Production method for fluoroalkyl aromatic compound

Abstract

To provide: a useful production method for a fluoroalkyl aromatic compound; and a compound obtained by the production method.SOLUTION: This production method is for a compound represented by formula (4), and comprises a step C for reacting a compound represented by formula (1) and a compound represented by formula (3), in the presence of a reducing agent, a copper compound, and a ligand. RF-X1 (1), Ar-X2 (3) and Ar-RF (4) (where, RF represents a fluoroalkyl group optionally having at least one substituent, X1 represents Cl, Br, or I, X2 represents Cl, Br, or I, and Ar represents an aryl group optionally having at least one substituent or a heteroaryl group optionally having at least one substituent).SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a method for producing a fluoroalkyl aromatic compound and the like.

Background Art

[0002] Fluoroalkyl aromatic compounds are compounds useful as agricultural chemicals, pharmaceuticals, liquid crystal materials, etc. As a method for producing the compound, for example, in a high-boiling solvent such as N,N-dimethylformamide (DMF) or dimethyl sulfoxide (DMSO), C5F 11 I, C6F 13 A method of producing a fluoroalkyl aromatic compound by reacting a fluoroalkyl iodide such as I with an aryl iodide such as iodobenzene and copper powder is known (Patent Documents 1 to 2 and Non-Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Non-Patent Documents

[0004]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The method of Patent Document 1 requires high-temperature conditions and has room for improvement in terms of yield. Further, since the methods of Patent Documents 1 to 2 and Non-Patent Document 1 all use a high-boiling solvent, complicated operations such as extraction with water multiple times, distillation under reduced pressure, and crystallization are required to extract the product from the high-boiling solvent.

[0006] An object of the present disclosure includes providing a useful method for producing a fluoroalkyl aromatic compound and a compound obtained by the production method.

Means for Solving the Problems

[0007] The present disclosure includes the following aspects. Item 1. Formula (2): M-R F (2) (In the formula, M is Cu having a ligand, R F is a fluoroalkyl group which may have one or more substituents.) A method for producing a compound represented by the formula, in the presence of a reducing agent, the formula (1): R F -X 1 (1) (In the formula, R F has the same meaning as described above, X 1 is Cl, Br or I.) A production method including a step A of reacting a compound represented by the formula with a copper compound and a ligand. Item 2. Formula (4): Ar-R F (4) (In the formula, Ar is an aryl group which may have one or more substituents, or a heteroaryl group which may have one or more substituents, R F is a fluoroalkyl group which may have one or more substituents.) A method for producing a compound represented by the formula, In the presence of a reducing agent, formula (1): R F -X 1 (1) (In the formula, R F has the same meaning as described above, X 1 is Cl, Br or I.) Reacting the compound represented by with a copper compound and a ligand in step A, and Reacting the reaction product of step A with a compound represented by formula (3): Ar-X 2 (3) (In the formula, Ar has the same meaning as described above, X 2 is Cl, Br or I.) A production method including step B of reacting with a compound represented by Item 3. Formula (4): Ar-R F (4) (In the formula, Ar is an aryl group which may have one or more substituents, or a heteroaryl group which may have one or more substituents, R F is a fluoroalkyl group which may have one or more substituents.) A production method of the compound represented by, In the presence of a reducing agent, a copper compound, and a ligand, formula (1): R F -X 1 (1) (In the formula, R F has the same meaning as described above, X 1 is Cl, Br or I.) Reacting the compound represented by with a compound represented by formula (3): Ar-X 2 (3) (In the formula, Ar has the same meaning as described above, X 2 is Cl, Br or I.) A production method including step C of reacting with a compound represented by Item 4. The production method according to any one of Items 1 to 3, wherein the reducing agent is a compound containing boron and / or silicon. Item 5. The production method according to any one of Items 1 to 4, wherein the reducing agent is at least one selected from the group consisting of diboron compounds, silylborane compounds, and disilane compounds. Item 6. The diboron compound is of formula (A):

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Advantages of the Invention

[0008] According to the present disclosure, for example, a useful production method of a fluoroalkyl aromatic compound and a compound obtained by the production method are provided.

Modes for Carrying Out the Invention

[0009] The above summary of the present disclosure is not intended to describe each disclosed embodiment or all implementations of the present disclosure.

[0010] The following description of the present disclosure exemplifies the exemplary embodiments more specifically. In some places of the present disclosure, guidance is provided through examples, and these examples can be used in various combinations. In each case, the group of examples can function as a non-exclusive and representative group. All publications, patents, and patent applications cited herein are hereby incorporated by reference in their entirety.

[0011] 1. Terms Unless otherwise specifically limited, the symbols and abbreviations in this specification can be understood in the meaning commonly used in the technical field to which the present disclosure belongs in accordance with the context of this specification.

[0012] In this specification, the term "comprising" is used with the intention of including the terms "consisting essentially of" and "consisting of".

[0013] Unless otherwise specifically limited, the processes, treatments, or operations described in this specification can be carried out at room temperature. In this specification, room temperature can mean a temperature within the range of 10 to 40 °C.

[0014] In this specification, the notation "C n-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 commonly understood by those skilled in the art.

[0015] In this specification, examples of "halogen" include, for example, fluorine (F), chlorine (Cl), bromine (B r), and iodine (I).

[0016] In this specification, examples of "alkyl group" include linear or branched C 1-20 alkyl groups such as methyl, ethyl, propyl (n-propyl, isopropyl), butyl (n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl, and hexyl.

[0017] In this specification, examples of the "alkoxy group" include linear or branched C alkoxy groups such as methoxy, ethoxy, propoxy (n-propoxy, isopropoxy), butoxy (n-butoxy, isobutoxy, sec-butoxy, tert-butoxy), pentyloxy, and hexyloxy. 1-20 Examples thereof include an alkoxy group.

[0018] In this specification, examples of the "alkylthio group" include linear or branched C alkylthio groups such as methylthio, ethylthio, propylthio (n-propylthio, isopropylthio), butylthio (n-butylthio, isobutylthio, sec-butylthio, tert-butylthio), pentylthio, and hexylthio. 1-20 Examples thereof include an alkylthio group.

[0019] In this specification, examples of the "cycloalkyl group" include C cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. 3-20 Examples thereof include a cycloalkyl group.

[0020] In this specification, the "aryl group" can be, for example, monocyclic, bicyclic, tricyclic, or tetracyclic. Examples of the "aryl group" include C aryl groups such as phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl. 6-20 Examples thereof include an aryl group.

