Method for producing fluorinated organic compound

Abstract

Provided is a novel method for producing a fluorinated organic compound. This production method is a method for producing a fluorine adduct of a compound represented by formula (1) # imgabs0 # (in the formula, R1, R2 and n are as defined in the symbols described in the description. ) The production method comprises: a step for reacting a compound represented by formula (1) with (A), (B), and (C), and adding fluorine to the double bond or triple bond: (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, an iodo-aliphatic compound and an iodo-aromatic ring compound; and (C) at least one compound selected from the group consisting of compounds represented by formula (2-1) having or not having one or more substituents, and multimers thereof: # imgabs1 # (in the formula, X represents a conjugated base of a Bronsted acid. ).

Description

Technical Field

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

[0002] Fluorinated organic compounds are extremely important compounds that can be used as various chemical products such as functional materials, pharmaceutical and pesticide compounds, electronic materials, and their intermediates.

[0003] As a method for producing fluorinated organic compounds, for example, non-patent document 1 proposes a method for difluorination by reacting an olefin represented by the formula: CH2=CH-CH2-R with p-iodotoluene (catalyst), Selectfluor (trademark) (1-chloromethyl-4-fluoro-1,4-diazabicyclo[2.2.2]octane bis(tetrafluoroborate)) and an HF source in a solvent such as dichloroethane.

[0004] Prior art literature

[0005] Non-patent literature

[0006] Non-patent document 1: J. Am. Chem. Soc., 2016, 138, 5004-5007 Summary of the invention

[0007] Technical problem to be solved by the invention

[0008] Selectfluor (trademark) of Non-Patent Document 1 is expensive and difficult to recover after the reaction, so there is room for improvement in production cost.

[0009] The object of the present disclosure is to provide a novel method for producing fluorinated organic compounds.

[0010] Technical solutions for solving technical problems

[0011] The present disclosure includes the following aspects.

[0012] [Item 1]

[0013] A method for producing a fluorine adduct of a compound represented by the following formula (1):

[0014] [Chemistry 1]

[0015]

[0016] (Where,

[0017] R 1 and R 2 is independently a hydrogen atom or an organic group, or may form a ring together with two adjacent carbon atoms;

[0018] n is 1 or 2;

[0019] symbol:

[0020] [Chemistry 2]

[0021]

[0022] A double or triple bond.

[0023] in,

[0024] When the symbol is a triple bond, n is 1,

[0025] When the symbol is a double bond, n is 2;

[0026] 2 Rs 1 Same or different from each other,

[0027] 2 Rs 2 are the same as or different from each other, or

[0028] 2 Rs 1 or 2 R 2 They may also form a ring together with adjacent carbon atoms. ).

[0029] The production method comprises: reacting the compound represented by the formula (1) with the following (A), (B) and (C) to add fluorine to the double bond or triple bond.

[0030] (A) at least one fluorine source selected from hydrogen fluoride, a hydrogen fluoride salt and a fluoride salt;

[0031] (B) at least one iodine source selected from the group consisting of iodine, iodinated aliphatic compounds, and iodinated aromatic ring compounds; and

[0032] (C) at least one compound selected from the group consisting of compounds represented by the following formula (2-1) which may have one or more substituents, and multimers thereof:

[0033] [Chemistry 3]

[0034]

[0035] (Wherein, X represents the conjugate base of the Bronsted acid.).

[0036] [Item 2]

[0037] The production method according to item 1, wherein the compound (C) is a compound represented by the following formula (2-2) which may have one or more substituents:

[0038] [Chemistry 4]

[0039]

[0040] (In the formula, X has the same meaning as above.).

[0041] [Item 3]

[0042] The production method according to item 1, wherein the compound (C) is a compound represented by the following formula (2-3) which may have one or more substituents:

[0043] [Chemistry 5]

[0044]

[0045] (In the formula, X has the same meaning as above.).

[0046] [Item 4]

[0047] The production method according to item 3, wherein the compound (C) is a compound represented by the formula (2-3).

[0048] [Item 5]

[0049] The production method according to any one of items 1 to 4, wherein the amount of the compound (C) used is in the range of 0.1 to 10 mol per 1 mol of the compound represented by the formula (1).

[0050] [Item 6]

[0051] The production method according to any one of items 1 to 4, wherein the compound (C) is used in an amount exceeding 1 mol of the F atom on the N atom in the compound (C) based on 1 mol of the compound represented by the formula (1).

[0052] [Item 7]

[0053] The production method according to any one of items 1 to 4, wherein the fluorine source (A) is at least one selected from hydrogen fluoride, an amine hydrogen fluoride salt, an alkali metal fluoride salt, and an alkaline earth metal fluoride salt.

[0054] [Item 8]

[0055] The production method according to any one of items 1 to 4, wherein the amount of the fluorine source (A) used is in the range of 0.1 to 1000 mol per 1 mol of the compound represented by the formula (1).

[0056] [Item 9]

[0057] The production method according to any one of items 1 to 4, wherein the amount of the iodine source (B) used is in the range of 0.1 to 10 mol per 1 mol of the compound represented by the formula (1).

[0058] [Item 10]

[0059] The production method according to any one of items 1 to 4, wherein the reaction is performed in the presence of a solvent.

[0060] [Item 11]

[0061] The production method according to any one of items 1 to 4, wherein 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-(In these formulas, 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. ), or R 1 and R 2 Together with two adjacent carbon atoms, it forms a ring.

[0062] [Item 12]

[0063] The production method according to any one of items 1 to 4, further comprising: a step of separating the compound (C) and / or its derivative from the reaction mixture after the reaction.

[0064] [Item 13]

[0065] The production method according to any one of items 1 to 4, further comprising: a step of reducing the reaction mixture after the reaction using a reducing agent.

[0066] [Item 14]

[0067] The production method according to item 13, wherein the reducing agent is a sulfur-based reducing agent.

[0068] [Item 15]

[0069] A composition comprising at least one selected from the following fluorine source (A) and the following iodine source (B), and the following compound (C),

[0070] (A) at least one fluorine source selected from hydrogen fluoride, a hydrogen fluoride salt and a fluoride salt;

[0071] (B) at least one iodine source selected from the group consisting of iodine, iodinated aliphatic compounds and iodinated aromatic ring compounds;

[0072] (C) at least one compound selected from the group consisting of the compound represented by the above formula (2-1) which may have one or more substituents, and multimers thereof:

[0073] [Chemistry 6]

[0074]

[0075] (Wherein, X represents the conjugate base of the Bronsted acid.).

[0076] [Item 16]

[0077] A fluorinating agent comprising the composition according to item 15.

[0078] Effects of the Invention

[0079] According to the present disclosure, a novel method for producing a fluorinated organic compound can be provided. DETAILED DESCRIPTION

[0080] The above summary of the present disclosure is not intended to describe every disclosed embodiment or every form of the present disclosure.

[0081] The subsequent description of the disclosure more particularly exemplifies example implementations.

[0082] Several locations in this disclosure provide guidance through illustration, and the illustrations can be used in various combinations.

[0083] In various cases, the illustrated groups can serve as non-exclusive and representative groups.

[0084] All publications, patents and patent applications cited in this specification are incorporated herein by reference as such.

