Method for producing aromatic compound having perfluoroalkylene group

Abstract

To provide a method for producing an aromatic compound having a perfluoroalkylene group, simply and efficiently.SOLUTION: A perfluoroalkylenediyl iodide compound (A), a dialkylzinc (B), and a halogenated aromatic compound (C) are subjected to a reaction in the presence of a copper(I) catalyst to simply and efficiently yield an aromatic compound having a perfluoroalkylene group.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing an aromatic compound having a perfluoroalkylene group. An aromatic compound having a perfluoroalkylene group is an industrially useful compound as an intermediate for producing functional materials such as a crosslinking agent for fluororubber and an electrolyte membrane for fuel cells.

Background Art

[0002] As a method for producing an aromatic compound having a perfluoroalkylene group, Ullmann coupling in which a perfluoroalkylenediiodide and an aromatic halide are reacted with copper powder is known (for example, Non-Patent Document 1, Non-Patent Document 2). In Ullmann coupling, since an excessive amount of 4 to 9 molar equivalents of copper powder is used with respect to 1 mol of perfluoroalkylenediiodide, a large amount of waste is generated, and there has been a problem that post-treatment of the reaction becomes difficult.

[0003] On the other hand, as a method for producing an aromatic compound having a perfluoroalkylene group, a perfluoroalkylenediiodide and diethylzinc are reacted overnight at -78 ° C to room temperature in pentane, N,N'-dimethylpropyleneurea is added, and a perfluoroalkylene zinc complex is isolated as a white solid. Then, a method of cross-coupling in the presence of 1 molar equivalent of copper(I) chloride with respect to the aromatic halide is known (Non-Patent Document 3). In the method of Non-Patent Document 3, a low-temperature reaction is required to prepare the perfluoroalkylene zinc complex, which is time-consuming, and there is a problem that the number of steps in the production process increases in order to isolate the perfluoroalkylene zinc complex.

Prior Art Documents

Non-Patent Documents

[0004]

Non-Patent Document 1

Non-Patent Document 2

Non-Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] An object of the present invention is to provide a method for simply and efficiently producing an aromatic compound having a perfluoroalkylene group.

Means for Solving the Problems

[0006] As a result of intensive studies on aromatic compounds having a perfluoroalkylene group, the present inventors have found that an aromatic compound having a perfluoroalkylene group can be simply and efficiently obtained by reacting a perfluoroalkylenediiodide compound (A), a dialkylzinc (B), and an aromatic halide compound (C) in the presence of a copper(I) catalyst, and have thus completed the present invention.

[0007] That is, the present invention relates to the following gist. [1] A perfluoroalkylenediiodide compound (A) represented by the general formula (1): I-(CF2CF2) n -I (In the general formula (1), n represents an integer of 1 to 4.) and A dialkylzinc (B) represented by the general formula (2): ZnR1R2 (In the general formula (2), R1 and R2 each independently represent an alkyl group having 1 to 4 carbon atoms.) and An aromatic halide compound (C) represented by the general formula (3): X-Ar (In the general formula (3), X represents a bromine atom or an iodine atom, Ar represents an aromatic ring selected from the group consisting of a benzene ring, a heteroatom-containing aromatic ring, and a polycyclic aromatic hydrocarbon, where Ar may have one or more substituents, and the substituents are selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms containing one or more fluorine atoms, an acyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an acetal group having 3 to 10 carbon atoms, a formyl group, a nitro group, a cyano group, and an amino group.) reacting with a halogenated aromatic compound (C) represented by in the presence of a copper(I) catalyst, characterized in that General formula (4): Ar-(CF2CF2) n -Ar (In general formula (4), n represents an integer from 1 to 4, and Ar represents the same as in general formula (3).) A method for producing an aromatic compound having a perfluoroalkylene group. [2] The production method according to item [1], wherein the step of reacting the perfluoroalkylene diiodide compound (A) with the dialkylzinc (B) and the step of reacting with the halogenated aromatic compound (C) are continuously carried out. [3] The method according to item [1] or item [2], wherein n in general formula (1) is 2 or 3, and R1 and R2 in general formula (2) are ethyl groups. [4] A fluorine-containing zinc reagent obtained by mixing a perfluoroalkylene diiodide compound (A) represented by general formula (1) and a dialkylzinc (B) represented by general formula (2) in a solvent having an amide bond. [5] A fluorine-containing zinc reagent obtained by mixing 0.8 molar equivalent to 2.5 molar equivalents of a dialkylzinc (B) represented by general formula (2) with 1 mole of a perfluoroalkylene diiodide compound (A) represented by general formula (1) in a solvent having an amide bond. [6] An aromatic compound having a perfluoroalkylene group represented by the following formula (a) or (b).

Chemical formula

Chemical formula

Advantages of the Invention

[0008] According to the present invention, an aromatic compound having a perfluoroalkylene group, which is useful as a production intermediate of a functional material, can be produced simply and efficiently.

Embodiments for Carrying Out the Invention

[0009] One aspect of the present invention relates to a method for producing an aromatic compound having a perfluoroalkylene group. Each term and detail will be described below.