[0021] In this specification, the "heteroaryl group" can be, for example, monocyclic, bicyclic, tricyclic, or tetracyclic. The "heteroaryl group" can be, for example, a 5- to 18-membered heteroaryl group. The "heteroaryl group" can be, for example, a heteroaryl group containing 1, 2, 3, or 4 heteroatoms selected from oxygen atoms, sulfur atoms, and nitrogen atoms in addition to carbon atoms as ring-constituting atoms. The "heteroaryl group" includes a "monocyclic heteroaryl group" and an "aromatic condensed heterocyclic group".

[0022] Examples of the "monocyclic heteroaryl 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), thiazolyl (e.g., 2-thiazolyl, 4-thiazolyl, 5-thiazolyl), triazolyl (e.g., 1,2,3-triazol-3-yl, 1,2,4-triazol-4-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, 1,2,4-5-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), and pyrazinyl, etc.

[0023] Examples of the "condensed aromatic heterocyclic group" include isoindolyl (e.g., 1-isoind Ril, 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), 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 - benzisothiazol - 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, 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, and imidazo[1,2-a]pyridin-8-yl), etc.

[0024] In this specification, in the "alkyl group which may have one or more substituents", -CH2- which may be present inside the alkyl group may be replaced by -O-, -S-, or -NH-. Examples of the substituents of the alkyl group include halogen, hydroxy group, alkoxy group, mercapto group, alkylthio group, alkoxycarbonyl (alkyl -O-CO-) group, alkylcarbonyloxy (alkyl -CO-O-) group, aryl group, and combinations of two or more thereof (e.g., haloalkoxy group). When the alkyl group has a substituent, the number of substituents can be selected from the range of 1 to the maximum number that can be substituted, and can be, for example, 1, 2, 3, 4, or 5. When the number of substituents is 2 or more, each substituent may be the same as or different from each other.

[0025] Examples of the above "alkyl group which may have one or more substituents" include an alkyl group which may be substituted with one or more halogens (e.g., fluorine). An alkyl group substituted with one or more halogens is referred to as a "haloalkyl group", and may be referred to as a "fluoroalkyl group" when the substituent halogen is fluorine, for example. The "fluoroalkyl group" may be a perfluoroalkyl group or a non-perfluoroalkyl group. Examples of the "fluoroalkyl group" include linear or branched fluoro C such as trifluoromethyl group, perfluoroethyl group, perfluoropropyl group (e.g., perfluoro n-propyl, perfluoroisopropyl group), perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, etc. 1-20It includes an alkyl group. Examples of the "fluoroalkyl group which may have one or more substituents" include, in addition to the above fluoroalkyl group, a fluoroalkyl group substituted with one or more substituents (e.g., an alkoxy group; a haloalkoxy group such as a fluoroalkoxy group; an alkoxycarbonyl group; a haloalkoxycarbonyl group such as a fluoroalkoxycarbonyl group), and specific examples thereof are CF3-O-CF2-, CF3-O-CF(CF3)-, CF3-O-CH2-CH2-, CF3-O-CH(CF3)-CH2-, CF3-O-CF2-CF2-, CF3-CF2-O-CF2-, CF3-CF2-O-CF2-CF2-, CF3-O-CF2-O-CF2-, CF3-CF2-CF2-O-CH2-CF2-, CF3-CF2-CF2-O-CF2-CF2-, CF3-CF2-CF2-O-CF(CF3)-CF2-, CF3-CF2-CF2-O-CF(C F3)-CF2-O-CF(CF3)-CF2-, CF3-CF2-CF2-O-[CF(C F3)-CF2-O-]2-CF(CF3)-CF2-, etc., which are linear or branched fluoro C 1-20 alkyl groups substituted with one or more substituents.

[0026] In the present specification, in the "aryl group which may have one or more substituents" and the "heteroaryl group which may have one or more substituents", examples of the substituents include halogen, hydroxy group, alkyl group, alkoxy group, alkylthio group, and combinations of two or more thereof (e.g., haloalkyl group, haloalkoxy group). When the aryl group has a substituent, the number of substituents can be selected from the range of 1 to the maximum number that can be substituted, and can be, for example, 1, 2, 3, 4, or 5. When the number of substituents is 2 or more, each substituent may be the same as or different from each other.

[0027] In the present specification, the "alkylene group", "cycloalkylene group", and "arylene group" are each a divalent group formed by removing one H from the "alkyl group", "cycloalkyl group", and "aryl group", respectively.

[0028] 2. Method for producing the compound represented by formula (2) In one embodiment of the present disclosure, a method for producing a compound represented by formula (2) (which may be referred to as a "fluoroalkyl copper reagent") includes step A of reacting a compound represented by formula (1) with a copper compound and a ligand in the presence of a reducing agent. R F -X 1 (1) M-R F (2) (In the formula, R F is a fluoroalkyl group which may have one or more substituents, X 1 is Cl, Br or I, M is Cu having a ligand.)

[0029] [Compound represented by formula (1)] R F In, the lower limit of the number of carbon atoms of the fluoroalkyl group can be, for example, 1, 2, or 3, and the upper limit can be, for example, 20, 16, 14, 12, or 10. R F is preferably a fluoroC 1-20 alkyl group (e.g., perfluoroC 1-20 alkyl group), more preferably a fluoroC 1-12 alkyl group (e.g., perfluoroC 1-12 alkyl group), and even more preferably a fluoroC 1-10 alkyl group (e.g., perfluoroC 1-10 alkyl group).

[0030] X 1 is preferably Br or I. In one embodiment, X 1 is preferably Br. In another embodiment, X 1 is preferably I.

[0031] [Copper compound] The copper compound is not particularly limited as long as it contains copper. The copper compound may be, for example, elemental copper or a monovalent or divalent copper compound. In one embodiment, the copper compound is preferably a monovalent copper compound.

[0032] Examples of the copper compound include copper powder, copper(I) halides such as copper(I) iodide, copper(I) oxide, copper(I) sulfide, copper(I) hydroxide, copper(I) acetate, copper(II) halides such as copper(II) iodide, copper(II) oxide, copper(II) sulfate, copper(II) hydroxide, copper(II) acetate, etc. These copper compounds may be used in combination with, for example, alkoxides, aryloxides, thioalkoxides, or thioaryloxides of alkali metals such as lithium, sodium, and potassium. Alternatively, as the copper compound, a copper alkoxide, aryloxide, thioalkoxide, or thioaryloxide may be used. Examples of the alkoxide or aryloxide include C 1-6 alkoxides such as methoxide, ethoxide, propoxide, butoxide (e.g., t-butoxide), and C 6-10 aryloxides such as phenoxide. Examples of the thioalkoxide or thioaryloxide include those in which O of the alkoxide or aryloxide is replaced by S.