[0085] 1. Terminology

[0086] Unless otherwise specified, the symbols and abbreviations in this specification can be understood according to the context of this specification as having the commonly used meanings in the technical field to which this disclosure belongs.

[0087] In this specification, the sentence pattern "comprising" is used to include the sentence pattern "consisting essentially of" and the sentence pattern "consisting of".

[0088] Unless otherwise specified, the steps, treatments, or operations described in this specification can be performed at room temperature.

[0089] In this specification, room temperature may refer to a temperature within a range of 10 to 40°C.

[0090] In this specification, the expression "C n -C m "(Here, n and m are each an integer greater than 1, and n<m.)" means that the number of carbon atoms is greater than n and less than m, as generally understood by those skilled in the art.

[0091] In the present specification, the sentence "a compound represented by formula (N)" (where N is an integer of 1 or more) may be referred to as compound (N).

[0092] In the present specification, unless otherwise specified, examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0093] In the present specification, an "organic group" refers to a group containing one or more carbon atoms.

[0094] Examples of the “organic group” include 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, a 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 are independently 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, or a heteroaryl group which may have one or more substituents.).

[0095] In the present specification, unless otherwise specified, examples of the "hydrocarbon group" may 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 a combination thereof.

[0096] In this specification, unless otherwise specified, examples of "alkyl" may 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.

[0097] In the present specification, unless otherwise specified, examples of "alkenyl" may 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.

[0098] In the present specification, unless otherwise specified, examples of "alkynyl" may 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.

[0099] In the present specification, unless otherwise specified, examples of "cycloalkyl" include C3-C7 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.

[0100] In the present specification, unless otherwise specified, examples of the "cycloalkenyl group" may include C3-C7 cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and cycloheptenyl.

[0101] In the present specification, unless otherwise specified, examples of the "cycloalkadienyl group" may include C4-C10 cycloalkadienyl groups such as cyclobutadienyl, cyclopentadienyl, cyclohexadienyl, cycloheptadienyl, cyclooctadienyl, cyclononadienyl, and cyclodecadienyl.

[0102] In the present specification, unless otherwise specified, the "aryl group" may be a monocyclic ring, a bicyclic ring, a tricyclic ring, or a tetracyclic ring.

[0103] In the present specification, unless otherwise specified, the "aryl group" may be a C6-C18 aryl group.

[0104] In the present specification, unless otherwise specified, examples of the "aryl group" may include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, and 2-anthryl.

[0105] In the present specification, unless otherwise specified, examples of the “aralkyl group” may include benzyl, phenethyl, diphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 2-biphenylylmethyl, 3-biphenylylmethyl, and 4-biphenylylmethyl.

[0106] In the present specification, unless otherwise specified, the "non-aromatic heterocyclic group" may be a monocyclic, bicyclic, tricyclic, or tetracyclic group.

[0107] In the present specification, unless otherwise specified, the "non-aromatic heterocyclic group" may be, for example, a non-aromatic heterocyclic group containing 1 to 4 heteroatoms selected from oxygen atoms, sulfur atoms and nitrogen atoms as ring-constituting atoms in addition to carbon atoms.

[0108] In the present specification, unless otherwise specified, the "non-aromatic heterocyclic group" may be saturated or unsaturated.

[0109] In the present specification, unless otherwise specified, examples of the “non-aromatic heterocyclic group” include tetrahydrofuranyl, oxazolidinyl, imidazolinyl (e.g., 1-imidazolinyl, 2-imidazolinyl, 4-imidazolinyl), aziridine (e.g., 1-aziridine, 2-aziridine), azetidinyl (e.g., 1-azetidinyl, 2-azetidinyl), pyrrolidinyl (e.g., 1-pyrrolidinyl, 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-azepanyl, 2-azepanyl, 3-azepanyl, 4-azepanyl), piperazinyl (e.g., 1,4-piperazin-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), diazacyclooctanyl (e.g., 1,4-diazacyclooctan-1-yl, 1,4-diazacyclooctan-2-yl, 1,4-diazacyclooctan-6-yl), 1,4-diazacyclooctan-6-yl, 1,5-diazacyclooctan-1-yl, 1,5-diazacyclooctan-2-yl, 1,5-diazacyclooctan-3-yl), tetrahydropyranyl (e.g., tetrahydropyran-4-yl), morpholinyl (e.g., 4-morpholinyl), thiomorpholinyl (e.g., 4-thiomorpholinyl), 2-oxazolidinyl, dihydrofuranyl, dihydropyranyl and dihydroquinolinyl, etc.

[0110] In the present specification, unless otherwise specified, examples of "heteroaryl" may include monocyclic aromatic heterocyclic groups (eg, 5- or 6-membered monocyclic aromatic heterocyclic groups) and aromatic condensed heterocyclic groups (eg, 5- to 18-membered aromatic condensed heterocyclic groups).

[0111] In the present specification, unless otherwise specified, examples of the “5- or 6-membered monocyclic aromatic heterocyclic group” may 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), thiazolyl (for example: 2-thiazolyl, 4-thiazolyl, 5-thiazolyl), triazolyl (for example: 1,2,3-triazol-4-yl, 1,2,4-triazol-3-yl), oxadiazolyl (for example: 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl), thiadiazolyl (for example: 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl), tetrazolyl, pyridyl (for example: 2-pyridyl, 3-pyridyl, 4-pyridyl), pyridazinyl (for example: 3-pyridazinyl, 4-pyridazinyl), pyrimidinyl (for example: 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl), pyrazinyl, etc.

[0112] In the present specification, unless otherwise specified, examples of the “5- to 18-membered aromatic fused heterocyclic group” may 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]thienyl, 4-benzo[b]thienyl, 5-benzo[b]thienyl, 6-benzo[b]thienyl, 7-benzo[b]thienyl), phenyl), 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-benzoisoxazol-5-yl, 1,2-benzoisoxazol-6-yl, 1,2-benzoisoxazol-7-yl), benzoxazolyl (e.g., 2-benzoxazolyl, 4-benzoxazolyl, 5-benzoxazolyl, 6-benzoxazolyl, 7-benzoxazolyl), 1,2-benzisothiazol-3-yl, 1,2-benzisothiazol-4-yl, 1,2-benzisothiazol-5-yl, 1,2-benzisothiazol-6-yl, 1,2-benzisothiazol-7-yl),2-benzoisothiazol-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 ( For example: 3-cinnolinyl, 4-cinnolinyl, 5-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 8-cinnolinyl), phthalazinyl (for example: 1-phthalazinyl, 4-phthalazinyl, 5-phthalazinyl, 6-phthalazinyl, 7-phthalazinyl, 8-phthalazinyl), quinazolinyl (for example: 2-quinazolinyl, 4-quinazolinyl, 5-quinazolinyl, 6-quinazolinyl, 7-quinazolinyl, 8-quinazolinyl), quinoxalinyl (for example: quinoxalinyl, ... : 2-quinoxalinyl, 3-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl, 7-quinoxalinyl, 8-quinoxalinyl), pyrazolo[1,5-a]pyridinyl (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]pyridinyl (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), etc.

