Method for producing fluoroalkyl aromatic compounds

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 such a compound, for example, in a high-boiling solvent such as N,N-dimethylformamide (DMF) or dimethyl sulfoxide (DMSO), C 5 F 11 I, C 6 F 13 A method is known in which a fluoroalkyl iodide such as I and an aryl iodide such as iodobenzene are reacted with copper powder to produce a fluoroalkyl aromatic compound (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. In addition, the methods of Patent Documents 1 and 2 and Non-Patent Document 1 all use high-boiling point solvents, and therefore require complicated operations such as multiple water extractions, vacuum distillation, and crystallization to remove the product from the high-boiling point solvent.

[0006] Objects of the present disclosure include providing useful methods for producing fluoroalkyl aromatic compounds, and the compounds obtained thereby. [Means for solving the problem]

[0007] The present disclosure encompasses the following aspects. Section 1. Formula (2): MR F (2) (In the formula, M is Cu with ligands; R F is a fluoroalkyl group which may have one or more substituents. A method for producing a compound represented by the formula (1): R F -X 1 (1) (In the formula, R F has the same meaning as above, X 1 is Cl, Br or I. A production method comprising a step A of reacting a compound represented by the following formula (I): Section 2. Formula (4): Ar-R F (4) (In the formula, Ar is an aryl group optionally having one or more substituents, or a heteroaryl group optionally having 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 following formula: In the presence of a reducing agent, a reaction of formula (1): R F -X 1 (1) (In the formula, R F has the same meaning as above, X 1 is Cl, Br or I. A step A of reacting a compound represented by the formula: The reaction product of step A and formula (3): Ar-X 2 (3) (In the formula, Ar is as defined above. X 2 is Cl, Br or I. A production method comprising step B of reacting a compound represented by the formula: Section 3. Formula (4): Ar-R F (4) (In the formula, Ar is an aryl group optionally having one or more substituents, or a heteroaryl group optionally having 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 following formula: In the presence of a reducing agent, a copper compound, and a ligand, a reaction of formula (1): R F -X 1 (1) (In the formula, R F has the same meaning as above, X 1 is Cl, Br or I. and a compound represented by formula (3): Ar-X 2 (3) (In the formula, Ar is as defined above. X 2 is Cl, Br or I. A production method comprising a step C of reacting a compound represented by the formula: Section 4. Item 4. The method according to any one of Items 1 to 3, wherein the reducing agent is a compound containing boron and / or silicon. Section 5. 5. The 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. Section 6. The diboron compound has the formula (A): [ka] (In the formula, 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 R's that can exist adjacent to each other 1 may be taken together to form a ring, Two R's that can exist adjacent to each other 2 may be taken together to form a ring, k1 and k2 are each independently an integer of 0 or 1 or more. A compound represented by the formula: The silylborane compound has the formula (B): [ka] (In the formula, Z 11 is a single bond, a double bond, or CH 2 and R 11 is an alkyl group, Two R's that can exist adjacent to each other 11 may be taken together to form a ring, R 12 , R 13 , and R 14 are each independently an alkyl group or an aryl group, and k3 is 0 or an integer of 1 or more. A compound represented by the formula: The disilane compound has the formula (C): [ka] (In the formula, R 21 , R 22 , R 23 , R 24 , R 25 , and R 26 are each independently H, a halogen, an alkyl group, an alkoxy group, or an aryl group. Item 6. The method according to item 5, wherein the compound is represented by the formula: Section 7. Item 7. The method according to any one of items 1 to 6, which is carried out in an organic solvent. Section 8. Item 8. The method according to Item 7, wherein the organic solvent has a boiling point of 150° C. or lower at normal pressure. Section 9. Item 9. The method according to item 7 or 8, wherein the organic solvent is at least one selected from the group consisting of ether solvents and aromatic hydrocarbon solvents. Section 10. Item 10. The method according to any one of items 1 to 9, wherein the copper compound is a monovalent copper compound. Section 11. 11. The method according to any one of items 1 to 10, wherein the copper compound is an alkoxide, an aryloxide, a thioalkoxide, or a thioaryloxide of Cu. Section 12. 12. The method according to any one of items 1 to 11, wherein the ligand is at least one selected from the group consisting of pyridine-containing ligands and phosphine ligands. Section 13. Item 13. The method according to any one of items 2 to 12, wherein step B or step C is carried out at 50° C. or lower. Section 14. Item 14. The method according to any one of Items 2 to 13, wherein Ar is an aryl group which may have one or more substituents. Section 15. Item 15. The method according to any one of Items 2 to 14, wherein Ar is an aryl group having one or more fluorine or fluoroalkyl groups. Section 16. Formula (4A): [ka] (In the formula, A 1 represents 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 the formula: Section 17. Formula (5A): [ka] (In the formula, A 2 represents 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 the formula: Section 18. Formula (5A): [ka] (In the formula, A 2 represents 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. The compound represented by the formula (1) has an Al, Cr, Cu, Fe, Ni, and Zn content of 1000 ppm or less, respectively. Section 19. Formula (5A): [ka] (In the formula, A 2represents 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. The compound represented by the formula (1) has a total content of Al, Cr, Cu, Fe, Ni, and Zn of 6000 ppm or less. Section 20. Formula (5): [ka] (In the formula, A is a single bond, -O-, -S-, an alkylene group optionally having one or more substituents, a cycloalkylene group optionally having one or more substituents, or an arylene group optionally having 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. The compound represented by the formula (1) has a Pd content of 1000 ppm or less. Effect of the Invention

