygen atoms between carbon atoms). Or an aromatic group that may have a substituent; R ²⁴ and R ²⁵ may be linked to each other to form a ring.

[6] R ²⁴ and R ²⁵ are linked to each other to form a ring which may have a substituent, and the rings are an inden ring, an indan ring, a dihydronaphthalene ring, a dihydrobenzoannelene ring, and a chromane ring. , Chroman ring, isochromen ring, dihydrothiophene ring, benzothiophene ring, dihydrobenzothiophene ring, thiopyran ring, dihydrothiopyran ring, benzothiopyran ring, and dihydrobenzothiopyran ring. ]. The method for producing a fluorine-containing compound.
[7] R ²⁴ and R ²⁵ independently have a C _1-30 alkyl group which may have a _{substituent, a C 6-14} aryl group which may have a substituent, and a substituent. The method for producing a fluorine-containing compound according to the above [5], which is one selected from the group consisting of nitrogen-containing heteroaryl groups which may have.
[8] The method for producing a fluorine-containing compound according to the above [5], wherein ^{R 24} _{is a C 1-30} alkoxy group which may have a substituent.
[9] The method for producing a fluorine-containing compound according to any one of [5] to [8], wherein a fluorine atom is introduced into the substrate compound at a temperature of 100 ° C. or lower.

Similar to NFSI, the compound according to the present invention can introduce a fluorine atom into a wide range of substrates having unsaturated bonds. In particular, in the fluorination reaction of a silyl enol ether compound, the compound can be produced by preferentially synthesizing a monofluorinated product over a difluorinated product to selectively produce a monofluorinated product. Therefore, the compound is very useful as a fluorinating agent for synthesizing a monofluorinated compound.

In the present invention and the present specification, "C _p1-p2 " (p1 and p2 are positive integers satisfying p1 <p2) means that the group has p1 to p2 carbon atoms.

In the present invention and the specification of the present application, the "ether-bonded oxygen atom" is an oxygen atom that connects carbon atoms, and does not include an oxygen atom in which oxygen atoms are connected in series. An alkyl group having Nc carbon atoms (Nc is an integer of 2 or more) can have a maximum of Nc-1 ether-bonding oxygen atoms.

In the present invention and the present specification, the "C _6-14 aryl group" is an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a C _6-12 aryl group is particularly preferable. Examples of the C _6-14 aryl group include a phenyl group, a naphthyl group, an anthryl group, a 9-fluorenyl group and the like, and a phenyl group is particularly preferable.

In the present invention and the present specification, the "C _6-14 aryl group having a substituent" is one or more hydrogen atoms bonded to the carbon atom of the _{C 6-14 aryl group, preferably one.} ~ 3 are groups substituted with other functional groups. When having two or more substituents, the substituents may be the same kind or different from each other. Examples of the substituent include a C _1-6 alkyl group, a C _1-6 alkoxy group, a methylenedioxy group (-O-CH _2- O-), a halogen atom (fluorine atom, chlorine atom, bromine atom, or iodine atom). ), Trihalomethyl group, cyano group, nitro group and the like. _{Examples of "C 6-14} aryl groups that may have a substituent" include a phenyl group, a naphthyl group, an anthryl group, a 2-methylphenyl group, a 4-methylphenyl group, and a 3,5-dimethylphenyl group. , 2,6-dimethylphenyl group, 2,4-dimethylphenyl group, 2-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3,5-di (trifluoromethyl) phenyl group, 2,6- Di (trifluoromethyl) phenyl group, 2,4-di (trifluoromethyl) phenyl group, 2-methoxyphenyl group, 4-methoxyphenyl group, 2,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, Examples thereof include 3-chlorophenyl group, 4-cyanophenyl group, 4-nitrophenyl group, 1,3-benzodioxol-5-yl group and the like.

In the present invention and the present specification, the "heteroaryl group" is a cyclic group having aromaticity, and the ring is a group composed of a carbon atom and an atom other than the carbon atom. The heteroaryl group may be a group containing a nitrogen atom (nitrogen-containing heteroaryl group), a group containing an oxygen atom (oxygen-containing heteroaryl group), or a group containing a sulfur atom (sulfur-containing heteroaryl group). It may be a heteroaryl group). Further, the number of atoms other than the carbon atom constituting the aromatic ring may be two or more. Examples of the heteroaryl group include a pyrrolyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isooxazolyl group, a thiazolyl group, an isothiazolyl group, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a furanyl group, a pyranyl group and a thienyl group. Can be mentioned.

In the present invention and the present specification, the "heteroaryl group having a substituent" is one or more hydrogen atoms bonded to an atom constituting the aromatic ring of the heteroaryl group, preferably 1 to 3. The individual is a group substituted with another functional group. When having two or more substituents, the substituents may be the same kind or different from each other. Examples of the substituent include a C _1-6 alkyl group, a C _1-6 alkoxy group, a methylenedioxy group (-O-CH _2- O-), a halogen atom (fluorine atom, chlorine atom, bromine atom, or iodine atom). ), Trihalomethyl group, cyano group, nitro group and the like.

In the present invention and the present specification, the "aromatic group" is an aryl group (aromatic hydrocarbon group) which may have a substituent and a heteroaryl group (heterocycle) which may have a substituent. Includes both formulas).

In the present invention and the present specification, the "C _1-30 alkyl group" is an alkyl group having 1 to 30 carbon atoms, and may be a straight chain or a branched chain. The "C _2-30 alkyl group" is an alkyl group having 2 to 30 carbon atoms, and may be a straight chain or a branched chain. Examples of C _1-30 alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert- Pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecil group, eicosyl group, heneicosyl group. , Docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group and the like.

