Method for producing fluoroalkyl aromatic compound

Abstract

Provided are a useful method for producing a fluoroalkyl aromatic compound, and a compound obtained by the production method. The method for producing a compound represented by formula (4) includes a step (C) in which a compound represented by formula (1) and a compound represented by formula (3) are reacted in the presence of a reducing agent, a copper compound, and a ligand. RF-X1 (1) Ar-X2 (3) Ar-RF (4) (In the formula, RF is a fluoroalkyl group which may have one or more substituents, X1 is Cl, Br, or I, X2 is Cl, Br, or I, and Ar is an aryl group which may have one or more substituents, or a heteroaryl group which may have one or more substituents)

Description

Technical Field

[0001] The present disclosure relates to a method for producing a fluoroalkyl aromatic compound, etc. Background Art

[0002] Fluoroalkyl aromatic compounds are compounds that can be used as pesticides, medicines, liquid crystal materials, etc. As a method for producing such compounds, for example, a method is known in which C5F is reacted with a high boiling point solvent such as N,N-dimethylformamide (DMF) or dimethyl sulfoxide (DMSO) to produce a fluorinated compound. 11 I. C6F 13 A method for producing a fluoroalkyl aromatic compound by reacting a fluoroalkyl iodide such as iodobenzene with copper powder (Patent Documents 1 and 2 and Non-Patent Document 1).

[0003] Prior art literature Patent Literature Patent Document 1: U.S. Patent No. 3,408,411 Patent Document 2: U.S. Patent Publication No. 2016 / 152636 Non-patent literature Non-patent document 1: D. Wiedenfeld et al., Journal of Fluorine Chemistry, 104 (2000), 303-306 Summary of the Invention

[0004] Technical problem to be solved by the invention The method of Patent Document 1 not only requires high temperature conditions but also leaves room for improvement in terms of yield. Furthermore, the methods of Patent Documents 1-2 and Non-Patent Document 1 all use high-boiling-point solvents, requiring multiple, complex steps such as extraction with water, vacuum distillation, and crystallization to extract the product from the high-boiling-point solvent.

[0005] The present disclosure aims to provide a useful method for producing a fluoroalkyl aromatic compound and a compound obtained by the method.

[0006] Technical solutions to technical problems The present disclosure includes the following aspects.

[0007] Item 1. A method for producing a compound represented by formula (2), MR F (2) (Where, M is Cu with ligands, R F is a fluoroalkyl group which may have one or more substituents. The production method comprises: 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) (Where, R F Has the same meaning as above, X 1 is Cl, Br or I. ).

[0008] Item 2. A method for producing a compound represented by formula (4), Ar-R F (4) (Where, 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. ), The production method comprises: step A of reacting a compound represented by formula (1), a copper compound, and a ligand in the presence of a reducing agent, and step B of reacting the reaction product of step A with a compound represented by formula (3). R F -X 1 (1) (Where, R F Has the same meaning as above, X 1 is Cl, Br or I. ), Ar-X 2 (3) (Where, Ar has the same meaning as above, X 2 is Cl, Br or I. ).

[0009] Item 3. A method for producing a compound represented by formula (4), Ar-R F (4) (Where, 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. ), The production method comprises: 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; R F -X 1 (1) (Where, R F Has the same meaning as above, X 1 is Cl, Br or I. ), Ar-X 2 (3) (Where, Ar has the same meaning as above, X 2 is Cl, Br or I. ).

[0010] 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.

[0011] 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 a diboron compound, a silyl borane compound, and a disilane compound.

[0012] Item 6. The production method according to item 5, wherein the diboron compound is a compound represented by formula (A), [Chemistry 1]

[0013] (Where, 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 alkyl group, Two Rs can exist next to each other 1 can form a ring together, Two Rs can exist next to each other 2 can form a ring together, k1 and k2 are each independently an integer of 0 or greater. ), The silaborane compound is a compound represented by formula (B), [Chemistry 2]

[0014] (Where, Z 11 is a single bond, a double bond or CH2, R 11 is an alkyl group, Two Rs can exist next to each other 11 can form a ring together, R 12 、R 13 and R 14 Each is independently an alkyl group or an aryl group, and k3 is an integer greater than or equal to 0. ), The disilane compound is a compound represented by formula (C), [Chemistry 3]

[0015] (Where, R 21 、R 22 、R 23 、R 24 、R 25 and R 26 are each independently H, halogen, alkyl, alkoxy or aryl.).

[0016] Item 7. The production method according to any one of items 1 to 6, which is carried out in an organic solvent.

[0017] Item 8. The production method according to item 7, wherein the boiling point of the organic solvent at normal pressure is 150° C. or lower.

[0018] Item 9. The production method according to item 7 or 8, wherein the organic solvent is at least one selected from ether solvents and aromatic hydrocarbon solvents.

[0019] Item 10. The production method according to any one of items 1 to 9, wherein the copper compound is a monovalent copper compound.

[0020] Item 11. The production method according to any one of items 1 to 10, wherein the copper compound is an alkoxide, an aryl oxide, a thioalkoxide, or a thioaryl oxide of Cu.

[0021] Item 12. The production method according to any one of items 1 to 11, wherein the ligand is at least one selected from a pyridine-containing ligand and a phosphine ligand.

[0022] Item 13. The production method according to any one of items 2 to 12, wherein the step B or the step C is performed at 50° C. or lower.

[0023] Item 14. The production method according to any one of items 2 to 13, wherein Ar is an aryl group which may have one or more substituents.

[0024] Item 15. The production method according to any one of items 2 to 14, wherein Ar is an aryl group having one or more fluorine or fluoroalkyl groups.

