Method for producing fluorinated organic compound

Abstract

To provide a new method for producing a fluorinated organic compound in which removal or separation of an auxiliary is easy and which is advantageous in production cost.SOLUTION: A compound represented by the following formula (1): wherein R1, R2 and n are as defined in the description. The method comprises reacting the compound represented by the formula (1) with (A) at least one fluorine source selected from hydrogen fluoride, a hydrogen fluoride salt and a fluoride salt, (B) at least one iodine source selected from iodine and ammonium iodide, and (C) a compound having at least one fluorinated quaternary nitrogen atom in the molecule. A step of difluorinating the compound represented by the formula (1), wherein the amount of the iodine source (B) used is less than 1.0 mol per 1 mol of the compound represented by the formula (1).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to methods for producing fluorinated organic compounds. [Background technology]

[0002] Fluorinated organic compounds are extremely important compounds used in a variety of chemical products, such as functional materials, pharmaceutical and agricultural chemical compounds, and electronic materials, as well as intermediates thereof. As a method for producing a fluorinated organic compound, for example, Non-Patent Document 1 describes a method for difluorinating an olefin represented by the formula: CH2=CH-CH2-R in a solvent such as dichloroethane by reacting it with p-iodotoluene (catalyst), Selectfluor™ (1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate)), and an HF source. A method has been proposed. [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] J. Am. Chem. Soc. 2016, 138, 5004-5007 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present disclosure is to provide a novel method for producing a fluorinated organic compound, which allows for easy removal or separation of auxiliary agents and is advantageous in terms of production costs. [Means for solving the problem]

[0005] The present disclosure includes the following aspects. [Section 1] The following formula (1): [ka] (In the formula, R1 and R 2 are independently a hydrogen atom or an organic group, or may form a ring together with two adjacent carbon atoms, n is 1 or 2, symbol: [ka] is a double or triple bond. however, When the symbol is a triple bond, n is 1; When the symbol is a double bond, n is 2; 2 R's 1 may be the same or different from each other, 2 R's 2 may be the same or different from each other, or 2 R's 1 , or two R 2 may form a ring together with the adjacent carbon atom. A method for producing a difluorinated compound represented by the following formula: The compound represented by the formula (1), (A) at least one fluorine source selected from hydrogen fluoride, hydrogen fluoride salts, and fluoride salts; (B) at least one iodine source selected from iodine and ammonium iodide; and (C) A compound having at least one fluorinated quaternary nitrogen atom in the molecule to difluorinate the compound represented by formula (1), The production method, wherein the amount of the iodine source (B) used is less than 1.0 mole per mole of the compound represented by formula (1). [Section 2] Item 2. The method according to Item 1, wherein the iodine source (B) is iodine. [Section 3] Item 3. The method according to Item 1 or 2, wherein the amount of the iodine source (B) used is 0.2 moles or less per mole of the compound represented by formula (1). [Section 4] Item 4. The method according to any one of Items 1 to 3, wherein the compound (C) is at least one selected from the group consisting of 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2,2,2]octane bis(tetrafluoroborate), N-fluoropyridinium salts, and multimers thereof. [Section 5] Item 5. The production method according to any one of Items 1 to 4, wherein the compound (C) is 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2,2,2]octane bis(tetrafluoroborate). [Section 6] Item 6. The method according to any one of Items 1 to 5, wherein the amount of the compound (C) used is within a range of 0.1 to 10 moles per mole of the compound represented by formula (1). [Section 7] Item 7. The method according to any one of Items 1 to 6, wherein the compound (C) is used in an amount in which the number of F atoms on N atoms in the compound (C) exceeds 1 mole per mole of the compound represented by formula (1). [Section 8] The method according to any one of Items 1 to 7, wherein the fluorine source (A) is hydrogen fluoride. [Item 9] Item 10. The method according to any one of Items 1 to 9, wherein the amount of the fluorine source (A) used is within a range of 0.1 to 1000 moles per mole of the compound represented by formula (1). [Section 10] the fluorine source (A) is hydrogen fluoride; the iodine source (B) is iodine or tetrabutylammonium iodide, and The compound (C) is 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2,2,2]octane bis(tetrafluoroborate) or 1,1'-difluoro-2,2'-bipyridinium bis(tetrafluoroborate). Item 10. The method for producing according to any one of items 1 to 9. [Section 11] Item 11. The production method according to any one of Items 1 to 10, wherein the reaction is carried out in the presence of a solvent. [Section 12] R 1 and R 2 are independently a hydrogen atom, an alkyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, an aryl group which may have one or more substituents, an aralkyl group which may have one or more substituents, a non-aromatic heterocyclic group which may have one or more substituents, a cyano group, a formyl group, R A O-, R A CO-, R A SO2-, R A COO-, (R A )(R B )NCO-, R A OCO-, R A CONR B -, R A OSO2-, or (R A )(R B )NSO2-(wherein R A and R B are independently an alkyl group which may have one or more substituents, an aryl group which may have one or more substituents, or an aralkyl group which may have one or more substituents; R 1 and R 2 forms a ring together with two adjacent carbon atoms, Item 12. The method for producing according to any one of items 1 to 11. [Section 13] (B) at least one iodine source selected from iodine and ammonium iodide; (C) a compound having at least one fluorinated quaternary nitrogen atom in the molecule; (However, when the iodine source (B) is iodine, the compound (C) is not an N-fluoropyridinium salt or a polymer thereof.) [Section 14] Item 14. The composition according to item 13, further comprising (A) at least one fluorine source selected from hydrogen fluoride, a hydrogen fluoride salt, and a fluoride salt. [Section 15] Item 15. The composition according to item 13 or 14, wherein the iodine source (B) is ammonium iodide. [Section 16] Item 16. The composition according to any one of Items 13 to 15, wherein the content of the iodine source (B) is 0.2 mol or less per 1 mol of the compound (C). [Section 17] Item 17. A fluorinating agent comprising the composition according to any one of items 13 to 16. [Effects of the Invention]

[0006] According to the present disclosure, a novel method for producing a fluorinated organic compound is provided, which allows for easy removal or separation of auxiliary agents and is advantageous in terms of production costs. DETAILED DESCRIPTION OF THE INVENTION

[0007] The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure.

[0008] The remainder of the disclosure more particularly exemplifies example embodiments.

[0009] In several places in this disclosure, guidance is provided through examples, which examples can be used in various combinations.

[0010] In each instance, the exemplified group can serve as a non-exclusive and representative group.

[0011] All publications, patents, and patent applications cited herein are hereby incorporated by reference in their entirety.

[0012] 1. Terminology Unless otherwise specified, the symbols and abbreviations used in this specification should be understood to have the meanings commonly used in the technical field to which this disclosure pertains, in accordance with the context of this specification.

[0013] As used herein, the phrase "comprising" is intended to encompass the phrases "consisting essentially of" and "consisting of."

[0014] Unless otherwise specified, the processes, treatments, or operations described herein can be carried out at room temperature.

[0015] In this specification, room temperature can mean a temperature within the range of 10 to 40 °C.

[0016] In this specification, the notation "C n- C m " (where n and m are each an integer of 1 or more and n < m) represents that the number of carbon atoms is n or more and m or less, as is normally understood by those skilled in the art.

[0017] In this specification, the phrase "compound represented by formula (N)" (where N is an integer of 1 or more) can be referred to as compound (N).

[0018] In this specification, unless otherwise limited, examples of the "halogen atom" can include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0019] In this specification, the "organic group" means a group containing one or more carbon atoms. Examples of the "organic group" are an alkyl group which may have one or more substituents, an alkenyl group which may have one or more substituents, an alkynyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, a cycloalkenyl group which may have one or more substituents, a cycloalkadienyl group which may have one or more substituents, an aryl group which may have one or more substituents, an aralkyl group which may have one or more substituents, a non-aromatic heterocyclic group which may have one or more substituents, a heteroaryl group which may have one or more substituents, a cyano group, an aldehyde group, carboxyl group, R r O-, R r CO-, R r COO-, R r SO2-, R r OCO-, and R r OSO2- (In these formulas, R r is, independently, an alkyl group optionally having one or more substituents; an alkenyl group optionally having one or more substituents; an alkynyl group optionally having one or more substituents; a cycloalkyl group optionally having one or more substituents; a cycloalkenyl group optionally having one or more substituents, a cycloalkadienyl group optionally having one or more substituents, an aryl group optionally having one or more substituents; an aralkyl group optionally having one or more substituents; a non-aromatic heterocyclic group optionally having one or more substituents, or It is a heteroaryl group which may have one or more substituents. can be included.

[0020] In this specification, unless otherwise specified, examples of the "hydrocarbon group" include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkadienyl group, an aryl group, an aralkyl group, and groups that are combinations thereof.