[0008] The present disclosure provides, for example, useful methods for producing fluoroalkyl aromatic compounds, and compounds obtained by the methods. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

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

[0011] 1. Terminology Unless otherwise 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 particularly 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, as is commonly understood by those skilled in the art, that the number of carbon atoms is n or more and m or less.

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

[0016] In this specification, examples of "alkyl group" include, for example, 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 1-20 alkoxy groups such as methoxy, ethoxy, propoxy (n-propoxy, isopropoxy), butoxy (n-butoxy, isobutoxy, sec-butoxy, tert-butoxy), pentyloxy, and hexyloxy.

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

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

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

[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 "monocyclic heteroaryl groups" and "aromatic condensed heterocyclic groups".

[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 "aromatic fused heterocyclic group" include isoindolyl (e.g., 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl), indolyl (e.g., 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl), benzo[b]furanyl (e.g., 2-benzo[b]furanyl, 3-benzo[b]furanyl, 4-benzo[b]furanyl, 5- benzo[b]furanyl, 6-benzo[b]furanyl, 7-benzo[b]furanyl), benzo[c]furanyl (e.g., 1-benzo[c]furanyl, 4-benzo[c]furanyl, 5-benzo[c]furanyl), benzo[b]thienyl, (e.g., 2-benzo[b]thienyl, 3-benzo[b]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-2-yl, 1,2-benzisoxazol-1 ... 1,2-benzoisoxazolyl (e.g. 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-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. can be mentioned.,

[0024] In this specification, in the "alkyl group which may have one or more substituents", -CH that may be present inside the alkyl group 2- may be replaced by -O-, -S-, or -NH-. Examples of the substituent 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 of these (e.g., haloalkoxy group). When the alkyl group has a substituent, the number of the substituents can be selected from the range of 1 to the maximum number of possible substitutions, and can be, for example, 1, 2, 3, 4, or 5. When the number of the substituents is 2 or more, each substituent may be the same or different from each other.

[0025] Examples of the above "alkyl group which may have one or more substituents" include alkyl groups which may be substituted with one or more halogens (e.g., fluorine). An alkyl group substituted with one or more halogens is expressed as a "haloalkyl group", and when the substituted halogen is fluorine, it may be expressed as a "fluoroalkyl group". The "fluoroalkyl group" may be a perfluoroalkyl group or a non-perfluoroalkyl group. Examples of the "fluoroalkyl group" include linear or branched fluoro-C groups such as a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group (e.g., a perfluoro n-propyl group, a perfluoroisopropyl group), a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group. 1-20 Examples of the "fluoroalkyl group which may have one or more substituents" include, in addition to the above-mentioned fluoroalkyl groups, fluoroalkyl groups substituted with one or more substituents (e.g., alkoxy groups; haloalkoxy groups such as fluoroalkoxy groups; alkoxycarbonyl groups; haloalkoxycarbonyl groups such as fluoroalkoxycarbonyl groups), and specific examples thereof include CF 3 -O-CF 2 -, CF 3 -O-CF(CF 3 )-, CF 3 -O-CH 2 -CH 2 -, CF 3 -O-CH(CF 3)-CH 2 -, CF 3 -O-CF 2 -CF 2 -, CF 3 -CF 2 -O-CF 2 -, CF 3 -CF 2 -O-CF 2 -CF 2 -, CF 3 -O-CF 2 -O-CF 2 -, CF 3 -CF 2 -CF 2 -O-CH 2 -CF 2 -, CF 3 -CF 2 -CF 2 -O-CF 2 -CF 2 -, CF 3 -CF 2 -CF 2 -O-CF(CF 3 )-CF 2 -, CF 3 -CF 2 -CF 2 -O-CF(CF 3 )-CF 2 -O-CF(CF 3 )-CF 2 -, CF 3 -CF 2 -CF 2 -O-[CF(CF 3 )-CF 2 -O-] 2 -CF(CF 3 )-CF 2 -, or any other linear or branched fluoro-C 1-20 Alkyl groups are included.