[0025] Item 16. The compound represented by formula (4A), [Chemistry 4]

[0026] (Where, 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.).

[0027] Item 17. The compound represented by formula (5A), [Chemistry 5]

[0028] (Where, 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.).

[0029] Item 18. The compound represented by formula (5A), [Chemistry 6]

[0030] (Where, 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. ), Among them, the contents of Al, Cr, Cu, Fe, Ni and Zn are each 1000 ppm or less.

[0031] Item 19. The compound represented by formula (5A), [Chemistry 7]

[0032] (Where, A 2is 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. ), However, the total content of Al, Cr, Cu, Fe, Ni and Zn is 6000 ppm or less.

[0033] Item 20. The compound represented by formula (5) [Chemistry 8]

[0034] (Where, 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, alkyl or fluoroalkyl, n and m are each independently 0, 1 or 2.) However, the content of Pd is 1000 ppm or less.

[0035] Effects of the Invention According to the present disclosure, for example, a useful method for producing a fluoroalkyl aromatic compound and a compound obtained by the production method are provided. DETAILED DESCRIPTION

[0036] The above summary of the present disclosure is not intended to describe every disclosed embodiment or every example of the present disclosure.

[0037] The following description of the present disclosure more specifically illustrates the embodiments of the present invention. In many places of the present disclosure, guidance is provided by way of illustration, and the illustrations can be used in various combinations. In different situations, the illustrated groups can function as non-exclusive and representative groups.

[0038] All publications, patents, and patent applications cited in this specification are hereby incorporated by reference into this specification as they are.

[0039] 1. Terminology Unless otherwise specified, the symbols and abbreviations in this specification may be understood according to the context of this specification as having the commonly used meanings in the technical field to which this disclosure belongs.

[0040] In this specification, the sentence pattern "comprising" is used to include the sentence pattern "consisting essentially of" and the sentence pattern "consisting of."

[0041] Unless otherwise specified, the steps, treatments, or operations described in this specification can be performed at room temperature. In this specification, room temperature may refer to a temperature within the range of 10 to 40°C.

[0042] In this specification, the expression "C n-m "" (herein, n and m are each an integer greater than or equal to 1, and n<m.) means that the number of carbon atoms is greater than or equal to n and less than or equal to m, as generally understood by those skilled in the art.

[0043] In this specification, examples of the “halogen” include fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

[0044] In the present specification, examples of the "alkyl group" include linear or branched C groups such as methyl, ethyl, propyl (n-propyl, isopropyl), butyl (n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl and hexyl. 1-20 alkyl.

[0045] In the present specification, examples of the "alkoxy group" include linear or branched C groups such as methoxy, ethoxy, propoxy (n-propoxy, isopropoxy), butoxy (n-butoxy, isobutoxy, sec-butoxy, tert-butoxy), pentyloxy, and hexyloxy. 1-20 Alkoxy.

[0046] In the present 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 Alkylthio.

[0047] In the present specification, examples of the "cycloalkyl group" include C groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl. 3-20 Cycloalkyl.

[0048] In this specification, the "aryl group" can be, for example, a monocyclic, bicyclic, tricyclic, or tetracyclic ring. Examples of the "aryl group" include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl. 6-20 Aryl.

[0049] In this specification, a "heteroaryl group" can be, for example, a monocyclic, bicyclic, tricyclic, or tetracyclic ring. 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, in addition to carbon atoms, one, two, three, or four heteroatoms selected from oxygen, sulfur, and nitrogen atoms as ring atoms. The "heteroaryl group" includes a "monocyclic heteroaryl group" and an "aromatic fused heterocyclic group."

[0050] 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), and isothiazolyl (e.g., 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl). yl), 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-thiadiazol-5-yl), tetrazolyl, pyridyl (e.g., 2-pyridyl, 3-pyridyl, 4-pyridyl), pyridazinyl (e.g., 3-pyridazinyl, 4-pyridazinyl), pyrimidinyl (e.g., 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl), and pyrazinyl, etc.

[0051] Examples of the “aromatic fused heterocyclic group” include isoindolyl (e.g., 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, and 7-isoindolyl), indolyl (e.g., 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, and 7-indolyl), benzo[b]furanyl (e.g., 2-benzo[b]furanyl, 3-benzo[b]furanyl, 4-benzo[b]furanyl, ] furyl, 5-benzo[b] furyl, 6-benzo[b] furyl, 7-benzo[b] furyl), benzo[c] furyl (e.g., 1-benzo[c] furyl, 4-benzo[c] furyl, 5-benzo[c] furyl), 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-benzisoxazol-3-yl, 1,2-benzisoxazol-3-yl -4-yl, 1,2-benzoisothiazol-5-yl, 1,2-benzoisothiazol-6-yl, 1,2-benzoisothiazol-7-yl), benzoxazolyl (e.g., 2-benzoxazolyl, 4-benzoxazolyl, 5-benzoxazolyl, 6-benzoxazolyl, 7-benzoxazolyl), 1,2-benzisothiazol-3-yl, 1,2-benzisothiazol-4-yl, 1,2-benzisothiazol-5-yl, 1,2-benzisothiazol-6-yl, 1,2-benzisothiazol-7-yl),2-benzoisothiazol-7-yl), benzothiazolyl (e.g., 2-benzothiazolyl, 4-benzothiazolyl, 5-benzothiazolyl, 6-benzothiazolyl, 7-benzothiazolyl), isoquinolyl (e.g., 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl), quinolyl (e.g., 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 8-quinolyl), cinnolinyl ( For example: 3-cinnolinyl, 4-cinnolinyl, 5-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 8-cinnolinyl), phthalazinyl (for example: 1-phthalazinyl, 4-phthalazinyl, 5-phthalazinyl, 6-phthalazinyl, 7-phthalazinyl, 8-phthalazinyl), quinazolinyl (for example: 2-quinazolinyl, 4-quinazolinyl, 5-quinazolinyl, 6-quinazolinyl, 7-quinazolinyl, 8-quinazolinyl), quinoxalinyl (for example: 2-quinoxalinyl, 3-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl, 7-quinoxalinyl, 8-quinoxalinyl), pyrazolo[1,5-a]pyridinyl (e.g., pyrazolo[1,5-a]pyridin-2-yl, pyrazolo[1,5-a]pyridin-3-yl, pyrazolo[1,5-a]pyridin-4-yl, pyrazolo[1,5-a]pyridin-5-yl, pyrazolo[1,5-a]pyridin-6-yl), 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.

