TW201223930A - Method for producing biaryl compound - Google Patents

Abstract

Disclosed is a method for producing a biaryl compound represented by formula (2) shown below, which comprises a step wherein a compound represented by formula (1) shown below is coupled in the presence of an amine compound that has at least two tertiary amino groups in each molecule, copper metal and a copper salt. Ar-Cl (1) (In formula (1), Ar represents an aromatic group that may have a substituent.) Ar-Ar (2) (In formula (2), Ar is as defined above.)

Description

201223930 VI. Description of the Invention: [Technical Field to Which the Invention Is Ascribed] The present invention relates to a method for producing a biaryl compound. [Prior Art] A biaryl compound, particularly a biaryl compound having an electron withdrawing group such as a sulfo group, is a useful compound as a pharmaceutical, a pesticide, a liquid crystal material, an organic electroluminescent material, and a synthetic intermediate thereof. JP-A-2000-161493 discloses a reaction mixture obtained by reacting 2,2'-benzenedisulfonic acid with sodium nitrite, for example, and mixed with hydrochloric acid containing copper chloride in sodium hydroxide. And the method of producing disodium 4,4,-dichloro-2,2'-biphenyldisulfonate. [Invention] The present invention provides the following: <1> One is represented by the formula (2) Method for producing biaryl compound

Ar-Ar (2) (wherein Ar represents an aromatic group which may have a substituent), and the method comprises the presence of an amine compound having at least two tertiary amino groups in the molecule, metallic copper and a copper salt The step of coupling the compound represented by the formula (1): Ο)

The method of the present invention, wherein the nitrogen atom constituting the tertiary amino group contained in the amine compound is the same as the above, wherein the Ar is the same as the above-mentioned. The carbon atom-bonded nitrogen atom; wherein the amine compound having at least two tertiary amino groups in the molecule is a 2, 2'-linked group which may have a substituent; A pyridine compound or a 1,10 phenanthroline compound which may have a substituent, wherein the copper salt is produced by self-displaying 10, according to any one of <1> to <3>. The salt of the sulphate base and the copper cation formed by the removal of hydrogen ions by the cleavage constant (pKa) of the following acid dissociation constant (pKa); &lt;5 &gt;&lt;5&gt; The special acid is hydrogen halide, sulfuric acid, thiocyanate, phosphoric acid, carbonic acid, nitric acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, acetic acid, trifluoroacetic acid, pentafluoropropionic acid, acetylacetone, phenol. And at least one selected from the group consisting of pentafluorophenol and thiophenol » &lt;6&gt; as in any of &lt;1&gt;~&lt;5&gt; The manufacturing method of the invention, wherein the copper salt is copper halide, copper sulfate, copper thiocyanate, copper phosphate, copper carbonate, copper nitrate, copper methanesulfonate, copper (I)-benzene complex of trifluoromethanesulfonate, Copper (I)-toluene complex of trifluoromethanesulfonate, copper (11) trifluoromethanesulfonate, copper benzenesulfonate, copper acetate, copper trifluoroacetate, copper pentafluoropropionate, copper acetylacetonate (Π), at least one selected from the group consisting of copper phenolate, copper pentoxide, and copper thiophenolate: <7> The method according to any one of <1> to <5> The method for producing a salt according to any one of the above-mentioned items, wherein the salt is used in an amount relative to the amine compound 1 〇·01 Mo The manufacturing method according to any one of <1>, wherein the amine compound is composed of 2,2'-bipyridine, i, i〇-phenoline, and the method of any one of &lt;1&gt;丨'4,7-trimethyl, 4 5 *7, triazacyclononane, &gt;1 less, ;^,:^,-tetramethylethylenediamine and &gt;^,&gt;1, , 1 ^, _ tetraethyl ethylene diamine group selected to The production method according to any one of <1> to <9>, wherein the amine compound is used in an amount of 0.0001 mol to 0.5 based on the aryl chloride compound 1 molar. The manufacturing method according to any one of <1>, wherein Ar is an aromatic group having at least one electron-withdrawing group; &lt;12&gt; The production method according to any one of the above-mentioned, wherein the compound represented by the formula (1) is a compound represented by the formula (3):