[0113] In this manual, “R r Examples of "O-" may include: alkoxy (for example: C1-C10 alkoxy such as methoxy, ethoxy, propoxy, butoxy), cycloalkoxy (for example: C3-C7 cycloalkoxy such as cyclopentyloxy and cyclohexyloxy), aryloxy (for example: C6-C18 aryloxy such as phenoxy and naphthoxy) and aralkyloxy (for example: C7-C19 aralkyloxy such as benzyloxy and phenethoxy).

[0114] In this manual, “R r Examples of "CO-" may include alkylcarbonyl [e.g., acetyl, propionyl, butyryl, etc. (C1-C10 alkyl)carbonyl], cycloalkylcarbonyl [e.g., cyclopentanoyl, cyclohexanoyl, etc. (C3-C7 cycloalkyl)carbonyl], arylcarbonyl [e.g., benzoyl, naphthoyl, etc. (C6-C18 aryl)carbonyl], and aralkylcarbonyl [e.g., benzylcarbonyl, phenethylcarbonyl, etc. (C7-C19 aralkyl)carbonyl].

[0115] In this manual, “R rExamples of "COO-" may include: alkylcarbonyloxy [e.g., acetyloxy, propionyloxy, butyryloxy, etc. (C1-C10 alkyl)carbonyloxy], cycloalkylcarbonyloxy [e.g., cyclopentanoyloxy, cyclohexanoyloxy, etc. (C3-C7 cycloalkyl)carbonyloxy], arylcarbonyloxy [e.g., benzoyloxy, naphthoyloxy, etc. (C6-C18 aryl)carbonyloxy], and aralkylcarbonyloxy [e.g., benzylcarbonyloxy, phenethylcarbonyloxy, etc. (C7-C19 aralkyl)carbonyloxy].

[0116] In this manual, “R r Examples of SO2-" may include: alkylsulfonyl (e.g., C1-C10 alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, and propylsulfonyl), cycloalkylsulfonyl (e.g., C4-C8 cycloalkylsulfonyl such as cyclopentylsulfonyl and cyclohexylsulfonyl), arylsulfonyl (e.g., C6-C18 arylsulfonyl such as phenylsulfonyl and naphthylsulfonyl), and aralkylsulfonyl (e.g., C7-C19 aralkylsulfonyl such as benzylsulfonyl and phenethylsulfonyl).

[0117] In this manual, “R r Examples of "OCO-" may include alkoxycarbonyl [e.g., methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, etc. (C1-C10 alkoxy)carbonyl], cycloalkyloxycarbonyl [e.g., cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, etc. (C3-C7 cycloalkyloxy)carbonyl], aryloxycarbonyl [e.g., phenoxycarbonyl, naphthoxycarbonyl, etc. (C6-C18 aryloxy)carbonyl], and aralkyloxycarbonyl [e.g., benzyloxycarbonyl, phenethoxycarbonyl, etc. (C7-C19 aralkyloxy)carbonyl].

[0118] In this manual, “R r Examples of OSO2-" may include alkoxysulfonyl (e.g., C1-C10 alkoxysulfonyl such as methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, etc.), cycloalkoxysulfonyl (e.g., C3-C7 cycloalkoxysulfonyl such as cyclopentyloxysulfonyl, cyclohexyloxysulfonyl, etc.), aryloxysulfonyl (e.g., C6-C18 aryloxysulfonyl such as phenoxysulfonyl, naphthyloxysulfonyl, etc.), and aralkyloxysulfonyl (e.g., C7-C19 aralkyloxysulfonyl such as benzyloxysulfonyl, phenethyloxysulfonyl, etc.).

[0119] In the present specification, examples of the “substituent” in “a hydrocarbon group which may have one or more substituents”, “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”, “an aryl group which may have one or more substituents”, “an arylalkyl group which may have one or more substituents”, “a non-aromatic heterocyclic group which may have one or more substituents”, and “a heteroaryl group which may have one or more substituents” may include a halo group, a nitro group, a cyano group, an oxo group, a thio group, a carboxyl group, a sulfonyl group, an aminosulfonyl group, an aminosulfinyl group (sulphinamoyl), an aminothio group (sulphenamoyl), an R r O-、R r CO-、R r COO-, R r SO2-、R r OCO-, and R r OSO2-(In these formulas, R r Same meaning as above).

[0120] Among the substituents, examples of the "halogeno group" may include a fluoro group, a chloro group, a bromo group, and an iodo group.

[0121] The number of the substituents can be in the range of 1 to the maximum number of substituents (eg, 1, 2, 3, 4, 5, 6).

[0122] In this specification, the "electron withdrawing group" refers to a group having a positive σp value according to Hammett's rule.

[0123] 2. Method for producing a fluorine adduct of compound (1)

[0124] The method for producing a fluorine addition product of compound (1) comprises a step A of reacting compound (1) with a fluorine source (A), an iodine source (B) and a compound (C) to add fluorine (e.g., monofluorine or difluorine) to the double bond or triple bond of compound (1).

[0125] 2-1. Compound (1)

[0126] In one embodiment of compound (1), preferably 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, RA 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-(In these formulas, 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).

[0127] The substituent can be any group having a replaceable structure on the object, for example, it can be 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 can be selected from 1 to the maximum number of replaceable groups (for example, 1, 2, 3).

[0128] In the embodiment described, R 1 and R 2 At least one of them may be cyano, formyl, R A CO-、R A SO2-、R A OCO-, R A The reaction also proceeds with respect to such a compound (1) having a double bond or a triple bond with insufficient electrons.

[0129] In another embodiment of compound (1), preferably R 1 and R 2 Together with two adjacent carbon atoms, it forms a ring. The ring formation is usually when the symbol is a double bond and n is 2. Examples of the ring include a cycloolefin ring corresponding to the group exemplified by "cycloalkenyl" and a non-aromatic heterocyclic ring corresponding to a group having a carbon-carbon double bond among the groups exemplified by "non-aromatic heterocyclic group".

[0130] The ring may have one or more substituents. Examples of the substituents include hydrocarbon groups, halogen groups, nitro groups, cyano groups, oxo groups, thio groups, carboxyl groups, sulfonyl groups, aminosulfonyl groups, aminosulfinyl groups, aminothio groups, R r O-、R r CO-、R r COO-, R r SO2-、Rr OCO-, and R r OSO2-(In these formulas, R r The number of the substituents can be selected from the range of 1 to the maximum number of substituents (for example, 1, 2, 3, 4, 5).

[0131] Preferred examples of the compound (1) include a compound represented by the following formula (1A) and a compound represented by the following formula (1B):

[0132] [Chemistry 7]

[0133]

[0134] (Where,

[0135] R 11 , R 12 , R 21 and R 22 are independently a hydrogen atom or an organic group;

[0136] R 11 and R 12 , or R 21 and R 22 Together with an adjacent carbon atom, form a ring; or

[0137] R 11 and R 21 , R 11 and R 22 , R 12 and R 21 , or R 12 and R 22 Together with the two adjacent carbon atoms, it forms a ring;

[0138] symbol:

[0139] [Chemistry 8]

[0140]

[0141] Indicates cis or trans configuration. )

[0142] [Chemistry 9]

[0143]

[0144] (Where R 13 and R 23 are independently a hydrogen atom or an organic group. ).