[0052] In this specification, the term "alkyl group optionally having one or more substituents" means that -CH2- within the alkyl group may be replaced with -O-, -S-, or -NH-. Examples of substituents for the alkyl group include halogen, hydroxyl, alkoxy, mercapto, alkylthio, alkoxycarbonyl (alkyl-O-CO-), alkylcarbonyloxy (alkyl-CO-O-), aryl, and combinations of two or more thereof (e.g., haloalkoxy). When the alkyl group has substituents, the number of substituents can be selected from one to the maximum number of substituents that can be substituted, and can be, for example, one, two, three, four, or five. When the number of substituents is two or more, the substituents may be the same or different.

[0053] Examples of the above-mentioned "alkyl group which may have one or more substituents" include: alkyl groups which may be substituted with one or more halogens (e.g., fluorine). Alkyl groups substituted with one or more halogens are referred to as "haloalkyl groups." For example, when the substituted halogen is fluorine, it is sometimes referred to as "fluoroalkyl groups." "Fluoroalkyl groups" may be perfluoroalkyl groups or non-perfluoroalkyl groups. Examples of "fluoroalkyl groups" include: trifluoromethyl groups, perfluoroethyl groups, perfluoropropyl groups (e.g., perfluoro-n-propyl groups, perfluoro-isopropyl groups), perfluorobutyl groups, perfluoropentyl groups, perfluorohexyl groups, and other linear or branched fluoroalkyl groups. 1-20 Alkyl. 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; halogenated alkoxy groups such as fluoroalkoxy groups; alkoxycarbonyl groups; halogenated alkoxycarbonyl groups such as fluoroalkoxycarbonyl groups), and specific examples thereof include 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-CF Straight-chain or branched fluorine-containing C 2-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(CF3)-CF2-O-CF(CF3)-CF2-, CF3-CF2-CF2-O-[CF(CF3)-CF2-O-]2-CF(CF3)-CF2- 1-20 alkyl.

[0054] In this specification, examples of substituents in "aryl groups which may have one or more substituents" and "heteroaryl groups which may have one or more substituents" include halogen, hydroxyl, alkyl, alkoxy, alkylthio, and combinations of two or more thereof (e.g., haloalkyl, haloalkoxy). When the aryl group has substituents, the number of substituents can be selected from one to the maximum number of substituents that can be substituted, and can be, for example, one, two, three, four, or five. When there are two or more substituents, the substituents may be the same or different.

[0055] In the present specification, an "alkylene group," a "cycloalkylene group," and an "arylene group" are divalent groups formed by removing one hydrogen atom from an "alkyl group," a "cycloalkyl group," and an "aryl group," respectively.

[0056] 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 "fluoroalkylcopper 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.

[0057] R F -X 1 (1) MR F (2) (Where, R F is a fluoroalkyl group which may have one or more substituents, X 1 is Cl, Br or I, M is Cu with a ligand.) [Compound represented by formula (1)] R F In the example, the lower limit of the number of carbon atoms of the fluoroalkyl group can be 1, 2 or 3, and the upper limit can be 20, 16, 14, 12 or 10, for example. F Preferably, the fluorine C 1-20 Alkyl (eg perfluoroC 1-20 Alkyl), more preferably fluorine C which may have one or more substituents 1-12 Alkyl (eg perfluoro 1-12 Alkyl), more preferably fluorine C which may have one or more substituents 1-10 Alkyl (eg perfluoroC 1-10 alkyl).

[0058] X 1 Br or I is preferred.

[0059] In one embodiment, X 1 Br is preferred.

[0060] In another embodiment, X 1 Preferably 1.

[0061] [Copper compounds] The copper compound is not particularly limited as long as it contains copper. The copper compound may be, for example, a single substance of copper or a monovalent or divalent copper compound. In one embodiment, the copper compound is preferably a monovalent copper compound.

[0062] 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 can be used in combination with, for example, alkoxides, aryl oxides, thioalkoxides, or thioaryl oxides of alkali metals such as lithium, sodium, and potassium. Alternatively, copper alkoxides, aryl oxides, thioalkoxides, or thioaryl oxides can also be used as the copper compound. Examples of the alkoxides or aryl oxides include methoxides, ethoxides, propoxides, butoxides (e.g., tert-butoxide) of C 1-6 C of alcoholates, phenolates, etc. 6-10 Aryl oxide. Examples of the thioalkoxide or thioaryl oxide include those in which O of the above-mentioned alkoxide or aryl oxide is replaced by S.