[0010] <Perfluoroalkylenediiodide compound (A)> In the production method of the present invention, the perfluoroalkylenediiodide compound (A) is a raw material for the aromatic compound having a perfluoroalkylene group. Examples of the perfluoroalkylenediiodide compound that can be used are not limited to the following examples, and include, for example, I-CF2CF2-I, I-(CF2CF2)2-I, I-(CF2CF2)3-I, I-(CF2CF2)4-I. From the viewpoint of suppressing bioaccumulation and environmental persistence, I-CF2CF2-I, I-(CF2CF2)2-I, I-(CF2CF2)3-I are preferable, and from the viewpoint of improving the physical properties of the functional material, I-(CF2CF2)2-I, I-(CF2CF2)3-I are more preferable.

[0011] <Dialkylzinc (B)> In the production method of the present invention, the dialkylzinc (B) is necessary for improving the yield of the reaction. The dialkylzinc (B) is considered to zincate the perfluoroalkylenediiodide compound (A), and the resulting fluorine-containing zinc reagent becomes an active species in the cross-coupling reaction and contributes to the improvement of the yield.

[0012] In the production method of the present invention, as the zinc compound used for zincation, dialkylzinc is preferable because of its high yield and high reactivity. When zincating a perfluoroalkylene diiodide compound (A) with zero-valent zinc such as zinc powder, a compound in which iodine in the perfluoroalkylene diiodide compound (A) is replaced by hydrogen may be by-produced, and the yield may decrease. When zincating is carried out with an alkylzinc halide, a compound in which iodine in the perfluoroalkylene diiodide compound (A) is replaced by hydrogen is by-produced, and in addition, the reactivity of the generated zinc compound is poor, and the yield of the reaction may decrease.

[0013] In the production method of the present invention, the dialkylzinc that can be used is not limited to the following examples. For example, dimethylzinc, diethylzinc, diisopropylzinc, dipropylzinc, diisobutylzinc, and dibutylzinc can be mentioned. From the viewpoint of availability, dimethylzinc, diethylzinc, and diisopropylzinc are preferred. Among these, diethylzinc or diisopropylzinc is particularly preferred because of its high boiling point and the ability to adjust the reaction temperature.

[0014] In the production method of the present invention, high-purity dialkylzinc may be used as it is, or a diluted one with a solvent may be used. Since dialkylzinc generally has pyrophoricity, it is preferable to use a diluted one with a solvent. In the production method of the present invention, dialkylzinc prepared in advance or purchased may be used, or the one prepared immediately before the reaction may be used as it is.

[0015] In the production method of the present invention, the method for adding dialkylzinc to the reactor is not limited to the following examples. For example, · A method of mixing a perfluoroalkylene diiodide compound (A) and dialkylzinc (B) to prepare a fluorine-containing zinc reagent, and then performing a coupling reaction · A method of gradually adding or sequentially adding dialkylzinc (B) to perform a cross-coupling reaction while preparing a fluorine-containing zinc reagent · A method of gradually adding or sequentially adding a perfluoroalkylene diiodide compound (A) to perform a cross-coupling reaction while preparing a fluorine-containing zinc reagent include.

[0016] In the production method of the present invention, the temperature at which dialkylzinc (B) and perfluoroalkylene diiodide compound (A) are mixed is not particularly limited, but is preferably -20°C to 150°C, more preferably -10°C to 100°C, and even more preferably -5°C to 50°C. When the temperature is lower than -20°C, equipment such as a low-temperature reactor is required, and simple production may be difficult. When the temperature is higher than 100°C, the yield may decrease due to the decomposition of the resulting fluorine-containing zinc reagent.

[0017] In the production method of the present invention, the mixing of dialkylzinc (B) and perfluoroalkylene diiodide compound (A) can be carried out in an organic solvent, and is not particularly limited as long as the organic solvent does not inhibit the reaction. Specific examples of the organic solvent to be used include, for example, ether solvents such as tetrahydrofuran, diethyl ether, 2-methyltetrahydrofuran, cyclopentyl methyl ether, 1,4-dioxane, methyl tert-butyl ether, 1,2-dimethoxyethane; aliphatic hydrocarbon solvents such as hexane, pentane, cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene; nitrile solvents such as acetonitrile, propionitrile; sulfoxide solvents such as dimethyl sulfoxide, diethyl sulfoxide; solvents having an amide bond such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea; halogen solvents such as dichloromethane, chloroform, and two or more of the above may be mixed and used. Among these, in terms of the excellent stability of the fluorine-containing zinc reagent, tetrahydrofuran, diethyl ether, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea are preferred. Among them, in particular, in terms of the excellent stability of the fluorine-containing zinc reagent, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea are more preferred. Among them, in terms of excellent yield, 1,3-dimethyl-2-imidazolidinone and N,N-dimethylformamide are preferred.

[0018] In the production method of the present invention, as the equivalent amount of the dialkylzinc (B) used, 0.2 molar equivalent to 4.0 molar equivalents is preferred, 0.5 molar equivalent to 2.0 molar equivalents is more preferred, and 0.8 to 1.2 molar equivalents is particularly preferred, relative to 1 mol of the perfluoroalkylene diiodide compound (A). When the amount of dialkylzinc (B) is less than 0.2 molar equivalent, the perfluoroalkylene diiodide (A) may remain and the yield may decrease. When the amount of dialkylzinc (B) is more than 4.0 molar equivalents, the yield may decrease due to side reactions.