In the present invention and the present specification, the "C _1-10 alkyl group" is an alkyl group having 1 to 10 carbon atoms, and may be a straight chain or a branched chain. The "C _2-10 alkyl group" is an alkyl group having 2 to 10 carbon atoms, and may be a straight chain or a branched chain. Examples of C _1-10 alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert- Examples thereof include a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group.

In the present invention and the present specification, the "C _1-6 alkyl group" is an alkyl group having 1 to 6 carbon atoms, and may be a straight chain or a branched chain. Examples of C _1-6 alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert- Examples include a pentyl group and a hexyl group.

In the present invention and the present specification, the "C _1-4 alkyl group" is an alkyl group having 1 to 4 carbon atoms, and may be a straight chain or a branched chain. Examples of the C _1-4 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

In the present invention and the present specification, the "C _1-3 alkyl group" is an alkyl group having 1 to 3 carbon atoms, and may be a straight chain or a branched chain. Examples of the C _1-3 alkyl group include a methyl group, an ethyl group, a propyl group and an isopropyl group.

In the present invention and the present specification, the "C _p1-p2 alkyl group having a substituent" refers to one or more hydrogen atoms bonded to the carbon atom of _{the C p1-p2 alkyl group, preferably one.} ~ 3 are groups substituted with other functional groups. When having two or more substituents, the substituents may be the same kind or different from each other. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, or iodine atom), a _C6-14 aryl group which may have a substituent, a cyano group, a nitro group, and the like.

_{Examples of the "C p1-p2} alkyl group having a substituent" include, for example, a C _6-14 aryl-C _1-6 alkyl group. A "C _6-14 aryl-C _1-6 alkyl group" is a group in which one hydrogen atom bonded to a carbon atom of _{a C 1-6} alkyl group is replaced with a _{C 6-14 aryl group.} The _{C 6-14} aryl group in the C _6-14 aryl _{-C 1-6} alkyl group, a phenyl group, a naphthyl group, an anthryl group, can be exemplified a 9-fluorenyl group, a phenyl group, and a 9-fluorenyl group are particularly preferred .. As the _{C 1-6} alkyl group in the C _6-14 aryl _{-C 1-6} alkyl _{group, C 1-4} alkyl groups are preferred. Examples of C _6-14 aryl-C _1-6 alkyl groups include benzyl group, diphenylmethyl group, triphenylmethyl group, 2-phenylethyl group, 9-anthrylmethyl group, 9-fluorenylmethyl group and the like. Can be mentioned.

In the present invention and the present specification, the "C _1-30 aliphatic hydrocarbon group" may have a C _1-30 alkyl group which may have a substituent and a C _{2-30 which may have a substituent.} It contains all of an alkenyl group and a _{C 2-30} alkynyl group which may have a substituent. The "C _1-30 aliphatic hydrocarbon group" may be a straight chain, a branched chain, or a cyclic group. Examples of the C _2-30 alkenyl group include a group in which a single bond between at least one carbon atom among the groups listed in the _{C 2-30 alkyl group is a double bond.} Examples of the C _2-30 alkynyl group include a group in which a single bond between at least one carbon atom among the groups listed in the _{C 2-30 alkyl group is a triple bond.} More specifically, the C _2-30 alkenyl group includes a vinyl group, a propenyl group, a 2-propenyl group, a butenyl group, a 1-methylpropenyl group, a 2-methylpropenyl group, a pentenyl group, a hexenyl group and a heptenyl group. Examples thereof include an octenyl group, a nonenyl group, a decenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group and the like. Examples of the C _2-30 alkynyl group include an ethynyl group, a propynyl group, a butynyl group, a 1-methylpropynyl group, a pentynyl group, a 2-methylbutynyl group, a hexynyl group, a heptynyl group, an octynyl group and the like.

In the present invention and the present specification, the "C _p1-p2 aliphatic hydrocarbon group having a substituent" is one of the hydrogen atoms bonded to the carbon atom of _{the C p1-p2 aliphatic hydrocarbon group or} A plurality, preferably 1 to 3, are groups having a substituent on another functional group. When having two or more substituents, the substituents may be the same kind or different from each other. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, or iodine atom), a _C6-14 aryl group which may have a substituent, a cyano group, a nitro group, and the like.

In the present invention and the present specification, the "C _1-30 alkoxy group" refers to a group in which an oxygen atom is bonded to the bond end of a linear or branched alkyl group having 1 to 30 carbon atoms. _{Examples of the} linear or branched alkyl group having 1 to 30 carbon atoms in the C _{1-30 alkoxy group include the same group as the C 1-30} alkyl group.

In the present invention and the present specification, the "C _1-10 alkoxy group" refers to a group in which an oxygen atom is bonded to the bond end of a linear or branched alkyl group having 1 to 10 carbon atoms. _{Examples of the} linear or branched alkyl group having 1 to 10 carbon atoms in the C _{1-10 alkoxy group include the same group as the C 1-10} alkyl group.

In the present invention and the present specification, the "C _1-6 alkoxy group" refers to a group in which an oxygen atom is bonded to the bond end of a linear or branched alkyl group having 1 to 6 carbon atoms. _{Examples of the} linear or branched alkyl group having 1 to 6 carbon atoms in the C _{1-6 alkoxy group include the same group as the C 1-6} alkyl group. Examples of the C _1-6 alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group and the like.