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

[0027] In this specification, an "alkylene group", a "cycloalkylene group", and an "arylene group" are divalent groups formed by removing one H from an "alkyl group", a "cycloalkyl group", and an "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) (sometimes referred to as a "fluoroalkyl copper reagent") includes step A of reacting a compound represented by formula (1), a copper compound, and a ligand in the presence of a reducing agent. R F -X 1 (1) MR 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 with ligands.

[0029] [Compound represented by formula (1)] R F In the formula (I), the lower limit of the number of carbon atoms in 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. F is a fluoro C which may have one or more substituents1-20 Alkyl group (e.g. Perfluoro C 1-20 alkyl group), and more preferably a fluoro C 1-12 Alkyl group (e.g. Perfluoro C 1-12 alkyl group), more preferably a fluoro C 1-10 Alkyl group (e.g. Perfluoro C 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, copper alone 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, and copper(II) acetate. These copper compounds may be used in combination with an alkoxide, aryloxide, thioalkoxide, or thioaryloxide of an alkali metal such as lithium, sodium, or potassium. Alternatively, an alkoxide, aryloxide, thioalkoxide, or thioaryloxide of copper may be used as the copper compound. Examples of the alkoxide or aryloxide include C alkoxides such as methoxide, ethoxide, propoxide, and butoxide (e.g., t-butoxide). 1-6 Alkoxides, phenoxides, etc. 6-10Examples of the thioalkoxide or thioaryloxide include those in which O in the alkoxide or aryloxide is replaced with S.

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

[0034] [Ligand] The ligand is not particularly limited as long as it can be coordinated with copper, and examples of the ligand include a pyridine-containing ligand and a phosphine ligand.

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

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

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

[0038] The amount of the ligand used is, for example, 0.5 moles or more, preferably 1 mole or more, more preferably 1.5 moles or more, relative to 1 mole of the compound represented by formula (1). The amount of the ligand used is, for example, 5 moles or less, preferably 4 moles or less, more preferably 3 moles or less, relative to 1 mole of the compound represented by formula (1). The amount of the ligand used is, for example, within the range of 0.5 to 5 moles, preferably within the range of 1 to 4 moles, more preferably within the range of 1.5 to 3 moles, relative to 1 mole 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 low temperatures, the use of a high-boiling point solvent and the associated complicated removal procedure can be avoided, and even compounds that are easily decomposed at high temperatures 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 a diboron compound, a silylborane compound, and a disilane compound.

[0041] The diboron compound includes, for example, a compound represented by the formula (A). [ka] (In the formula, Z 1and Z 2 are each independently a single bond, a double bond, or CH 2 and R 1 and R 2 are each independently an organic group; Two R's that can exist adjacent to each other 1 may be taken together to form a ring, Two R's that can exist adjacent to each other 2 may be taken together to form a ring, k1 and k2 are each independently an integer of 0 or 1 or more.

[0042] In one embodiment, Z 1 and Z 2 and are preferably both single bonds. In another embodiment, Z 1 and Z 2 and are preferably both double bonds. In yet another embodiment, Z 1 and Z 2 Both are CH 2 It is preferable that:

[0043] R 1 and R 2 are each independently preferably an alkyl group, more preferably C 1-6 Alkyl groups, more preferably C 1-4 Alkyl groups, even more preferably C 1-2 It is an alkyl group.

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

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

[0046] The silylborane compound may, for example, be a compound represented by the formula (B). [ka] (In the formula, Z 11 is a single bond, a double bond, or CH 2 and R 11 is an organic group, Two R's that can exist adjacent to each other 11 may be taken together to form a ring, R 12 , R 13 , and R 14 are each independently an organic group; k3 is an integer of 0 or 1 or more.

[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 CH 2 It is preferable that:

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

[0049] R 12 , R 13 , and R 14are each preferably independently an alkyl group or an aryl group, more preferably C 1-6 Alkyl group or C 6-14 Aryl groups, more preferably C 1-4 Alkyl group or C 6-12 Aryl groups, even more preferably C 1-2 Alkyl group or C 6-10 It is an aryl group.