[0145] In one embodiment of compound (1A), preferably R 11 , R 12 , R21 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-(In these formulas, 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).

[0146] In the above embodiment, preferably R 22 is a hydrogen atom, and more preferably R 12 and R 22 is a hydrogen atom. In addition, R 12 , R 21 and R 22 A hydrogen atom.

[0147] In the above embodiment, it is also preferred that R 12 and R 22 is a hydrogen atom, R 11 and R 21 The reaction also proceeds smoothly for such a compound (1) having a double bond inside. 11 and R 21 At least one of them may be cyano, formyl, R A CO-、R A SO2-、R A OCO-, R A The reaction also proceeds with respect to such a compound (1) having an electron-deficient double bond.

[0148] Preferred examples of the compound (1A) include compounds represented by the following formulae (1a) to (1d):

[0149] [Chemistry 10]

[0150]

[0151] (Where,

[0152] 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,

[0153] 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,

[0154] R 1c is 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,

[0155] R 2c is an alkyl group which may have one or more substituents,

[0156] R 1d is 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,

[0157] 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. ).

[0158] The substituent can be any group having a replaceable structure on the object, for example, it can be 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 can be selected from 1 to the maximum number of replaceable groups (for example, 1, 2, 3).

[0159] In one embodiment of compound (1a), R 1a It is an alkyl group which may have one or more substituents (for example, a halo group, a hydroxyl group, or an alkoxycarbonyl group), or an aralkyl group which may have one or more substituents (for example, a halo group, a hydroxyl group, or an alkoxycarbonyl group).

[0160] In one embodiment of compound (1c), R 1c It is an aryl group which may have one or more substituents (for example, a halogeno group).

[0161] In one embodiment of compound (1d), R 1dis an aryl group which may have one or more substituents (e.g., a halide group), R 2d It is an alkyl group which may have one or more substituents (for example, a halogeno group), or an aryl group which may have one or more substituents (for example, a halogeno group).

[0162] In one embodiment of compound (1B), preferably R 13 and R 23 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-(In these formulas, 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).

[0163] In the above embodiment, it is also preferred that R 13 and R 23 The reaction also proceeds smoothly for such a compound (1) having a triple bond inside. 13 and R 23 At least one of them may be cyano, formyl, R A CO-、R A SO2-、R A OCO-, R A The reaction also proceeds with respect to such a compound (1) having an electron-deficient triple bond.

[0164] 2-2. Fluorine source (A)

[0165] Among the fluorine sources (A), hydrogen fluoride can be used in the form of an aqueous solution (hydrofluoric acid). The aqueous solution can be, for example, an aqueous solution having a hydrogen fluoride concentration of 10 to 70% by weight.

[0166] Among the fluorine sources (A), examples of hydrogen fluoride salts include amine hydrogen fluoride salts and ammonium hydrogen fluoride salts.

[0167] In the hydrogen fluoride amine salt, the amine may be a chain amine or a cyclic amine.

[0168] Examples of chain 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.

[0169] 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]non-5-ene, and 1,4-diazabicyclo[2.2.2]octane. Examples of aromatic cyclic amines include pyridine, pyrimidine, pyrazine, quinoline, and imidazole.

[0170] Suitable examples of hydrogen fluoride amine salts include triethylamine hydrogen fluoride salt (Et3N·xHF (x is an integer greater than 1, preferably 1 to 10, and more preferably 3 to 7)), pyridinium hydrogen fluoride salts (Py·xHF (x is an integer greater than 1, preferably 1 to 10)) such as Olah's reagent, and combinations thereof.

[0171] Examples of ammonium hydrogen fluoride salts include compounds represented by the following formula (A1):

[0172] NQ4F·xHF(A1)

[0173] (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 greater than 1.)

[0174] In one embodiment of compound (A1), Q is preferably an alkyl group, more preferably a C1-C6 alkyl group.

[0175] Preferred examples of the 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.

[0176] Examples of fluoride salts among the fluorine sources (A) include compounds represented by the following formula (A2):

[0177] M 1 F m1 (A2)

[0178] (Where,

[0179] M 1 is an alkali metal or an alkaline earth metal; and

[0180] m1 according to M 1 The valence of is 1 or 2. ).

[0181] 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 For K.

[0182] The fluoride salt can preferably be an alkali metal fluoride salt (M 1 is an alkali metal and m1 is 1 (A2)) or an alkaline earth metal fluoride salt (M 1 is an alkaline earth metal and m1 is 2 (A2)).

[0183] 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, an amine hydrogen fluoride salt, an alkali metal fluoride salt, and an alkaline earth metal fluoride salt.

[0184] 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, further preferably 0.4 mol or more, and particularly preferably 0.5 mol or more relative to 1 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, further preferably 100 mol or less, further more preferably 90 mol or less, and particularly preferably 80 mol or less relative to 1 mol of compound (1). The amount of the fluorine source (A) used can be, for example, in the range of 0.1 to 1000 mol, preferably in the range of 0.2 to 500 mol, more preferably in the range of 0.3 to 100 mol, further preferably in the range of 0.4 to 90 mol, and particularly preferably in the range of 0.5 to 80 mol.

[0185] The residual component after the reaction, the fluorine source (A), can be collected and discarded, but is preferably recovered and reused from the viewpoint of production cost. The collected residual component after the reaction can be washed with water or alkaline water, for example.

[0186] 2-3. Iodine source (B)

[0187] In the iodine source (B), the iodinated aliphatic compound can be, for example, of the formula: R C-I (where R C is an alkyl group which may have one or more substituents. )

[0188] R C Preferred examples include C1-C12 alkanes that may have one or more substituents. Examples of the substituents include halogen atoms (e.g., iodine atoms). The number of the substituents can be selected from 1 to the maximum number of substitutable substituents (e.g., 1, 2, 3).

[0189] Examples of the iodinated aliphatic compound include methyl iodide, ethyl iodide, 1-iodopropane, 2-iodopropane, 1-iodobutane, 1-iodo-2-methylpropane, 1-iodopentane, 1-iodo-3-methylbutane, 1-iodohexane, 1-iodoheptane, 1-iodooctane, diiodomethane, 1,8-diiodooctane and 1,10-diiododecane.

[0190] Among the iodine sources (B), the iodinated aromatic ring compound can be, for example, of the formula: R D -I (where R D is an aryl group which may have one or more substituents or a heteroaryl group which may have one or more substituents. )

[0191] R D Preferred examples include: C6-C18 aryl groups which may have one or more substituents, and 5- or 6-membered monocyclic aromatic heterocyclic groups which may have one or more substituents. Examples of the substituents include: halogen atoms (e.g., chlorine atoms, iodine atoms), alkyl groups (e.g., C1-C4 alkyl groups), fluoroalkyl groups (e.g., fluoro C1-C4 alkyl groups), R E O-(where R E The number of the substituents can be selected from 1 to the maximum number of substituents (for example, 1, 2, 3).