[0019] In the production method of the present invention, the concentration of the dialkylzinc is not particularly limited, but 0.01 M to 3.0 M is preferred, 0.1 M to 2.0 M is more preferred, and 0.5 M to 1.5 M is more preferred. When the concentration is less than 0.01 M, the reaction rate may decrease and a long reaction time may be required. When the concentration is more than 2.0 M, a large amount of salt may precipitate and the reaction may become difficult.

[0020] <Fluorine-containing zinc reagent> In the production method of the present invention, the prepared fluorine-containing zinc reagent is necessary for increasing the reaction rate and improving the reaction yield. The fluorine-containing zinc reagent is considered to be an active species in the cross-coupling reaction and contributes to the improvement of the yield. In the production method of the present invention, the fluorine-containing zinc reagent to be prepared is prepared by mixing a perfluoroalkylenediiodide compound (A) and a dialkylzinc (B).

[0021] In that the mixture of the perfluoroalkylenediiodide compound (A) and the dialkylzinc (B) is used as it is for the reaction, it is essentially different from that described in Non-Patent Document 3 (P.T. Kaplan et al., Organometallics, 2013, 32, 7552 - 7558).

[0022] That is, in Non-Patent Document 3, the Zn complex 7 is formed by the following formula (2).

Chemical formula

[0023] By adding a reactant to this Zn complex 7, as observed in the following formula (7), fluoroalkylated products 15 and 16 are obtained.

Chemical formula

[0024] In contrast, in the present invention, the Zn complex 7 obtained in Non-Patent Document 3 is not used. That is, as shown in the examples described later, a process is carried out in which a solvent having an amide bond such as 1,3-dimethyl-2-imidazolidinone, a dialkylzinc, a perfluoroalkylenediiodide compound (A), and a reactant (methyl 2-iodobenzoate etc. in the examples) are added to a reaction vessel, stirred, and then a copper(I) catalyst is added to cause a reaction. By adopting such a process, the target product can be produced simply and efficiently. Therefore, it is convenient and practical that the fluorine-containing zinc reagent of the present invention exhibits its characteristics based on the above process. In order to carry out the reaction more efficiently, it is preferable to mix 0.8 to 2.5 molar equivalents of dialkylzinc (B) with 1 mole of the perfluoroalkylene diiodide compound (A) in a solvent having an amide bond.

[0025] <Aromatic halogen compound (C)> In the production method of the present invention, an aromatic halogen compound (C) represented by the general formula (3): X-Ar is used. Here, in the general formula (3), X represents a bromine atom or an iodine atom.

[0026] In the general formula (3), Ar represents an aromatic ring selected from the group consisting of a benzene ring, a heteroatom-containing aromatic ring, and a polycyclic aromatic hydrocarbon. Examples of the benzene ring include a phenyl group. Examples of the heteroatom-containing aromatic ring include those containing one or more nitrogen atoms, sulfur atoms, or oxygen atoms on the aromatic ring. For example, a furyl group (furan ring), a pyrrolyl group (pyrrole ring), a thienyl group (thiophene ring), an imidazolyl group (imidazole ring), an oxazolyl group (oxazole ring), a thiazolyl group (thiazole ring), a pyridinyl group (pyridine ring), a pyrimidinyl group (pyrimidine ring), a pyrazinyl group (pyrazine ring), a pyridazinyl group (pyridazine ring), a quinolyl group (quinoline ring), an isoquinolinyl group (isoquinoline ring), an indolinyl group (indole ring), a benzothienyl group (benzothiophene ring), a benzofuryl group (benzofuran ring), a purinyl group (purine ring), a 1,10-phenanthrolinyl group (1,10-phenanthroline ring). Examples of the polycyclic aromatic hydrocarbon include, for example, a naphthyl group (naphthalene ring), an anthracenyl group (anthracene ring), a tetracenyl group (tetracene ring), a pentacenyl group (pentacene ring), a heptacenyl group (heptacene ring), a phenanthrenyl group (phenanthrene ring), a pyrenyl group (pyrene ring), a chrysenyl group (chrysene ring), a triphenylenyl group (triphenylene ring), a perylenyl group (perylene ring), a coronulenyl group (coronulene ring), a coronenyl group (coronene ring).

[0027] Ar may also have one or more substituents, and the substituents are selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms containing one or more fluorine atoms, an acyl group having 1 to 10 carbon atoms, an (alkoxy having 1 to 10 carbon atoms)carbonyl group, an alkoxy group having 1 to 10 carbon atoms, an acetal group having 3 to 10 carbon atoms, a formyl group, a nitro group, a cyano group, and an amino group.

[0028] <Copper(I) catalyst> In the production method of the present invention, the copper(I) catalyst can contribute to improving the yield as a catalyst for the cross-coupling reaction. In the production method of the present invention, as the copper(I) catalyst, any of a copper(I) salt, a combination of a copper(I) salt and a ligand, or a complex composed of a copper(I) ion and a ligand, or a combination thereof can be used.