[0033] The amount of the copper compound used is, for example, 0.5 mol or more, preferably 1 mol or more, more preferably 1.5 mol or more, per 1 mol of the compound represented by formula (1). The amount of the copper compound used is, for example, 5 mol or less, preferably 4 mol or less, more preferably 3 mol or less, per 1 mol of the compound represented by formula (1). The amount of the copper compound used is, for example, in the range of 0.5 to 5 mol, preferably in the range of 1 to 4 mol, more preferably in the range of 1.5 to 3 mol, per 1 mol of the compound represented by formula (1).

[0034] [Ligand] The ligand is not particularly limited as long as it coordinates with copper. Examples of the ligand include pyridine-containing ligands, phosphine ligands, and the like.

[0035] Examples of the pyridine-containing ligands include phenanthroline (e.g., 1,10-phenanthroline), 2,2'-bipyridyl, pyridine, methylpyridine, lutidine (e.g., 2,6-lutidine), and the like.

[0036] As the phosphine ligand, trialkylphosphine or triarylphosphine is preferred. Examples of the trialkylphosphine include tri(C 3-20 alkyl)phosphines such as triisopropylphosphine, di-t-butylmethylphosphine, tri-t-butylphosphine, trihexylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, triadamantylphosphine, tribicyclo[2,2,2]octylphosphine, trinorbornylphosphine, and the like. Examples of the triarylphosphine include tri(monocyclic aryl)phosphines such as triphenylphosphine, trimesitylphosphine, tri(o-tolyl)phosphine, and the like. Among these, triphenyl phosphine, tricyclohexylphosphine, and tri-t-butylphosphine are preferred.

[0037] In one embodiment, the ligand is preferably a bidentate ligand. Preferred examples of the bidentate ligand include 1,10-phenanthroline and the like.

[0038] The amount of the ligand used is, for example, 0.5 mol or more, preferably 1 mol or more, more preferably 1.5 mol or more, per 1 mol of the compound represented by formula (1). The amount of the ligand used is, for example, 5 mol or less, preferably 4 mol or less, more preferably 3 mol or less, per 1 mol of the compound represented by formula (1). The amount of the ligand used is, for example, in the range of 0.5 to 5 mol, preferably in the range of 1 to 4 mol, more preferably in the range of 1.5 to 3 mol, per 1 mol of the compound represented by formula (1).

[0039] [Reducing agent] By carrying out the reaction of Step A in the presence of a reducing agent, the reaction can be carried out at a low temperature, the use of a high-boiling solvent and the accompanying complicated removal operation can be avoided, and even a compound that is easily decomposed at a high temperature can be easily synthesized.

[0040] The reducing agent is not particularly limited as long as it has reducing ability. In one embodiment, the reducing agent is preferably a compound containing boron and / or silicon. Examples of the reducing agent include diboron compounds, silylborane compounds, disilane compounds, and the like.

[0041] Examples of the diboron compound include a compound represented by the formula (A). [Chemical formula] (In the formula, Z 1 and Z 2 are each independently a single bond, a double bond, or CH2, R 1 and R 2 are each independently an organic group, Two R 1 that may be adjacent to each other may combine together to form a ring, Two R 2 that may be adjacent to each other may combine together to form a ring, k1 and k2 are each independently 0 or an integer of 1 or more.)

[0042] In one embodiment, it is preferable that both Z 1 and Z 2 are single bonds. In another embodiment, it is preferable that both Z 1 and Z 2 are double bonds. In yet another embodiment, it is preferable that both Z 1 and Z 2 are CH2.

[0043] R 1 and R 2 are each independently preferably an alkyl group, more preferably a C 1-6 alkyl group, still more preferably a C 1-4 alkyl group, even more preferably a C 1-2 alkyl group.

[0044] Z 1 and Z 2 is a single bond, k1 and k2 are each 0, 1, 2, 3, or 4. Z 1 and Z 2 is a double bond, k1 and k2 are each 0, 1, or 2. Z 1 and Z 2 is CH2, k1 and k2 are each 0, 1, 2, 3, 4, 5, or 6.

[0045] Examples of the compound represented by formula (A) include compounds represented by formula (A1), (A2), (A3), or (A4), etc.

Chemical formula

[0046] Examples of the silyl borane compound include compounds represented by formula (B), etc.

Chemical formula

[0047] In one embodiment, Z 11 is preferably a single bond. In another embodiment, Z 11 is preferably a double bond. In yet another embodiment, Z 11 is preferably CH2.

[0048] R 11 is preferably a hydrocarbon group, more preferably an alkyl group, still more preferably a C 1-6 alkyl group, even more preferably a C 1-4 alkyl group, particularly preferably a C 1-2 alkyl group.

[0049] R 12 、R 13 、and R 14 are each independently preferably an alkyl group or an aryl group, more preferably a C 1-6 alkyl group or a C 6-14 aryl group, still more preferably a C 1-4 alkyl group or a C 6-12 aryl group, even more preferably a C 1-2 alkyl group or a C 6-10 aryl group.

[0050] Z 11 is a single bond, k3 is 0, 1, 2, 3, or 4. When Z 11 is a double bond, k3 is 0, 1, or 2. When Z 11 is CH2, k3 is 0, 1, 2, 3, 4, 5, or 6.

[0051] Examples of the compound represented by formula (B) include compounds represented by formula (B1).

Chemical formula

[0052] Examples of the disilane compound include compounds represented by formula (C). [Chemical formula] (wherein, R 21 , R 22 , R 23 , R 24 , R 25 , and R 26 are each independently H, halogen, or an organic group.)

[0053] R 21 , R 22 , R 23 , R 24 , R 25 , and R 26 are each independently preferably H, halogen, an alkyl group, an alkoxy group, or an aryl group, more preferably H, halogen, C 1-6 alkyl group, C 1-6 alkoxy group, or C 6-14 aryl group, even more preferably H, halogen, C 1-4 alkyl group, C 1-4 alkoxy group, or C 6-12 aryl group, and even more preferably H, halogen (especially Cl), C 1-2 alkyl group, C 1-2 alkoxy group, or C 6-10 aryl group.