[0021] In this specification, unless otherwise limited, examples of the "alkyl group" include linear or branched C1-16 alkyl groups (e.g., C1-C14 alkyl groups, C1-C12 alkyl groups) such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl.

[0022] In this specification, unless otherwise limited, examples of the "alkenyl group" include linear or branched C2-C10 alkenyl groups 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.

[0023] Unless otherwise specified, examples of the "alkynyl group" used herein include linear or branched C2-C10 alkynyl groups such as ethynyl, 1-propyn-1-yl, 2-propyn-1-yl, 4-pentyn-1-yl, and 5-hexyn-1-yl.

[0024] In this specification, unless otherwise limited, examples of the "cycloalkyl group" include C3-C7 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.

[0025] In this specification, unless otherwise limited, examples of the "cycloalkenyl group" include C3-C7 cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, etc.

[0026] In this specification, unless otherwise limited, examples of the "cycloalkadienyl group" include C4-C10 cycloalkadienyl groups such as cyclobutadienyl, cyclopentadienyl, cyclohexadienyl, cycloheptadienyl, cyclooctadienyl, cyclononadienyl, and cyclodecadienyl.

[0027] In this specification, unless otherwise specified, the "aryl group" may be monocyclic, bicyclic, tricyclic, or tetracyclic.

[0028] In this specification, unless otherwise specified, the "aryl group" can be a C6-C18 aryl group.

[0029] In this specification, unless otherwise limited, examples of the "aryl group" include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl.

[0030] In this specification, unless otherwise limited, examples of the "aralkyl group" include benzyl, phenethyl, diphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 2-biphenylylmethyl, 3-biphenylylmethyl, and 4-biphenylylmethyl.

[0031] In this specification, unless otherwise specified, the "non-aromatic heterocyclic group" may be monocyclic, bicyclic, tricyclic, or tetracyclic.

[0032] In this specification, unless otherwise specified, the "non-aromatic heterocyclic group" may be, for example, a non-aromatic heterocyclic group containing, as ring-constituting atoms, in addition to carbon atoms, 1 to 4 heteroatoms selected from oxygen atoms, sulfur atoms, and nitrogen atoms.

[0033] In this specification, unless otherwise specified, the "non-aromatic heterocyclic group" may be saturated or unsaturated.

[0034] In this specification, unless otherwise limited, examples of the "non-aromatic heterocyclic group" include tetrahydrofuryl, oxazolidinyl, imidazolinyl (e.g., 1-imidazolinyl, 2-imidazolinyl, 4-imidazolinyl), aziridinyl (e.g., 1-aziridinyl, 2-aziridinyl), azetidinyl (e.g., 1-azetidinyl, 2-azetidinyl), pyrrolidinyl (e.g., 1-pyrrolidinyl), and the like. nyl, 2-pyrrolidinyl, 3-pyrrolidinyl), piperidinyl (e.g., 1-piperidinyl, 2-piperidinyl, 3-piperidinyl), azepanyl (e.g., 1-azepanyl, 2-azepanyl, 3-azepanyl, 4-azepanyl), azocanyl (e.g., 1-azocanyl, 2-azocanyl, 3-azocanyl, 4-azocanyl), piperazinyl (e.g., 1,4-piperazine-1 -yl, 1,4-piperazin-2-yl), diazepinyl (e.g., 1,4-diazepin-1-yl, 1,4-diazepin-2-yl, 1,4-diazepin-5-yl, 1,4-diazepin-6-yl), diazocanyl (e.g., 1,4-diazocan-1-yl, 1,4-diazocan-2-yl, 1,4-diazocan-5-yl, 1,4-diazocan-6-yl, 1,5-diazocan-1-yl, 1,5-diazocan-2-yl, 1,5-diazocan-3-yl), tetrahydropyranyl (e.g., tetrahydropyran-4-yl), morpholinyl (e.g., 4-morpholinyl), thiomorpholinyl (e.g., 4-thiomorpholinyl), 2-oxazolidinyl, dihydrofuryl, dihydropyranyl, and dihydroquinolyl.

[0035] In this specification, unless otherwise limited, examples of the "heteroaryl group" include monocyclic aromatic heterocyclic groups (e.g., 5- or 6-membered monocyclic aromatic heterocyclic groups) and aromatic fused heterocyclic groups (e.g., 5- to 18-membered aromatic fused heterocyclic groups).

[0036] In this specification, unless otherwise limited, examples of the "5- or 6-membered monocyclic aromatic heterocyclic group" 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-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl), 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), aryl), thiazolyl (e.g., 2-thiazolyl, 4-thiazolyl, 5-thiazolyl), triazolyl (e.g., 1,2,3-triazol-4-yl, 1,2,4-triazol-3-yl), oxadiazolyl (e.g., 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl), thiadiazolyl (e.g., 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl), tetrazolyl, pyridyl (e.g., 2-pyridyl, 3-pyridyl, 4-pyridyl), pyridazinyl (e.g., 3-pyridazinyl, 4-pyridazinyl), pyrimidinyl (e.g., 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl), pyrazinyl, and the like.

[0037] In this specification, unless otherwise limited, examples of the "5- to 18-membered aromatic fused heterocyclic group" include isoindolyl (e.g., 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl), indolyl (e.g., 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl), benzo[b]furanyl (e.g., 2-benzo[b]furanyl, 3-benzo[b]furanyl, 4-benzo[b]furanyl, 5-benzo[b]furanyl, 6-benzo[b]furanyl, 7-benzo[b]furanyl), benzo[c]furanyl (e.g., 1-benzo[c]furanyl, 4-benzo[c]furanyl, 5-benzo[c]furanyl), benzo[b]thienyl, (e.g., 2-benzo[b]thienyl, 3-benzo[b]furanyl,benzo[b]thienyl, 4-benzo[b]thienyl, 5-benzo[b]thienyl, 6-benzo[b]thienyl, 7-benzo[b]thienyl), benzo[c]thienyl (e.g., 1-benzo[c]thienyl, 4-benzo[c]thienyl, 5-benzo[c]thienyl), indazolyl (e.g., 1-indazolyl, 2-indazolyl, 3-indazolyl, 4-indazolyl, 5-indazolyl, 6-indazolyl, 7-indazolyl), benzimidazolyl (e.g., 1-benzimidazolyl, 2-benzimidazolyl, 4-benzimidazolyl, 5-benzimidazolyl) ), 1,2-benzisoxazolyl (e.g., 1,2-benzisoxazol-3-yl, 1,2-benzisoxazol-4-yl, 1,2-benzisoxazol-5-yl, 1,2-benzisoxazol-6-yl, 1,2-benzisoxazol-7-yl), benzoxazolyl (e.g., 2-benzoxazolyl, 4-benzoxazolyl, 5-benzoxazolyl, 6-benzoxazolyl, 7-benzoxazolyl), 1,2-benzisothiazolyl (e.g., 1,2-benzisothiazol-3-yl, 1,2-benzisothiazolyl), benzothiazol-4-yl, 1,2-benzisothiazol-5-yl, 1,2-benzisothiazol-6-yl, 1,2-benzisothiazol-7-yl), benzothiazolyl (e.g., 2-benzothiazolyl, 4-benzothiazolyl, 5-benzothiazolyl, 6-benzothiazolyl, 7-benzothiazolyl), isoquinolyl (e.g., 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl), quinolyl (e.g., 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 8-quinolyl), cinnolinyl (e.g., 3-cinnolinyl, 4-cinnolinyl, cinnolinyl, 5-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 8-cinnolinyl), phthalazinyl (e.g., 1-phthalazinyl, 4-phthalazinyl, 5-phthalazinyl, 6-phthalazinyl, 7-phthalazinyl, 8-phthalazinyl), quinazolinyl (e.g., 2-quinazolinyl, 4-quinazolinyl, 5-quinazolinyl, 6-quinazolinyl, 7-quinazolinyl, 8-quinazolinyl), quinoxalinyl (e.g., 2-quinoxalinyl, 3-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl, 7-quinoxalinyl, 8-quinoxalinyl), pyrazolo[1,5-a]pyridyl (e.g., pyrazolo[1,5-a]pyridin-2-yl, pyrazolo[1,5-a]pyridin-3-yl, pyrazolo[1,5-a]pyridin-4-yl, pyrazolo[1,5-a]pyridin-5-yl, pyrazolo[1,5-a]pyridin-6-yl, pyrazolo[1,5-a]pyridin-7-yl), imidazo[1,2-a]pyridyl (e.g., imidazo[1,2-a]pyridin-2-yl, imidazo[1,2-a]pyridin-3-yl, imidazo[1,2-a]pyridin-5-yl, imidazo[1,2-a]pyridin-6-yl, imidazo[1,2-a]pyridin-7-yl, imidazo[1,2-a]pyridin-8-yl), and the like.