In the present invention and the present specification, the "C _p1-p2 alkoxy group having a substituent" refers to one or more hydrogen atoms bonded to the carbon atom of _{the C p1-p2 alkoxy group, preferably one.} ~ 3 are groups substituted with other functional groups. When having two or more substituents, the substituents may be the same kind or different from each other. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, or iodine atom), a _C6-14 aryl group which may have a substituent, a cyano group, a nitro group, and the like.

In the following, "compound (n)" means a compound represented by the formula (n).

Subsequent chemical reactions can be carried out in a solvent that is inert to the reaction. Examples of the solvent include inert solvents such as methanol, 1,4-dioxane, diethyl ether, tetrahydrofuran, dichloromethane, acetonitrile, benzene, toluene, N, N-dimethylformamide and N, N-dimethylacetamide.

[Fluorinating agent]
The compound according to the present invention is a compound represented by the following general formula (A1).

In the general formula (A1), R ¹ _{is a C 6-14} aryl group which may have a substituent. As the compound (A1), the _{C 6-14} aryl group which may have the substituent in ^{R 1} is preferably a phenyl group which may have 1 to 3 substituents, and C _1-. More phenyl groups may have 1 to 3 substituents selected from the group consisting of ₆ alkyl groups, C _1-6 alkyl groups, C _{1-6 alkoxy groups, halogen atoms, and trihalomethyl groups.} Preferably, phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 4-trifluoromethyl group, 3-trifluoromethyl group, 2,6 -Di (trifluoromethyl) phenyl group, 3,4-di (trifluoromethyl) phenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2,4-dimethoxyphenyl group, 3,4-dimethoxyphenyl group , 3-Chlorophenyl group, 4-chlorophenyl group, 2,6-dichlorophenyl group, 3,4-dichlorophenyl group, 4-nitrophenyl group are more preferable, and phenyl group is particularly preferable.

In the general formula (A1), R ² may have a substituent C _1-30 alkyl group (may have 1 to 5 ether-bonding oxygen atoms between carbon atoms). , Or an aromatic group that may have a substituent.

When the R ² _{is a C 1-30} alkyl group which may have a substituent, the alkyl group may have 1 to 5 ether-bonding oxygen atoms between carbon atoms. .. As the compound (A1), wherein R ² is optionally C _1-10 alkyl group is preferable which may have a substituent, more preferably a C _1-6 alkyl group which may have a substituent group, a substituted A C _1-6 alkyl group having no group and a C _6-14 aryl-C _1-6 alkyl group are more preferable, and a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and sec. More preferably, it is a -butyl group, a tert-butyl group, a benzyl group, a diphenylmethyl group, a triphenylmethyl group, a 2-phenylethyl group, a 9-anthrylmethyl group, and a 9-fluorenylmethyl group. Particularly preferably, it is a tert-butyl group, a benzyl group, and a 2-phenylethyl group.

When the R ² is an aromatic group which may have a substituent, the aromatic group may be an aryl group or a heteroaryl group. As the compound (A1), wherein R ² is optionally substituted C _6-14 aryl group, and preferably nitrogen-containing heteroaryl group which may have a substituent, have a substituent _{The C 6-14} aryl group, which may be used, _{is more preferable, and is selected from the group consisting of a C 1-6} alkyl group, a C _1-6 alkoxy group, a trifluoromethyl group, a halogen atom, a cyano group, and a nitro group. A phenyl group which may have 1 to 3 substituents is more preferable, and a phenyl group, a 2-methylphenyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, and a 2,6-dimethylphenyl group. , 2,4-Dimethylphenyl group, 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3,5-di (trifluoromethyl) phenyl group, 2,6- Di (trifluoromethyl) phenyl group, 2,4-di (trifluoromethyl) phenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2,4-dimethoxyphenyl group, 3, 5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2,6-dichlorophenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,4-difluorophenyl group, 3,5-difluorophenyl group, 2,6-difluorophenyl group, 4-cyanophenyl group, 4- Nitrophenyl groups are even more preferred, phenyl groups, 2-trifluoromethylphenyl groups, 4-trifluoromethylphenyl groups, 3,5-di (trifluoromethyl) phenyl groups, 2,6-di (trifluoromethyl). Phenyl group, 2,4-di (trifluoromethyl) phenyl group, 2-chlorophenyl group, 4-chlorophenyl group, 3,5-dichlorophenyl group, 2,6-dichlorophenyl group, 2,4-dichlorophenyl group, 2-fluoro Particularly preferred are a phenyl group, a 4-fluorophenyl group, a 3,5-difluorophenyl group, a 2,6-difluorophenyl group, a 2,4-difluorophenyl group, and a 4-cyanophenyl group.