[0054] Examples of the compound represented by formula (C) include compounds represented by formula (C1), (C2), (C3), (C4), (C5), (C6), (C7), (C8), or (C9). [Chemical formula]

[0055] The usage amount of the reducing agent is, for example, 0.7 mol or more, preferably 0.8 mol or more, more preferably 0.9 mol or more, per 1 mol of the compound represented by the formula (1). The usage amount of the reducing agent is, for example, 3 mol or less, preferably 2 mol or less, more preferably 1.5 mol or less, per 1 mol of the compound represented by the formula (1). The usage amount of the reducing agent is, for example, in the range of 0.7 to 3 mol, preferably in the range of 0.8 to 1 mol, more preferably in the range of 0.9 to 1.5 mol, per 1 mol of the compound represented by the formula (1).

[0056] [Organic solvent] The reaction of step A is preferably carried out in the presence of an organic solvent. In one embodiment, it is preferable that the organic solvent is not a high-boiling solvent (or is a low-boiling solvent), and the boiling point at normal pressure is preferably 150 °C or lower, 140 °C or lower, 130 °C or lower, 120 °C or lower, or 110 °C or lower. Examples of the organic solvent include ether solvents (e.g., cyclic ether solvents such as tetrahydrofuran), aromatic hydrocarbon solvents (e.g., toluene, xylene, etc.), and mixed solvents of two or more of these.

[0057] The usage amount of the organic solvent is, for example, 0.5 mL or more, preferably 1 mL or more, more preferably 1.5 mL or more, per 1 mmol of the compound represented by the formula (1). The usage amount of the organic solvent is, for example, 40 mL or less, preferably 30 mL or less, more preferably 20 mL or less, per 1 mmol of the compound represented by the formula (1). The usage amount of the organic solvent is, for example, in the range of 0.5 to 40 mL, preferably in the range of 1 to 30 mL, more preferably in the range of 1.5 to 20 mL, per 1 mmol of the compound represented by the formula (1).

[0058] [Reaction temperature and reaction time] The reaction temperature and reaction time of step A are not particularly limited as long as the reaction proceeds. The reaction temperature is, for example, -30°C or higher, preferably -10°C or higher, more preferably 0°C or higher. The reaction temperature is, for example, 40°C or lower, preferably 35°C or lower, more preferably 30°C or lower. The reaction temperature is, for example, in the range of -30 to 40°C, preferably in the range of -10 to 35°C, more preferably in the range of 0 to 30°C.

[0059] The reaction time is, for example, 5 minutes or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer, still more preferably 1 hour or longer. The reaction time is, for example, 48 hours or shorter, preferably 24 hours or shorter, more preferably 12 hours or shorter. The reaction time is, for example, in the range of 5 minutes to 48 hours, preferably in the range of 10 minutes to 24 hours, more preferably in the range of 1 to 12 hours.

[0060] [Optional additional steps] The production method may further include a step of isolating or purifying the compound represented by the formula (2). The isolation or purification of the compound represented by the formula (2) can be carried out by methods such as filtration, extraction, concentration, chromatography, or a combination of these methods.

[0061] 3. Method for producing the compound represented by formula (4) In one embodiment of the present disclosure, the method for producing the compound represented by the formula (4) includes step A and step B of reacting the reaction product of step A (particularly the compound represented by the formula (2)) with the compound represented by the formula (3). Ar-X 2 (3) Ar-R F (4) (In the formula, Ar is an aryl group which may have one or more substituents, or a heteroaryl group which may have one or more substituents, X 2 is Cl, Br or I, R F has the same meaning as described above.)

[0062] [Compound represented by formula (3)] Ar is a C which may have one or more substituents6-14 It is preferably an aryl group or a 5- to 14-membered heteroaryl group which may have one or more substituents, and C which may have one or more substituents 6-12 It is more preferably an aryl group or a 5- to 12-membered heteroaryl group which may have one or more substituents, and C which may have one or more substituents 6-10 It is even more preferably an aryl group or a 5- to 10-membered heteroaryl group which may have one or more substituents. The heteroatom contained in the heteroaryl group is preferably selected from the group consisting of O, S, and N.

[0063] In one embodiment, Ar is preferably an aryl group which may have one or more substituents. The substituent may be an organic group. Specifically, it is an alkyl group which may have one or more further substituents, an aryl group which may have one or more further substituents, a heteroaryl group which may have one or more further substituents, a carbonyl group (-L 1 -CO-Q 1 or -CO-L 1 -Q 1 ; Q 1 represents H or a hydrocarbon group which may have one or more further substituents, and L 1 represents a single bond or -O-) (an amide group (-L 2 -CO-NQ 2 Q 3 or -NQ 4 -CO-L 3 -Q 5 ; Q 2 、Q 3 、Q 4 、and Q 5 each independently represent H or a hydrocarbon group which may have one or more further substituents, and L 2 and L 3 each independently represent a single bond or -O-), an alkoxy group, a hydroxy group, a halogen (halogeno group), and combinations thereof. In one embodiment, the substituent is preferably fluorine and / or a fluoroalkyl group, and the substituent may be a fluoroalkyl group.

[0064] X 2 is preferably Br or I. In one embodiment, X 2 is preferably Br. In another embodiment, X 2 is preferably I.

[0065] In one embodiment, the compound represented by formula (3) is preferably a compound represented by formula (3A) or formula (3B). X 21 -Ar 1 -A 0 -Ar 2 -X 22 (3A) X 23 -Ar 3 -X 24 (3B) (Wherein, Ar 1 Ar 2 and Ar 3 are each independently an arylene group which may have one or more substituents, or a heteroarylene group which may have one or more substituents, and A 0 is a single bond, -O-, -S-, an alkylene group which may have one or more substituents, a cycloalkylene group which may have one or more substituents, or an arylene group which may have one or more substituents, X 21 X 22 X 23 and X 24 are each independently Cl, Br or I.)

[0066] Ar 1 and Ar 2 may be the same as or different from each other. Preferred examples of Ar 1 Ar 2 and Ar 3 include divalent groups corresponding to the preferred examples of Ar.