[0038] In this specification, "R r Examples of "O-" include alkoxy (e.g., C1-C10 alkoxy such as methoxy, ethoxy, propoxy, butoxy, etc.), cycloalkoxy (e.g., C3-C7 cycloalkoxy such as cyclopentoxy, cyclohexoxy, etc.), aryloxy (e.g., C6-C18 aryloxy such as phenoxy, naphthoxy, etc.), and aralkyloxy (e.g., C7-C19 aralkyloxy such as benzyloxy, phenethyloxy, etc.).

[0039] In this specification, "R r Examples of "CO-" include alkylcarbonyl [e.g., (C1-C10 alkyl)carbonyl such as acetyl, propionyl, butyryl, etc.], cycloalkylcarbonyl [e.g., (C3-C7 cycloalkyl)carbonyl such as cyclopentanoyl, cyclohexanoyl, etc.], arylcarbonyl [e.g., (C6-C18 aryl)carbonyl such as benzoyl, naphthoyl, etc.], and aralkylcarbonyl [e.g., (C7-C19 aralkyl)carbonyl such as benzylcarbonyl, phenethylcarbonyl, etc.].

[0040] In this specification, "R rExamples of "COO-" include alkylcarbonyloxy [e.g., (C1-C10 alkyl)carbonyloxy such as acetyloxy, propionyloxy, butyryloxy, etc.], cycloalkylcarbonyloxy [e.g., (C3-C7 cycloalkyl)carbonyloxy such as cyclopentanoyl, cyclohexanoyloxy, etc.], arylcarbonyloxy, and the like. Examples of the carbonyloxy include (C6-C18 aryl)carbonyloxy such as benzoyloxy and naphthoyloxy, and aralkylcarbonyloxy such as (C7-C19 aralkyl)carbonyloxy such as benzylcarbonyloxy and phenethylcarbonyloxy.

[0041] In this specification, "R r Examples of SO- include alkylsulfonyl (e.g., C1-C10 alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, etc.), cycloalkylsulfonyl (e.g., C4-C8 cycloalkylsulfonyl such as cyclopentylsulfonyl, cyclohexylsulfonyl, etc.), arylsulfonyl (e.g., C6-C18 arylsulfonyl such as phenylsulfonyl, naphthylsulfonyl, etc.), and aralkylsulfonyl (e.g., C7-C19 aralkylsulfonyl such as benzylsulfonyl, phenethylsulfonyl, etc.).

[0042] In this specification, "R r Examples of "OCO-" include alkoxycarbonyl [e.g., (C1-C10 alkoxy)carbonyl such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, etc.], cycloalkoxycarbonyl [e.g., (C3-C7 cycloalkoxy)carbonyl such as cyclopentoxycarbonyl, cyclohexoxycarbonyl, etc.], aryloxycarbonyl [e.g., (C6-C18 aryloxy)carbonyl such as phenoxycarbonyl, naphthoxycarbonyl, etc.], and aralkyloxycarbonyl [e.g., (C7-C19 aralkyloxy)carbonyl such as benzyloxycarbonyl, phenethyloxycarbonyl, etc.].

[0043] In this specification, "R rExamples of "OSO2-" include alkoxysulfonyl (e.g., C1-C10 alkoxysulfonyl such as methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, etc.), cycloalkoxysulfonyl (e.g., C3-C7 cycloalkoxysulfonyl such as cyclopentoxysulfonyl, cyclohexoxysulfonyl, etc.), aryloxysulfonyl (e.g., C6-C18 aryloxysulfonyl such as phenoxysulfonyl, naphthoxysulfonyl, etc.), and aralkyloxysulfonyl (e.g., C7-C19 aralkyloxysulfonyl such as benzyloxysulfonyl, phenethyloxysulfonyl, etc.).

[0044] In this specification, "a hydrocarbon group which may have one or more substituents"; "An alkyl group which may have one or more substituents" "an alkenyl group optionally having one or more substituents"; "an alkynyl group optionally having one or more substituents" "a cycloalkyl group optionally having one or more substituents"; "a cycloalkenyl group optionally having one or more substituents", "a cycloalkadienyl group optionally having one or more substituents", "an aryl group optionally having one or more substituents"; "an aralkyl group optionally having one or more substituents"; "a non-aromatic heterocyclic group optionally having one or more substituents", and "Heteroaryl group optionally having one or more substituents" Examples of the "substituents" in the above are a halo group, a nitro group, a cyano group, an oxo group, a thioxo group, a carboxyl group, an amino group, a quaternary ammonium group, a sulfo group, a sulfamoyl group, a sulfinamoyl group, a sulfenamoyl group, R r O-, R r CO-, R r COO-, R r SO2-, R r OCO- and R r OSO2- (wherein Rr has the same meaning as above.

[0045] Among the substituents, examples of the "halo group" include a fluoro group, a chloro group, a bromo group, and an iodo group.

[0046] The number of such substituents can be within the range of 1 to the maximum number of possible substitutions (eg, 1, 2, 3, 4, 5, 6).

[0047] In this specification, the term "electron-withdrawing group" refers to a group whose σp value according to Hammett's rule is positive.

[0048] 2. Method for producing difluorinated compound (1) The method for producing a difluorinated compound of compound (1) includes step A of reacting compound (1) with a fluorine source (A), an iodine source (B), and compound (C) to difluorinate compound (1).

[0049] 2-1. Compound (1) In one embodiment of compound (1), R 1 and R 2 are independently a hydrogen atom, an alkyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, an aryl group which may have one or more substituents, an aralkyl group which may have one or more substituents, a non-aromatic heterocyclic group which may have one or more substituents, a cyano group, a formyl group, R A O-, R A CO-, R A SO2-, R A COO-, (R A )(R B )NCO-, R A OCO-, R A CONR B -, R A OSO2-, or (R A )(R B )NSO2-(wherein R A and R Bare each independently an alkyl group which may have one or more substituents, an aryl group which may have one or more substituents, or an aralkyl group which may have one or more substituents.

[0050] The substituent may be any group having a structure that can be substituted, for example, at least one selected from the group consisting of a halo group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, an arylcarbonyloxy group, an aryloxycarbonyl group, and an aryl group. The number of the substituents may be selected from the range of 1 to the maximum number that can be substituted (e.g., 1, 2, or 3).

[0051] In the above embodiment, R 1 and R 2 At least one of the groups is a cyano group, a formyl group, or R A CO-, R A SO2-, R A OCO-, R A The reaction also proceeds with compounds (1) having such electron-deficient double or triple bonds.

[0052] In another embodiment of compound (1), R 1 and R 2 preferably forms a ring together with the two adjacent carbon atoms. A ring is usually formed when the symbol is a double bond and n is 2. Examples of such rings include cycloalkene rings corresponding to the groups exemplified as "cycloalkenyl groups" and non-aromatic heterocyclic rings corresponding to the groups having a carbon-carbon double bond among the groups exemplified as "non-aromatic heterocyclic groups."

[0053] The ring may have one or more substituents. Examples of the substituents include a hydrocarbon group, a halo group, a nitro group, a cyano group, an oxo group, a thioxo group, a carboxyl group, a sulfo group, a sulfamoyl group, a sulfinamoyl group, a sulfenamoyl group, and R r O-, Rr CO-, R r COO-, R r SO2-, R r OCO- and R r OSO2- (wherein R r has the same meaning as defined above.) The number of the substituents can be selected from the range of 1 to the maximum number of substituents possible (e.g., 1, 2, 3, 4, 5).

[0054] A suitable example of compound (1) is a compound represented by the following formula (1A): [ka] (In the formula, R 11 , R 12 , R 21 , and R 22 are independently a hydrogen atom or an organic group; R 11 and R 12 , or R 21 and R 22 is taken together with one adjacent carbon atom to form a ring, or R 11 and R 21 , R 11 and R 22 , R 12 and R 21 , or R 12 and R 22 forms a ring together with two adjacent carbon atoms, symbol: [ka] indicates a cis or trans configuration. and a compound represented by the following formula (1B): [ka] (In the formula, R 13 and R 23 are independently a hydrogen atom or an organic group. The compound includes compounds represented by the formula:

[0055] In one embodiment of compound (1A), R 11 , R 12 , R 21 , and R 22 are independently a hydrogen atom, an alkyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, an aryl group which may have one or more substituents, an aralkyl group which may have one or more substituents, a non-aromatic heterocyclic group which may have one or more substituents, a cyano group, a formyl group, R A O-, R A CO-, R A SO2-, R A COO-, (R A )(R B )NCO-, R A OCO-, R A CONR B -, R A OSO2-, or (R A )(R B )NSO2-(wherein R A and R B are each independently an alkyl group which may have one or more substituents, an aryl group which may have one or more substituents, or an aralkyl group which may have one or more substituents.