(wherein R1, R2 and R3 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a group selected from the following G group, and may have a carbon selected from the following group G) An alkoxy group having 1 to 20 alkoxy groups, an aryl group having 6 to 20 carbon atoms which may be selected from the group G, and an aryloxy group having 6 to 20 carbon atoms which may have a group selected from the group G below And an aralkyl group having 7 to 20 carbon atoms selected from the group consisting of the following G group, an aralkyloxy group having 7 to 20 carbon atoms which may have a group selected from the group G below, or having The amine group of the hydrocarbon group having a carbon number of 1 to 20 201223930 selected from the group G below, and R4 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a group selected from the group G below, and may have The alkoxy group having 1 to 20 carbon atoms selected from the group G, and the aryl group having 6 to 20 carbon atoms which may be selected from the group G, may have a group selected from the group G below. An aryloxy group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms which may be selected from the group G, and a carbon number 7 which may have a substituent selected from the group G below. 20 aralkoxy, or having the following G group The amine group of the hydrocarbon group having 1 to 20 carbon atoms, and R1 and R2, R2 and R3, or R3 and R4 respectively bonded to adjacent carbon atoms may be formed together with the carbon atoms respectively bonded thereto. Ring, E represents a pull electron group, [G group] fluorine atom; cyano group: alkoxy group having 1 to 12 carbon atoms; aryl group having 6 to 12 carbon atoms; and aryloxy group having 6 to 12 carbon atoms, The biaryl compound represented by the formula (2) is a biaryl compound represented by the formula (4): R2 R1 R1 R2

Veer4 (wherein, R1, R2, R3, R4 and E respectively represent the same meaning as described above) f &lt;U&gt; The manufacturing method as described in <11> or <12>, wherein the electron-withdrawing group is (5) Representation base: 201223930 ——S——(Γ Υ (5)

C (wherein Υ represents a hydrogen ion, an alkali metal ion, and an ion represented by the formula (6): Υ2 Υ1—I—Υ3 (6)

I Υ 4 (wherein Υ 1, Υ 2, Υ 3 and Υ 4 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms), may have a carbon number of 20 selected from the group G below, or may have a aryl group having a carbon number of 6 to 20 selected from the group G below [G group] fluorine atom; a cyano group; an alkoxy group having 1 to 12 carbon atoms; an aryl group having 6 to 12 carbon atoms; A method of producing a compound represented by the formula (1), wherein the compound represented by the formula (1) is represented by the formula (10), wherein the compound of the formula (1) is represented by the formula (10). Compound: (R,0)k

(Γ Y (where Y represents hydrogen ion, alkali metal ion, ammonium represented by formula (6) -9- 201223930 Υ2 Y1—Ν—Υ3 (6) Υ4 (where '1' Υ2, Υ3 and Υ4 Each of the carbon atoms having 1 to 10 carbon atoms independently representing a hydrogen atom or a group having a carbon number of 1 to 10, which may be selected from the group G below, or having a carbon number of 6 selected from the group G below The aryl group of ～20, R1G each independently represents a fluorine atom, may have an alkyl group having 1 to 20 carbon atoms selected from the group of the following G group, and may have a carbon number of 1 to 20 selected from the group of the following G group. The alkoxy group may have an aryl group having 6 to 20 carbon atoms which may be selected from the group G, and an aryloxy group having 6 to 20 carbon atoms which may have a group selected from the group G below, and may have The group selected from the group G below has a carbon number of 2 to 20 or a cyano group, and k represents an integer of 0 to 3, and in addition, two carbon atoms bonded to adjacent carbon atoms may be bonded and bonded thereto. The carbon atoms of the junction form a ring together, [G group] fluorine atom; cyano group; alkoxy group having 1 to 12 carbon atoms; aryl group having 6 to 12 carbon atoms; and aryloxy group having 1 to 12 carbon atoms) The biaryl compound represented by the formula (2) is a combination represented by the formula (Π) Aryl compounds:

0' Y

〇· Y (wherein RtG, Y and k represent the same meaning as described above); -10-201223930 &lt;15&gt; The manufacturing method as described in <13> or <14>, wherein γ is an alkali metal ion The manufacturing method according to <11> or <12>, wherein the electron withdrawing group is nitrate 3S. (-N02); &lt;17&gt; as &lt;1&gt;~&lt;1〇&gt; The production method according to any one of the preceding claims, wherein Ar is an aromatic heterocyclic group (however, the heterocyclic group may have a substituent), and &lt;18&gt; is produced as described in &lt;1&gt; The method wherein the hetero atom contained in the Ar is directly bonded to the carbon atom bonded to the carbon atom of Ar of C1 » &lt;19&gt; as in any of &lt;1&gt;~&lt;10&gt; The production method according to the above, wherein the compound represented by the formula (1) is a compound represented by the formula (7): R1La

(wherein R11 and R12 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a group selected from the following G group, and may have a carbon number of 1 selected from the following G group; ～20 alkoxy group, an aryl group having 6 to 20 carbon atoms which may be selected from the group G below, and an aryloxy group having 6 to 20 carbon atoms which may have a group selected from the group G below And an aralkyl group having 7 to 20 carbon atoms selected from the group consisting of the following G group, an aralkyloxy group having 7 to 20 carbon atoms which may have a group selected from the group G below, or having The amine group of the hydrocarbon group having 1 to 20 carbon atoms selected from the following 0 groups, and R14 represents a hydrogen atom, and may have a carbon number of the group selected from the group G below - 11 - 201223930 1 to 2 0 alkyl group, An alkoxy group having 1 to 20 carbon atoms selected from the group consisting of the following G groups, and an aryl group having 6 to 20 carbon atoms which may have a group selected from the following group G, may be selected from the following group G The aryloxy group having 6 to 20 carbon atoms, the aralkyl group having 7 to 20 carbon atoms which may be selected from the group G, and the carbon number which may have a group selected from the following group G 7 a aralkyloxy group of ~20 or a carbon which may have a group selected from the group G below The amine group of the hydrocarbon group of 1 to 20, and R11 and R12 respectively bonded to the adjacent carbon atom, or R12 and R14 may form a ring together with the carbon atom respectively bonded, and Α represents an oxygen atom or a sulfur atom, [ Group G] a fluorine atom; a cyano group; an alkoxy group having 1 to 12 carbon atoms; an aryl group having 6 to 12 carbon atoms; and an aryloxy group having 1 to 12 carbon atoms; a biaryl group represented by the formula (2) The compound is a biaryl compound represented by the formula (8):