[0063] The amount of the copper compound used is, for example, 0.5 mol or more, preferably 1 mol or more, and more preferably 1.5 mol or more, relative to 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, and more preferably 3 mol or less, relative to 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 1 to 4 mol, and more preferably 1.5 to 3 mol, relative to 1 mol of the compound represented by formula (1).

[0064] [ligand] The ligand is not particularly limited as long as it coordinates with copper. Examples of the ligand include pyridine-containing ligands and phosphine ligands.

[0065] Examples of the pyridine-containing ligand include phenanthroline (eg, 1,10-phenanthroline), 2,2′-bipyridine, pyridine, picoline, and lutidine (eg, 2,6-lutidine).

[0066] As the phosphine ligand, a trialkylphosphine or a triarylphosphine is preferred. Examples of the trialkylphosphine include triisopropylphosphine, di-tert-butylmethylphosphine, tri-tert-butylphosphine, trihexylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, triadamantylphosphine, tribicyclo[2,2,2]octylphosphine, trinorbornylphosphine and the like. 3-20 Examples of the triarylphosphine include tri(monocyclic aryl)phosphines such as triphenylphosphine, tri(mesityl)phosphine, and tri(o-tolyl)phosphine. Among them, triphenylphosphine, tricyclohexylphosphine, and tri-tert-butylphosphine are preferred.

[0067] In one embodiment, the ligand is preferably a bidentate ligand. Preferred examples of bidentate ligands include 1,10-phenanthroline.

[0068] The amount of the ligand used is, for example, 0.5 mol or more, preferably 1 mol or more, and more preferably 1.5 mol or more, relative to 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, and more preferably 3 mol or less, relative to 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 1 to 4 mol, and more preferably 1.5 to 3 mol, relative to 1 mol of the compound represented by formula (1).

[0069] [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-point solvent and the accompanying complicated removal operation can be avoided, and even compounds that are easily decomposed at high temperatures can be easily synthesized.

[0070] As a reducing agent, there is no particular limitation 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, silaborane compounds, disilane compounds, and the like.

[0071] Examples of the diboron compound include compounds represented by formula (A).

[0072] [Chemistry 9]

[0073] (Where, 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 Rs can exist next to each other 1 can form a ring together, Two Rs can exist next to each other 2 can form a ring together, k1 and k2 are each independently an integer of 0 or greater.) In one embodiment, Z 1 and Z 2 Preferably, they are all single bonds.

[0074] In another embodiment, Z 1 and Z 2 Preferably, both are double bonds.

[0075] In yet another embodiment, Z 1 and Z2 Preferably both are CH2.

[0076] R 1 and R 2 Each is independently preferably an alkyl group, more preferably a C 1-6 Alkyl, more preferably C 1-4 Alkyl, more preferably C 1-2 alkyl.

[0077] In Z 1 and Z 2 In the case of a single bond, k1 and k2 are 0, 1, 2, 3 or 4. 1 and Z 2 In the case of a double bond, k1 and k2 are 0, 1 or 2 respectively. 1 and Z 2 In the case of CH2, k1 and k2 are 0, 1, 2, 3, 4, 5 or 6 respectively.

[0078] Examples of the compound represented by formula (A) include compounds represented by formula (A1), (A2), (A3) or (A4).

[0079] [Chemistry 10]

[0080] Examples of the silaborane compound include compounds represented by formula (B).

[0081] [Chemistry 11]

[0082] (Where, Z 11 is a single bond, a double bond or CH2, R 11 is an organic group, Two Rs can exist next to each other 11 can form a ring together, R 12 、R 13 and R 14 are each independently an organic group, k3 is an integer greater than or equal to 0 or 1.) In one embodiment, Z 11 It is preferably a single bond.

[0083] In another embodiment, Z 11 A double bond is preferred.

[0084] In yet another embodiment, Z 11 Preferred is CH2.

[0085] R 11 It is preferably a hydrocarbon group, more preferably an alkyl group, and further preferably a C 1-6 Alkyl, more preferably C 1-4 Alkyl, particularly preferably C 1-2 alkyl.

[0086] R 12 、R 13 and R 14 Each is independently preferably an alkyl group or an aryl group, more preferably a C 1-6 Alkyl or C 6-14 Aryl, more preferably C 1-4 Alkyl or C 6-12 Aryl, more preferably C 1-2 Alkyl or C 6-10 Aryl.

[0087] In Z 11 When Z is a single bond, k3 is 0, 1, 2, 3 or 4. 11 In the case of a double bond, k3 is 0, 1 or 2. 11 In the case of CH2, k3 is 0, 1, 2, 3, 4, 5 or 6.

[0088] Examples of the compound represented by formula (B) include compounds represented by formula (B1).

[0089] [Chemistry 12]

[0090] Examples of the disilane compound include compounds represented by formula (C).

[0091] [Chemistry 13]

[0092] (Where, R 21 、R 22 、R 23 、R 24 、R 25 and R 26 Each is independently H, halogen or an organic group.) R 21 、R 22 、R 23 、R 24 、R 25 and R 26 Each is independently preferably H, halogen, alkyl, alkoxy or aryl, more preferably H, halogen, C 1-6 Alkyl, C 1-6 Alkoxy or C 6-14Aryl, more preferably H, halogen, C 1-4 Alkyl, C 1-4 Alkoxy or C 6-12 Aryl, more preferably H, halogen (especially Cl), C 1-2 Alkyl, C 1-2 Alkoxy or C 6-10 Aryl.

[0093] Examples of the compound represented by formula (C) include compounds represented by formula (C1), (C2), (C3), (C4), (C5), (C6), (C7), (C8), or (C9).