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

[0051] An example of the compound represented by formula (B) is a compound represented by formula (B1). [ka]

[0052] An example of the disilane compound is a compound represented by the formula (C). [ka] (In the formula, R 21 , R 22 , R 23 , R 24 , R 25 , and R 26 are each independently H, a halogen, or an organic group.

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

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

[0056] [Organic solvents] The reaction in step A is preferably carried out in the presence of an organic solvent. In one embodiment, the organic solvent is preferably not a high-boiling point solvent (or is a low-boiling point solvent), and the boiling point at normal pressure is preferably 150° C. or less, 140° C. or less, 130° C. or less, 120° C. or less, or 110° C. or less. 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 amount of the organic solvent used is, for example, 0.5 mL or more, preferably 1 mL or more, and more preferably 1.5 mL or more, per 1 mmol of the compound represented by formula (1). The amount of the organic solvent used is, for example, 40 mL or less, preferably 30 mL or less, and more preferably 20 mL or less, per 1 mmol of the compound represented by formula (1). The amount of the organic solvent used is, for example, within the range of 0.5 to 40 mL, preferably within the range of 1 to 30 mL, and more preferably within the range of 1.5 to 20 mL, per 1 mmol of the compound represented by formula (1).

[0058] [Reaction temperature and reaction time] The reaction temperature and reaction time in 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, and more preferably 0°C or higher. The reaction temperature is, for example, 40°C or lower, preferably 35°C or lower, and more preferably 30°C or lower. The reaction temperature is, for example, within the range of -30 to 40°C, preferably within the range of -10 to 35°C, and more preferably within the range of 0 to 30°C.

[0059] The reaction time is, for example, 5 minutes or more, preferably 10 minutes or more, more preferably 30 minutes or more, and even more preferably 1 hour or more. The reaction time is, for example, 48 hours or less, preferably 24 hours or less, and even more preferably 12 hours or less. The reaction time is, for example, within the range of 5 minutes to 48 hours, preferably within the range of 10 minutes to 24 hours, and even more preferably within 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 formula (2). The compound represented by formula (2) can be isolated or purified by a method 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 formula (4) includes step A and step B of reacting the reaction product of step A (particularly the compound represented by formula (2)) with the compound represented by 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 preferably a C 6-14 aryl group which may have one or more substituents, or a 5- to 14-membered heteroaryl group which may have one or more substituents, more preferably a C 6-12 aryl group which may have one or more substituents, or a 5- to 12-membered heteroaryl group which may have one or more substituents, still more preferably a C 6-10 aryl group which may have one or more substituents, 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, 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 1represents H or a hydrocarbon group which may have one or more further substituents, 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 represents H or a hydrocarbon group which may have one or more further substituents; L 2 and L 3 each independently represents a single bond or -O-), an alkoxy group, a hydroxy group, a halogen (halogeno group), and a combination thereof. In one embodiment, the substituent is preferably a 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) (In the formula, Ar 1 , Ar 2 , and Ar 3 each independently represents an arylene group which may have one or more substituents, or a heteroarylene group which may have one or more substituents; A0 represents 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 or different. 1 , Ar 2 , and Ar 3 Suitable examples of include divalent groups corresponding to the suitable examples of Ar.

[0067] A 0 When A is an alkylene group which may have one or more substituents, the lower limit of the number of carbon atoms in the alkylene group may be, for example, 1 or 2, and the upper limit may be, for example, 6, 5, 4, 3, or 2. 0 is preferably C which may have one or more substituents 1-6 An alkylene group, more preferably a C 1-6 An alkylene group, more preferably a C 1-4 An alkylene group, more preferably a C 1-2 The substituent is an 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 ), amide group (-L 2 -CO-NQ 2 Q 3 Or -NQ 4 -CO-L 3 -Q5 ) 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 6-14 arylene group which may have one or more substituents, more preferably a C 6-12 arylene group which may have one or more substituents, still more preferably a C 5-10 arylene group.

[0070] X 21 X 22 X 23 and X 24 are each preferably independently 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 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, more preferably 0.15 mol or more, relative to 1 mol of the compound represented by formula (2). The amount of the compound represented by formula (3) used is, for example, 3 mol or less, preferably 2 mol or less, more preferably 1.5 mol or less, relative to 1 mol of the compound represented by formula (2). The amount of the compound represented by formula (3) used is, for example, within the range of 0.05 to 3 mol, preferably within the range of 0.1 to 2 mol, more preferably within the range of 0.15 to 1.5 mol, relative to 1 mol of the compound represented by formula (2).