(In the formula, A, R11, R12, and R14 respectively represent the same meaning as described above); and the manufacturing method according to any one of <1> to <19>, wherein the coupling step is The step is carried out in the presence of an aprotic polar solvent. [Embodiment] The biaryl compound represented by the formula (2) (hereinafter referred to as the production method of the compound (2), which comprises an amine compound containing at least two tertiary amino groups in the molecule, metallic copper and copper In the presence of a salt, a step of coupling a compound of the formula 223930 (hereinafter referred to simply as a compound (丨)) represented by the formula (1). The amount of the metal copper used is usually 〇5 mol to 20 mol with respect to the compound (丨" molar. The range of the ear is preferably in the range of 1 mole to 5 moles. When the amount of metal copper used is 0.5 mole or more, it is preferred because of the tendency to increase the yield of the obtained compound (2). When the amount used is 2 〇 mol% or less, the treatment operation tends to be simple after recovering the compound (2) from the reaction system. The shape of the metal copper is exemplified by powder, linear, or foil. The cutting shape and the particle shape are preferably in the form of powder in terms of the operation of the metal copper. The metal copper can be easily obtained from the market. The commercially available metallic copper can also be a part of its surface due to the environment. Oxidation to oxygen oxide The copper metal containing a trace amount of copper oxide may be directly used in the coupling reaction of the compound (1), and may also be, for example, tetramethylammonium hydroxide, monoethanolamine, ethylenediaminetetraacetic acid, hydroxyethanedisulfonic acid, or the like. A cleaning agent such as tea phenol, gallic acid, oxalic acid, citric acid, hydroxylamine, 2-mercaptoethanol, thioglycerol or the like removes the trace amount of copper oxide and is used in the coupling reaction. It is composed of a copper cation and an anion, and may be a copper salt composed of a monovalent copper cation and an anion, or a copper salt composed of a divalent copper cation and an anion. The anion is preferably an acid dissociation constant of 10 or less. (pKa) of Bruce's acid to remove the hydrogen sulfide to form the Bronsted base. The acid dissociation constant (pKa) is 25 ° C, the number in the water, and can be revised by the chemical notes 5 ΙΙ-331~Π- 343 (edited by the Chemical Society of Japan, published by Jiushan Co., Ltd.). When the lincolnic acid is a polybasic acid, the acid dissociation constant (PKai) of the first stage is preferably 10 or less. -13- 201223930 Anion, better dissociation from acid a Brunsten base formed by removing hydrogen ions by a Bruce's acid having a constant (PKa) of 6 or less, preferably a Brunsten formed by removing the hydrogen ions from the Bronsted acid having an acid dissociation constant (pKa) of 3 or less. Further, as the anion, it is preferred that the Bronsted acid is formed by removing the hydrogen ion from the Bronsted acid having an acid dissociation constant (pKa) of -10 or more. Preferably, the Bronsted acid introduced into the anion is exemplified as hydrogen halide ( pKa: -4 to 2.7), sulfuric acid (pKa: 2 or less), thiocyanic acid (pKa: -0.9), phosphoric acid (pKa: 1.8), carbonic acid (pKa: 6.1), nitric acid (pKa: -1.8), methanesulfonate Acid (pKa: -1.2), trifluoromethanesulfonic acid, benzenesulfonic acid (pKa: -2.5), acetic acid (pKa: 4.7), trifluoroacetic acid (pKa: 0.2), pentafluoropropionic acid, acetylacetone ( pKa: 8.8), phenol (pKa: 9.9), pentafluorophenol and thiophene (pKa: 6 · 4) β The copper salt is exemplified by copper halide, copper sulfate, copper thiocyanate, copper phosphate, copper carbonate, copper nitrate, Copper methane sulfonate, copper p-toluenesulfonate, copper (I)-benzene complex of trifluoromethanesulfonate, copper (I)-toluene complex of trifluoromethanesulfonate, trifluoromethanesulfonic acid (II), benzenesulfonic acid, copper acetate, copper trifluoroacetate acetate, copper pentafluoropropionate, copper acetyl pyruvate ([pi), acid copper, acid copper and sulfur pentafluoro acid copper. Copper halides are exemplified by copper fluoride, copper chloride, copper bromide and copper iodide. The copper salt may also be used in combination of two or more selected from the above. The copper salt may also be a hydrate, but is preferably an anhydride. The copper salt may be used as it is, or may be prepared by mixing a one- or two-valent copper compound with an acid. It is preferred to use copper oxide or copper hydroxide as the monovalent or divalent copper compound. As the acid, the aforementioned nucleus acid is preferably used. -14- 201223930 Among them, copper halide, copper sulfate, copper thiocyanate, copper nitrate, copper difluoromethanesulfonate (1)-benzene complex, copper trifluoromethanesulfonate (1)_toluene is preferred. π, copper difluoromethanesulfonate (Π) 'copper acetylacetonate copper (1) and copper thiophenolate, more preferably copper halide, copper sulfate, copper nitrate, copper trifluoromethanesulfonate (1) - The complex compound, copper difluoromethanesulfonate (π) and copper (H) yttrium copper acetylate are used in an amount of from 1 mol to 10 mol per mol of the amine compound. The range is preferably in the range of 0 02 moles to 1 mole, more preferably 1/3 mole to 丨/30 moles. The lower limit of the amount of copper salt used is relative to the compound (1) 1 mole , usually 〇.〇〇〇〇1 molar, preferably 0 000 1 mole, more preferably () 〇〇 1 mole. The upper limit of the amount of copper salt used relative to the compound 〇) 1 mole usually 〇.5莫耳' is preferably 0.3 mol, more preferably 〇1 mol. That is, the amount of copper salt used is relative to the compound (1) 00 m. / ❶, usually 〇〇〇1 Mole%~50% of the range of 'better' 1 mole %~5〇% of the range of moles, more preferably 0.1% by mole to 50% by mole. The yield of the compound (2) which is the target and the copper salt removal after the completion of the reaction, etc. From the viewpoint of workability, it is preferably in the range of 0.1 mol% to 3 mol%, more preferably in the range of 〇5 mol% to 10 mol%. The so-called molecular contains at least two tertiary amines. The tertiary amine group of the amine compound means a substituent formed by a nitrogen atom bonded to three carbon atoms, and the nitrogen atom constituting the tertiary amino group contained in the amine compound means a bond with three carbon atoms a nitrogen atom of the junction. The carbon atom may also be aromatic, and a tertiary amino group having a nitrogen atom -15-201223930 bonded to an aromatic carbon atom as a constituent atom may be contained in at least two molecules. The amine compound is exemplified by a 2,2'-bipyridine compound which may have a substituent, and a 1,1 fluorene phenanthroline compound which may have a substituent. The two tertiary amine groups contained in the amine compound are preferably permeated. Two carbon atoms are bonded. As for the amine compound 'is listed as 2,2,-bipyridine, 1,1 〇 -Porphyrin, 1,4,7-dimethyl-i,4,7-triazaindole, ν,Ν,Ν'Ν'-tetramethylethylenediamine and N,N,N', N'-tetraethylethylenediamine. The amount of the amine compound used relative to the copper salt is usually in the range of 〇1 mol to 1 〇〇mol, preferably 1 mol to 5 〇. The range is more preferably in the range of 3 moles to 30 moles. When the amount of the amine compound is 1 mole or more with respect to the copper salt, there is a tendency to increase the yield of the compound (2). When the temperature is below 10 moles, the reaction rate tends to increase. Therefore, the upper limit of the amount of the amine compound used is usually 50 moles per mole of the compound (丨). The amination is preferably 20 moles, more preferably 5 moles, most