[0029] Examples of the copper(I) salt that can be used include, but are not limited to, the following examples. For example, copper(I) acetate, copper(I) cyanide, copper(I) thiocyanate, copper(I) 2-thiophenecarboxylate, copper(I) trifluoromethanesulfonate benzene complex, tetrakis(acetonitrile)copper(I) hexafluorophosphate, tetrakis(acetonitrile)copper(I) tetrafluoroborate, tetrakis(acetonitrile)copper(I) trifluoromethanesulfonate, copper(I) fluoride, copper(I) chloride, copper(I) bromide, copper(I) iodide, etc. Among these, copper(I) chloride, copper(I) bromide, and copper(I) iodide are preferred from the viewpoints of economy and availability, and copper(I) iodide is particularly preferred because it is easy to handle.

[0030] Examples of ligands that can be used include, but are not limited to, 2,3-lutidine, 2,4-lutidine, 2,5-lutidine, 2,6-lutidine, 3,4-lutidine, 3,5-lutidine, 4-methyl-2-(p-tolyl)pyridine, 2-(2-pyridyl)indole, 2-(2-pyridyl)benzoxazole, 3-(2-pyridyl)-1,2,4-triazole, 2,5-diphenylpyridine, 3,5-di(2-pyridyl)pyrazole, 3,6-di(2-pyridyl)-1,2,4,5-tetrazole, 2,6-bis(2-benzimidazolyl)pyridine, 2,6-di(1-pyrazolyl)pyridine, 2,6-di(2H-1,2,3-triazol-4-yl)pyridine, methylbis(2-pyridylmethyl)amine, 2,4,6-tri(2-pyridyl)-1,3,5-triazine, 2,4,6-tri(4-pyridyl)-1,3,5-triazine, tris(2-pyridylmethyl)amine, N,N,N’,N’-tetrakis(2-pyridylmethyl)ethylenediamine and other pyridine ligands, 2,2’-bipyridyl, 2,2-di-4-picolyl, 6,6’-di-3-picolyl, 6,6’-di-2-picolyl, 2,2’-bipyridine-4,4’-dimethanol, 6,6’-dicyano-2,2’-bipyridyl, 5,5’-bis(trifluoromethyl)-2,2’-bipyridyl, 4,4’-bis(trifluoromethyl)-2,2’-bipyridyl, 4,4’-di-tert-butyl-2,2’-bipyridyl, 4,4’-dinonyl-2,2’-bipyridyl, 4,4’-dimethoxycarbonyl-2,2’-bipyridine, diethyl[2,2’-bipyridine]-4,4’-dicarboxylate, 6,6’-dimethoxycarbonyl-2,2’-bipyridine, 4,4’-dimethoxy-2,2’-bipyridyl, 4,4’-diamino-2,2’-bipyridyl, [2,2’-bipyridine]-4,4’-diylbis(phosphonic acid) tetraethyl, 1,2-bis(4’-methyl-2,2’-bipyridin-4-yl)ethane, 2,2’:6’,2’’-terpyridine, 2,6-bis(2-pyridyl)-4(1H)-pyridone, 4’-(p-tolyl)-2,2’:6’,2’’-terpyridine, 4’-(4-methoxyphenyl)-2,2’:6’,2’’-terpyridine, 1,4-di[[2,2’:6’,2’’-terpyridine]-4’-yl]benzene, 2,2'-Biquinoline, bipyridine ligands such as 2,2'-bipyrimidyl and terpyridine ligands, 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, 2,9-dibutyl-1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline, 1,10-phenanthroline-5,6-dione, 2,9-dichloro-1,10-phenanthroline, bathophenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 2,9-diphenyl-1,10-phenanthroline, 2,9-di(naphthalen-2-yl)-4,7-diphenyl-1,10-phenanthroline, phenanthroline ligands such as dipyrido[3,2-a:2',3'-c]phenazine, NHC ligands such as 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, 1,3-bis(2,6-di-3-pentylphenyl)imidazol-2-ylidene, 1,3-dimesitylimidazol-2-ylidene, 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene, triphenylphosphine, tri(o-tolyl)-phosphine, tri(m-tolyl)-phosphine, tri(p-tolyl)-phosphine, tri(2-furyl)phosphine, tri(2-thienyl)phosphine, tris(o-anisyl)phosphine, tris(p-anisyl)phosphine, tris(2,6-dimethoxyphenyl)phosphine, tris(4-fluorophenyl)phosphine, tris(pentafluorophenyl)phosphine, tris[3,5-bis(trifluoromethyl)phenyl]phosphine, cyclohexyldiphenylphosphine, dicyclohexylphenylphosphine, di-tert-butylphenylphosphine, tributylphosphine, trihexylphosphine, tri-n-octylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,5-bis(diphenylphosphino)pentane, 1,6-bis(diphenylphosphino)hexane, 1,Phosphine ligands such as 2-bis(diphenylphosphino)benzene, (±)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, 1,8-bis(diphenylphosphino)naphthalene, bis[2-(diphenylphosphino)phenyl]ether, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, 1,1'-bis(diphenylphosphino)ferrocene, 1,1'-bis(di-tert-butylphosphino)ferrocene, 1,1'-bis(dicyclohexylphosphino)ferrocene, 1,4-bis(di-tert-butylphosphino)butane, 1,4-bis(dicyclohexylphosphino)butane, Buchwald ligands such as JohnPhos, tBuXphos, tert-ButylBrettPhos, CyJohnPhos, Xphos, BrettPhos, RuPhos, SPhos, MePhos, DavePhos, PhDave-Phos, etc. Triphenylphosphine, 1,3-bis(diphenylphosphino)propane, 1,10-phenanthroline, 2,2'-bipyridyl are preferred because of their good availability and economy, and 2,2'-bipyridyl is more preferred in terms of better yield.