[0067] A 0When it is an alkylene group which may have one or more substituents, the lower limit of the number of carbon atoms of the alkylene group can be, for example, 1 or 2, and the upper limit can be, for example, 6, 5, 4, 3, or 2. A 0 is preferably a C 1-6 alkylene group which may have one or more substituents, more preferably a C 1-6 alkylene group which may have one or more substituents, still more preferably a C 1-4 alkylene group which may have one or more substituents, and even more preferably a C 1-2 alkylene group. The substituent may be an organic group. Specifically, it may be an alkyl group which may have one or more further substituents, an aryl group which may have one or more further substituents, a heteroaryl group which may have one or more further substituents, a carbonyl group (-L 1 -CO-Q 1 or -CO-L 1 -Q 1 ), an amide group (-L 2 -CO-NQ 2 Q 3 or -NQ 4 -CO-L 3 -Q 5 ), an alkoxy group, a hydroxy group, a halogen (halogeno group), or a combination thereof.

[0068] A 0 When it is a cycloalkylene group which may have one or more substituents, it is preferably a C 5-14 cycloalkylene group which may have one or more substituents, more preferably a C 5-12 cycloalkylene group which may have one or more substituents, still more preferably a C 5-10 cycloalkylene group.

[0069] A 0 When it is an arylene group which may have one or more substituents, it is preferably a C 6-14An arylene group, more preferably a C which may have one or more substituents 6-12 arylene group, even more preferably a C which may have one or more substituents 5-10 is an arylene group.

[0070] X 21 , X 22 , X 23 , and X 24 are each independently preferably Br or I. X 21 and X 22 may be the same as or different from each other. X 23 and X 24 may be the same as or different from each other.

[0071] The amount of the compound represented by the formula (3) (especially the total amount of Cl, Br and I) is, for example, 0.05 mol or more, preferably 0.1 mol or more, even more preferably 0.15 mol or more, based on 1 mol of the compound represented by the formula (2). The amount of the compound represented by the formula (3) is, for example, 3 mol or less, preferably 2 mol or less, even more preferably 1.5 mol or less, based on 1 mol of the compound represented by the formula (2). The amount of the compound represented by the formula (3) is, for example, in the range of 0.05 to 3 mol, preferably in the range of 0.1 to 2 mol, even more preferably in the range of 0.15 to 1.5 mol, based on 1 mol of the compound represented by the formula (2).

[0072] [Organic solvent] The reaction of Step B is preferably carried out in the presence of an organic solvent. In one embodiment, the organic solvent is preferably not a high-boiling solvent (or is a low-boiling solvent), and the boiling point at normal pressure is preferably 150 °C or lower, 140 °C or lower, 130 °C or lower, 120 °C or lower, or 110 °C or lower. Examples of the organic solvent include ether solvents (e.g., cyclic ether solvents such as tetrahydrofuran), aromatic hydrocarbon solvents (e.g., toluene, xylene, etc.), and mixed solvents of two or more of these. The organic solvent may be different from the organic solvent used in Step A, but is preferably the same.

[0073] [Reaction Temperature and Reaction Time] The reaction temperature and reaction time in Step B are not particularly limited as long as the reaction proceeds. The reaction temperature is, for example, 0°C or higher, preferably 10°C or higher, and more preferably 20°C or higher. The reaction temperature is, for example, 125°C or lower, preferably 100°C or lower, and more preferably 80°C or lower. The reaction temperature is, for example, in the range of 0 to 125°C, preferably in the range of 10 to 100°C, and more preferably in the range of 20 to 80°C.

[0074] The reaction time is, for example, 30 minutes or longer, preferably 1 hour or longer, and more preferably 2 hours or longer. The reaction time is, for example, 48 hours or shorter, preferably 24 hours or shorter, and more preferably 12 hours or shorter. The reaction time is, for example, in the range of 30 minutes to 48 hours, preferably in the range of 1 to 24 hours, and more preferably in the range of 2 to 12 hours.

[0075] In another embodiment of the present disclosure, the method for producing the compound represented by formula (4) includes Step C of reacting the compound represented by formula (1) with the compound represented by formula (3) in the presence of a reducing agent, a copper compound, and a ligand.

[0076] Examples of the compound represented by formula (1) and the compound represented by formula (3) are the same as those exemplified in Step A and Step B, respectively.

[0077] The amount of the compound represented by formula (3) used (particularly the total amount of Cl, Br, and I) is, for example, 0.05 mol or more, preferably 0.1 mol or more, and more preferably 0.15 mol or more per 1 mol of the compound represented by formula (1). The amount of the compound represented by formula (3) used is, for example, 3 mol or less, preferably 2 mol or less, and more preferably 1.5 mol or less per 1 mol of the compound represented by formula (1). The amount of the compound represented by formula (3) used is, for example, in the range of 0.05 to 3 mol, preferably in the range of 0.1 to 2 mol, and more preferably in the range of 0.15 to 1.5 mol per 1 mol of the compound represented by formula (1).

[0078] Examples of the reducing agent, copper compound, and ligand include the same ones as those exemplified in Step A. The amounts of the reducing agent, copper compound, and ligand used with respect to the compound represented by formula (1) can also be selected from the same ranges as those exemplified in Step A.

[0079] [Organic solvent] The reaction in Step C is preferably carried out in the presence of an organic solvent. Examples of the organic solvent include the same ones as those exemplified in Step A. The amount of the organic solvent used with respect to the compound represented by formula (1) can also be selected from the same ranges as those exemplified in Step A.

[0080] [Reaction temperature and reaction time] The reaction temperature and reaction time in Step C are not particularly limited as long as the reaction proceeds. The reaction temperature and reaction time can also be selected from the same ranges as those exemplified in Step A.

[0081] [Optional additional steps] In the production method, for example, when using the compound represented by formula (3A), a compound represented by formula (4B) and / or a compound represented by formula (4C) may be produced as by-products. X 21 -Ar 1 -A 0 -Ar 2 -R F (4B) R F -Ar 1 -A 0 -Ar 2 -X 22 (4C) The production method may further include a step of isolating or purifying the compound represented by formula (4). The isolation or purification of the compound represented by formula (4) can be carried out by methods such as filtration, extraction, concentration, chromatography, or a combination of these methods.

[0082] 4. Compound represented by formula (4A) The compound of one embodiment of the present disclosure is a compound represented by formula (4A). [Chemical formula] (In the formula, A 1 is a single bond, -O-, -S-, an alkylene group which may have one or more substituents, a cycloalkylene group which may have one or more substituents, or an arylene group which may have one or more substituents.)