As the compound (A1), ¹ to _{3 R 1 is selected from the group consisting of a C 1-6} alkyl group, a C _1-6 alkyl group, a C _1-6 alkoxy group, a halogen atom, and a trihalomethyl group. A phenyl group which may have a substituent ^{, R 2} _{may have a substituent C 1-6} alkyl group, a C _1-10 alkoxy group which may have a substituent, and _{A compound which is a C 6-14} aryl group which may have a substituent is preferable, and R ¹ is a phenyl group, a 4-methylphenyl group, a 3-methylphenyl group, a 2,6-dimethylphenyl group, 3,4. -Dimethylphenyl group, 4-trifluoromethyl group, 3-trifluoromethyl group, 2,6-di (trifluoromethyl) phenyl group, 3,4-di (trifluoromethyl) phenyl group, 4-methoxyphenyl group , 3-methoxyphenyl group, 2,4-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,6-dichlorophenyl group, 3,4-dichlorophenyl group, and 4- _{C 1-6} alkyl group, C _6-14 aryl-C _1-6 alkyl group, C _1-6 alkyl group, C _1-6 alkyl group, which is a nitrophenyl group and R ² does not have a substituent. A compound which is a phenyl group which may have 1 to 3 substituents selected from the group consisting of an alkoxy group, a trifluoromethyl group, a halogen atom, a cyano group, and a nitro group is more preferable, and R ¹ is more preferable. Phenyl group, R ² is tert-butyl group, benzyl group, 2-phenylethyl group, phenyl group, 2-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3,5-di (trifluoromethyl) ) Phenyl group, 2,6-di (trifluoromethyl) phenyl group, 2,4-di (trifluoromethyl) phenyl group, 2-chlorophenyl group, 4-chlorophenyl group, 3,5-dichlorophenyl group, 2,6 -Dichlorophenyl group, 2,4-dichlorophenyl group, 2-fluorophenyl group, 4-fluorophenyl group, 3,5-difluorophenyl group, 2,6-difluorophenyl group, 2,4-difluorophenyl group, and 4- Compounds that are cyanophenyl groups are more preferred.

The compound (A1) synthesizes a sulfonylcarbamic acid ester by a condensation reaction between a carboxylic acid such as a fatty acid or a benzoic acid derivative and a sulfonamide, and replaces the hydrogen atom bonded to the nitrogen atom of this amino group with a lithium atom. Further, it can be synthesized by substituting this lithium atom with a fluorine atom. In the formulas, ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in general formula (A1).

[Manufacturing method of fluorine-containing compound]
Compound (A1) can be used as an active ingredient of a fluorinating agent in various reactions. Compound (A1) can fluorinate carbon atoms in various organic compounds in the same manner as NFSI. Examples of the organic compound serving as a substrate include compounds having an unsaturated bond such as an alkene, an allyl compound, an alkyne, and an aromatic compound. The unsaturated bond may be a bond formed between carbon atoms or a bond between a carbon atom and an atom other than the carbon atom.

Compound (A1) is particularly suitable as a fluorinating agent for silyl enol ether compounds. For example, by using the compound (A1) as a fluorinating agent, one fluorine atom is introduced into the substrate compound (silyl enol ether compound) represented by the general formula (A2), and the general formula (A3) or ( The fluorine-containing compound represented by A4) can be produced.

It is considered that the compound (A3) and the compound (A4) can be easily converted into each other.

For example, compound (A3) can be converted to compound (A4) by adding a desilylating agent. As the desilylating agent, for example, the compound described in the section of "Green Ethers" on page 201 of "Greene's Protective Groups in Organic Synthesis 5th Edition" can be used. Specifically, for example, inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as formic acid and acetic acid, inorganic fluoride salts such as cesium fluoride, and organic fluorides such as tetrabutylammonium fluoride (TBAF). Examples include salts, inorganic fluoride compounds such as sodium hydroxide, and alkoxides such as sodium methoxyde. As the desilylating agent, inorganic acids, organic acids, and organic fluoride salts are preferable, and tetrabutylammonium fluoride is particularly preferable.

From compound (A4) to compound (A3), the silylating agents (R ²¹ R ²² R ²³ SiX: R ²¹ , R ²² and R ²³ are the same as in the general formula (A3), where X is a halogen atom. Yes) and can be converted by adding a base. As the silylating agent and the base, for example, the compounds described in the section of Silk Ethers on page 201 of "Greene's Protective Groups in Organic Synthesis 5th Edition" can be used. Examples of the silylating agent include silane chlorides such as _{Me 3} SiCl, Et ₃ SiCl, iPr ₃ SiCl, and t-BuMe _{2 SiCl.} Examples of the base include organic bases such as triethylamine, pyridine and imidazole. The silylating agent used for the conversion of the compound (A4) to the compound (A3) _{is preferably Me 3} SiCl, and the base is preferably imidazole.

In the general formula (A2), R ²¹ , R ²² , and R ²³ are independently C _1-4 alkyl groups. As the compound (A2), since the selectivity to the monofluorinated compound is high, a compound in which R ²¹ , R ²² , and R ²³ are independently methyl group and ethyl group, respectively, is preferable, and R ²¹ , Compounds in which R ²² and R ²³ are all methyl groups and ethyl groups are more preferable, and compounds in which R ²¹ , R ²² and R ²³ are all methyl groups are particularly preferable.

In the general formula (A2), R ²⁴ has a hydrogen atom and a C _1-30 aliphatic hydrocarbon group which may have a substituent (having 1 to 5 ether-bonding oxygen atoms between carbon atoms). It is a C _1-30 alkoxy group which may have a substituent, or an aromatic group which may have a substituent. Further, in the general formula (A2), R ²⁵ _{is a C 1-30} aliphatic hydrocarbon group which may have a hydrogen atom and a substituent (1 to 5 ether-bonded oxygen atoms between carbon atoms). It is an aromatic group which may have a substituent.

When the R ²⁴ or R ²⁵ _{is a C 1-30} aliphatic hydrocarbon group which may have a substituent, the aliphatic hydrocarbon group has 1 to 5 ether-bonding groups between carbon atoms. It may have an oxygen atom. As the C _1-30 aliphatic hydrocarbon group, a C _1-30 alkyl group which may have a substituent is preferable, and a C _1-10 alkyl group which may have a substituent is more preferable. A C _1-6 alkyl group which may have a substituent is more preferable, and a C _1-6 alkyl group which does not have a substituent is particularly preferable.