[0192] Examples of iodinated aromatic ring compounds include iodobenzene, 2-iodotoluene, 3-iodotoluene, 4-iodotoluene, 2,4,6-trimethyliodobenzene, 2-ethyliodobenzene, 3-ethyliodobenzene, 4-ethyliodobenzene, 2-iodoanisole, 3-iodoanisole, 4-iodoanisole, 1-chloro-2-iodobenzene, 1-chloro-3-iodobenzene, 1-chloro-4-iodobenzene, 1,2-diiodobenzene, 1,3-diiodobenzene, 1,4-diiodobenzene, 1-iodo-2-nitrobenzene, 1-iodo -3-nitrobenzene, 1-iodo-4-nitrobenzene, 1-iodo-2-cyanobenzene, 1-iodo-3-cyanobenzene, 1-iodo-4-cyanobenzene, 1-iodo-4-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)benzene, p-iodobenzoic acid, 4-iodobiphenyl, 4,4′-diiodobiphenyl, 4,4″-diiodo-p-terphenyl, 2-iodopyridine, 3-iodopyridine, 4-iodopyridine, 3-iodopyrazole, and 4-iodopyrazole.

[0193] The iodine source (B) can be used alone or in combination of two or more.

[0194] The amount of the iodine source (B) used is not particularly limited. The lower limit of the amount of the iodine source (B) used can be, for example, 0.01 mol or more, preferably 0.05 mol or more, more preferably 0.1 mol or more, further preferably 0.15 mol or more, and particularly preferably 0.2 mol or more, relative to 1 mol of compound (1). The upper limit of the amount of the iodine source (B) used can be, for example, 10 mol or less, preferably 9 mol or less, more preferably 8 mol or less, further preferably 7 mol or less, and further more preferably 6 mol or less, relative to 1 mol of compound (1). The amount of the iodine source (B) used can be, for example, in the range of 0.01 to 10 mol, preferably in the range of 0.05 to 9 mol, more preferably in the range of 0.1 to 8 mol, further preferably in the range of 0.15 to 7 mol, and further more preferably in the range of 0.2 to 6 mol, relative to 1 mol of compound (1).

[0195] The iodine source (B) remaining after the reaction may be collected and discarded, but is preferably recovered and reused from the viewpoint of production cost. The remaining component after the reaction may be collected and washed with water or alkaline water, for example.

[0196] 2-4. Compound (C)

[0197] In one embodiment, compound (C) is compound (2-1) which may have one or more substituents. In the "conjugate base of the Bronsted acid" represented by X in formula (2-1), examples of Bronsted acids include inorganic acids and organic acids. Examples of inorganic acids include hydrofluoric acid, hydrochloric acid, perchloric acid, sulfuric acid, persulfate, fluorosulfuric acid, chlorosulfuric acid, phosphoric acid, boric acid, nitric acid, HBF4, HB2F7, HBCl4, HBCl3F, HBBr3F, HPF6, HAsF6, HSbF4, HSbF6, HSbCl6, HSbCl5F, HSb2F 11 , HAlF4, HAlCl4, HAlCl3F, and HAlF3Cl. Examples of organic acids include carboxylic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, and pentafluoropropionic acid; and 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; alkylsulfuric acids such as methylsulfuric acid; and sulfonylimidic acids such as bis(methylsulfonyl)imidic acid and bis(trifluoromethanesulfonyl)imidic acid.

[0198] Examples of the conjugate base of the Bronsted acid include: - OClO3, - OSO2OH, - OSO2F, - OSO2Cl, - BF4, - B2F7, - PF6, - AsF6, - SbF6, - AlF4, - AlCl4, - SbCl6, - SbCl5F, - SbF 11 , - OSO2CH3, - OSO2CF3, - OSO2CCl3, - OSO2C4F9, - OSO2C6H5, - OSO2C6H4CH3, - OSO2C6H4NO2, - OSO2OCH3, - N(SO2CH3)2, and - N(SO2CF3)2.

[0199] Examples of substituents that may be substituted in compound (2-1) include: halogen atoms, hydroxyl groups, alkyl groups that may have one or more further substituents (e.g., halogen atoms) (e.g., C1-C15 alkyl groups), alkenyl groups that may have one or more further substituents (e.g., halogen atoms) (e.g., C1-C15 alkenyl groups), alkynyl groups that may have one or more further substituents (e.g., halogen atoms) (e.g., C1-C15 alkynyl groups), aryl groups that may have one or more further substituents (e.g., halogen atoms, alkyl groups) (e.g., C6-C15 aryl groups), nitro groups, cyano groups, 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-(In these formulas, R F and R G The alkyl group is 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 1 to the maximum number of substitutable groups (e.g., 1, 2, 3, 4, 5).

[0200] In another embodiment, compound (C) is a polymer of compound (2-1) which may have one or more substituents. As an example of such a polymer, a compound represented by the following formula (2-2) which may have one or more substituents can be cited:

[0201] [Chemistry 11]

[0202]

[0203] (In the formula, X has the same meaning as above.).

[0204] Examples of the compound (2-2) which may have one or more substituents include compounds represented by the following formulae (2-3) to (2-7) which may have one or more substituents:

[0205] [Chemistry 12]

[0206]

[0207] (In the formula, X has the same meaning as above.).

[0208] Among them, the compound (2-3) which may have one or more substituents is preferred, and the compound (2-3) (which has no substituent) is more preferred.

[0209] Examples of substituents that can be substituted on compounds (2-2), (2-3), (2-4), (2-5), (2-6) and (2-7) include the same examples as the substituents that can be substituted on compound (2-1). The number of substituents can be selected from 1 to the maximum number of substitutable substituents (e.g., 1, 2, 3, 4, 5, 6, 7, 8).

[0210] Another example of the multimer includes a polymer including a polymer unit represented by the following formula (2-8) which may have one or more substituents:

[0211] [Chemistry 13]

[0212]

[0213] (wherein, X has the same meaning as above, L is a single bond, -CH2- or -O-, and z is an integer greater than 2.)

[0214] In the polymer, the content of the polymerized units (2-8) is preferably 50 mol% or more, more preferably 60 mol% or more.

[0215] In addition to the polymerized units (2-8), the polymer may further include copolymerized units. Examples of the copolymerized units include: arylene groups that may have one or more substituents (e.g., C6-C12 arylene groups such as phenylene and naphthalene diyl), and heteroarylene groups that may have one or more substituents (e.g., thiophene diyl, furan diyl, pyrrole diyl, pyridine diyl). Examples of substituents that can be substituted on these copolymerized units include the same examples as those that can be substituted on the above-mentioned polymerized units (2-8).

[0216] There is no particular limitation on z as long as it is an integer of 2 or more, and z is preferably 2, 3 or 4. The average molecular weight of the polymer is preferably within a range of 100 to 500,000.

[0217] As the compound (C), for example, an N-fluoropyridinium salt described in Japanese Unexamined Patent Publication No. 11-040164 can be used.

[0218] The compound (C) can be used alone or in combination of two or more.

[0219] 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 mol or more, preferably 0.2 mol or more, more preferably 0.3 mol or more, further preferably 0.4 mol or more, and particularly preferably 0.5 mol or more, relative to 1 mol of compound (1). The upper limit of the amount of compound (C) used can be, for example, 10 mol or less, preferably 9 mol or less, more preferably 8 mol or less, further preferably 7 mol or less, and further more preferably 6 mol or less, relative to 1 mol of compound (1). The amount of compound (C) used can be, for example, in the range of 0.1 to 10 mol, preferably in the range of 0.2 to 9 mol, more preferably in the range of 0.3 to 8 mol, further preferably in the range of 0.4 to 7 mol, and further more preferably in the range of 0.5 to 6 mol, relative to 1 mol of compound (1).