[0083] A 1 When is an alkylene group which may have one or more substituents, the lower limit of the number of carbon atoms of the alkylene group can be, for example, 1 or 2, and the upper limit can be, for example, 6, 5, 4, 3, or 2. A 1 is preferably a C 1-6 alkylene group which may have one or more substituents, more preferably a C 1-6 alkylene group which may have one or more substituents, still more preferably a C 1-4 alkylene group which may have one or more substituents, and even more preferably a C 1-2 alkylene group which may have one or more substituents. The substituent may be an organic group. Specifically, it is an alkyl group which may have one or more further substituents, an aryl group which may have one or more further substituents, a heteroaryl group which may have one or more further substituents, a carbonyl group (-L 1 -CO-Q 1 or -CO-L 1 -Q 1 ), an amide group (-L 2 -CO-NQ 2 Q 3 or -NQ 4 -CO-L 3 -Q 5 ), an alkoxy group, a hydroxy group, a halogen (halogeno group), or a combination thereof.)

[0084] A 1 When is a cycloalkylene group which may have one or more substituents, it is preferably a C 5-14 cycloalkylene group which may have one or more substituents, more preferably a C5-12 a cycloalkylene group, more preferably a C cycloalkylene group which may further have one or more substituents 5-10 is a cycloalkylene group.

[0085] A 1 When A is an arylene group which may have one or more substituents, it is preferably a C arylene group which may have one or more substituents 6-14 arylene group, more preferably a C arylene group which may have one or more substituents 6-12 arylene group, still more preferably a C arylene group which may have one or more substituents 5-10 is an arylene group.

[0086] The compound represented by formula (4A) can be produced, for example, in the method for producing the compound represented by the above formula (4), by reacting a compound in which Ar and Ar 1 in formula (3A) are phenylene groups, a compound in which R 2 in formula (1) is CF2Cl-CFCl-CF2-CF2-, a copper compound, and a ligand (or a compound in which R F in formula (2) is CF2Cl-CFCl-CF2-CF2- which is produced by reacting these). F can be produced by reacting with).

[0087] 5. Compound represented by formula (5A) The compound of one embodiment of the present disclosure is a compound represented by formula (5A). [Chemical formula] (In the formula, A 2 is a single bond, -O-, -S-, an alkylene group which may have one or more substituents, a cycloalkylene group which may have one or more substituents, or an arylene group which may have one or more substituents)

[0088] A 2When it is an alkylene group which may have one or more substituents, the lower limit of the number of carbon atoms of the alkylene group can be, for example, 1 or 2, and the upper limit can be, for example, 6, 5, 4, 3, or 2. A 2 is preferably a C 1-6 alkylene group which may have one or more substituents, more preferably a C 1-6 alkylene group which may have one or more substituents, still more preferably a C 1-4 alkylene group which may have one or more substituents, still more preferably a C 1-2 alkylene group. The substituent may be an organic group. Specifically, it may be an alkyl group which may have one or more further substituents, an aryl group which may have one or more further substituents, a heteroaryl group which may have one or more further substituents, a carbonyl group (-L 1 -CO-Q 1 or -CO-L 1 -Q 1 ), an amide group (-L 2 -CO-NQ 2 Q 3 or -NQ 4 -CO-L 3 -Q 5 ), an alkoxy group, a hydroxy group, a halogen (halogeno group), and combinations thereof.

[0089] A 2 When it is a cycloalkylene group which may have one or more substituents, it is preferably a C 5-14 cycloalkylene group which may have one or more substituents, more preferably a C 5-12 cycloalkylene group which may have one or more substituents, still more preferably a C 5-10 cycloalkylene group.

[0090] A 2 When it is an arylene group which may have one or more substituents, it is preferably a C 6-14An arylene group, more preferably a C which may have one or more substituents 6-12 An arylene group, even more preferably a C which may have one or more substituents 5-10 is an arylene group.

[0091] The compound represented by formula (5A) can be produced, for example, by a dechlorination reaction of the compound represented by formula (4A). The dechlorination reaction can be carried out under conditions known or customary in the art.

[0092] The compound represented by formula (5A) may contain Al, Cr, Cu, Fe, Ni, and Zn, and may not contain some or all of these metals. The contents of Al, Cr, Cu, Fe, Ni, and Zn in the compound represented by formula (5A) are each, for example, 1000 ppm or less, preferably 800 ppm or less, more preferably 500 ppm or less. Since the lower the content of the above metals, the more preferable, the lower limit is not particularly limited, but may be, for example, 0.001 ppm or more. Al, Cr, Cu, Fe , Ni, and Zn contents can each be measured, for example, by ICP (inductively coupled plasma) optical emission spectrometry. In one embodiment, the contents of Al, Cr, Cu, Fe, Ni, and Zn are each preferably below the detection limit by ICP optical emission spectrometry.

[0093] The total content of Al, Cr, Cu, Fe, Ni, and Zn in the compound represented by formula (5A) is, for example, 6000 ppm or less, preferably 4800 ppm or less, more preferably 3000 ppm or less. In one embodiment, the total content of the above metals may be 1000 ppm or less, 800 ppm or less, or 500 ppm or less. Since the total content of the above metals is preferably as low as possible, the lower limit is not particularly limited, but may be, for example, 0.001 ppm or more. The total content of Al, Cr, Cu, Fe, Ni, and Zn can be measured, for example, by ICP (inductively coupled plasma) emission spectrometry. In one embodiment, the total content of Al, Cr, Cu, Fe, Ni, and Zn is preferably below the detection limit by ICP emission spectrometry.

[0094] The compound represented by formula (5A) may or may not contain Pd. The content of Pd in the compound represented by formula (5A) is, for example, 1000 ppm or less, preferably 800 ppm or less, more preferably 500 ppm or less. Since the content of Pd is preferably as low as possible, the lower limit is not particularly limited, but may be, for example, 0.001 ppm or more. The content of Pd can be measured, for example, by ICP emission spectrometry. In one embodiment, the content of Pd is preferably below the detection limit by ICP emission spectrometry.

[0095] 7. Compound represented by formula (5) A compound according to an embodiment of the present disclosure is a compound represented by formula (5). [Chemical formula] (In the formula, A is a single bond, -O-, -S-, an alkylene group which may have one or more substituents, a cycloalkylene group which may have one or more substituents, or an arylene group which may have one or more substituents, R 31 、R 32 、R 33 、R 34 、R 35 、R41 , R 42 , R 43 , R 44 , and R 45 are each independently a fluorine, an alkyl group, or a fluoroalkyl group, and n and m are each independently 0, 1, or 2.)