[0072] [Organic solvents] The reaction in 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 point solvent (or is a low-boiling point solvent), and the boiling point at normal pressure is preferably 150° C. or less, 140° C. or less, 130° C. or less, 120° C. or less, or 110° C. or less. 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 that can be 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, within the range of 0 to 125° C., preferably within the range of 10 to 100° C., and more preferably within the range of 20 to 80° C.

[0074] The reaction time is, for example, 30 minutes or longer, preferably 1 hour or longer, more preferably 2 hours 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, within the range of 30 minutes to 48 hours, preferably within the range of 1 to 24 hours, more preferably within 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) include the same ones as exemplified in steps A and B, respectively.

[0077] The amount of the compound represented by formula (3) used (especially the total amount of Cl, Br, and I) is, for example, 0.05 mol or more, preferably 0.1 mol or more, 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, 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, within the range of 0.05 to 3 mol, preferably within the range of 0.1 to 2 mol, more preferably within 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, the copper compound, and the ligand include the same ones as exemplified in step A. The amounts of the reducing agent, the copper compound, and the ligand used relative to the compound represented by formula (1) can also be selected from the same ranges as 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 as those exemplified in step A. The amount of the organic solvent used relative to the compound represented by formula (1) can also be selected from the same range 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 be selected from the same ranges as those exemplified in step A.

[0081] [Optional additional steps] In the production method, for example, when a compound represented by formula (3A) is used, a compound represented by formula (4B) and / or a compound represented by formula (4C) may be produced as a by-product. 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 compound represented by formula (4) can be isolated or purified by a method such as filtration, extraction, concentration, chromatography, or a combination of these methods.

[0082] 4. Compound represented by formula (4A) One embodiment of the compound of the present disclosure is a compound represented by formula (4A). [ka] (In the formula, A 1 represents 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 A is an alkylene group which may have one or more substituents, the lower limit of the number of carbon atoms in the alkylene group may be, for example, 1 or 2, and the upper limit may be, for example, 6, 5, 4, 3, or 2. 1 is preferably C which may have one or more substituents 1-6 An alkylene group, more preferably a C 1-6 An alkylene group, more preferably a C 1-4 An alkylene group, more preferably a C 1-2 The substituent is an 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 ), 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.

[0084] A 1 When is a cycloalkylene group optionally having one or more substituents, it is preferably a C 5-14 A cycloalkylene group, more preferably a C 5-12 A cycloalkylene group, more preferably a C 5-10 It is a cycloalkylene group.

[0085] A 1When is an arylene group optionally having one or more substituents, it is preferably an arylene group optionally having one or more substituents, 6-14 An arylene group, more preferably a C 6-12 An arylene group, more preferably a C 5-10 It is an arylene group.

[0086] The compound represented by formula (4A) can be prepared, for example, by adding Ar 1 and Ar 2 is a phenylene group, and a compound represented by the formula (1) F CF 2 Cl-CFCl-CF 2 -CF 2 -, a copper compound, and a ligand (or a ligand formed by reacting these compounds) of formula (2) F CF 2 Cl-CFCl-CF 2 -CF 2 -(a compound which is a substituted or unsubstituted aryl group)

[0087] 5. Compound represented by formula (5A) One embodiment of the compound of the present disclosure is a compound represented by formula (5A). [ka] (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 2 When A is an alkylene group which may have one or more substituents, the lower limit of the number of carbon atoms in the alkylene group may be, for example, 1 or 2, and the upper limit may be, for example, 6, 5, 4, 3, or 2. 2 is preferably C which may have one or more substituents1-6 An alkylene group, more preferably a C 1-6 An alkylene group, more preferably a C 1-4 An alkylene group, more preferably a C 1-2 The substituent is an 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 ), 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 is a cycloalkylene group optionally having one or more substituents, it is preferably a C 5-14 A cycloalkylene group, more preferably a C 5-12 A cycloalkylene group, more preferably a C 5-10 It is a cycloalkylene group.

[0090] A 2 When is an arylene group optionally having one or more substituents, it is preferably C 6-14 An arylene group, more preferably a C 6-12 An arylene group, more preferably a C 5-10 It is an arylene group.