[0220] Compound (C) is also preferably used in an amount in which the F atom on the N atom in compound (C) exceeds 1 mol (e.g., within the range of 1.1 to 3 mol, within the range of 1.2 to 2.5 mol, or within the range of 1.3 to 2 mol) based on 1 mol of compound (1).

[0221] From the viewpoint of production cost, the compound (C) remaining as a residual component after the reaction is preferably recovered and reused.

[0222] The fluorine source (A), the iodine source (B) and the compound (C) may be added to the reaction system separately, or may be added together (for example, in the form of a composition described later).

[0223] 2-5. Solvent

[0224] The reaction of step A can be carried out in the presence or absence of a solvent. The solvent can be a non-polar solvent or a polar solvent. The solvent can 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 solvents, or a combination thereof.

[0225] 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 suitable examples thereof include ethyl acetate.

[0226] Examples of the ketone as the solvent include acetone, methyl ethyl ketone, diethyl ketone, hexanone, methyl isobutyl ketone, heptanone, diisobutyl ketone, hexanedione, methyl hexanone, acetophenone, cyclohexanone, diacetone alcohol, and suitable examples thereof include acetone.

[0227] Examples of the aromatic hydrocarbon as the solvent include benzene, toluene, xylene, and ethylbenzene, and suitable examples thereof include benzene and toluene.

[0228] Examples of the alcohol as the solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, pentanol, hexanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, 1,2-propylene glycol (propylene glycol), dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-propylene glycol (trimethylene glycol) and hexanetriol, and suitable examples thereof include methanol and ethanol.

[0229] Examples of the ether as the solvent include diethyl ether, dibutyl ether, tetrahydrofuran, tetrahydropyran, dioxane, dimethoxyethane, diethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME; alias: 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.

[0230] Examples of the amine as the solvent include monoethanolamine, diethanolamine, and triethanolamine.

[0231] 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 suitable examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone.

[0232] Examples of the nitrile as the solvent include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and adiponitrile, and suitable examples thereof include acetonitrile.

[0233] Examples of the halogenated hydrocarbon as the solvent include dichloromethane, dichloroethane, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane, chlorobenzene, dichlorobenzene and chlorotoluene, and suitable examples thereof include dichloromethane and chloroform.

[0234] Examples of the aliphatic hydrocarbon as the solvent include hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane and mineral spirits, and suitable examples thereof include cyclohexane and heptane.

[0235] Examples of the fluorine-based solvent include perfluorobenzene, trifluorotoluene, difluorobenzene or trifluorobenzene, and trifluoroethanol, and suitable examples thereof include perfluorobenzene and trifluoroethanol.

[0236] Examples of the carbonate as the solvent include dimethyl tetralincarbonate, ethyl methyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate, and suitable examples thereof include ethylene carbonate and propylene carbonate.

[0237] Examples of the other solvents include acetic acid, pyridine, dimethyl sulfoxide, sulfolane and water.

[0238] The solvent may preferably be at least one selected from aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and nitriles, may more preferably be at least one selected from halogenated hydrocarbons and nitriles, and may further preferably be halogenated hydrocarbons.

[0239] The solvent can be used alone or in combination of two or more.

[0240] The amount of the solvent used can be, for example, 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 in the range of 5 to 50 parts by mass, relative to 1 part by mass of the compound (1).

[0241] Each component may be added to the reaction system of step A all at once, in divided portions, or continuously.

[0242] 2-6. Temperature and time

[0243] The temperature in step A can be generally 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 further preferably in the range of 40 to 60°C.

[0244] The time of step A can be generally in the range of 0.1 to 72 hours, preferably in the range of 0.5 to 48 hours, and more preferably in the range of 1 to 36 hours.

[0245] 2-7. Optional additional step B

[0246] The method for producing a fluorine adduct of compound (1) may further comprise step B of isolating or purifying compound (1) in addition to step A. Isolation or purification of compound (1) can be carried out by filtration, extraction, stripping, dissolution, concentration, precipitation, dehydration, adsorption or chromatography, or a combination thereof.

[0247] In one embodiment, step B is a step of separating compound (C) and / or its derivatives from the reaction mixture obtained by the reaction in step A. The separation step is preferably a step of reducing the reaction mixture using a reducing agent. By such a reduction treatment, compound (C) and / or its derivatives can be separated simply and highly.

[0248] Examples of the reducing agent include sulfur-based reducing agents, and suitable examples thereof include bisulfites, sulfites, and thiosulfates. Examples of bisulfites include ammonium bisulfite; and alkali metal bisulfites such as sodium bisulfite and potassium bisulfite. 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.

[0249] The reducing agent can be used alone or in combination of two or more.

[0250] 3. Composition

[0251] The composition of the present disclosure comprises at least one selected from a fluorine source (A) and an iodine source (B) and a compound (C). Examples of the fluorine source (A), the iodine source (B) and the compound (C) include the same examples as those exemplified in the above-mentioned "2.2. Method for producing a fluorine adduct of compound (1)".

[0252] Examples of the above composition include composition α comprising a fluorine source (A) and a compound (C), composition β comprising an iodine source (B) and a compound (C), and composition γ comprising a fluorine source (A), an iodine source (B) and a compound (C).

[0253] In the above composition, the fluorine source (A) may be, for example, 0.1 mol or more, 0.2 mol or more, or 0.3 mol or more, and may be 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, relative to 1 mol of the compound (C). In the above composition, the fluorine source (A) may be contained, for example, in the range of 0.1 to 600 mol, preferably in the range of 0.2 to 300 mol, and more preferably in the range of 0.3 to 70 mol, relative to 1 mol of the compound (C).

[0254] In the above composition, the iodine source (B) may be, for example, 0.01 mol or more, 0.05 mol or more, or 0.1 mol or more, and may be 6 mol or less, 5.5 mol or less, or 5 mol or less, relative to 1 mol of the compound (C). In the above composition, the iodine source (B) may be contained, for example, in the range of 0.01 to 6 mol, preferably in the range of 0.05 to 6 mol, and more preferably in the range of 0.1 to 5 mol, relative to 1 mol of the compound (C).

[0255] The above composition can be suitably used as a fluorinating agent (particularly a fluorinating agent for a compound having a carbon-carbon double bond or triple bond such as compound (1)). Therefore, the present disclosure includes a fluorinating agent (particularly a fluorinating agent for a compound having a carbon-carbon double bond or triple bond such as compound (1)) containing the above composition.

[0256] Example

[0257] Hereinafter, an embodiment of the present disclosure will be described in more detail by way of examples, but the present disclosure is not limited thereto.