[0096] When A is an alkylene group which may have one or more substituents, the lower limit of the number of carbon atoms of the alkylene group can be, for example, 1 or 2, and the upper limit can be, for example, 6, 5, 4, 3, or 2. A is preferably a C 1-6 alkylene group which may have one or more substituents, more preferably a C 1-6 alkylene group which may have one or more substituents, still more preferably a C 1-4 alkylene group which may have one or more substituents, still more preferably a C 1-2 alkylene group. The substituent may be an organic group, specifically, an alkyl group which may have one or more further substituents, an aryl group which may have one or more further substituents, a heteroaryl group which may have one or more further substituents, a carbonyl group (-L 1 -CO-Q 1 or -CO-L 1 -Q 1 ), an amide group (-L 2 -CO-NQ 2 Q 3 or -NQ 4 -CO-L 3 -Q 5 ), an alkoxy group, a hydroxy group, a halogen (halogeno group), and combinations thereof.

[0097] When A is a cycloalkylene group which may have one or more substituents, preferably a C 5-14 cycloalkylene group which may have one or more substituents, more preferably a C 5-12 cycloalkylene group which may have one or more substituents, still more preferably a C5-10 It is a cycloalkylene group.

[0098] When A is an arylene group which may have one or more substituents, preferably it is a C 6-14 arylene group, more preferably a C 6-12 arylene group, still more preferably a C 5-10 arylene group.

[0099] R 31 , R 32 , R 33 , R 34 , R 35 , R 41 , R 42 , R 43 , R 44 , and R 45 are each independently preferably fluorine, a C 1-6 alkyl group, or a fluorinated C 1-6 alkyl group, more preferably fluorine, a C 1-4 alkyl group, or a fluorinated C 1-4 alkyl group, still more preferably fluorine, a C 1-2 alkyl group, or a fluorinated C 1-2 alkyl group. In one embodiment, R 31 , R 32 , R 33 , R 34 , and R 35 are each preferably the same as R 41 , R 42 , R 43 , R 44 , and R 45 .

[0100] In one embodiment, it is preferable that both n and m are 0. In another embodiment, it is preferable that both n and m are 1. In still another embodiment, it is preferable that both n and m are 2.

[0101] The compound represented by formula (5) may contain Al, Cr, Cu, Fe, Ni, and Zn, or may not contain some or all of these metals. The contents of Al, Cr, Cu, Fe, Ni, and Zn in the compound represented by formula (5) are each, for example, 1000 ppm or less, preferably 800 ppm or less, and more preferably 500 ppm or less. Since the lower the content of the above metals, the more preferable, the lower limit is not particularly limited, but may be, for example, 0.001 ppm or more. The contents of Al, Cr, Cu, Fe, Ni, and Zn can each be measured, for example, by ICP (inductively coupled plasma) optical emission spectrometry. In one embodiment, the contents of Al, Cr, Cu, Fe, Ni, and Zn are each preferably below the detection limit by ICP optical emission spectrometry.

[0102] The total content of Al, Cr, Cu, Fe, Ni, and Zn in the compound represented by formula (5) is, for example, 6000 ppm or less, preferably 4800 ppm or less, and more preferably 3000 ppm or less. In one embodiment, the total content of the above metals may be 1000 ppm or less, 800 ppm or less, or 500 ppm or less. Since the lower the total content of the above metals, the more preferable, the lower limit is not particularly limited, but may be, for example, 0.001 ppm or more. The total content of Al, Cr, Cu, Fe, Ni, and Zn can be measured, for example, by ICP (inductively coupled plasma) optical emission spectrometry. In one embodiment, the total content of Al, Cr, Cu, Fe, Ni, and Zn is preferably below the detection limit by ICP optical emission spectrometry.

[0103] The compound represented by formula (5) may or may not contain Pd. The content of Pd in the compound represented by formula (5) is, for example, 1000 ppm or less, preferably 800 ppm or less, more preferably 500 ppm or less. Since the lower the content of Pd, the more preferable it is, the lower limit is not particularly limited, but it may be, for example, 0.001 ppm or more. The content of Pd can be measured by, for example, ICP emission spectrometry. In one embodiment, it is preferable that the content of Pd is below the detection limit by ICP emission spectrometry.

[0104] The compound represented by formula (5) is, for example, in the method for producing the compound represented by the above formula (4), Ar of formula (3A) 1 and Ar 2 is a compound having a phenylene group, and R of formula (1) F is CR 35 R 34 Cl-CR 33 Cl-(CR 32 R 31 ) n - and / or a compound in which R of formula (1) F is CR 45 R 44 Cl-CR 43 Cl-(CR 42 R 41 ) m - is reacted with a copper compound and a ligand (or a compound of formula (2) produced by reacting these), and the compound of formula (4) produced by the reaction is subjected to a dechlorination reaction. The dechlorination reaction can be carried out under conditions known or customary in the art.

Examples

[0105] 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. Each abbreviation in the examples is as follows. B2pin2: Bis(pinacolato)diboron DMF: N,N-Dimethylformamide HPLC: High Performance Liquid Chromatography PhMe2SiBpin: (Dimethylphenylsilyl)boronic acid pinacol ester tBu: t-butyl THF: Tetrahydrofuran

[0106] Example 1

Chem.

[0107] Example 2

Chem.

[0108] Example 3 The same procedure as above was carried out except that B2Pin2 was changed to PhMe2SiBpin (0.12 mmol), and the title compound (4-1) was found to be produced in a yield of 63% by 19F NMR. 19

[0109] Example 4 The same procedure as above was carried out except that THF was changed to diethyl ether, and it was confirmed by 19F NMR that compound (4-1) was produced in a yield of 8%. 19

[0110] Example 5 The same procedure as above was carried out except that THF was changed to toluene, and it was confirmed by 19F NMR that compound (4-1) was produced in a yield of 30% 19

[0111] Example 6

Chemical Structure

[0112] Example 7

Chemical formula

[0113] Example 8 [Chemical formula] In a glove box, zinc powder (6.5 mmol, 438 mg) and zinc chloride (0.65 mmol, 87.9 mg) were weighed into a 50 mL two-necked eggplant flask, and DMF (3 mL) was added. Compound (4-2) (0.65 mmol, 428.3 mg) was dissolved in DMF (3 mL), and the solution was added to the reaction solution. The container was washed twice with DMF (2 mL), and the washing solution was added to the reaction solution. Then, it was stirred at 60 °C for 2 hours under a nitrogen atmosphere. After the reaction was completed, filtration, extraction, and purification by HPLC were performed, and compound (5-1) was obtained in a yield of 93%. 1 H NMR (400 MHz, CDCl3): δ7.63 (dd, 8H) 19 F NMR (MHz, CDCl3): δ-89.9 (m, 1F), δ-106.6 (m, 1F), δ-112.5 (d, 2F), δ-118.2 (t, 2F), δ-187.1 (m, 1F) GCMS m / z: 513 When the obtained compound (5-1) was analyzed by ICP-AES (Pd detection limit: 1 ppm), Pd was not detected.