[0094] [Chemistry 14]

[0095] The amount of the reducing agent used is, for example, 0.7 mol or more, preferably 0.8 mol or more, and 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, and 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, in the range of 0.7 to 3 mol, preferably 0.8 to 1 mol, and more preferably 0.9 to 1.5 mol, relative to 1 mol of the compound represented by formula (1).

[0096] [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 preferably has a boiling point at normal pressure of 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 thereof.

[0097] 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, relative to 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, relative to 1 mmol of the compound represented by formula (1). The amount of the organic solvent used is, for example, in the range of 0.5 to 40 mL, preferably 1 to 30 mL, and more preferably 1.5 to 20 mL, relative to 1 mmol of the compound represented by formula (1).

[0098] [Reaction temperature and reaction time] The reaction temperature and reaction time of step A are not particularly limited as long as the reaction proceeds.

[0099] 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, in the range of -30 to 40°C, preferably -10 to 35°C, and more preferably 0 to 30°C.

[0100] 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, in the range of 5 minutes to 48 hours, preferably 10 minutes to 24 hours, and even more preferably 1 to 12 hours.

[0101] [Optional additional steps] The production method may further comprise the step of isolating or purifying the compound represented by formula (2). The isolation or purification of the compound represented by formula (2) can be carried out by methods such as filtration, extraction, concentration, chromatography, or a combination of these methods.

[0102] 3. Method for producing the compound represented by formula (4) In one embodiment of the present disclosure, a method for producing a compound represented by formula (4) comprises step A and step B of reacting the reaction product of step A (particularly the compound represented by formula (2)) with a compound represented by formula (3).

[0103] Ar-X 2 (3) Ar-R F (4) (Where, 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 above.) [Compound represented by formula (3)] Ar is preferably a C 6-14 Aryl, or a 5- to 14-membered heteroaryl group which may have one or more substituents, more preferably a C 6-12 An aryl group, or a 5- to 12-membered heteroaryl group which may have one or more substituents, more preferably a C 6-10An 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.

[0104] In one embodiment, Ar is preferably an aryl group which may have one or more substituents. The substituent may be an organic group, and specifically, may include 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, L 1 represents a single bond or -O-), 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 hydroxyl group, a halogen (halogenated group), or a combination thereof. In one embodiment, the substituent is preferably fluorine and / or a fluoroalkyl group, and the substituent may be a fluoroalkyl group.

[0105] X 2 Br or I is preferred.

[0106] In one embodiment, X 2 Br is preferred.

[0107] In another embodiment, X 2 Preferably 1.

[0108] In one embodiment, the compound represented by formula (3) is preferably a compound represented by formula (3A) or formula (3B).

[0109] X 21 -Ar 1 -A 0 -Ar 2 -X 22 (3A) X 23 -Ar 3 -X24 (3B) (Where, 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, 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.) Ar 1 and Ar 2 They may be the same or different from each other. 1 、Ar 2 and Ar 3 Preferred examples of include divalent groups corresponding to the preferred examples of Ar.

[0110] In A 0 In the case of 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. 0 Preferably, C 1-6 Alkylene, more preferably C 1-6 Alkylene, more preferably C 1-4 Alkylene, more preferably C 1-2 The substituent may be an organic group, and specifically includes 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 ), alkoxy, hydroxy, halogen (halo), and combinations thereof.

[0111] In A0 In the case of a cycloalkylene group which may have one or more substituents, preferably a C 5-14 Cycloalkylene, more preferably C 5-12 Cycloalkylene, more preferably C 5-10 Cycloalkylene.

[0112] In A 0 In the case of an arylene group which may have one or more substituents, it is preferably a C 6-14 Arylene, more preferably C 6-12 Arylene, more preferably C 5-10 Arylene.

[0113] X 21 、X 22 、X 23 and X 24 Preferably, each independently is Br or I. X 21 and X 22 They can be the same or different. 23 and X 24 They can be the same or different from each other.

[0114] The amount of the compound represented by formula (3) used (particularly the total amount of Cl, Br, and I) relative to 1 mol of the compound represented by formula (2) is, for example, 0.05 mol or more, preferably 0.1 mol or more, and more preferably 0.15 mol or more. 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, relative to 1 mol of the compound represented by formula (2). The amount of the compound represented by formula (3) used is, for example, in the range of 0.05 to 3 mol, preferably 0.1 to 2 mol, and more preferably 0.15 to 1.5 mol relative to 1 mol of the compound represented by formula (2).

[0115] [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 thereof. The organic solvent may be different from the organic solvent used in step A, but is preferably the same.

[0116] [Reaction temperature and reaction time] The reaction temperature and reaction time of step B are not particularly limited as long as the reaction proceeds.

[0117] 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 10 to 100°C, and more preferably 20 to 80°C.

[0118] The reaction time is, for example, 30 minutes or more, preferably 1 hour or more, and more preferably 2 hours or more. The reaction time is, for example, 48 hours or less, preferably 24 hours or less, and more preferably 12 hours or less. The reaction time is, for example, 30 minutes to 48 hours, preferably 1 to 24 hours, and more preferably 2 to 12 hours.

[0119] 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.

[0120] Examples of the compound represented by formula (1) and the compound represented by formula (3) include the same compounds as exemplified in step A and step B, respectively.

[0121] The amount of the compound represented by formula (3) used (particularly the total amount of Cl, Br, and I) relative to 1 mol of the compound represented by formula (1) is, for example, 0.05 mol or more, preferably 0.1 mol or more, and more preferably 0.15 mol or more. 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, relative to 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 0.1 to 2 mol, and more preferably 0.15 to 1.5 mol relative to 1 mol of the compound represented by formula (1).