[0056] In the above embodiment, R 22 is preferably a hydrogen atom, and R 12 and R 22 It is more preferable that R is a hydrogen atom. 12 , R 21 , and R 22 It is also preferred that is a hydrogen atom.

[0057] In the above embodiment, R 12 and R 22 is a hydrogen atom, and R 11 and R 21 It is also preferable that R is other than a hydrogen atom. The reaction proceeds successfully even for compound (1) having such a double bond inside. 11and R 21 At least one of the groups is a cyano group, a formyl group, or R A CO-, R A SO2-, R A OCO-, R A The reaction also proceeds for compounds (1) having electron-deficient double bonds.

[0058] Suitable examples of compound (1A) include compounds represented by the following formulae (1a) to (1d): [ka] (In the formula, R 1a is an alkyl group which may have one or more substituents, an aryl group which may have one or more substituents, or an aralkyl group which may have one or more substituents, and R 1b and R 2b are independently an alkyl group which may have one or more substituents, an aryl group which may have one or more substituents, or an aralkyl group which may have one or more substituents, R 1c represents a hydrogen atom, an alkyl group which may have one or more substituents, an aryl group which may have one or more substituents, or an aralkyl group which may have one or more substituents, R 2c is an alkyl group which may have one or more substituents, R 1d represents a hydrogen atom, an alkyl group which may have one or more substituents, an aryl group which may have one or more substituents, or an aralkyl group which may have one or more substituents, R 2d is an alkyl group which may have one or more substituents, an aryl group which may have one or more substituents, or an aralkyl group which may have one or more substituents. The substituent may be any group having a structure that can be substituted with the target, and may be, for example, at least one selected from the group consisting of a halo group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, an arylcarbonyloxy group, an aryloxycarbonyl group, and an aryl group. The number of the substituents may be selected from the range of 1 to the maximum number that can be substituted (e.g., 1, 2, or 3). In one embodiment of compound (1a), R 1a represents an alkyl group optionally having one or more substituents (e.g., a halo group, a hydroxy group, an alkoxycarbonyl group), or an aralkyl group optionally having one or more substituents (e.g., a halo group, a hydroxy group, an alkoxycarbonyl group). In one embodiment of compound (1c), R 1c is an aryl group which may have one or more substituents (eg, halo groups). In one embodiment of compound (1d), R 1d is an aryl group which may have one or more substituents (e.g., halo groups), and R 2d is an alkyl group which may have one or more substituents (eg, halo groups), or an aryl group which may have one or more substituents (eg, halo groups).

[0059] In one embodiment of compound (1B), R 13 and R 23 are independently hydrogen atoms, 1 an alkyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, an aryl group which may have one or more substituents, an aralkyl group which may have one or more substituents, a non-aromatic heterocyclic group which may have one or more substituents, a cyano group, a formyl group, R A O-, R A CO-, R A SO2-, R A COO-, (R A )(R B )NCO-, R A OCO-, RA CONR B -, R A OSO2-, or (R A )(R B )NSO2-(wherein R A and R B are each independently an alkyl group which may have one or more substituents, an aryl group which may have one or more substituents, or an aralkyl group which may have one or more substituents.

[0060] In the above embodiment, R 13 and R 23 It is also preferable that R is other than a hydrogen atom. The reaction proceeds successfully even with compound (1) having such a triple bond inside. 13 and R 23 At least one of the groups is a cyano group, a formyl group, or R A CO-, R A SO2-, R A OCO-, R A The reaction also proceeds with compound (1) having such an electron-deficient triple bond.

[0061] 2-2. Fluorine Source (A) In the method for producing a difluoride of compound (1), the fluorine source (A) is at least one selected from hydrogen fluoride, a hydrogen fluoride salt, and a fluoride salt.

[0062] Of the fluorine sources (A), hydrogen fluoride can be used as an aqueous solution (hydrofluoric acid). The aqueous solution can be, for example, an aqueous solution with a hydrogen fluoride concentration of 10 to 70 mass %.

[0063] Among the fluorine sources (A), examples of hydrogen fluoride salts include amine hydrogen fluoride salts and ammonium hydrogen fluoride salts.

[0064] In the amine hydrogen fluoride salt, the amine can be a chain amine or a cyclic amine.

[0065] Examples of linear amines include aliphatic primary amines, aliphatic secondary amines, and aliphatic tertiary amines. Examples of aliphatic primary amines include C1-C6 alkylamines such as methylamine, ethylamine, propylamine, butylamine, pentylamine, and hexylamine. Examples of aliphatic secondary amines include di-C1-C6 alkylamines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, and dihexylamine. Examples of aliphatic tertiary amines include tri-C1-C6 alkylamines such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine, and N,N,N',N'-tetramethylethylenediamine.

[0066] Examples of cyclic amines include aliphatic cyclic amines and aromatic cyclic amines. Examples of aliphatic cyclic amines include piperidine, piperazine, pyrrolidine, morpholine, N-methylpiperazine, N-methylpyrrolidine, 5-diazabicyclo[4.3.0]nonan-5-ene, and 1,4-diazabicyclo[2.2.2]octane. Examples of aromatic cyclic amines include pyridine, pyrimidine, pyrazine, quinoline, and imidazole.

[0067] Suitable examples of the hydrogen fluoride amine salt include hydrogen fluoride triethylamine salt (EtN·xHF (x is an integer of 1 or more, preferably 1 to 10, and more preferably 3 to 7)), hydrogen fluoride pyridine salt (Py·xHF (x is an integer of 1 or more, preferably 1 to 10)) such as Oller's reagent, and combinations thereof.

[0068] An example of an ammonium hydrogen fluoride salt is represented by the following formula (A1): NQ4F·xHF (A1) (In the formula, each Q is independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, or two or three Qs are bonded to each other to form a ring, and x is an integer of 1 or greater.) The compound includes compounds represented by the formula:

[0069] In one embodiment of compound (A1), Q is preferably an alkyl group, more preferably a C1-C6 alkyl group. x is preferably 1 to 10.

[0070] Suitable examples of compound (A1) include ammonium hydrogen fluoride (NH4F·HF), hydrogen fluoride-tetramethylammonium fluoride, hydrogen fluoride-tetraethylammonium fluoride, hydrogen fluoride-tetrapropylammonium fluoride, and hydrogen fluoride-tetrabutylammonium fluoride.

[0071] Among the fluorine sources (A), examples of fluoride salts include those represented by the following formula (A2): M 1 F m1 (A2) (In the formula, M 1 is an alkali metal or alkaline earth metal; and m1 is M 1 1 or 2 depending on the valence of The compound includes compounds represented by the formula:

[0072] In one embodiment of compound (A2), Preferably, M 1 is Li, Na, K, Ca, or Cs, More preferably, M 1 is Na, K, or Ca, More preferably, M 1 is K.

[0073] The fluoride salt is preferably an alkali metal fluoride salt (M 1 is an alkali metal and m1 is 1) or an alkaline earth metal fluoride salt (M 1 is an alkaline earth metal and m1 is 2).

[0074] The fluorine source (A) can be used alone or in combination of two or more. In a preferred embodiment, the fluorine source (A) is at least one selected from hydrogen fluoride, hydrogen fluoride amine salts, alkali metal fluoride salts, and alkaline earth metal fluoride salts.

[0075] The amount of the fluorine source (A) used is not particularly limited. The lower limit of the amount of the fluorine source (A) used can be, for example, 0.1 mol or more, preferably 0.2 mol or more, more preferably 0.3 mol or more, even more preferably 0.4 mol or more, and particularly preferably 0.5 mol or more, per mol of compound (1). The upper limit of the amount of the fluorine source (A) used can be, for example, 1000 mol or less, preferably 500 mol or less, more preferably 300 mol or less, even more preferably 100 mol or less, even more preferably 90 mol or less, and particularly preferably 80 mol or less, per mol of compound (1). The amount of the fluorine source (A) used can be, for example, within a range of 0.1 to 1000 mol, preferably within a range of 0.2 to 500 mol, more preferably within a range of 0.3 to 100 mol, even more preferably within a range of 0.4 to 90 mol, and particularly preferably within a range of 0.5 to 80 mol.

[0076] The fluorine source (A) remaining after the reaction may be trapped and discarded, but is preferably recovered and reused from the viewpoint of production costs. The trapped fluorine source (A) remaining after the reaction may be washed with, for example, water or alkaline water.

[0077] 2-3. Iodine Source (B) In the method for producing a difluoride of compound (1), the iodine source (B) is at least one selected from iodine and ammonium iodide. There have been no reports of a difluorination reaction using an iodine source in an amount less than the equivalent. By using a reduced amount of the iodine source, separation or removal becomes easier, thereby reducing production costs.