1 range of moir. It is preferably 0.5 0.0 0 0 1 m. That is, the amination is 1 mole, usually 0.0000 丨 Mo 1 mole to 20 moles, more preferably 0.0001 moles to 〇 5 moles

Compound (1) 1 Mo is used in an amount relative to the compound (1) 丨mol, [ear. That is, the amine compound is preferably in the range of 0.001 mol to 2 〇 mol −16-201223930, preferably 0·(Η莫耳~5 mol range. The compound (1) has a better coupling reaction. It is carried out in the presence of a solvent. The solvent is exemplified by dimethyl hydrazine, hydrazine-methyl-2-pyrrolidone, hydrazine, hydrazine _: methylformamide, hydrazine, hydrazine-dimethylacetamide, hexamethyl An amorphic polar solvent such as triammonium phosphate, an aliphatic hydrocarbon solvent such as hexane, heptane or octane, an aromatic hydrocarbon solvent such as toluene or xylene, tetrahydrofuran, i.4-dioxane or diethylene glycol. An ether solvent such as dimethyl ether or an ester solvent such as ethyl acetate, butyl acetate, dimethyl carbonate or diethyl carbonate. The solvent may be used singly or in combination of two or more. - an aprotic polar solvent such as methyl-2-pyrrolidone, toluene, diethylene glycol dimethyl ether, and ethyl acetate. The solvent is used in an amount of usually 0.5 part by weight to 20 parts by weight based on 1 part by weight of the compound (1). The range of parts by weight is preferably from 1 part by weight to 10 parts by weight. The coupling reaction of the compound (1) is preferably in the form of nitrogen. The reaction temperature of the coupling reaction may be appropriately adjusted according to the kind of the compound (1), the amount thereof, the amount of the metal copper used, the amount of the copper halide used, etc., but usually The range of 0 ° C to 3 00 ° c, preferably in the range of 50 ° C to 2 50 ° C, more preferably in the range of 100 ° C to 200 ° C, preferably in the range of 140 ° C to 180 ° C When the reaction temperature is 〇 ° C or more, the production rate of the compound (2) is increased, and the reaction time is shortened. Therefore, when the reaction temperature is 300 ° C or lower, the decomposition of the compound (2) is inhibited. The tendency of the side reaction to occur is preferred. The reaction time of the coupling reaction can be usually adjusted to a range of from 1 hour to 48 hours. Alternatively, a part of the reaction mixture can be sampled at a specific time, -17-201223930 using, for example, a liquid layer Analytical methods such as analysis and gas chromatography analysis are used to analyze the sample sample, calculate the degree of disappearance of the compound (1), or the degree of formation of the biaryl compound (2), and adjust the reaction time. The production method according to the present invention ,be usable The compound (1) which is easy to be used as a starting material produces the corresponding biaryl compound (2). Further, the compound (1) tends to have a low reactivity in the coupling reaction, but according to the production method of the present invention, Even if the compound (1) having low reactivity is used as a starting material, the corresponding biaryl compound (2) can be produced. In the production method of the present invention, two or more compounds (1) may be used in combination. When the two compounds (1) of Ari-Cl and Ar2-Cl are used, three kinds of biaryl compounds (2) of AJ-Ai·1, Ai^-Ar2 and Ar2-Ar2 can be obtained. Preferably, in the production method of the present invention A compound (1) of one kind is used. Ar of the compound (1) is an aromatic group which may have a substituent. The "aromatic group which may have a substituent" means a group formed by removing a hydrogen atom bonded to an aromatic ring of an aromatic compound which may have a substituent. Aromatic compounds having no substituents, exemplified by benzene, naphthalene, anthracene, anthracene, biphenyl, anthracene, 9,9'-bifluorene phenanthrene, anthracene, benzophenanthrene, naphthacene, pentacene, and three butterflies A compound obtained by obtaining an aromatic cyclic hydrocarbon group such as pyridine, furan, thiophene, benzothiadiazole, pyrrole, porphyrin, porphyrin, pyrimidine, pyrazine or the like to obtain an aromatic heterocyclic group. Compound, and ferrocene. The aromatic