[0031] In the production method of the present invention, the copper(I) catalyst may be a pre-prepared or purchased one, or a freshly prepared one may be used directly.

[0032] In the production method of the present invention, the method for adding copper(I) to the reactor is not limited to the following examples, and examples include adding the copper(I) catalyst to the reaction vessel in advance and then carrying out the reaction, and gradually or sequentially adding the copper(I) catalyst during the reaction.

[0033] In the production method of the present invention, the amount of the copper(I) catalyst used is not particularly limited, but in terms of good reaction rate and yield, it is desirable to use 0.001 to 1.0 molar equivalents, more preferably 0.01 to 0.5 molar equivalents, and even more preferably 0.05 to 0.30 molar equivalents per 1 mole of the perfluoroalkylenediiodide compound (A). When the amount of the copper(I) salt is less than 0.001 molar equivalent, the reaction rate is slow and the yield may decrease due to the decomposition of the substrate. When the amount of the copper(I) salt is more than 1.0 molar equivalent, the post-treatment of the reaction may become complicated due to the precipitation of the salt.

[0034] <Reaction> The production method of the present invention can be carried out in an organic solvent, and is not particularly limited as long as the organic solvent does not inhibit the reaction. Specific examples of the organic solvent to be used include, for example, ether solvents such as tetrahydrofuran, diethyl ether, 2-methyltetrahydrofuran, cyclopentyl methyl ether, 1,4-dioxane, methyl tert-butyl ether, 1,2-dimethoxyethane; aliphatic hydrocarbon solvents such as hexane, pentane, cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene; nitrile solvents such as acetonitrile, propionitrile; sulfoxide solvents such as dimethyl sulfoxide, diethyl sulfoxide; solvents having an amide bond such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea; halogen solvents such as dichloromethane, chloroform, and two or more of the above may be mixed and used. Among these, tetrahydrofuran, diethyl ether, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea are preferable in terms of excellent stability of the fluorine-containing zinc reagent. Among them, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea are more preferable in terms of particularly excellent stability of the fluorine-containing zinc reagent. Among them, 1,3-dimethyl-2-imidazolidinone and N,N-dimethylformamide are preferable in terms of excellent yield.

[0035] In the production method of the present invention, the organic solvent used in the reaction may be the same as that used for preparing the fluorine-containing zinc reagent.

[0036] In the production method of the present invention, there is no particular limitation on the reaction temperature, but for example, it can be carried out at an appropriate temperature from 0°C to 200°C. From the viewpoint of good yield, 15°C to 150°C is preferable, 50°C to 120°C is more preferable, and particularly 70°C to 100°C is preferable. When the temperature is lower than 0°C, the reaction may take a long time. When the temperature is higher than 200°C, the yield may decrease due to decomposition of the fluorine-containing zinc reagent or progress of the homocoupling reaction.

[0037] In the production method of the present invention, there is no particular limitation on the reaction time, but from the viewpoint of good yield, 1 hour to 100 hours is preferable, and 2 hours to 80 hours is more preferable. When the reaction time is shorter than 1 hour, the yield may decrease due to the remaining raw materials. When the reaction time is longer than 100 hours, the yield may decrease due to decomposition of the product.

[0038] As a side reaction in the production method of the present invention, the side reactions that occur during the coupling reaction are not limited to the following examples, but for example, homocoupling products of organic zinc reagents, protonated products of organic zinc reagents, homocoupling products of halogenated aromatic compounds caused by transmetalation, compounds in which the alkyl group of dialkylzinc is coupled with a halogenated aromatic compound, compounds in which the alkyl group of dialkylzinc is coupled with a fluorine-containing zinc reagent, and the like.

[0039] The production method of the present invention can also continuously perform a step of reacting a perfluoroalkylenediiodide compound (A) with a dialkylzinc (B) and a step of reacting with a halogenated aromatic compound (C). Here, "continuously performing" means, for example, · adding a perfluoroalkylenediiodide compound (A), a dialkylzinc (B), and a halogenated aromatic compound (C) to the reaction system together for reaction, · following the step of "reacting a perfluoroalkylenediiodide compound (A) with a dialkylzinc (B)", adding a halogenated aromatic compound (C) to the reaction system and performing a reaction step. including

[0040] By continuously performing the reaction in this way, the next step can be carried out without taking measures such as isolation of the reaction product obtained in the step of "reacting the perfluoroalkylene diiodide compound (A) with dialkylzinc (B)", and the target product can be efficiently obtained as a whole reaction.