[0078] In the iodine source (B), iodine means molecular iodine (I2).

[0079] Among the iodine sources (B), ammonium iodide is, for example, a compound represented by the formula: N(R B )4I (where 4 R B are independently a hydrogen atom or an alkyl group which may have one or more substituents.

[0080] R B Suitable examples include C1-C12 alkanes which may have one or more substituents. Examples of the substituents include a halogen atom (e.g., an iodine atom). The number of the substituents can be selected from the range of 1 to the maximum number of substituents (e.g., 1, 2, or 3).

[0081] Examples of ammonium iodides are ammonium iodide (NH4I), tetramethylammonium iodide (TMAI), tetraethylammonium iodide (TEAI), tetrapropylammonium iodide, tetrabutylammonium iodide (TBAI), tetrapentylammonium iodide, tetrahexylammonium iodide, tetraheptylammonium iodide, tetraoctylammonium iodide, ethyltripropylammonium iodide, 5-azoniaspiro[4,4]nonane iodide, and benzyltriethylammonium iodide. iodide, dimethyldioctadecylammonium iodide, ethyltrimethylammonium iodide, (2-hydroxyethyl)triethylammonium iodide, triethylphenylammonium iodide, trimethylphenylammonium iodide, tributylmethylammonium iodide, choline iodide, butylthiocholine iodide, β-methylcholine iodide, acetylcholine iodide, acetylthiocholine iodide, benzoylcholine iodide, benzoylthiocholine iodide, isopropamide iodide, and decamethonium iodide.

[0082] The iodine source (B) can be used alone or in combination of two or more.

[0083] The amount of iodine source (B) used is not particularly limited as long as it is less than 1.0 mol per mole of compound (1). The lower limit of the amount of iodine source (B) used is, for example, 0.001 mol or more, preferably 0.005 mol or more, more preferably 0.01 mol or more, even more preferably 0.05 mol or more, and particularly preferably 0.1 mol or more per mole of compound (1). The upper limit of the amount of iodine source (B) used is preferably 0.9 mol or less, more preferably 0.7 mol or less, even more preferably 0.5 mol or less, even more preferably 0.4 mol or less, and particularly preferably 0.2 mol or less per mole of compound (1). The amount of iodine source (B) used is, for example, in the range of 0.001 mol or more to less than 1.0 mol per mole of compound (1), preferably 0.005 to 0.9 mol, more preferably 0.01 to 0.7 mol, even more preferably 0.05 to 0.4 mol, and even more preferably 0.1 to 0.2 mol. Even when such a small amount of the iodine source (B) is used, the reaction proceeds in good yield.

[0084] The residual iodine source (B) after the reaction may be trapped and discarded, but is preferably recovered and reused from the viewpoint of production costs. The residual trapped iodine source after the reaction may be washed with, for example, water or alkaline water. Unlike conventional organic iodine compounds, the iodine source (B) can be easily removed by washing with water. The use of such an iodine source (B) in a relatively low amount By using the above method, the difluorinated compound as the target product can be easily purified, and therefore the production cost of the difluorinated compound can be further reduced.

[0085] 2-4. Compound (C) In the method for producing a difluorinated product of compound (1), compound (C) is a compound having at least one fluorinated quaternary nitrogen atom in the molecule.

[0086] In one embodiment, compound (C) is a salt comprising a cation having at least one fluorinated quaternary nitrogen atom and a counteranion.

[0087] In the above embodiment, the compound (C) may be, for example, a compound represented by the general formula (2): (R C )3N + -F (2) (wherein three R C are independently an organic group, or three R C may each be joined together with the adjacent nitrogen atom to form a ring. The compound may contain a cation represented by the following formula (hereinafter, sometimes simply referred to as "cation (2)").

[0088] In general formula (2), R C Suitable examples include C1-C12 alkanes which may have one or more substituents. Examples of the substituents include a halogen atom (e.g., an iodine atom). The number of the substituents can be selected from the range of 1 to the maximum number of substituents (e.g., 1, 2, or 3).

[0089] In general formula (2), three R C preferably form a ring together with the adjacent nitrogen atom. Examples of such rings include non-aromatic heterocycles corresponding to the groups having a tertiary nitrogen atom among the groups exemplified as "non-aromatic heterocyclic groups," and aromatic heterocycles corresponding to the groups having a tertiary nitrogen atom among the groups exemplified as "heteroaryl groups." Examples of such rings include bicyclo rings such as azabicyclo rings and diazabicyclo rings. That is, specific examples of such rings include 5-diazabicyclo[4.3.0]nonan-5-ene and 1,4-diazabicyclo[2.2.2]octane.

[0090] The ring may have one or more substituents. Examples of the substituents include a halogen atom, a hydroxy group, an alkyl group (e.g., a C1-C15 alkyl group) optionally having one or more further substituents (e.g., a halogen atom), an alkenyl group (e.g., a C1-C15 alkenyl group) optionally having one or more further substituents (e.g., a halogen atom), an alkynyl group (e.g., a C1-C15 alkynyl group) optionally having one or more further substituents (e.g., a halogen atom), an aryl group (e.g., a C6-C15 aryl group) optionally having one or more further substituents (e.g., a halogen atom, an alkyl group), a nitro group, a cyano group, R F O-, R F CO-, R F SO2-, R F COO-, (R F )(R G )NCO-, R F OCO-, R F CONR G -, R F OSO2-, and (R F )(R G )NSO2-(wherein R F and R G are independently an alkyl group which may have one or more substituents (e.g., a halogen atom), or an aryl group which may have one or more substituents (e.g., a halogen atom, an alkyl group). The number of the substituents can be selected from within the range from 1 to the maximum number of substituents (e.g., 1, 2, 3, 4, or 5).

[0091] Compound (C) preferably contains a conjugate base of a Bronsted acid as a counter anion of cation (2). Examples of Bronsted acids include inorganic and organic acids. Examples of inorganic acids include hydrofluoric acid, hydrochloric acid, perchloric acid, sulfuric acid, persulfuric acid, fluorosulfuric acid, chlorosulfuric acid, phosphoric acid, boric acid, nitric acid, HBF, HBF, HBCl, HBClF, HBBrF, HPF, HAsF, HSbF, HSbF, HSbCl, HSbClF, and HSbF. 11 , HAlF4, HAlCl4, HAlCl3F, and HAlF3Cl. Examples of organic acids include carboxylic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, and pentafluoropropionic acid, sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid, ethanesulfonic acid, perfluoroethanesulfonic acid, propanesulfonic acid, perfluoropropanesulfonic acid, butanesulfonic acid, perfluorobutanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, and nitrobenzenesulfonic acid, alkyl sulfuric acids such as methyl sulfuric acid, and sulfonylimide acids such as bis(methanesulfonyl)imide acid and bis(trifluoromethanesulfonyl)imide acid.

[0092] Examples of conjugate bases of the Bronsted acids include: - OClO3, - OSO2OH, - OSO2F, - OSO2Cl, - BF4, - B2F7, - PF6, - AsF6, - SbF6, - AlF4, - AlCl4, - SbCl6, - SbCl5F, - Sb2F 11 , - OSO2CH3, - OSO2CF3, - OSO2CCl3, - OSO2C4F9, - OSO2C6H5, - OSO2C6H4CH3, - OSO2C6H4NO2, - OSO2OCH3, - N(SO2CH3)2, and - Includes N(SO2CF3)2.

[0093] Examples of compound (C) include 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2,2,2]octane bis(tetrafluoroborate) (Selectfluor), 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2,2,2]octane fluoride (tetrafluoroborate), 1-fluoro-4-hydroxy-1,4-diazoniabicyclo[2,2,2]octane bis(tetrafluoroborate), 1-fluoro-4-methyl-1,4-diazoniabicyclo[2,2,2]octane bis(tetrafluoroborate), and N-fluoro-quinuclidinium triflate.

[0094] In the above embodiment, compound (C) may be an N-fluoropyridinium salt or a multimer thereof. As will be apparent to those skilled in the art, the above cation (2) encompasses N-fluoropyridinium cations and multimers thereof. In this case, three R C are each taken together with the adjacent nitrogen atom to form a pyridine ring.

[0095] Examples of N-fluoropyridinium salts include compounds represented by the following formula (2-1), which may have one or more substituents: [ka] (wherein X represents the conjugate base of a Bronsted acid). Examples of the compound include compounds represented by the following formula:

[0096] An example of the N-fluoropyridinium salt multimer is a multimer of compound (2-1) which may have one or more substituents. One example of the multimer is a compound of the following formula (2-2): [ka] (wherein X has the same meaning as defined above). Examples of the compound include compounds represented by the following formula:

[0097] The compound (2-2) which may have one or more substituents is a compound represented by the following formulae (2-3) to (2-7), which may have one or more substituents: [ka] (wherein X has the same meaning as defined above). Among these, the compound (2-3) which may have one or more substituents is preferred, and the compound (2-3) (which has no substituents) is more preferred.