[0258] [Example 1]

[0259] TEA (triethylamine)·5HF (1.25 mL) and 1,1′-difluoro-2,2′-bipyridinium bis(tetrafluoroborate) (0.75 mmol) were added to a DCE (dichloroethane) (2 mL) solution of 1-dodecene (0.5 mmol) and 4-iodotoluene (0.1 mmol), and the mixture was reacted at 40°C for 22 hours. The reaction mixture was poured into saturated sodium bicarbonate, and then sodium sulfite was added. 2M NaOH was added, and the mixture was extracted with ethyl acetate. The ethyl acetate extract was then washed with 2M HCl. The organic layer was washed with a saturated sodium chloride aqueous solution, dried with anhydrous sodium sulfate, and the solvent was removed with an evaporator. Methyl 4-fluorobenzoate was added as an internal standard, and the mixture was dried with 1% HCl. 19 F NMR analysis revealed that the yield of 1,2-difluorododecane was 68%.

[0260] On the other hand, 2M NaOH was added to the aqueous layer to make it alkaline, and then extracted with ethyl acetate (20 mL) three times. After washing with a saturated sodium chloride aqueous solution, it was dried with anhydrous sodium sulfate, the solvent was removed with an evaporator, and it was dried with a dryer under reduced pressure. 2,2′-bipyridine was recovered with a yield of 84%.

[0261] [Example 2]

[0262] Py(pyridine)·9HF (0.52mL, 20mmol HF) and 1,1′-difluoro-2,2′-bipyridinium bis(tetrafluoroborate) (1.2mmol) were added to a solution of ethyl cinnamate (1.0mmol) and 4-iodotoluene (0.2mmol) in DCM (dichloromethane) (5mL), and the mixture was reacted at 40°C for 24 hours. The reaction mixture was injected into saturated sodium bicarbonate, and then an aqueous sodium thiosulfate solution was added. 2M NaOH was added and extracted with ethyl acetate. The ethyl acetate extract was then washed with 2M HCl. The organic layer was washed with a saturated aqueous sodium chloride solution, dried with anhydrous sodium sulfate, and the solvent was removed with an evaporator. Fluorobenzene was added as an internal standard and the mixture was dried with 2M HCl. 19F NMR analysis revealed that the yield of the target product, ethyl 3,3-difluoro-2-phenylpropionate, was 50%.

[0263] On the other hand, 2M NaOH was added to the aqueous layer to make it alkaline, and then extracted with ethyl acetate. After washing with a saturated sodium chloride aqueous solution, it was dried with anhydrous sodium sulfate, the solvent was removed with an evaporator, and it was dried with a desiccator under reduced pressure. 2,2′-bipyridine was recovered at a yield of 49%.

[0264] [Example 3]

[0265] TEA (triethylamine)·5HF (2.5 mL) and 1,1′-difluoro-2,2′-bipyridinium bis(tetrafluoroborate) (1.5 mmol) were added to a DCM (dichloromethane) (5 mL) solution of 1-octene (1 mmol) and 4-iodotoluene (0.2 mmol), and the mixture was reacted at 40°C for 22 hours. The reaction mixture was injected into saturated sodium bicarbonate, and then sodium sulfite was added. 2M NaOH was added and extracted with ethyl acetate. The ethyl acetate extract was then washed with 2M HCl. The organic layer was washed with a saturated sodium chloride aqueous solution, dried with anhydrous sodium sulfate, and the solvent was removed with an evaporator. Methyl 4-fluorobenzoate was added as an internal standard and the mixture was dried with 10% HCl. 19 F NMR analysis revealed that the yield of 1,2-difluorooctane was 54%.

[0266] [Example 4]

[0267] Except that 1-octene was changed to 10-undecene-1-ol, the same operation as in Example 3 was carried out to obtain 10,11-difluoroundecan-1-ol at a rate of 62%.

[0268] [Example 5]

[0269] Except that 1-octene was changed to 5-bromo-1-pentene, the same operation as in Example 3 was carried out to obtain 5-bromo-1,2-difluoropentane in an amount of 73%.

[0270] [Example 6]

[0271] TEA (triethylamine)·5HF (1 mL) and 1,1′-difluoro-2,2′-bipyridinium bis(tetrafluoroborate) (0.5 mmol) were added to a DCE (dichloroethane) (2 mL) solution of 10-methylacetate-1-nonene (0.4 mmol) and 4-iodotoluene (0.08 mmol), and the mixture was reacted at 40°C for 22 hours. The reaction mixture was poured into saturated sodium bicarbonate, and then sodium sulfite was added. 2M NaOH was added, and the mixture was extracted with ethyl acetate. The ethyl acetate extract was then washed with 2M HCl. The organic layer was washed with a saturated sodium chloride aqueous solution, dried with anhydrous sodium sulfate, and the solvent was removed with an evaporator. Methyl 4-fluorobenzoate was added as an internal standard, and the mixture was dried with 1% HCl. 19 F NMR analysis revealed that the yield of 10-methylacetate-1,2-difluorononane was 67%.

[0272] [Example 7]

[0273] The same operation as in Example 6 was carried out except that 10-methylacetate-1-nonene was changed to allylbenzene, thereby obtaining 2,3-difluoropropylbenzene in an amount of 85%.

[0274] [Example 8]

[0275] TEA (triethylamine)·5HF (1.25 mL) and 1,1′-difluoro-2,2′-bipyridinium bis(tetrafluoroborate) (0.63 mmol) were added to a DCM (dichloromethane) (3 mL) solution of 1-allyl-2-methylbenzene (0.5 mmol) and 4-iodotoluene (0.1 mmol), and the mixture was reacted at 40°C for 22 hours. The reaction mixture was injected into saturated sodium bicarbonate, and then sodium sulfite was added. 2M NaOH was added and extracted with ethyl acetate. The ethyl acetate extract was then washed with 2M HCl. The organic layer was washed with a saturated sodium chloride aqueous solution, dried with anhydrous sodium sulfate, and the solvent was removed with an evaporator. Methyl 4-fluorobenzoate was added as an internal standard and the mixture was dried with 1% HCl. 19 F NMR analysis revealed that the yield of 1-(2,3-difluoropropyl)-2-methylbenzene was 100%.

[0276] [Example 9]

[0277] Py(pyridine)·9HF(0.26mL, 10mmol HF) and 1,1′-difluoro-2,2′-bipyridinium bis(tetrafluoroborate)(1.2mmol) were added to a DCM(dichloromethane) (3mL) solution of ethyl 3-(4-bromophenyl)acrylate (0.5mmol) and 4-iodotoluene (0.1mmol), and the mixture was reacted at 40°C for 20 hours. The reaction mixture was injected into saturated sodium bicarbonate, and then an aqueous sodium thiosulfate solution was added. 2M NaOH was added and extracted with ethyl acetate. The ethyl acetate extract was then washed with 2M HCl. The organic layer was washed with a saturated sodium chloride aqueous solution, dried with anhydrous sodium sulfate, and the solvent was removed with an evaporator. Fluorobenzene was added as an internal standard and the mixture was dried with 2M HCl. 19 The yield of the target product, ethyl 2-(4-bromophenyl)-3,3-difluoropropionate, was 95% as determined by F NMR analysis.