[0041] <Purification> In the production method of the present invention, the aromatic compound having a perfluoroalkylene group can be purified by various methods as necessary. There is no particular limitation on the method for purifying the aromatic compound having a perfluoroalkylene group, but examples include solvent extraction, filtration, column chromatography, preparative thin-layer chromatography, preparative liquid chromatography, recrystallization, reprecipitation, sublimation, distillation, and the like. Further, isolation can also be carried out as necessary by these methods.

Examples

[0042] The present invention will be specifically described below with reference to examples, but the present invention is not limited to only these examples.

[0043] In the analysis, the following equipment was used. Gas chromatograph-mass spectrometer (GC-MS): GCMS-QP2010PLus manufactured by Shimadzu Corporation 1 HNMR, 13 CNMR and 19 FNMR: JNM-ECZ-600R manufactured by JEOL Ltd.

[0044] [Reference Example 1] Preparation of copper catalyst 0.95 g (5.0 mmol) of copper(I) iodide, 0.78 g (5.0 mmol) of 2,2'-bipyridyl, and 150 mL of tetrahydrofuran were added to a 200 mL eggplant flask and stirred at room temperature for 1 hour. After concentration under reduced pressure, filtration and drying were carried out to obtain a copper catalyst (equivalent to 5.0 mmol).

[0045] [Example 1] Synthesis of Compound (3-1) [Chemical Formula]

[0046] After heating and drying a 100 mL eggplant flask with a cock and replacing it with argon, this process was repeated three times. In an argon atmosphere, 5.0 mL of 1,3-dimethyl-2-imidazolidinone (dehydrated grade) and 5.0 mL of diethylzinc in a hexane solution (concentration 1.08 M, 5.4 mmol) were mixed in a 100 mL eggplant flask with a cock. In an ice bath, 2.8 g (5.0 mmol) of I-(CF2CF2)3-I and 2.6 g (9.8 mmol) of methyl 2-iodobenzoate were added, and the mixture was stirred at 0 °C for 10 minutes. 0.17 g (0.5 mmol) of a copper(I) catalyst prepared by the same procedure as in Reference Example 1 was added, and the reaction was carried out at 80 °C for 16 hours. After quenching with 30 mL of 1 M hydrochloric acid, the mixture was filtered through celite with 100 mL of dichloromethane, washed with 60 mL of saturated brine, dried over sodium sulfate, and concentrated under reduced pressure to obtain Compound (3-1). Using 1,3,5-trimethoxybenzene as an internal standard substance, the reaction yield was determined by NMR to be 82%. The results are shown in Table 1.

[0047] The following shows the NMR results. 1 1H NMR (CDCl3, 600 MHz): δ = 7.62 - 7.56 (m, 8H), 3.88 (s, 6H). 13 13C NMR (CDCL3, 150 MHz): δ = -52.77 (s, 2C), -110.97 (s, 2C), -111.54 (s, 2C), -116.42 (s, 2C), -126.62 (s, 2C), -128.47 (s, 2C), -129.05 (s, 2C), -130.21 (s, 2C), -131.77 (s, 2C), -133.24 (s, 2C), -168.29 (s, 2C). 19 19F NMR (CDCl3, 564 MHz): δ = -106.0 (s, 4F), -120.2 (s, 4F), -122.6 (s, 4F).

[0048] [Examples 2 to 5] The reaction was carried out in the same manner as in Example 1 except that the reaction temperature and reaction time were changed. The results are shown in Table 1.

[0049] [Examples 6 to 8] The reaction was carried out in the same manner as in Example 1 except that the ligand of Reference Example 1 was changed from 2,2'-bipyridyl to 4,4'-di-tert-butyl-2,2'-bipyridyl and the molar equivalent of the copper catalyst was varied. The results are shown in Table 1.

[0050] [Examples 9 to 12] The reaction was carried out in the same manner as in Example 1 except that the ligand of Reference Example 1 was changed to another ligand, or copper(I) iodide was used as the copper catalyst as it was in the reaction, and the amount of diethylzinc in the hexane solution was 10 mL (10.8 mmol). The results are shown in Table 1.

[0051] [Example 13] The reaction was carried out in the same manner as in Example 1 except that the copper catalyst was not prepared in advance, a mixture of 190 mg (1.0 mmol) of copper(I) iodide and 180 mg (1.0 mmol) of 1,10-phenanthroline was added, and the amount of diethylzinc in the hexane solution was 10 mL (10.8 mmol). The results are shown in Table 1.

[0052] [Example 14] The reaction was carried out in the same manner as in Example 1 except that diethylzinc was a toluene solution of 10 mL (concentration 1.0 M) and copper(I) iodide was used as the copper catalyst. The results are shown in Table 1.

[0053] [Examples 15 to 16] The reaction was carried out in the same manner as in Example 1 except that 1,3-dimethyl-2-imidazolidinone was changed to N,N-dimethylformamide (DMF) or tetrahydrofuran (THF) and the heating temperature was changed. The results are shown in Table 1.