Claims

1. Formula (2): M-R Ｆ (2) (wherein M is Cu having a ligand, R Ｆ is a fluoroalkyl group which may have one or more substituents.) A method for producing a compound represented by the formula in the presence of a reducing agent, Formula (1): R Ｆ -X １ (1) (wherein R Ｆ has the same meaning as described above, X １ is Cl, Br or I.) A production method including a step A of reacting a compound represented by the formula with a copper compound and a ligand.)

2. Formula (4): Ar-R Ｆ (4) (wherein Ar is an aryl group which may have one or more substituents, or a heteroaryl group which may have one or more substituents, R Ｆ is a fluoroalkyl group which may have one or more substituents.) A method for producing a compound represented by the formula, In the presence of a reducing agent, Formula (1): R Ｆ -X １ (1) (wherein R Ｆ has the same meaning as described above, X １ is Cl, Br or I.) A step A of reacting a compound represented by the formula with a copper compound and a ligand, and The reaction product of step A and Formula (3): Ar-X ２ (3) (wherein Ar has the same meaning as described above, X ２ is Cl, Br or I.) A production method including a step B of reacting with a compound represented by the formula.)

3. Formula (4): Ar-R Ｆ (4) (wherein Ar is an aryl group which may have one or more substituents, or a heteroaryl group which may have one or more substituents, R Ｆ is a fluoroalkyl group which may have one or more substituents.) A method for producing a compound represented by the formula, In the presence of a reducing agent, a copper compound, and a ligand, Formula (1): R Ｆ -X １ (1) (wherein R Ｆ has the same meaning as described above, X １ is Cl, Br, or I.) A compound represented by the formula and Formula (3): Ar-X ２ (3) (wherein Ar has the same meaning as described above, X ２ is Cl, Br or I.) A production method including a step C of reacting with a compound represented by the formula.)

4. The production method according to any one of claims 1 to 3, wherein the reducing agent is a compound containing boron and / or silicon.

5. The production method according to any one of claims 1 to 3, wherein the reducing agent is at least one selected from the group consisting of diboron compounds, silylborane compounds, and disilane compounds.

6. The diboron compound is of formula (A): 【Chemical 1】 (wherein Z １ and Z ２ are each independently a single bond, a double bond, or CH ２ and R １ and R ２ are each independently an alkyl group, Two Rs that may be adjacent to each other １ may combine to form a ring, Two Rs that may be present adjacent to each other ２ may combine to form a ring, k1 and k2 are each independently 0 or an integer of 1 or more.) A compound represented by the formula, The silylborane compound is of formula (B): 【Chemical 2】 (wherein Z １１ is a single bond, a double bond, or CH ２ and R １１ is an alkyl group, Two Rs that may exist adjacent to each other １１ may combine to form a ring R １２ , R １３ , and R １４ are each independently an alkyl group or an aryl group, and k3 is an integer of 0 or 1 or more.) A compound represented by the formula, The disilane compound is of formula (C): [Chemical Formula 3] (wherein R ２１ 、 R ２２ 、 R ２３ 、 R ２４ 、 R ２５ 、 and R ２６ are each independently H, halogen, an alkyl group, an alkoxy group, or an aryl group.) A compound represented by the formula, the production method according to claim 5.)

7. The production method according to any one of claims 1 to 3, which is carried out in an organic solvent.

8. The production method according to claim 7, wherein the boiling point of the organic solvent at normal pressure is 150 °C or lower.

9. The production method according to claim 7, wherein the organic solvent is at least one selected from the group consisting of ether solvents and aromatic hydrocarbon solvents.

10. The production method according to any one of claims 1 to 3, wherein the copper compound is a monovalent copper compound.

11. The production method according to any one of claims 1 to 3, wherein the copper compound is a Cu alkoxide, aryloxide, thioalkoxide, or thioaryloxide.

12. The production method according to any one of claims 1 to 3, wherein the ligand is at least one selected from the group consisting of a pyridine ligand and a phosphine ligand.

13. The production method according to claim 2 or 3, wherein step B or step C is carried out at 50 °C or lower.

14. The production method according to claim 2 or 3, wherein Ar is an aryl group which may have one or more substituents.

15. The production method according to claim 2 or 3, wherein Ar is an aryl group having one or more fluorine or fluoroalkyl groups.

16. Formula (4A): 【Chemical Formula 4】 (In the formula, A １ is a single bond, -O-, -S-, an alkylene group which may have one or more substituents, a cycloalkylene group which may have one or more substituents, or an arylene group which may have one or more substituents.) A compound represented by.

17. Formula (5A): 【Chemical Formula 5】 (In the formula, A ２ is a single bond, -O-, -S-, an alkylene group which may have one or more substituents, a cycloalkylene group which may have one or more substituents, or an arylene group which may have one or more substituents.) A compound represented by.

18. Formula (5A): 【Chemical Formula 6】 (In the formula, A ２ is a single bond, -O-, -S-, an alkylene group which may have one or more substituents, a cycloalkylene group which may have one or more substituents, or an arylene group which may have one or more substituents.) A compound represented by, wherein the contents of Al, Cr, Cu, Fe, Ni, and Zn are each 1000 ppm or less.

19. Formula (5A): 【Chemical Formula 7】 (In the formula, A ２ is a single bond, -O-, -S-, an alkylene group which may have one or more substituents, a cycloalkylene group which may have one or more substituents, or an arylene group which may have one or more substituents. A compound represented by, wherein the total content of Al, Cr, Cu, Fe, Ni, and Zn is 6000 ppm or less.

20. Formula (5): 【Chemical Formula 8】 (In the formula, A is a single bond, -O-, -S-, an alkylene group which may have one or more substituents, a cycloalkylene group which may have one or more substituents, or an arylene group which may have one or more substituents, R ３１ 、 R ３２ 、 R ３３ 、 R ３４ 、 R ３５ 、 R ４１ 、 R ４２ 、 R ４３ 、 R ４４ 、 and R ４５ are each independently fluorine, an alkyl group, or a fluoroalkyl group, n and m are each independently 0, 1, or 2.) A compound represented by, wherein the content of Pd is 1000 ppm or less.

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