[0278] [Example 10]

[0279] To a solution of chalcone (0.4 mmol) and 4-iodotoluene (0.08 mmol) in DCE (dichloroethane) (1.5 mL), add TEA (triethylamine)·5HF (1.5 mL) and 1,1′-difluoro-2,2′-bipyridinium bis(tetrafluoroborate) (0.6 mmol), and react at 50°C for 22 hours. Pour the reaction mixture into saturated sodium bicarbonate, and then add an aqueous sodium thiosulfate solution. Add 2M NaOH and extract with ethyl acetate. Then, wash the ethyl acetate extract with 2M HCl. Wash the organic layer with a saturated sodium chloride aqueous solution, dry it with anhydrous sodium sulfate, and remove the solvent with an evaporator. Add fluorobenzene as an internal standard and use 19 F NMR analysis revealed that the yield of the target product, 3,3-difluoro-1,2-diphenyl-1-propanone, was 91%.

[0280] [Example 11]

[0281] The same operation as in Example 10 was carried out except that chalcone was changed to 3-(4-fluorophenyl)-1-phenyl-2-propene-1-one, thereby obtaining 3,3-difluoro-2-(4-fluorophenyl)-1-phenylpropan-1-one in an amount of 95%.

[0282] [Example 12]

[0283] The same operation as in Example 10 was carried out except that chalcone was changed to 3-(4-fluorophenyl)-1-tolyl-2-propene-1-one, thereby obtaining 3,3-difluoro-2-(4-fluorophenyl)-1-tolylpropane-1-one at a rate of 92%.

[0284] [Example 13]

[0285] The same operation as in Example 10 was carried out except that chalcone was changed to 3-phenyl-1-(p-tolyl)-2-propene-1-one, thereby obtaining 3,3-difluoro-2-phenyl-1-(p-tolyl)propan-1-one in an amount of 85%.

[0286] [Example 14]

[0287] The same operation as in Example 10 was carried out except that chalcone was changed to 1-(4-chlorophenyl)-3-phenyl-2-propene-1-one, thereby obtaining 1-(4-chlorophenyl)-3,3-difluoro-2-phenylpropan-1-one in an amount of 87%.

[0288] [Example 15]

[0289] The same operation as in Example 10 was carried out except that chalcone was changed to 1-(4-fluorophenyl)-3-phenyl-2-propene-1-one, thereby obtaining 1-(4-fluorophenyl)-3,3-difluoro-2-phenylpropan-1-one in an amount of 94%.

[0290] [Example 16]

[0291] The same operation as in Example 10 was carried out except that chalcone was changed to 4-phenyl-3-buten-2-one, thereby obtaining 4,4-difluoro-3-phenylbutan-2-one at a rate of 47%.

[0292] [Comparative Example 1]

[0293] TEA·5HF (1.0 mL) and Selectfluor (trademark) (0.48 mmol) were added to a DCE (2 mL) solution of 1-dodecene (0.4 mmol) and 4-iodotoluene (0.08 mmol), and the mixture was reacted at 40°C for 21 hours. The reaction mixture was poured into saturated sodium bicarbonate, and sodium sulfite (1 g) was added. 2M NaOH was added, and the mixture was extracted with ethyl acetate. The ethyl acetate extract was then washed with 2M HCl. The organic layer was washed with a saturated sodium chloride aqueous solution, dried with anhydrous sodium sulfate, and the solvent was removed with an evaporator. Methyl 4-fluorobenzoate was added as an internal standard, and the mixture was dried with anhydrous sodium sulfate. 19 F NMR analysis revealed that the yield of 1,2-difluorododecane was 80%.

[0294] On the other hand, 2M NaOH was added to the water layer to make it alkaline, and then extracted with ethyl acetate. No Selectlfuor (trademark) or its derivatives were observed in the ethyl acetate after extraction on H-NMR. According to this experiment, Selectfluor (trademark) is difficult to recover by organic solvent extraction.

Claims

1. A method for producing a fluorine adduct of a compound represented by the following formula (1), characterized in that: In formula (1), R 1 and R 2 is independently a hydrogen atom or an organic group, or forms a ring together with two adjacent carbon atoms, or does not form a ring, n is 1 or 2, symbol: is a double bond or a triple bond, in, When the symbol is a triple bond, n is 1, When the symbol is a double bond, n is 2, 2 R's 1 Same or different from each other, 2 R's 2 are the same as or different from each other, or 2 Rs 1 or 2 R 2 They form a ring or not form a ring together with adjacent carbon atoms; The production method comprises: reacting the compound represented by the formula (1) with the following (A), (B) and (C) to add fluorine to the double bond or triple bond. (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 the group consisting of iodine, iodinated aliphatic compounds, and iodinated aromatic ring compounds; and (C) at least one compound selected from the group consisting of compounds represented by the following formula (2-1) which may have one or more substituents, and multimers thereof: In the formula (2-1), X represents a conjugate base of a Bronsted acid.

2. The manufacturing method according to claim 1, wherein: The compound (C) is a compound represented by the following formula (2-2) which may have one or more substituents: In formula (2-2), X has the same meaning as described above.

3. The manufacturing method according to claim 1, wherein: The compound (C) is a compound represented by the following formula (2-3) which may have one or more substituents: In formula (2-3), X has the same meaning as described above.

4. The manufacturing method according to claim 3, wherein: The compound (C) is the compound represented by the formula (2-3).

5. The production method according to any one of claims 1 to 4, wherein The amount of the compound (C) used is in the range of 0.1 to 10 mol per 1 mol of the compound represented by the formula (1).

6. The production method according to any one of claims 1 to 4, wherein The compound (C) is used in an amount in which the F atom on the N atom in the compound (C) exceeds 1 mol based on 1 mol of the compound represented by the formula (1).

7. The production method according to any one of claims 1 to 4, wherein The fluorine source (A) is at least one selected from hydrogen fluoride, hydrogen fluoride amine salt, alkali metal fluoride salt and alkaline earth metal fluoride salt.

8. The production method according to any one of claims 1 to 4, wherein The amount of the fluorine source (A) used is in the range of 0.1 to 1000 mol per 1 mol of the compound represented by the formula (1).

9. The production method according to any one of claims 1 to 4, wherein The amount of the iodine source (B) used is in the range of 0.1 to 10 mol per 1 mol of the compound represented by the formula (1).

10. The production method according to any one of claims 1 to 4, wherein: The reaction is carried out in the presence of a solvent.

11. The production method according to any one of claims 1 to 4, wherein: 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-, in the above formula, 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; or R 1 and R 2 Together with two adjacent carbon atoms, it forms a ring.

12. The production method according to any one of claims 1 to 4, wherein: The production method further comprises: a step of separating the compound (C) and / or its derivative from the reaction mixture after the reaction.

13. The production method according to any one of claims 1 to 4, wherein: The production method further comprises: a step of reducing the reaction mixture after the reaction using a reducing agent.

14. The manufacturing method according to claim 13, wherein: The reducing agent is a sulfur-based reducing agent.

15. A composition, characterized in that comprising at least one selected from the following fluorine source (A) and the following iodine source (B), and the following compound (C), (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 the group consisting of iodine, iodinated aliphatic compounds and iodinated aromatic ring compounds; (C) at least one compound selected from the group consisting of compounds represented by the following formula (2-1) which may have one or more substituents, and multimers thereof: In the formula (2-1), X represents a conjugate base of a Bronsted acid.

16. A fluorinating agent, characterized in that The fluorinating agent comprises the composition of claim 15 .

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