[0054] [Comparative Example 1] Add 3.18 g (50 mmol) of copper powder to a 100 mL eggplant flask with a cock, heat-dry the 100 mL eggplant flask with a cock, and perform argon replacement. The heat-drying and argon replacement were repeated 3 times. DMSO (dehydrated grade, 15 mL), 2.64 g (10.0 mmol) of methyl 2-iodobenzoate, and 2.8 g (5.0 mmol) of I-(CF2CF2)3-I were added and stirred at 110 °C for 22 hours. Filter with celite using 60 mL of dichloroethane, and filter with filter paper using 20 mL of dichloroethane. Remove DMSO with 60 mL of water, dry over sodium sulfate, and concentrate under reduced pressure to obtain compound (3-1). The results are shown in Table 1.

[0055] [Table 1] ZnEt2 [eq.]: Molar equivalent of diethylzinc to the perfluoroalkylenediiodide compound Phen: 1,10-phenanthroline Bpy: 2,2'-bipyridyl Bphen: Bathophenanthroline Di t-Bu bpy: 4,4'-di-tert-butyl-2,2'-bipyridyl

[0056] From Examples 1 to 16 and Comparative Example 1, it can be seen that aromatic compounds having a perfluoroalkylene group can be synthesized simply and efficiently as compared with the Ullmann coupling of the prior art (Comparative Example 1). From Examples 2 to 5, it can be seen that the reaction proceeds at 15 °C or higher and reacts sufficiently at 70 °C or higher, and the reaction time is sufficient by performing the reaction for 1 hour or more. From Examples 6 to 8, it can be seen that an equivalent amount of copper(I) catalyst reacts sufficiently at 0.02 molar equivalent or more with respect to the perfluoroalkylenediiodide compound. From Example 6 and Examples 9 to 12, it can be seen that the reaction proceeds even with copper(I) iodide without a ligand, and the reaction also proceeds when various ligands are used. From Example 13 and Example 14, it can be seen that the coupling reaction proceeds under various conditions. In Example 1, the yield was 82%, in Example 15, the yield was 88%, and in Example 16, the yield was 37%. It can be seen that the yield is improved by using a solvent having an amide bond in the reaction.

[0057] [Example 17] Synthesis of compound (3-2) [Chemical formula]

[0058] The reaction was carried out in the same manner as in Example 1 except that the halogenated aromatic compound was ethyl 4-iodobenzoate and the heating temperature was 90 °C. The reaction yield was 61%. The results are shown in Table 2.

[0059] The NMR results are shown below. 1 HNMR (CDCl3, 600 MHz): δ = 8.14 - 8.10 (m, 2H), 7.64 - 7.62 (m, 2H), 4.37 (m, 2H), 1.37 (t, J = 7.8 Hz, 3H). 19 FNMR (CDCl3, 564 MHz): δ = -112.1 (s, 2F), -122.2 (s, 2F), -122.8 (s, 2F).

[0060] [Example 18] Synthesis of compound (3-3) [Chemical formula]

[0061] The reaction was carried out in the same manner as in Example 1 except that the halogenated aromatic compound was 1-bromo-3-iodobenzene and the heating was carried out at 90 °C for 24 hours. The reaction yield was 57%. The results are shown in Table 2.

[0062] The NMR results are shown below. 11H NMR (CDCl3, 600 MHz): δ = 7.72 (s, 2H), 7.70 (d, J = 8.4 Hz, 2H), 7.51 (d, J = 7.8 Hz, 2H), 7.37 (t, J = 7.92 Hz, 2H). 19 19F NMR (CDCl3, 564 MHz): δ = -111.7 (s, 2F), -122.4 (s, 2F), -123.0 (s, 2F).

[0063] [Example 19] Synthesis of Compound (3-4) [Chemical formula]

[0064] The reaction was carried out in the same manner as in Example 1, except that the halogenated aromatic compound was ethyl 3-iodobenzoate and the heating was carried out at 90 °C for 24 hours. The reaction yield was 72%. The results are shown in Table 2.

[0065] The following are the NMR results. 1 1H NMR (acetone-d6, 600 MHz): δ = 8.23 (d, 4H), 7.60 (d, 2H), 7.57 (t, 2H), 4.39 (t, J = 7.8 Hz, 4H), 1.39 (t, J = 7.8 Hz, 6H). 19 19F NMR (acetone-d6, 564 MHz): δ = -111.7 (s, 4F), -122.2 (s, 4F), -122.6 (s, 4F).

[0066] [Example 20] Synthesis of Compound (3-5) [Chemical formula]

[0067] The reaction was carried out in the same manner as in Example 1, except that the halogenated aromatic compound was 1-chloro-3-iodobenzene and the heating was carried out at 120 °C. The reaction yield was 53%. The results are shown in Table 2.

[0068] The NMR results are shown below. 1 HNMR(acetone-d6, 600 MHz): δ = 7.56 (s, 2H), 7.52 (d, 2H, J = 8.2 Hz), 7.46 (m, 4H). 19 FNMR(acetone-d6, 564 MHz): δ = -111.8 (s, 4F), -122.3 (s, 4F), -122.7 (s, 4F).