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

[0092] The compound represented by formula (5A) may contain Al, Cr, Cu, Fe, Ni, and Zn, or may not contain a part or all of these metals. The content of Al, Cr, Cu, Fe, Ni, and Zn in the compound represented by formula (5A) is, for example, 1000 ppm or less, preferably 800 ppm or less, and more preferably 500 ppm or less. The content of each of the above metals is preferably as small as possible, so the lower limit is not particularly limited, but may be, for example, 0.001 ppm or more. The 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 content of Al, Cr, Cu, Fe, Ni, and Zn is preferably below the detection limit of ICP 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, 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. The lower limit of the total content of the above metals is not particularly limited, since the lower the total content, the more preferable it is, but it 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 of ICP optical emission spectrometry.

[0094] The compound represented by formula (5A) may contain Pd 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, and more preferably 500 ppm or less. The lower limit of the Pd content is not particularly limited because the lower the Pd content, the more preferable it is, but it 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 of 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). [ka] (In the formula, A is a single bond, -O-, -S-, an alkylene group optionally having one or more substituents, a cycloalkylene group optionally having one or more substituents, or an arylene group optionally having 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.

[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 may be, for example, 1 or 2, and the upper limit may be, for example, 6, 5, 4, 3, or 2. A is preferably a C group which may have one or more substituents. 1-6 An alkylene group, more preferably a C 1-6An alkylene group, more preferably a C 1-4 An alkylene group, more preferably a C 1-2 The substituent is an 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 ), 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, it is preferably a cycloalkylene group which may have one or more substituents. 5-14 A cycloalkylene group, more preferably a C 5-12 A cycloalkylene group, more preferably a C 5-10 It is a cycloalkylene group.

[0098] When A is an arylene group which may have one or more substituents, it is preferably C 6-14 An arylene group, more preferably a C 6-12 An arylene group, more preferably a C 5-10 It is an 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 fluorine, C 1-6 Alkyl group or fluoro C 1-6 It is preferably an alkyl group, more preferably fluorine, C 1-4 Alkyl group or fluoro C 1-4 is an alkyl group, more preferably fluorine, C 1-2 Alkyl group or fluoro C 1-2 In one embodiment, R 31 , R 32 , R 33 , R 34 , and R 35 are R 41 , R 42 , R 43 , R 44 , and R 45 It is preferably the same as

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

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

[0103] The compound represented by formula (5) may contain Pd 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, and more preferably 500 ppm or less. The lower limit of the Pd content is not particularly limited because the lower the Pd content, the more preferable it is, but it 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 of ICP emission spectrometry.

[0104] The compound represented by formula (5) can be prepared, for example, by adding Ar 1 and Ar 2 is a phenylene group, and a compound represented by the formula (1) F CR 35 R 34 Cl-CR 33 Cl-(CR 32 R 31 ) n - and / or a compound of formula (1) F CR 45 R 44 Cl-CR 43 Cl-(CR 42 R 41 )m -, a copper compound, and a ligand (or a compound of formula (2) produced by reacting them), and then subjecting the compound of formula (4) produced by the reaction to a dechlorination reaction. The dechlorination reaction can be carried out under conditions known or commonly used in the art. EXAMPLES

[0105] Hereinafter, one embodiment of the present disclosure will be described in more detail with reference to examples, but the present disclosure is not limited thereto. The abbreviations in the examples are as follows. B 2 pin 2 :Bis(pinacolato)diboron DMF: N,N-dimethylformamide HPLC: High-performance liquid chromatography PhMe 2 SiBpin: (Dimethylphenylsilyl)boronic acid pinacol ester tBu: t-butyl THF: tetrahydrofuran

[0106] Example 1 [ka] Under a nitrogen atmosphere, a solution of CuOtBu (1 mmol, 134 mg) and 1,10-phenanthrorine (1 mmol, 180 mg) in THF (4 mL) was prepared in a screw-cap test tube. 2 pin 2 (0.5 mmol, 127 mg) and ICF 2 CF 2 CFClCF 2 A solution of Cl (0.5 mmol, 189 mg) in THF (1 mL) was added dropwise. The reaction solution was stirred at room temperature for 10 minutes and then filtered. The filtrate was concentrated and washed with ether to give the title compound as a brown solid (197.6 mg, 80% yield). 1 H NMR (400 MHz, THF-d 8): δ9.1 (br, 2H), 8.7 (br, 2H), 8.1 (br, 2H), 8.0 (br, 2H). 19 F NMR (376 MHz, THF-d 8 ): δ-65.7 (br, 2F), -111.5 (br, 2F), -120.3 (br, 2F), -132.3 (br, 1F).