[0098] Another example of the N-fluoropyridinium salt polymer is a polymer represented by the following formula (2-8): [ka] (wherein X is as defined above, L is a single bond, —CH—, or —O—, and z is an integer of 2 or greater.) Examples of the polymer include a polymer containing a polymer unit represented by the following formula:

[0099] The content of the polymerized units (2-8) in the polymer is preferably 50 mol % or more, and more preferably 60 mol % or more.

[0100] The polymer may contain copolymerized units in addition to the polymerized units (2-8). Examples of the copolymerized units include arylenes (e.g., C6-C12 arylenes such as phenylene and naphthalenediyl) which may have one or more substituents, and heteroarylenes (e.g., thiophenediyl, furandiyl, pyrrolediyl, pyridinediyl) which may have one or more substituents. Examples of the substituents that may be substituted on these copolymerized units include the same as the examples of the substituents that may be substituted on the polymerized units (2-8).

[0101] Although z is not particularly limited as long as it is an integer of 2 or more, it is preferably 2, 3, or 4. The average molecular weight of the polymer is preferably within the range of 100 to 500,000.

[0102] Examples of the conjugate base of the Bronsted acid represented by X, which constitutes the compounds (2-1) to (2-7) and the polymer (2-8), include the same as the "conjugate base of the Bronsted acid" exemplified as the counter anion of the cation (2). The conjugate base can be used alone or in combination of two or more.

[0103] Examples of the substituents that can be substituted on the compounds (2-1) to (2-7) and the polymer (2-8) include the three R c The number of substituents can be selected from the range of 1 to the maximum number of substituents (e.g., 1, 2, 3, 4, 5, 6, 7, 8).

[0104] Examples of N-fluoropyridinium salts and multimers thereof include 1-fluoro-pyridinium pyridine heptafluorodiborate, 1-fluoro-pyridinium tetrafluoroborate, 1-fluoro-pyridinium triflate, 1-fluoro-2,6-dichloropyridinium tetrafluoroborate, and 1,1′-difluoro-2,2′-bipyridinium bis(tetrafluoroborate) (Synfluor).

[0105] In the above embodiment, compound (C) is preferably at least one selected from 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2,2,2]octane bis(tetrafluoroborate) (Selectfluor), and N-fluoropyridinium salts and multimers thereof, and more preferably 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2,2,2]octane bis(tetrafluoroborate) (Selectfluor).

[0106] The compound (C) can be used alone or in combination of two or more.

[0107] The amount of compound (C) used is not particularly limited. The lower limit of the amount of compound (C) used can be, for example, 0.1 moles or more, preferably 0.2 moles or more, more preferably 0.3 moles or more, even more preferably 0.4 moles or more, and particularly preferably 0.5 moles or more, relative to 1 mole of compound (1). The upper limit of the amount of compound (C) used can be, for example, 10 moles or less, preferably 9 moles or less, more preferably 8 moles or less, even more preferably 7 moles or less, and even more preferably 6 moles or less, relative to 1 mole of compound (1). The amount of compound (C) used is, for example, within the range of 0.1 to 10 moles, preferably within the range of 0.2 to 9 moles, more preferably within the range of 0.3 to 8 moles, and even more preferably within the range of 0.5 to 10 moles, relative to 1 mole of compound (1). can be in the range of 0.4 to 7 mol, and even more preferably in the range of 0.5 to 6 mol.

[0108] Compound (C) is also preferably used in an amount in which the number of F atoms on N atoms in compound (C) exceeds 1 mole (for example, in a range of 1.1 to 3 moles, a range of 1.2 to 2.5 moles, or a range of 1.3 to 2 moles) per mole of compound (1).

[0109] From the viewpoint of production costs, it is preferable to recover and reuse the compound (C) remaining after the reaction.

[0110] The fluorine source (A), the iodine source (B), and the compound (C) may be added to the reaction system separately or all at once (for example, in the form of a composition described below).

[0111] In a preferred embodiment of the manufacturing method of the present disclosure, the fluorine source (A) is hydrogen fluoride; the iodine source (B) is iodine or tetrabutylammonium iodide, and Compound (C) is 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2,2,2]octane bis(tetrafluoroborate) (Selectfluor) or 1,1′-difluoro-2,2′-bipyridinium bis(tetrafluoroborate) (Synfluor).

[0112] 2-5. Solvent The reaction of step A can be carried out in the presence or absence of a solvent. The solvent may be either a nonpolar solvent or a polar solvent. The solvent may be an ester, a ketone, an aromatic hydrocarbon, an alcohol, an ether, an amine, a nitrogen-containing polar organic compound, a nitrile, a halogenated hydrocarbon, an aliphatic hydrocarbon, a fluorinated solvent, a carbonate, or other solvent, or a combination thereof.

[0113] Examples of the ester as the solvent include ethyl acetate, butyl acetate, amyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and a preferred example thereof is ethyl acetate.

[0114] Examples of ketones as the solvent include acetone, methyl ethyl ketone, diethyl ketone, hexanone, methyl isobutyl ketone, heptanone, diisobutyl ketone, acetonylacetone, methylhexanone, and acetophenone, cyclohexanone, diacetone alcohol, and a preferred example thereof is acetone.

[0115] Examples of aromatic hydrocarbons as the solvent include benzene, toluene, xylene, and ethylbenzene, and preferred examples thereof include benzene and toluene.

[0116] Examples of alcohols as the solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, pentanol, hexanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, trimethylene glycol, and hexanetriol, and preferred examples thereof include methanol and ethanol.

[0117] Examples of the ether solvent include diethyl ether, dibutyl ether, tetrahydrofuran, tetrahydropyran, dioxane, dimethoxyethane, diethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Suitable examples of the ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME; also known as 1-methoxy-2-propanol), propylene glycol monoethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, and anisole, and suitable examples thereof include diethyl ether and tetrahydrofuran.

[0118] Examples of the amine solvent include monoethanolamine, diethanolamine, and triethanolamine.

[0119] Examples of the nitrogen-containing polar organic compound as the solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone, and preferred examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.

[0120] Examples of the nitrile as the solvent include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, and adiponitrile, and a preferred example thereof is acetonitrile.

[0121] Examples of halogenated hydrocarbons as the solvent include dichloromethane, dichloroethane, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane, chlorobenzene, dichlorobenzene, and chlorotoluene, and preferred examples thereof include dichloromethane and chloroform.

[0122] Examples of aliphatic hydrocarbons as the solvent include hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral spirits, and preferred examples thereof include cyclohexane and heptane.

[0123] Examples of the fluorine-based solvent include perfluorobenzene, trifluorotoluene, ditrifluorobenzene, and trifluoroethanol, and preferred examples thereof include perfluorobenzene and trifluoroethanol.

[0124] Examples of carbonates as the solvent include tetralin dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate, and preferred examples thereof include ethylene carbonate and propylene carbonate.

[0125] Examples of such other solvents include acetic acid, pyridine, dimethyl sulfoxide, sulfolane, and water.

[0126] The solvent may preferably be at least one selected from aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and nitriles, more preferably at least one selected from halogenated hydrocarbons and nitriles, and even more preferably halogenated hydrocarbons.

[0127] The solvents can be used alone or in combination of two or more.

[0128] The amount of solvent used is, for example, Relative to 1 part by mass of compound (1), Usually, in the range of 0 to 200 parts by mass, Preferably, in the range of 1 to 100 parts by mass, and More preferably, it is within the range of 5 to 50 parts by mass. It can be.

[0129] Each component may be added to the reaction system in step A all at once, in several batches, or continuously.

[0130] 2-6. Temperature and time The temperature of step A is Usually in the range of 0 to 200°C. Preferably, in the range of 10 to 100°C. More preferably, in the range of 20 to 100°C, and More preferably, the temperature is within the range of 40 to 60°C. It can be.

[0131] The time for process A is Usually within the range of 0.1 to 72 hours Preferably, within a range of 0.5 to 48 hours, and More preferably, within the range of 1 to 36 hours. It can be.

[0132] 2-6. Optional additional step B The method for producing a fluorine adduct of compound (1) may further include step B of isolating or purifying compound (1) in addition to step A. Isolation or purification of compound (1) can be carried out by a method such as filtration, extraction, stripping, dissolution, concentration, precipitation, dehydration, adsorption, or chromatography, or a combination thereof.

[0133] In one embodiment, Step B is a step of separating compound (C) and / or a derivative thereof from the reaction mixture obtained by the reaction of Step A. The separation step is preferably a step of reducing the reaction mixture with a reducing agent. By such a reduction treatment, compound (C) and / or a derivative thereof can be separated simply and to a high degree.