[0069] [Example 21] Synthesis of Compound (3-6)

Chemical Structure

[0070] The reaction was carried out in the same manner as in Example 1, except that the halogenated aromatic compound was 4-iodobenzaldehyde and the heating was carried out at 120 °C. The reaction yield was 62%. The results are shown in Table 2.

[0071] The NMR results are shown below. 1 HNMR(acetone-d6, 600 MHz): δ = 10.01 (s, 2H) 8.00 (d, 4H, J = 8.3 Hz) 7.77 (d, 4H, J = 8.3 Hz) 19 FNMR(acetone-d6, 564 MHz): δ = -112.2 (s, 4F), -122.2 (s, 4F), -122.7 (s, 4F).

[0072] [Example 22] Synthesis of Compound (3-7)

Chemical Structure

[0073] The reaction was carried out in the same manner as in Example 1, except that the halogenated aromatic compound was 4-iodotoluene and the heating was carried out at 120 °C. The reaction yield was 65%. The results are shown in Table 2.

[0074] The NMR results are shown below. 1 HNMR (acetone-d6, 600 MHz): δ = 7.43 (d, 4H, J = 8.3 Hz), 7.27 (d, 4H, J = 7.6 Hz), 2.39 (s, 6H). 19 FNMR (acetone-d6, 564 MHz): δ = -111.3 (s, 4F), -122.3 (s, 4F), -123.0 (s, 4F).

[0075] [Example 23] Synthesis of Compound (3-8) [Chemical Structure]

[0076] The reaction was carried out in the same manner as in Example 1, except that the halogenated aromatic compound was 1-iodo-3,5-bis(trifluoromethyl)benzene and the heating was performed at 120 °C. The reaction yield was 44%. The results are shown in Table 2.

[0077] The following shows the NMR results. 1 HNMR (acetone-d6, 600 MHz): δ = 8.10 (s, 2H), 8.03 (s, 4H). 13 CNMR (CDCL3, 150 MHz): δ = -52.77 (s, 2C), -110.97 (s, 2C), -111.54 (s, 2C), -116.42 (s, 2C), -126.62 (s, 2C), -128.47 (s, 2C), -129.05 (s, 2C), -130.21 (s, 2C), -131.77 (s, 2C), -133.24 (s, 2C), -168.29 (s, 2C). 19 FNMR (acetone-d6, 564 MHz): δ = -64.0 (s, 12F), -112.0 (s, 4F), -122.2 (s, 8F).

[0078] [Table 2]

[0079] From Example 1 and Examples 17 to 23, it can be seen that aromatic compounds having various perfluoroalkylene groups can be synthesized simply and efficiently.

Industrial Applicability

[0080] The aromatic compound having a perfluoroalkylene group obtained by the present invention is expected to be used as a production intermediate for functional materials such as a crosslinking agent for fluororubber and an electrolyte membrane for fuel cells.

Claims

1. General formula (1): I-(CF ２ CF ２ ) ｎ -I A perfluoroalkylene diiodide compound (A) represented by (in general formula (1), n represents an integer of 1 to 4), and General formula (2): ZnR １ R ２ (In general formula (2), R １ and R ２ each independently represents an alkyl group having 1 to 4 carbon atoms.) and dialkylzinc (B) represented by General formula (3): X - Ar (In general formula (3), X represents a bromine atom or an iodine atom, Ar represents an aromatic ring selected from the group consisting of a benzene ring, a heteroatom-containing aromatic ring, and a polycyclic aromatic hydrocarbon. Here, Ar may have one or more substituents, and the substituents are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms containing one or more fluorine atoms, an acyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an acetal group having 3 to 10 carbon atoms, a formyl group, a nitro group, a cyano group, and an amino group. A substituent selected from the group consisting of substituents is shown.). Reacting a halogenated aromatic compound (C) represented by with a copper (I) catalyst in the presence of a copper (I) catalyst, characterized in that General formula (4): Ar-(CF ２ CF ２ ) ｎ -Ar A method for producing an aromatic compound having a perfluoroalkylene group represented by (in general formula (4), n represents an integer of 1 to 4, and Ar represents the same as in general formula (3)).

2. The production method according to claim 1, wherein the step of reacting the perfluoroalkylene diiodide compound (A) with dialkylzinc (B) and the step of reacting with the halogenated aromatic compound (C) are continuously performed.

3. n in the general formula (1) is 2 or 3, and R in the general formula (2) １ and R ２ The method according to claim 1 or claim 2, wherein is an ethyl group.

4. A fluorine-containing zinc reagent obtained by mixing a perfluoroalkylene diiodide compound (A) represented by general formula (1) and dialkylzinc (B) represented by general formula (2) in a solvent having an amide bond.

5. A fluorine-containing zinc reagent obtained by mixing 0.8 to 2.5 molar equivalents of dialkylzinc (B) represented by general formula (2) with respect to 1 mol of the perfluoroalkylene diiodide compound (A) represented by general formula (1) in a solvent having an amide bond.

6. An aromatic compound having a perfluoroalkylene group represented by the following formula (a) or (b). 【Chemical 13】 【Chemical Formula 14】

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