When the R ²⁴ or R ²⁵ is an aromatic group which may have a substituent, the aromatic group may be an aryl group or a heteroaryl group. The aromatic group is preferably a C _6-14 aryl group which may have a substituent or a nitrogen-containing heteroaryl group which may have a substituent, and may have a substituent. A C _6-14 aryl group is more preferable, a phenyl group which may have a substituent is further preferable, and a C _1-6 alkyl group, a C _1-6 alkoxy group, a trifluoromethyl group, a halogen atom, a cyano group, and the like. And a phenyl group which may have 1 to 3 substituents selected from the group consisting of nitro groups is even more preferred. A _{phenyl that may have 1 to 3 substituents selected from the group consisting of C 1-6} alkyl groups, C _1-6 alkoxy groups, trifluoromethyl groups, halogen atoms, cyano groups, and nitro groups. as the base, for example, the same groups as those previously mentioned in the R ² may be mentioned.

When the R ²⁴ _{is a C 1-30} alkoxy group which may have a substituent, the alkoxy group may have 1 to 5 ether-bonding oxygen atoms between carbon atoms. .. As the compound (A2), the R ²⁴ is preferably a C _1-10 alkoxy group which may have a substituent, and more preferably a _{C 1-6 alkoxy group which may have a substituent.} A C _1-6 alkoxy group having no group is further preferable, and a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a tert-butoxy group, a pentyloxy group, and a hexyloxy group are even more preferable.

The R ²⁴ and R ²⁵ may be connected to each other to form a ring. The ^{ring composed of R 24} and R ²⁵ is preferably a 5-membered ring, a 6-membered ring, and a 7-membered ring, and may be a ring in which an aromatic ring or a saturated ring is condensed. Further, it may be a hydrocarbon ring or a heterocycle. Examples of the ring include an inden ring, an indan ring, a dihydronaphthalene ring, a dihydrobenzoannelen ring, a chromane ring, a chromane ring, an isochromene ring, a dihydrothiophene ring, a benzothiophene ring, a dihydrobenzothiophene ring, a thiopyran ring, and a dihydrothione ring. Examples thereof include a pyran ring, a benzothiopyran ring, and a dihydrobenzothiopyran ring.

The ^{ring composed of R 24} and R ²⁵ may have a substituent. When having two or more substituents, the substituents may be the same kind or different from each other. The substituent may have a C _1-6 alkyl group, a C _1-6 alkoxy group, a halogen atom (fluorine atom, chlorine atom, bromine atom, or iodine atom), a trihalomethyl group, or a substituent. C _6-14 aryl group, cyano group, nitro group and the like can be mentioned.

The fluorination reaction of compound (A2) with compound (A1) can be allowed to proceed by incubating with fluorine gas at a temperature of 100 ° C. or lower in the presence of a desilylating agent. As the desilylating agent, a fluoride such as sodium fluoride can be used. The compound (A1) is preferably 0.5 to 100 mol, more preferably 0.5 to 50 mol, still more preferably 0.5 to 10 mol, based on 1 mol of the compound (A2).

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.

The NMR apparatus used for the analysis of Examples and Comparative Examples is JNM-ECS400 (400 MHz) manufactured by JEOL Ltd. ^{In 1 1} H NMR, tetramethylsilane was used as a reference value of 0 PPM, and in ¹⁹ F NMR, C ₆ F ₆ was used as a reference value of -162 PPM. For HPLC (High Performance Liquid Chromatograph), LC-20 manufactured by Shimadzu Corporation was used. The unit of yield (%) described in the examples is mol%.

[Example 1]
^{A compound in which R 1} in the general formula (A1) was a phenyl group and R ² was a phenyl group substituted with two trifluoromethyl groups was synthesized.

Compound (1) (1.29 g), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (1.15 g), N, N-dimethyl-4-aminopyridine (1.29 g), which are benzoic acid derivatives, under a nitrogen atmosphere. A solution prepared by dissolving 0.73 g) and sulfonamide (compound (2): 0.86 g) in 0.2 M methylene chloride was stirred at room temperature for 12 hours. Then, it was quenched with 1M hydrochloric acid, separated, the aqueous phase was extracted twice with ethyl acetate, and all the organic phases were combined and dried over sodium sulfate. Subsequently, the solvent was distilled off under reduced pressure, and silica gel column chromatography was performed in a hexane / ethyl acetate mixed solvent system to obtain the desired compound (3-H) (1.21 g) as a white solid.

^{1 1} H NMR (d ₆ -acetone): δ = 11.48 (s, 1H), 8.55 (s, 2H), 8.32 (s, 1H), 8.13-8.16 (d, 2H) ), 7.74-7.78 (t, 1H), 7.64-7.68 (t, 2H) ¹⁹ F NMR (d ₆ -acetone): δ = -63.40 (s, 6F).

A lithium salt of compound (3-H) was prepared. Specifically, an acetone / water mixed solution of compound (3-H) (0.79 g) and lithium hydroxide monohydrate (0.08 g) was stirred at room temperature for 12 hours. Subsequently, the solvent was distilled off under reduced pressure to directly obtain a lithium salt (3-Li) (0.79 g).

^{1 1} H NMR (d ₆ -acetone): δ = 8.61 (s, 2H), 8.12 (s, 1H), 7.99-8.01 (d, 2H), 7.47-7.56 (M, 3H) ¹⁹ F NMR (d ₆ -acetone): δ = -63.20 (s, 6F).