[0107] Example 2 [ka] Under a nitrogen atmosphere, a solution of CuOtBu (0.24 mmol, 32.1 mg) and 1,10-phenanthrorine (0.24 mmol, 43.2 mg) in THF (0.3 mL) was prepared in a screw-cap test tube. 2 pin 2 (0.12 mmol, 30.5 mg) and ICF 2 CF 2 CF 2 CF 3 (0.12 mmol, 20 μL) in THF (0.2 mL) was added dropwise to the reaction solution, which was stirred at room temperature for 1 hour, and then 4-fluoroiodobenzene (0.1 mmol, 11.6 μL) was added, sealed, and stirred at 40° C. for 18 hours to give the title compound in 82% yield. 19 F NMR (376 MHz, CDCl 3 ): -107.1 (s, 1F), -109.9 (t, 13 Hz, 2F), -122.5 (t, 9 Hz, 2F), -125.4 (m, 2F).

[0108] Example 3 B 2 Pin 2 PhMe 2 The procedure was repeated except for using SiBpin (0.12 mmol), and the title compound (4-1) was produced in 63% yield. 19 Confirmed by F NMR.

[0109] Example 4 The same procedure was carried out as above except that THF was replaced with diethyl ether, and compound (4-1) was produced in an 8% yield. 19 Confirmed by F NMR.

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

[0111] Example 6 [ka] In a glove box, a solution 1 of CuOtBu (4.8 mmol, 654.6 mg) and 1,10-phenanthrorine (4.8 mmol, 865.1 mg) in THF (4.8 mL) was prepared in a screw-cap test tube and cooled to -30 °C. 2 pin 2 (2.4 mmol, 610.1 mg) and ICF 2 CF 2 CFClCF 2 A solution of Cl (2.4 mmol, 426 μL) in THF (2.4 mL) was prepared. Solution 2 was slowly added dropwise to solution 1. The container of solution 2 was washed twice with THF (1.2 mL), and the washings were added to solution 1. The solution was stirred at room temperature for 1 hour, after which 4,4'-diiodobiphenyl (0.8 mmol, 325.3 mg) was added, the container was sealed, and the mixture was stirred at 40°C for 18 hours. After the reaction was completed, a mixture of compound (4-2) and compound (4-3) was obtained in a ratio of 10:1, and this mixture contained a small amount of compound (5-1). This mixture was filtered and purified by column chromatography to obtain compound (4-2) in an 82% yield. 1 H NMR (400 MHz, CDCl 3 ): δ7.65 (m, 8H) 19 F NMR (376 MHz, CDCl3 ): δ-63.3 (t, 2F), δ-107.0, -107.7, -108.5, -109.2 (m, 2F), δ-112.6, -113.4, -114.0, -114.7 (m, 2F), δ-130.0 (m, 1F)GCMS m / z: 656

[0112] Example 7 [ka] In a glove box, a solution 1 of CuOtBu (4.8 mmol, 654.6 mg) and 1,10-phenanthrorine (4.8 mmol, 865.1 mg) in THF (4.8 mL) was prepared in a screw-cap test tube and cooled to -30 °C. 2 pin 2 (2.4 mmol, 610.1 mg) and ICF 2 CF 2 CFClCF 2 A solution 2 (2.4 mL) of Cl (2.4 mmol, 426 μL) in THF was prepared. Solution 2 was slowly added dropwise to solution 1. The container of solution 2 was washed twice with THF (1.2 mL), and the washings were added to solution 1. The solution was stirred at room temperature for 1 hour, and then 4,4'-diiodobiphenyl (0.8 mmol, 325.3 mg), Zn (325 mg), ZnCl 2 (44 mg) and DMF (8.4 mL) were added, the flask was sealed, and the mixture was stirred for 18 hours at 40° C. After the reaction was completed, 232 mg of a crude product was obtained. When the product was analyzed by NMR, it was found that 4,4'-diiodobiphenyl, compound (4-2), and compound (4-4) were produced in a molar ratio of 0.7:1:1.4.

[0113] Example 8 [ka] 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. After washing twice with DMF (2 mL), the washings were added to the reaction solution, and the mixture 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, CDCl 3 ): δ7.63 (dd, 8H) 19 F NMR (MHz, CDCl 3 ): 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 The resulting compound (5-1) was analyzed by ICP-AES (Pd detection limit 1 ppm), and no Pd was detected.