group having no substituent is phenyl, naphthyl, anthracenyl, fluorenyl, phenylphenyl, anthracenyl, 9,9'-bifluorenyl, phenanthryl, anthryl, benzophenanyl, naphthalene An aromatic cyclic hydrocarbon group such as naphthacenyl group, pentaphenyl or triptyl, pyridyl, furyl, thienyl, benzo-18-201223930 thiadiazolyl, pyrrolyl, saliva An aromatic heterocyclic group such as a phenyl group, a quinoline ring group, a pyrimidinyl group or a pyrazinyl group, and a ferrocenyl group. The substituent which may have an aromatic group is exemplified as a pull electron group, and may have the following The alkyl group having a carbon number of 1 to 20 selected from the group G, an alkoxy group having 1 to 20 carbon atoms which may be selected from the group G, and a carbon group which may have a group selected from the following group G An aryl group having 6 to 20 aryl groups, an aryloxy group having 6 to 20 carbon atoms which may be selected from the group G, and an aralkyl group having 7 to 20 carbon atoms which may have a group selected from the group G below The group may have an aralkoxy group having 7 to 20 carbon atoms and a group having a hydrocarbon group having 1 to 20 carbon atoms which may have a group selected from the group G below. [G group] fluorine atom; cyano group; alkoxy group having 1 to 12 carbon atoms; aryl group having 6 to 12 carbon atoms; and aryloxy group having 6 to 12 carbon atoms. The "alkyl group having 1 to 20 carbon atoms" in the alkyl group having 1 to 20 carbon atoms which may be selected from the group G is exemplified by methyl group, ethyl group, propyl group, isopropyl group, butyl group or the like. Butyl, t-butyl, tert-butyl, pentyl, 2,2-dimethylpropyl, cyclopentyl, hexyl, cyclohexyl, heptyl, 2-methylpentyl, octyl, 2- Ethylhexyl, decyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, A linear, branched or cyclic alkyl group such as a nonadecyl group or an eicosyl group. The alkyl group which may have a substituent selected from the above-mentioned group G is a group in which one or more hydrogen atoms of the alkyl group are substituted with a group selected from the group G, and when the alkyl group has a substituent, The total number of carbon atoms of the substituent and the number of carbon atoms of the alkyl group is 1 to 20. Among these, an alkyl group having no substituent -19-201223930, and more preferably an alkyl group having no substituent. The "alkoxy group having 1 to 20 carbon atoms" in the alkoxy group having 1 to 20 carbon atoms which may be selected from the above-mentioned group G is exemplified by methoxy group, ethoxy group, propoxy group, and isopropoxy group. , butoxy, isobutoxy, second butoxy, tert-butoxy, pentyloxy, 2,2-dimethylpropoxy, cyclopentyloxy, hexyloxy, cyclohexyloxy , heptyloxy, 2-methylpentyloxy, octyloxy, 2-ethylhexyloxy, decyloxy, decyloxy, undecyloxy, dodecyloxy, tridecaneoxy Linear, branched, etc., tetradecyloxy, pentadecyloxy, hexadecanyloxy, heptadecyloxy, octadecyloxy, nonadecanyloxy, eicosyloxy Or a cyclic alkoxy group having 1 to 20 carbon atoms. The alkoxy group which may have a substituent selected from the above-mentioned group G is a group in which one or more hydrogen atoms of the alkoxy group are substituted with a group selected from the group G, and the alkoxy group has a substituent. The total number of carbon atoms of the substituent and the number of carbon atoms of the alkoxy group is 1 to 2 0. Among these, an alkoxy group which does not have a substituent is more preferably an alkoxy group having 1 to 10 carbon atoms which does not have a substituent. The "aryl group having 6 to 20 carbon atoms" in the aryl group having 6 to 20 carbon atoms which may be selected from the above-mentioned group G is exemplified by a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, 2,3-xylyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2.6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,3, 4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 3,4,5- Trimethylphenyl, 2,3,4,5-tetramethylphenyl, 2.3.4.6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl, Ethylphenyl, propylphenyl, isopropylphenyl, butylphenyl, t-butylphenyl, tert-butylphenyl, pentylphenyl, neopentylphenyl, hexylphenyl- 