Further, the compound (3-H) and the compound (3-Li) which is a lithium salt were fluorinated.

First, a solution of compound (3-H) (1.29 g) and sodium fluoride (0.42 g) in acetonitrile (120 g) was ice-cooled to 0 ° C. using an ice bath. A fluorine / nitrogen mixed gas of 2% by volume was adjusted to 100 mL / min with a mass flow controller, and 1 equivalent of fluorine gas was introduced into the reaction vessel over 40 minutes. Then, the precipitate was filtered, the solvent was distilled off under reduced pressure, and then the target product (4) (0.63 g was obtained) by silica gel column chromatography using a hexane / ethyl acetate mixed solvent system.

The lithium salt compound (3-Li) was used instead of the above compound (3-H). Specifically, when a 2% fluorine / nitrogen mixed gas was flowed in a solution of compound (3-Li) (0.86 g) and sodium fluoride (0.09 g) in acetonitrile (30 g) for 25 minutes, the compound ( 4) was obtained in an amount of 0.30 g.

^{1 1} H NMR (d ₆ -acetone): δ = 8.51 (s, 3H), 7.95-8.01 (m, 3H), 7.79-7.83 (t, 2H) ¹⁹ F NMR ( d ₆ -acetone): δ = -52.35 (s, 1F), -63.39 (s, 6F).

[Example 2]
The compound (4) was used as a fluorinating agent, and the silyl enol ether compound (9) was fluorinated.

The silyl enol ether compound (9) (16 mg) was added dropwise to a solution prepared by dissolving compound (4) (37 mg) in 0.1 M methylene chloride under a nitrogen atmosphere. Then, after stirring at 25 ° C. for 24 hours, the crude liquid was ^{quantified by 19} F NMR, and it was confirmed that the compound (10 m) was produced in a yield of 83%. At this time, it was also confirmed that the compound (10d) was produced in a yield of 2%.

¹⁹ F NMR (CDCl ₃ ) of compound (10 m): δ = -191.16 (d, 1F). ¹⁹ F NMR (CDCl ₃ ) of compound (10d): δ = -12.09 (t, 2F).

[Comparative Example 1]
The silyl enol ether compound (9) was fluorinated using NFSI as a fluorinating agent.

Under the same conditions as in Example 2, NFSI (28 mg) was used as the fluorinating agent instead of compound (4). As a result, it was confirmed that 7% of the compound (10 m) was produced, 36% of the compound (10d) was produced, and 8% of the compound (11 m) was produced. From these results, it was found that by using the compound (A1) as a fluorinating agent, a difluoro compound can be synthesized more selectively than a monofluoro compound.

¹⁹ F NMR (CDCl ₃ ) of compound (11 m): δ = -129.08 (s, 1F).

[Example 3]
^{A compound (13) in which R 1} in the general formula (A1) is a phenyl group and R ² is a heteroaryl group was synthesized.

A solution prepared by dissolving compound (12-H) (0.56 g) and sodium fluoride (0.27 g) in acetonitrile (30 g) was ice-cooled to 0 ° C. using an ice bath. A fluorine / nitrogen mixed gas having a volume ratio of 2% was adjusted to 100 mL / min with a mass flow controller, and an equal amount of fluorine gas was introduced into the reaction vessel over 25 minutes. After completion of the reaction, the crude solution was ^{quantified by 19} F NMR, and it was confirmed that compound (13) was produced in a yield of 35%.

¹⁹ F NMR (neat): δ = -47.67 (s, 1F).

[Example 4]
^{A compound (15) in which R 1} in the general formula (A1) is a phenyl group and R ² is a heteroaryl group substituted with two chlorine atoms was synthesized.

A solution prepared by dissolving compound (14-H) (0.40 g) and sodium fluoride (0.16 g) in acetonitrile (30 g) was ice-cooled to 0 ° C. using an ice bath. A fluorine / nitrogen mixed gas having a volume ratio of 2% was adjusted to 100 mL / min with a mass flow controller, and an equal amount of fluorine gas was introduced into the reaction vessel over 14 minutes. After completion of the reaction, the crude solution was ^{quantified by 19} F NMR, and it was confirmed that compound (15) was produced in a yield of 34%.

¹⁹ F NMR (neat): δ = -51.34 (s, 1F).

[Example 5]
The compound (4) was used as a fluorinating agent, and the silyl enol ether was fluorinated. Silyl enol ethers are ((6,7-dihydro-5H-benzo [7] annulen-9-yl) oxy) trimethylsilane, (E) -trimethyl ((1-phenylprop-1-ene-1-yl)). Oxy) silane, (E)-((1,2-diphenylvinyl) oxy) trimethylsilane, ((2H-chromen-4-yl) oxy) trimethylsilane, (E) -trimethyl ((1-phenylbut-1-) En-1-yl) oxy) silane and (E)-((1-([1,1'-biphenyl] -4-yl) prop-1-ene-1-yl) oxy) trimethylsilane were used. The reaction conditions were the same as in Example 2 except that the synthesis reaction of (E)-((1,2-diphenylvinyl) oxy) trimethylsilane was set to 50 hours.