[0122] Examples of the reducing agent, copper compound, and ligand include the same substances as exemplified in step A. The amounts of the reducing agent, copper compound, and ligand used relative to the compound represented by formula (1) can also be selected from the same ranges as exemplified in step A.

[0123] [Organic solvents] The reaction in step C is preferably carried out in the presence of an organic solvent. Examples of the organic solvent include the same organic solvents as 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 exemplified in step A.

[0124] [Reaction temperature and reaction time] The reaction temperature and reaction time of 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.

[0125] [Optional additional steps] For example, when the compound of formula (3A) is used, the production method can produce the compound represented by formula (4B) and / or the compound represented by formula (4C) as by-products.

[0126] 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 comprise the 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.

[0127] 4. Compound represented by formula (4A) The compound according to one embodiment of the present disclosure is a compound represented by formula (4A).

[0128] [Chemistry 15]

[0129] (Where, 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. In A 1 In the case of 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. 1 Preferably, C 1-6Alkylene, more preferably C 1-6 Alkylene, more preferably C 1-4 Alkylene, more preferably C 1-2 The substituent may be an organic group, and specifically includes 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 ), alkoxy, hydroxy, halogen (halo), and combinations thereof.

[0130] In A 1 In the case of a cycloalkylene group which may have one or more substituents, preferably a C 5-14 Cycloalkylene, more preferably C 5-12 Cycloalkylene, more preferably C 5-10 Cycloalkylene.

[0131] In A 1 In the case of an arylene group which may have one or more substituents, it is preferably a C 6-14 Arylene, more preferably C 6-12 Arylene, more preferably C 5-10 Arylene.

[0132] The compound represented by formula (4A) can be prepared, for example, by changing Ar of formula (3A) to 1 and Ar 2 The compound of phenylene and R of formula (1) F A compound of CF2Cl-CFCl-CF2-CF2-, a copper compound, and a ligand (or a ligand produced by reacting these, R of formula (2) F It is produced by the reaction of CF2Cl-CFCl-CF2-CF2-).

[0133] 5. Compound represented by formula (5A) The compound according to one embodiment of the present disclosure is a compound represented by formula (5A).

[0134] [Chemistry 16]

[0135] (Where, 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. In A 2 In the case of 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. 2 Preferably, C 1-6 Alkylene, more preferably C 1-6 Alkylene, more preferably C 1-4 Alkylene, more preferably C 1-2 The substituent may be an organic group, and specifically includes 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 ), alkoxy, hydroxy, halogen (halo), and combinations thereof.

[0136] In A 2 In the case of a cycloalkylene group which may have one or more substituents, preferably a C 5-14 Cycloalkylene, more preferably C 5-12 Cycloalkylene, more preferably C 5-10 Cycloalkylene.

[0137] In A 2 In the case of an arylene group which may have one or more substituents, it is preferably a C 6-14Arylene, more preferably C 6-12 Arylene, more preferably C 5-10 Arylene.

[0138] The compound represented by formula (5A) can be produced, for example, by dechlorination of the compound represented by formula (4A). The dechlorination reaction can be carried out under conditions known or commonly used in the art.

[0139] The compound represented by formula (5A) may contain Al, Cr, Cu, Fe, Ni and Zn, or may not contain some 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 lower the content of each of the above metals, the better, so the lower limit is not particularly limited, for example, it can be 0.001 ppm or more. The content of Al, Cr, Cu, Fe, Ni and Zn can be measured by, for example, ICP (high-frequency inductively coupled plasma) emission spectrometry. In one embodiment, the content of Al, Cr, Cu, Fe, Ni and Zn is preferably below the detection limit in ICP emission spectrometry.

[0140] 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 the total content of the above metals, the better, so the lower limit is not particularly limited, and 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 (high-frequency 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 in ICP emission spectrometry.

[0141] The compound represented by formula (5A) may or may not contain Pd. The Pd content 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 the Pd content, the better, so the lower limit is not particularly limited, and for example, it can be 0.001 ppm or more. The Pd content can be measured, for example, by ICP emission spectrometry. In one embodiment, the Pd content is preferably below the detection limit in ICP emission spectrometry.

[0142] 7. Compound represented by formula (5) The compound according to one embodiment of the present disclosure is a compound represented by formula (5).

[0143] [Chemistry 17]

[0144] (Where, 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, alkyl or fluoroalkyl, n and m are each independently 0, 1 or 2.) 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 1-6 Alkylene, more preferably C 1-6 Alkylene, more preferably C 1-4 Alkylene, more preferably C 1-2 The substituent may be an organic group, and specifically includes 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 ), alkoxy, hydroxy, halogen (halo), and combinations thereof.

[0145] When A is a cycloalkylene group which may have one or more substituents, it is preferably C 5-14Cycloalkylene, more preferably C 5-12 Cycloalkylene, more preferably C 5-10 Cycloalkylene.

[0146] When A is an arylene group which may have one or more substituents, it is preferably C 6-14 Arylene, more preferably C 6-12 Arylene, more preferably C 5-10 Arylene.

[0147] R 31 、R 32 、R 33 、R 34 、R 35 、R 41 、R 42 、R 43 、R 44 and R 45 Each independently preferably is fluorine, C 1-6 Alkyl or fluorine C 1-6 Alkyl, more preferably fluorine, C 1-4 Alkyl or fluorine C 1-4 Alkyl, more preferably fluorine, C 1-2 Alkyl or fluorine C 1-2 In one embodiment, R 31 、R 32 、R 33 、R 34 and R 35 Preferably, R 41 、R 42 、R 43 、R 44 and R 45 same.