Claims

1. Formula (2): M-R Ｆ (2) (In the formula, M is Cu bearing a ligand; R Ｆ is a fluoroalkyl group which may have one or more substituents. A method for producing a compound represented by the following formula: In the presence of a reducing agent, a compound of formula (1): R Ｆ -X １ (1) (In the formula, R Ｆ has the same meaning as above, X １ is Cl, Br or I. The method includes a step A of reacting a compound represented by the formula: the reducing agent is a compound containing boron and / or silicon, The production method, wherein the ligand is at least one selected from the group consisting of a pyridine-containing ligand and a phosphine ligand.

2. Formula (4): A-R Ｆ (4) (In the formula, Ar is an aryl group optionally having one or more substituents, or a heteroaryl group optionally having 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 following formula: In the presence of a reducing agent, a compound of formula (1): R Ｆ -X １ (1) (In the formula, R Ｆ has the same meaning as above, X １ is Cl, Br or I. A step A of reacting a compound represented by the formula: The reaction product of step A and formula (3): Ar-X ２ (3) (In the formula, Ar is as defined above. X ２ is Cl, Br or I. With a step B of reacting a compound represented by the reducing agent is a compound containing boron and / or silicon, The production method, wherein the ligand is at least one selected from the group consisting of a pyridine-containing ligand and a phosphine ligand.

3. Formula (4): A-R Ｆ (4) (In the formula, Ar is an aryl group optionally having one or more substituents, or a heteroaryl group optionally having 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 following formula: In the presence of a reducing agent, a copper compound, and a ligand, a compound represented by the formula (1): R Ｆ -X １ (1) (In the formula, R Ｆ has the same meaning as above, X １ is Cl, Br or I. and a compound represented by formula (3): Ar-X ２ (3) (In the formula, Ar is as defined above. X ２ is Cl, Br or I. With a step C of reacting a compound represented by the reducing agent is a compound containing boron and / or silicon, The production method, wherein the ligand is at least one selected from the group consisting of a pyridine-containing ligand and a phosphine ligand.

4. The 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.

5. The diboron compound has the formula (A): 【Chemistry 1】 (In the formula, 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 R's that may be adjacent to each other １ may be taken together to form a ring, Two R's that may be adjacent to each other ２ may be taken together to form a ring, k1 and k2 are each independently an integer of 0 or 1 or more. A compound represented by the formula: The silylborane compound has the formula (B): 【Chemistry 2】 (In the formula, Z １１ is a single bond, a double bond, or CH ２ and R １１ is an alkyl group, Two R's that may be adjacent to each other １１ may be taken together to form a ring, R １２ , R １３ , and R １４ are each independently an alkyl group or an aryl group, k3 is 0 or an integer of 1 or more. A compound represented by the formula: The disilane compound has the formula (C): 【Chemistry 3】 (In the formula, R ２１ , R ２２ , R ２３ , R ２４ , R ２５ , and R ２６ are each independently H, a halogen, an alkyl group, an alkoxy group, or an aryl group. The method according to claim 4, wherein the compound is represented by the formula:

6. The process according to any one of claims 1 to 3, which is carried out in an organic solvent.

7. The method according to claim 6, wherein the organic solvent has a boiling point of 150°C or lower at normal pressure.

8. The method according to claim 6, wherein the organic solvent is at least one selected from the group consisting of ether solvents and aromatic hydrocarbon solvents.

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

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

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

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

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

14. Formula (4A): 【Chemistry 4】 (In the formula, A １ represents 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 the formula:

15. Formula (5A): 【Chemistry 5】 (In the formula, A ２ represents 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 the formula:

16. Formula (5A): 【Chemistry 6】 (In the formula, A ２ represents 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. The compound represented by the formula (1) has an Al, Cr, Cu, Fe, Ni, and Zn content of 1000 ppm or less, respectively.

17. Formula (5A): 【Chemistry 7】 (In the formula, A ２ represents 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 the formula (1), wherein the total content of Al, Cr, Cu, Fe, Ni, and Zn is 6000 ppm or less.

18. Formula (5): 【Chemistry 8】 (In the formula, A represents a single bond, —O—, —S—, an alkylene 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 ４１ , R ４２ , and R ４３ are each independently fluorine, an alkyl group, or a fluoroalkyl group, R ３４ , R ３５ , R ４４ , and R ４５ each independently represents fluorine, an alkyl group, or a fluoroalkyl group (excluding a trifluoromethyl group), n and m are each independently 0, 1, or 2; The case where R 33 and R 43 are alkyl groups and R 34 , R 35 , R 44 and R 45 are all fluorine are excluded.) The compound having a Pd content of 1 ppm or less.

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