As a result, from ((6,7-dihydro-5H-benzo [7] annulen-9-yl) oxy) trimethylsilane, 6-fluoro-6,7,8,9-tetrahydro-5H-benzo [7] It was confirmed that Annelen-5-one was produced in a yield of 90%. In addition, a monofluorinated product (6-fluoro-6,7,8,9-tetrahydro-5H-benzo [7] annulen-5-one) and a difluorinated product (6,6-difluoro-6,7,8) , 9-Tetrahydro-5H-benzo [7] annulen-5-one) was synthesized in a monofluorinated form: difluorinated form = 98: 2.
From the (E) -trimethyl ((1-phenylprop-1-en-1-yl) oxy) silane, 2-fluoro-1-phenylpropan-1-one is produced in a yield of 87%. confirmed. The synthetic ratio of the monofluorinated product (2-fluoro-1-phenylpropane-1-one) and the difluorinated product (2,2-difluoro-1-phenylpropane-1-one) is the monofluorinated product. : Difluorinated product = 98: 2.
From (E)-((1,2-diphenylvinyl) oxy) trimethylsilane, it was confirmed that 2-fluoro-1,2-diphenylethane-1-one was produced in a yield of 71%. The synthetic ratio of the monofluorinated product (2-fluoro-1,2-diphenylethane-1-one) and the difluorinated product (2,2-difluoro-1,2-diphenylethane-1-one) is Mono-fluorinated product: di-fluorinated product = 99: 1.
It was confirmed that 3-fluorochroman-4-one was produced from ((2H-chromen-4-yl) oxy) trimethylsilane in a yield of 57%. The synthesis ratio of the monofluorinated product (3-fluorochroman-4-one) and the difluorinated product (3,3-difluorochroman-4-one) is as follows: monofluorinated product: difluorinated product = 98 :. It was 2.
It was confirmed that 2-fluoro-1-phenylbutane-1-one was produced from (E) -trimethyl ((1-phenylbut-1-en-1-yl) oxy) silane in a yield of 83%. did. The synthetic ratio of the monofluorinated product (2-fluoro-1-phenylbutane-1-one) and the difluorinated product (2,2-difluoro-1-phenylbutane-1-one) is the monofluorinated product. : Difluorinated product = 99: 1.
From (E)-((1-([1,1'-biphenyl] -4-yl) prop-1-ene-1-yl) oxy) trimethylsilane, 1-([1,1'-biphenyl] It was confirmed that -4-yl) -2-fluoropropane-1-one was produced in a yield of 96%. In addition, monofluorinated product (1-([1,1'-biphenyl] -4-yl) -2-fluoropropane-1-one) and difluorinated product (1-([1,1'-biphenyl]] The synthesis ratio of -4-yl) -2,2-difluoropropane-1-one) was monofluorinated product: difluorinated product = 99: 1.

[Example 6]
The compound (4) was used as a fluorinating agent, and the silyl enol ether compound (16) was fluorinated.

Silyl enol ether compound (16) (22.2 mg: 0.10 mmol) in a solution prepared by dissolving compound (4) (49.8 mg: 0.12 mmol) in 0.1 M methylene chloride (1 mL) under a nitrogen atmosphere. ) Was dropped. Then, after stirring at 25 ° C. for 42 hours, the crude liquid was ^{quantified by 19} F NMR, and it was confirmed that compound (17) was produced in a yield of 45%. At this time, no difluoro compound was detected.

[Example 7]
Using compound (4) as a fluorinating agent, the silyl enol ether compound (9-2) was fluorinated.

Silyl enol ether compound (9-2) (24 mg: 0.091 mmol) was added dropwise to a solution prepared by dissolving compound (4) (45.3 mg: 0.11 mmol) in 0.1 M methylene chloride under a nitrogen atmosphere. did. Then, after stirring at 25 ° C. for 24 hours, the crude liquid was ^{quantified by 19} F NMR, and it was confirmed that the compound (10 m) was produced in a yield of 54%. At this time, it was also confirmed that the compound (10d) was produced in a yield of 3%.

[Example 8]
Using compound (4) as a fluorinating agent, fluorinated silyl enol ether was carried out under the same conditions as in Example 7. The synthesized monofluorinated product and difluorinated product were ^{analyzed by 19} F NMR. ^{For 19} F NMR, 2,3,5,6-tetrafluoro-p-xylene was used as a reference value of -147PPM. ^{The 19} F NMR analysis values and synthesis ratios of the synthesized monofluorinated product and difluorinated product are shown together with the reaction formula. From these results, it was found that by using compound (4) as a fluorinating agent, a difluoro compound can be synthesized more selectively than a monofluoro compound from various substrates.

[Example 9]
Using compound (4) as a fluorinating agent, the silyl enol ether compound (18) was fluorinated in the same manner as in Example 2. The synthetic ratio of the synthesized monofluorinated product and the difluorinated product is shown together with the reaction formula.

[Example 10]
In the synthesis of the compound (4) from the compound (3-Li), the compound (19) which is a lithium salt is used instead of the compound (3-Li), and the compound which is a fluorinating agent is used in the same manner as in Example 1. (20) was obtained with a fluorination yield of 87% and an isolation yield of 51% by column chromatography. In the same manner, the lithium salt was changed to obtain the corresponding fluorinating agents (compounds (21) to (23)). The fluorination yield (values in parentheses) of the obtained fluorinating agent and the isolation yield by column chromatography (values in parentheses) are shown together with the reaction formula. In addition, these fluorinating agents were analyzed by NMR. ¹⁹ F NMR was carried out in the same manner as in Example 8.