[0134] Examples of the reducing agent include sulfur-based reducing agents, and preferred examples thereof include hydrogen sulfites, sulfites, and thiosulfates. Examples of hydrogen sulfites include ammonium hydrogen sulfite and alkali metal hydrogen sulfites such as sodium hydrogen sulfite and potassium hydrogen sulfite. Examples of sulfites include alkali metal sulfites such as sodium sulfite and potassium sulfite. Examples of thiosulfates include alkali metal thiosulfates such as sodium thiosulfate and potassium thiosulfate.

[0135] The reducing agents can be used alone or in combination of two or more.

[0136] In another embodiment, step B is a step of isolating or purifying compound (1) by separating or removing the fluorine source (A), the iodine source (B), and compound (C) from the reaction mixture obtained by the reaction in step A. This step can be carried out by a simple method such as extraction, back-extraction, or water washing. This step can also reduce the load of column chromatography and distillation, which are necessary when using an organic iodine compound, and therefore can significantly reduce the cost required for producing compound (1). Specifically, the method for producing a difluorinated product of compound (1) reduces the distillation time, the amount of adsorbent packed in the column, and the amount of solvent. It is possible.

[0137] 3. Composition The composition of the present disclosure comprises (B) at least one iodine source selected from iodine and ammonium iodide, and (C) a compound having at least one fluorinated quaternary nitrogen atom in the molecule (provided that when the iodine source (B) is iodine, the compound (C) is not an N-fluoropyridinium salt or a polymer thereof).

[0138] Examples of the iodine source (B) and the compound (C) include those exemplified in the above section "2-2. Production method for a fluorine adduct of compound (1)." In the above composition, the iodine source (B) is preferably ammonium iodide.

[0139] In one embodiment, the composition further comprises (A) at least one fluorine source selected from hydrogen fluoride, a hydrogen fluoride salt, and a fluoride salt. Examples of the fluorine source (A) include those exemplified in "2-2. Method for producing a fluorine adduct of compound (1)" above.

[0140] In the composition, the lower limit of the content of the fluorine source (A) can be, for example, 0.1 mol or more, 0.2 mol or more, or 0.3 mol or more per mol of the compound (C). The upper limit of the content of the fluorine source (A) can be, for example, 600 mol or less, 500 mol or less, 400 mol or less, 300 mol or less, 200 mol or less, 100 mol or less, 90 mol or less, 80 mol or less, or 70 mol or less per mol of the compound (C). In the composition, the fluorine source (A) is contained in an amount, for example, within a range of 0.1 to 600 mol, preferably within a range of 0.2 to 300 mol, and more preferably within a range of 0.3 to 70 mol, per mol of the compound (C).

[0141] In the composition, the lower limit of the content of the iodine source (B) can be, for example, 0.001 mol or more, 0.005 mol or more, 0.01 mol or more, 0.02 mol or more, 0.05 mol or more, or 0.1 mol or more per mol of compound (C). The upper limit of the content of the iodine source (B) can be, for example, 1 mol or less, 0.9 mol or less, 0.8 mol or less, 0.7 mol or less, 0.6 mol or less, 0.5 mol or less, 0.4 mol or less, 0.3 mol or less, 0.2 mol or less, or 0.1 mol or less per mol of compound (C). In the composition, the iodine source (B) is contained in an amount of, for example, 0.001 to 1 mol, preferably 0.005 to 0.4 mol, and more preferably 0.01 to 0.2 mol per mol of compound (C).

[0142] The composition can be suitably used as a fluorinating agent (particularly, a fluorinating agent for compounds having a carbon-carbon double bond or triple bond, such as compound (1)). Therefore, the present disclosure encompasses a fluorinating agent (particularly, a fluorinating agent for compounds having a carbon-carbon double bond or triple bond, such as compound (1)) comprising the composition.

[0143] In the above composition, the fluorine source (A), the iodine source (B), and the compound (C) can be added to the reaction system all at once, or they can be separated and removed all at once. [Example]

[0144] Hereinafter, one embodiment of the present disclosure will be described in more detail by way of examples, but the present disclosure is not limited thereto.

[0145] Example 1a 1-Dodecene (0.3 mmol), iodine (0.03 mmol) in DCE (dichloroethane) (1 mL) TEA (triethylamine)·5HF (0.5 mL, approximately 12 mmol HF) and Selectfluor™ (0.6 mmol) were added to the mixture, and the mixture was allowed to react at 40°C for 22 hours. The reaction mixture was poured into a saturated aqueous solution of sodium bicarbonate, and then sodium sulfite was added. The product was extracted three times with dichloromethane and dissolved in anhydrous sulfuric acid. The mixture was dried over sodium hydroxide, and the solvent was removed using an evaporator. Methyl 4-fluorobenzoate was added as an internal standard, and the yield of 1,2-difluorododecane was calculated. 19 Analysis by F NMR showed it to be 52%.

[0146] Example 1b By carrying out the same procedure as in Example 1a except that the reaction temperature was changed from 40°C to 50°C, 1,2-difluorododecane was obtained in a yield of 67%.

[0147] [Example 1c] By carrying out the same procedure as in Example 1a except that the reaction temperature was changed from 40°C to 60°C, 1,2-difluorododecane was obtained in a yield of 69%.

[0148] [Example 1d] By carrying out the same procedure as in Example 1a except that the reaction temperature was changed from 40°C to 70°C, 1,2-difluorododecane was obtained in a yield of 67%.

[0149] [Example 1e] The same procedure as in Example 1a was carried out except that the reaction temperature was changed from 40°C to 60°C and the amount of iodine used was changed from 0.03 mmol to 0.015 mmol, and 1,2-difluorododecane was obtained in a yield of 60%. I got it.

[0150] [Example 1f] The same procedure as in Example 1a was carried out except that the reaction temperature was changed from 40°C to 60°C and iodine (0.03 mmol) was replaced with tetrabutylammonium iodide (TBAI; 0.03 mmol), thereby obtaining 1,2-difluorododecane in a yield of 56%.

[0151] [Example 1g] The reaction temperature was changed from 40°C to 60°C, and Selectfluor™ was changed to Synfluor™. Except for this, the same procedure as in Example 1a was carried out to obtain 1,2-difluorododecane in a yield of 56%.

[0152] [Comparative Example 1] When the same procedure as in Example 1a was carried out except that iodine was not used, 1,2-difluorododecane was not obtained.

[0153] Comparative Example 2 The same procedure as in Example 1a was carried out except that the amount of iodine used was changed to 0.3 mmol and the reaction was carried out at room temperature for 21 hours, thereby obtaining 1-iodo-2-fluorododecane in a 100% yield. Dodecane was not obtained.

[0154] Comparative Example 3 Ethyl α-iodo-β-fluorocinnamate was obtained in 72% yield by the same procedure as in Example 1a, except that 1-dodecene was replaced with ethyl cinnamate, TEA (triethylamine)·5HF was replaced with Pyr·9HF (33 mmol HF), the amount of iodine used was changed to 0.3 mmol, and the reaction was carried out at room temperature for 21 hours. Ethyl 3,3-difluoro-2-phenylpropanoate was not obtained.

[0155] Example 2a 1,2-Difulvur was obtained by the same procedure as in Example 1c, except that 1-dodecene was replaced with 1-decene. Olodecane was obtained in 73% yield.

[0156] Example 2b The same procedure as in Example 1c was carried out, except that 1-dodecene was replaced with methyl 10-undecenoate. As a result, methyl 9,10-difluoroundecenoate was obtained in a yield of 68%.

[0157] [Example 2c] The same procedure as in Example 1c was carried out except that 1-dodecene was changed to 10-undecen-1-ol, thereby obtaining 10,11-difluoro-1-undecanol in a yield of 65%.

[0158] [Example 2d] 2,3-Difluoropropylbenzene was obtained in a yield of 73% by the same procedure as in Example 1c, except that 1-dodecene was changed to allylbenzene.

[0159] [Example 2e] The same procedure as in Example 1c was carried out except that 1-dodecene was changed to 2-allyltoluene, thereby obtaining 2-(2,3-difluoropropyl)toluene in a yield of 80%.

[0160] [Example 2f] N-(4,5-difluoropentenyl)phthalimide was obtained in a yield of 61% by the same procedure as in Example 1c, except that 1-dodecene was changed to N-(4-pentenyl)phthalimide.

[0161] Example 2g The same procedure as in Example 1c was carried out except that 1-dodecene was changed to 4-pentenyl benzoate, thereby obtaining 4,5-difluoropentyl benzoate in a yield of 65%.