[0148] In one embodiment, preferably both n and m are 0.

[0149] In another embodiment, preferably both n and m are 1.

[0150] In yet another embodiment, preferably both n and m are 2.

[0151] 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 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 lower the content of each of the above metals, the better, so the lower limit is not particularly limited, for example, it can be 0.001 ppm or more. The content of Al, Cr, Cu, Fe, Ni and Zn can be measured by, for example, ICP (high-frequency inductively coupled plasma) emission spectrometry. In one embodiment, the content of Al, Cr, Cu, Fe, Ni and Zn is preferably below the detection limit in ICP emission spectrometry.

[0152] 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 the total content of the above metals, the better, so the lower limit is not particularly limited, and 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 (high-frequency 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 in ICP emission spectrometry.

[0153] The compound represented by formula (5) may or may not contain Pd. The Pd content 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 the Pd content, the better, so the lower limit is not particularly limited, and may be, for example, 0.001 ppm or more. The Pd content can be measured, for example, by ICP emission spectrometry. In one embodiment, the Pd content is preferably below the detection limit in ICP emission spectrometry.

[0154] The compound represented by formula (5) can be produced, for example, by the following process: in the method for producing the compound represented by formula (4), Ar of formula (3A) is 1 and Ar 2 The compound of phenylene and R of formula (1) F CR 35 R 34 Cl-CR 33 Cl-(CR 32 R 31 )n - compounds and / or R 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 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 commonly used in the art.

[0155] Example Hereinafter, an embodiment of the present disclosure will be described in more detail by way of examples, but the present disclosure is not limited thereto. It should be noted that the respective abbreviations in the examples are as follows.

[0156] B2pin2: Bis(pinacol)diboron DMF: N,N-dimethylformamide HPLC: High Performance Liquid Chromatography PhMe2SiBpin: (dimethylphenylsilyl)boronic acid pinacol ester tBu: tert-butyl THF: Tetrahydrofuran Example 1 [Chemistry 18]

[0157] Under a nitrogen atmosphere, a solution of CuOtBu (1 mmol, 134 mg) and 1,10-phenanthroline (1 mmol, 180 mg) in THF (4 mL) was prepared in a screw-cap test tube. A THF solution (1 mL) of B2pin2 (0.5 mmol, 127 mg) and ICF2CF2CFClCF2Cl (0.5 mmol, 189 mg) was added dropwise. The reaction solution was stirred at room temperature for 10 minutes and then filtered. The filtrate was concentrated and washed with diethyl ether to obtain 197.6 mg of the title compound as a brown solid in an 80% yield.

[0158] 1 H NMR (400MHz, THF-d8): δ9.1 (br, 2H), 8.7 (br, 2H), 8.1 (br, 2H), 8.0 (br, 2H). 19 F NMR (376MHz, THF-d8): delta -65.7 (br, 2F), -111.5 (br, 2F), -120.3 (br, 2F), -132.3 (br, 1F). Example 2 [Chemistry 19]

[0159] Under nitrogen atmosphere, a solution of CuOtBu (0.24 mmol, 32.1 mg) and 1,10-phenanthroline (0.24 mmol, 43.2 mg) in THF (0.3 mL) was prepared in a screw-cap test tube. B2pin2 (0.12 mmol, 30.5 mg) and ICF2CF2CF2CF3 (0.12 mmol, 20 μ L) in THF solution (0.2 mL). The reaction solution was stirred at room temperature for 1 hour, and then 4-fluoroiodobenzene (0.1 mmol, 11.6 μ L), sealed, and stirred at 40°C for 18 hours to obtain the title compound in a yield of 82%.

[0160] 19 F NMR (376MHz, CDCl3): -107.1 (s, 1F), -109.9 (t, 13Hz, 2F), -122.5 (t, 9Hz, 2F), -125.4 (m, 2F). Example 3 The same operation as above was performed except that B2Pin2 was replaced with PhMe2SiBpin (0.12 mmol). 19 F NMR confirmed that the title compound (4-1) was produced in a yield of 63%.

[0161] Example 4 The same operation as above was carried out except that THF was replaced with diethyl ether. 19 F NMR confirmed that compound (4-1) was produced in a yield of 8%.

[0162] Example 5 The same operation as above was carried out except that THF was changed to toluene. 19 F NMR confirmed that compound (4-1) was produced in a yield of 30%.

[0163] Example 6 [Chemistry 20]

[0164] In a glove box, a solution of CuOtBu (4.8 mmol, 654.6 mg) and 1,10-phenanthroline (4.8 mmol, 865.1 mg) in THF (4.8 mL) was prepared in a screw-capped test tube. The solution was cooled to -30 °C. B2pin2 (2.4 mmol, 610.1 mg) and ICF2CF2CFClCF2Cl (2.4 mmol, 426 μ L) in THF solution 2 (2.4 mL). Solution 2 was slowly added dropwise to solution 1. The container of solution 2 was rinsed twice with THF (1.2 mL), and the washings were added to solution 1. After the solution was stirred at room temperature for 1 hour, 4,4′-diiodobiphenyl (0.8 mmol, 325.3 mg) was added, the container was sealed, and stirred at 40°C for 18 hours. After the reaction, compounds (4-2) and (4-3) were obtained as a 10:1 mixture, which contained a small amount of compound (5-1). The mixture was filtered and purified by column chromatography to obtain compound (4-2) with a yield of 82%.