NMR analysis value of compound (20)
^{1 1} H NMR (CDCl ₃ ): 7.98-8.00 (d, 2H), 7.85-7.87 (d, 2H), 7.77-7.82 (m, 3H), 7.61 -7.65 (t, 2H) ¹⁹ F NMR (CDCl ₃ ): -49.35 (s, 1F), -63.26 (s, 3F)

NMR analysis value of compound (21)
^{1 1} H NMR (d ₆ -acetone): 8.04 (d, 2H), 7.91 (t, 1H), 7.76 (t, 2H), 1.05 (s, 9H) ¹⁹ F NMR (d) ₆ -Acetone): -51.19 (s, 1F)

NMR analysis value of compound (22)
^{1 1} H NMR (d ₆ -acetone): 7.96-8.01 (m, 3H), 7.79-7.83 (t, 2H), 7.50-7.59 (m, 3H) ¹⁹ F NMR (d ₆ -acetone): -51.85 (s, 1F), -108.98 (s, 2F)

NMR analysis value of compound (23)
^{1 1} H NMR (d ₆ -acetone): 7.95-8.02 (m, 4H), 7.90-7.91 (m, 2H), 7.82-7.87 (t, 2H) ¹⁹ F NMR (d ₆ -acetone): -52.11 (s, 1F)

[Example 11]
Using compounds (20) to (23) as fluorinating agents, the silyl enol ether compound (9) was fluorinated in the same manner as in Example 2. The synthetic ratio of the synthesized monofluorinated product and the difluorinated product is shown together with the reaction formula. From these results, it was found that by using compounds (20) to (23) as a fluorinating agent, a difluoro compound can be synthesized more selectively than a monofluoro compound.

In the present invention, monofluorine in which one fluorine atom is introduced into a carbon atom different from the carbon atom to which the silyl ether group is bonded among the carbon atoms constituting the C = C bond with respect to the silyl enol ether compound. Provided are a fluorinating agent capable of selectively synthesizing a chemical compound, and a method for producing a monofluorinated compound using the fluorinating agent. Since the fluorinating agent according to the present invention can preferentially synthesize a monofluorinated compound over a difluorinated compound in which two fluorine atoms are introduced, it is particularly suitable for selective production of a monofluorinated compound. It is useful.

The specification, claims, drawings and abstracts of Japanese Patent Application No. 2019-173543 filed on September 24, 2019 and Japanese Patent Application No. 2020-128667 filed on July 29, 2020. The entire contents of the document are cited herein and incorporated as disclosure of the specification of the present invention.

Claims

A compound represented by the following general formula (A1).

However, the group in the formula means the following.
R 1 is a C 6-14 aryl group which may have a substituent and is a C 6-14 aryl group.
R 2 has a C 1-30 alkyl group which may have a substituent (may have 1 to 5 ether-bonding oxygen atoms between carbon atoms) or a substituent. It is an aromatic group that may be present.
R 1 is a phenyl group which may have 1 to 3 substituents and is a phenyl group.
R 2 may have a C 1-10 alkyl group which may have a substituent, a C 6-14 aryl group which may have a substituent, or a nitrogen-containing heteroaryl which may have a substituent. The compound according to claim 1, which is a group.
R 1 has 1 to 3 substituents selected from the group consisting of C 1-6 alkyl groups, C 1-6 alkyl groups, C 1-6 alkoxy groups, halogen atoms, and trihalomethyl groups. It is a phenyl group that may be
R 2 may have a substituent C 1-6 alkyl group, may have a substituent C 1-10 alkoxy group, or may have a substituent C 6-14 aryl The compound according to claim 1, which is a group.
A fluorinating agent containing the compound according to any one of claims 1 to 3 as an active ingredient.
Using a fluorinating agent containing the compound according to any one of claims 1 to 3 as an active ingredient, one fluorine atom is introduced into the substrate compound represented by the following general formula (A2), and the following A method for producing a fluorine-containing compound, which comprises producing a fluorine-containing compound represented by the general formula (A3) or (A4).

However, the group in each formula means the following.
R 21 , R 22 and R 23 are independently C 1-4 alkyl groups; R 24 is a C 1-30 aliphatic hydrocarbon group which may have a hydrogen atom and a substituent. (It may have 1 to 5 ether-bonding oxygen atoms between carbon atoms), it may have a substituent, it may have a C 1-30 alkoxy group, or it may have a substituent. A good aromatic group; R 25 is a C 1-30 aliphatic hydrocarbon group which may have a hydrogen atom, a substituent (having 1-5 ether-bonded oxygen atoms between carbon atoms). Or an aromatic group that may have a substituent; R 24 and R 25 may be linked to each other to form a ring.
R 24 and R 25 are linked to each other to form a ring which may have a substituent, and the rings are an inden ring, an indan ring, a dihydronaphthalene ring, a dihydrobenzoannurene ring, a chromane ring, and a chromane ring. , Isochromen ring, dihydrothiophene ring, benzothiophene ring, dihydrobenzothiophene ring, thiopyran ring, dihydrothiopyran ring, benzothiopyran ring, and dihydrobenzothiopyran ring. A method for producing a fluorine-containing compound.
R 24 and R 25 each independently have a C 1-30 alkyl group, which may have a substituent, a C 6-14 aryl group, which may have a substituent, and a substituent. The method for producing a fluorine-containing compound according to claim 5, which is a kind selected from the group consisting of a nitrogen-containing heteroaryl group which may be present.
The method for producing a fluorine-containing compound according to claim 5, wherein R 24 is a C 1-30 alkoxy group which may have a substituent.
The method for producing a fluorine-containing compound according to any one of claims 5 to 8, wherein a fluorine atom is introduced into the substrate compound at a temperature of 100 ° C. or lower.