[0162] Example 3a Ethyl cinnamate (0.3 mmol) and iodine (0.03 mmol) were dissolved in DCE (dichloroethane) (1 mL). Pyr·9HF (33 mmol HF) (0.31 mL, 40 mmol HF) and Selectfluor (0.6 mmol) were added to the solution, and the mixture was reacted at 60°C for 70 hours. The reaction mixture was poured into a saturated aqueous solution of sodium bicarbonate, and After that, sodium sulfite was added. Then, the mixture was extracted three times with dichloromethane and added with anhydrous sodium sulfate. The mixture was dried over an oven and the solvent was removed using an evaporator. Methyl 4-fluorobenzoate was added as an internal standard to determine the yield of ethyl 3,3-difluoro-2-phenylpropanoate. 19 Analysis by F NMR revealed that it was 86%.

[0163] Example 3b Ethyl 3,3-difluoro-2-(4-bromophenyl)propanoate was obtained in a yield of 81% by the same procedure as in Example 3a, except that ethyl cinnamate was replaced with ethyl 4-bromocinnamate and the reaction was carried out for 68 hours.

[0164] Example 3c Methyl 3,3-difluoro-2-(4-chlorophenyl)propanoate was obtained in a yield of 82% by the same procedure as in Example 3a, except that ethyl cinnamate was replaced with methyl 4-chlorocinnamate and the reaction was carried out for 68 hours.

[0165] [Example 3d] 2,2-Difluoroethylbenzene was obtained in a yield of 35% by the same procedure as in Example 3a, except that ethyl cinnamate was changed to styrene and the reaction was carried out for 22 hours.

[0166] [Example 3e] 1-Bromo-4-(2,2-difluoroethyl)benzene was obtained in a yield of 56% by the same procedure as in Example 3a, except that ethyl cinnamate was replaced with 4-bromostyrene and the reaction was carried out for 20 hours. Ta.

[0167] [Example 3f] 1-Chloro-4-(2,2-difluoroethyl)benzene was obtained in a yield of 64% by the same procedure as in Example 3a, except that ethyl cinnamate was replaced with 4-chlorostyrene and the reaction was carried out for 20 hours. Ta.

[0168] Example 4a An attempt was made to scale up the reaction of Example 1c. A solution of 1-dodecene (101 mg, 0.6 mmol) and iodine (15.2 mg, 0.06 mmol) in dichloroethane (DCE) (2 mL) was added with triethylamine (TEA)·5HF (1.0 mL, approximately 24 mmol HF) and Selectfluor™ (425 mg, 1.2 mmol), and the mixture was allowed to react at 60°C for 22 hours. The reaction mixture was poured into a saturated aqueous solution of sodium bicarbonate, followed by the addition of sodium sulfite. The product was extracted three times with hexane. The organic phases were combined, washed with water, and then purified. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and the solvent was removed using an evaporator. The extract was then dried in a desiccator to obtain 129 mg of a colorless oil. Quantitative analysis using methyl 4-fluorobenzoate as an internal standard revealed the following: 1 H NMR revealed that the purity of the compound was 88%. The yield was 92%.

[0169] Example 4b The reaction was carried out in the same manner as above. After the reaction, the reaction mixture was poured into a saturated aqueous solution of sodium bicarbonate, and then sodium sulfite was added. The product was extracted with ether (diethyl ether) three times. The organic phases were combined, washed with water, and then washed with saturated saline. The mixture was dried over anhydrous sodium sulfate, and the solvent was removed using an evaporator. The mixture was dried in a desiccator to obtain 126 mg of a pale yellow oil. Quantitative analysis using methyl 4-fluorobenzoate as an internal standard revealed that: 1 It was confirmed by H NMR that the product was 1,2-difluorododecane with a purity of 91%. The yield was 93%.

[0170] Comparative Example 4 A solution of 1-dodecene (67 mg, 0.4 mmol) and 4-iodotoluene (17 mg, 0.08 mmol) in dichloroethane (DCE) (2 mL) was added with triethylamine (TEA)·5HF (1.0 mL, approximately 24 mmol HF) and Selectfluor™ (213 mg, 0.6 mmol), and the mixture was allowed to react at 40°C for 21 hours. The mixture was poured into saturated sodium bicarbonate, and then sodium sulfite was added. The product was extracted three times with ethyl acetate. The organic phases were combined, washed with water, and then with saturated brine. Anhydrous sodium sulfate was added. The mixture was dried in a microwave oven, the solvent was removed using an evaporator, and the mixture was dried in a desiccator. Methyl 4-fluorobenzoate was added as an internal standard. 1 H NMR and 19 Quantitative analysis by F NMR confirmed that the product was 1,2-difluorododecane with a purity of 68%. The yield was 80%.

Claims

1. The following formula (1): 【Chemistry 1】 (In the formula, R １ and R ２ are independently a hydrogen atom or an organic group, or may be taken together with two adjacent carbon atoms to form a ring, n is 1 or 2; symbol: 【Chemistry 2】 is a double or triple bond. however, When the symbol is a triple bond, n is 1; When the symbol is a double bond, n is 2; Two R's １ may be the same or different from each other, Two R's ２ may be the same or different from each other, or Two R's １ , or two R ２ may form a ring together with the adjacent carbon atom.) A method for producing a difluorinated compound represented by the following formula: The compound represented by formula (1) (A) at least one fluorine source selected from hydrogen fluoride, hydrogen fluoride salts, and fluoride salts; (B) at least one iodine source selected from iodine and ammonium iodide; and (C) A compound having at least one fluorinated quaternary nitrogen atom in the molecule to difluorinate the compound represented by formula (1), The production method, wherein the amount of the iodine source (B) used is less than 1.0 mole per mole of the compound represented by formula (1).

2. 2. The method according to claim 1, wherein the iodine source (B) is iodine.

3. The method according to claim 1, wherein the amount of the iodine source (B) used is 0.2 moles or less per mole of the compound represented by formula (1).

4. The method according to any one of claims 1 to 3, wherein the compound (C) is at least one selected from 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2,2,2]octane bis(tetrafluoroborate), N-fluoropyridinium salts, and multimers thereof.

5. The method according to any one of claims 1 to 3, wherein the compound (C) is 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2,2,2]octane bis(tetrafluoroborate).

6. The method according to any one of claims 1 to 3, wherein the amount of the compound (C) used is within a range of 0.1 to 10 moles per mole of the compound represented by formula (1).

7. The method according to any one of claims 1 to 3, wherein the compound (C) is used in an amount such that the number of F atoms on N atoms in the compound (C) exceeds 1 mole per mole of the compound represented by formula (1).

8. The method according to any one of claims 1 to 3, wherein the fluorine source (A) is hydrogen fluoride.

9. The method according to any one of claims 1 to 3, wherein the amount of the fluorine source (A) used is within a range of 0.1 to 1000 moles per mole of the compound represented by formula (1).

10. the fluorine source (A) is hydrogen fluoride, the iodine source (B) is iodine or tetrabutylammonium iodide, and the compound (C) is 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2,2,2]octane bis(tetrafluoroborate) or 1,1′-difluoro-2,2′-bipyridinium bis(tetrafluoroborate); The method according to any one of claims 1 to 3.

11. The method according to any one of claims 1 to 3, wherein the reaction is carried out in the presence of a solvent.

12. R １ and R ２ are independently a hydrogen atom, an alkyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, an aryl group which may have one or more substituents, an aralkyl group which may have one or more substituents, a non-aromatic heterocyclic group which may have one or more substituents, a cyano group, a formyl group, R Ａ O-, R Ａ CO-, R Ａ SO ２ -, R Ａ COO-, (R Ａ ) (R Ｂ ) NCO-, R Ａ OCO-, R Ａ CONR Ｂ -, R Ａ OSO ２ -, or (R Ａ ) (R Ｂ ) NSO ２ - (wherein R Ａ and R Ｂ are independently an alkyl group which may have one or more substituents, an aryl group which may have one or more substituents, or an aralkyl group which may have one or more substituents; R １ and R ２ is taken together with two adjacent carbon atoms to form a ring, The method according to any one of claims 1 to 3.

13. (B) at least one iodine source selected from iodine and ammonium iodide; (C) a compound having at least one fluorinated quaternary nitrogen atom in the molecule; (However, when the iodine source (B) is iodine, the compound (C) is not an N-fluoropyridinium salt or a polymer thereof.)

14. 14. The composition of claim 13, further comprising (A) at least one fluorine source selected from hydrogen fluoride, a hydrogen fluoride salt, and a fluoride salt.

15. 14. The composition of claim 13, wherein the iodine source (B) is ammonium iodide.

16. The composition according to claim 13, wherein the content of the iodine source (B) is 0.2 mol or less per 1 mol of the compound (C).

17. A fluorinating agent comprising the composition of any one of claims 13 to 16.

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