[0165] 1 H NMR (400MHz, CDCl3): δ7.65 (m, 8H) 19 F NMR (376MHz, 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 Example 7 [Chemistry 21]

[0166] In a glove box, a solution of CuOtBu (4.8 mmol, 654.6 mg) and 1,10-phenanthroline (4.8 mmol, 865.1 mg) in THF (4.8 mL) was prepared in a screw-capped test tube. The solution was cooled to -30 °C. B2pin2 (2.4 mmol, 610.1 mg) and ICF2CF2CFClCF2Cl (2.4 mmol, 426 μL) in THF solution 2 (2.4 mL). Solution 2 was slowly added dropwise to solution 1. The container containing solution 2 was rinsed twice with THF (1.2 mL), and the rinse was added to solution 1. After the solution was stirred at room temperature for 1 hour, 4,4′-diiodobiphenyl (0.8 mmol, 325.3 mg), Zn (325 mg), ZnCl2 (44 mg), and DMF (8.4 mL) were added. The mixture was sealed and stirred at 40°C for 18 hours. After the reaction, 232 mg of crude product was obtained. NMR analysis showed that 4,4′-diiodobiphenyl, compound (4-2), and compound (4-4) were produced in a molar ratio of 0.7:1:1.4.

[0167] Example 8 [Chemistry 22]

[0168] 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 added to DMF (3 mL). 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 mixture was washed twice with DMF (2 mL), and the washings were added to the reaction solution. The mixture was then stirred at 60°C for 2 hours under a nitrogen atmosphere. After completion of the reaction, filtration and extraction were performed, and purification by HPLC was performed to obtain compound (5-1) in a 93% yield.

[0169] 1 H NMR (400MHz, 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 The obtained compound (5-1) was analyzed by ICP-AES (Pd detection limit 1 ppm), and no Pd was detected.

Claims

1. A method for producing a compound represented by formula (2), characterized in that: The method comprises the following steps: reacting a compound represented by formula (1), a copper compound and a ligand in the presence of a reducing agent; M-R F (2) In formula (2), M is Cu with ligands, R F is a fluoroalkyl group which may have one or more substituents, R F -X 1 (1) In formula (1), R F Has the same meaning as above, X 1 is Cl, Br or I.

2. A method for producing a compound represented by formula (4), characterized in that: The method comprises: a step A of reacting a compound represented by formula (1), a copper compound and a ligand in the presence of a reducing agent; and a step B of reacting the reaction product of step A with a compound represented by formula (3). On-R F (4) In formula (4), 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, R F -X 1 (1) In formula (1), R F Has the same meaning as above, X 1 is Cl, Br or I, Ar-X 2 (3) In formula (3), Ar has the same meaning as above, X 2 is Cl, Br or I.

3. A method for producing a compound represented by formula (4), characterized in that: The method comprises: a 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, On-R F (4) In formula (4), 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, R F -X 1 (1) In formula (1), R F Has the same meaning as above, X 1 is Cl, Br or I, Ar-X 2 (3) In formula (3), Ar has the same meaning as above, X 2 is Cl, Br or I.

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 4, wherein The reducing agent is at least one selected from the group consisting of diboron compounds, silaborane compounds, and disilane compounds.

6. The manufacturing method according to claim 5, wherein: The diboron compound is a compound represented by formula (A), ， In formula (A), 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 alkyl group, Two Rs can exist next to each other 1 Together to form a ring or not to form a ring, Two Rs can exist next to each other 2 Together to form a ring or not to form a ring, k1 and k2 are each independently an integer of 0 or 1 or greater, The silaborane compound is a compound represented by formula (B), ， In formula (B), Z 11 is a single bond, a double bond or CH2, R 11 is an alkyl group, Two Rs can exist next to each other 11 Together to form a ring or not to form a ring, R 12 、R 13 and R 14 are each independently an alkyl group or an aryl group, k3 is an integer of 0 or 1 or greater, The disilane compound is a compound represented by formula (C), ， In formula (C), R 21 、R 22 、R 23 、R 24 、R 25 and R 26 Each is independently H, halogen, alkyl, alkoxy or aryl. 7 . The production method according to claim 1 , which is carried out in an organic solvent.

8. The manufacturing method according to claim 7, wherein: The boiling point of the organic solvent under normal pressure is below 150°C.

9. The manufacturing method according to claim 7 or 8, 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 9, wherein The copper compound is a monovalent copper compound.

11. The production method according to any one of claims 1 to 10, wherein The copper compound is Cu alkoxide, aryl oxide, thioalkoxide or thioaryl oxide.

12. The production method according to any one of claims 1 to 11, wherein The ligand is at least one selected from the group consisting of pyridine-containing ligands and phosphine ligands.

13. The production method according to any one of claims 2 to 12, wherein The step B or step C is performed at 50° C. or lower.

14. The production method according to any one of claims 2 to 13, wherein Ar is an aryl group which may have one or more substituents.

15. The production method according to any one of claims 2 to 14, wherein Ar is an aryl group having one or more fluorine groups or a fluoroalkyl group.

16. The compound represented by formula (4A), characterized in that ， In formula (4A), A 1 It 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.

17. The compound represented by formula (5A), characterized in that ， In formula (5A), A 2 It 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.

18. The compound represented by formula (5A), characterized in that The contents of Al, Cr, Cu, Fe, Ni and Zn are less than 1000ppm respectively. ， In formula (5A), A 2 It 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.

19. The compound represented by formula (5A), characterized in that The total content of Al, Cr, Cu, Fe, Ni and Zn is 6000 ppm or less. ， In formula (5A), A 2 It 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.

20. The compound represented by formula (5), characterized in that The Pd content is less than 1000ppm, ， In formula (5), 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, alkyl or fluoroalkyl, n and m are each independently 0, 1 or 2.

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