20-201223930, octylphenyl, nonylphenyl, dodecylphenyl, tetradecylphenyl, naphthyl and anthracenyl. The aryl group which may have a substituent selected from the above-mentioned G group means that one or more hydrogen atoms of the above aryl group are substituted with a group selected from the above G group, and when the aryl group has a substituent, the substituent The total number of carbon atoms and the number of carbon atoms of the aryl group is 6 to 20. Among these, an aryl group having no substituent is preferred, and an aryl group having 6 to 10 carbon atoms which does not have a substituent is preferred, and a phenyl group is preferred. The aryloxy group having 6 to 20 carbon atoms which may have a substituent selected from the above-mentioned G group may be a phenoxy group, a butylphenoxy group, a 2-naphthyloxy group, a 2-decyloxy group or the like. The base is composed of oxygen atoms. The "aralkyl group having 7 to 20 carbon atoms" which may have a group selected from the above-mentioned group G is exemplified by a benzyl group, a (2-methylphenyl)methyl group or a (3-methylphenyl)methyl group ( 4-methylphenyl)methyl, (2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl, (2,5-dimethylphenyl)methyl , (2,6-dimethylphenyl)methyl, (3,4-dimethylphenyl)methyl, (4,6-dimethylphenyl)methyl, (2,3,4 -trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, (3,4,5-tri Methylphenyl)methyl, (2,4,6-trimethylphenylhydrazine) methyl, (2,3,4,5-tetramethylphenyl)methyl, (2,3,4,6 -tetramethylphenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl, (pentamethylphenyl)methyl, (ethylphenyl)methyl, (propyl Phenyl)methyl, (isopropylphenyl)methyl, (butylphenyl)methyl, (t-butylphenyl)methyl, (t-butylphenyl)methyl, (pentyl) Phenyl)methyl, (neopentylphenyl)methyl, (hexylphenyl)methyl, (octylphenyl)methyl, ( Yl) methyl, (decyl) methyl group, naphthylmethyl group and anthracenyl group. The aralkyl group which may have a group selected from the above-mentioned group G - 21,923,930 as a substituent means that one or more hydrogen atoms of the above aralkyl group are substituted with a group selected from the aforementioned group G, and the aralkyl group has a substituent. In the case of a group, the total number of carbon atoms of the substituent and the number of carbon atoms of the aralkyl group is 7 to 20. Among these, an aralkyl group having no substituent is preferred, and an aralkyl group having 7 to 10 carbon atoms which does not have a substituent is preferred, and a benzyl group is preferred. The "aralkyloxy group having 7 to 20 carbon atoms" which may have an aralkoxy group having 7 to 20 carbon atoms selected from the above-mentioned group G is exemplified by a benzyloxy group or a (2-methylphenyl) group. Oxyl, (3-methylphenyl)methoxy, (4-methylphenyl)methoxy, (2,3-dimethylphenyl)methoxy, (2,4-dimethyl Phenyl)methoxy, (2,5-dimethylphenyl)methoxy, (2,6-dimethylphenyl)methoxy, (3,4-dimethylphenyl)methoxy , (3,5-dimethylphenyl)methoxy, (2,3,4-trimethylphenyl)methoxy, (2,3,5-trimethylphenyl)methoxy , (2,3,6-trimethylphenyl)methoxy, (2,4,5-trimethylphenyl)methoxy, (2,4,6-trimethylphenyl)methoxy , (3,4,5-trimethylphenyl)methoxy, (2,3,4,5-tetramethylphenyl)methoxy, (2,3,4,6-tetramethyl Phenyl) methoxy, (2,3,5,6-tetramethylphenyl)methoxy, (pentamethylphenyl)methoxy, (ethylphenyl)methoxy, (C Phenyl) methoxy, (isopropylphenyl)methoxy, (butylphenyl) methoxy, (second butylphenyl) methoxy (t-butylphenyl)methoxy, (hexylphenyl)methoxy, (octylphenyl)methoxy, (nonylphenyl)methoxy, naphthylmethoxy, fluorenyl The oxy group or the like is composed of the aforementioned aralkyl group and an oxygen atom. The amine group substituted with a hydrocarbon group having 1 to 20 carbon atoms which may have a group selected from the above G group is exemplified by dimethylamino group, diethylamino group, dipropylamino group and diisopropylamino group. , Dibutylamino, di-tert-butylamino, di--22- 201223930 tributylamino, diisobutylamino, tert-butylisopropylamino, dihexylamino, two An octylamino group, a dinonylamino group and a diphenylamino group are preferred, and among these, a dimethylamino group and a diethylamino group are preferred. When Ar of the compound (1) has an electron withdrawing group, the carbon atom to which the electron withdrawing group is bonded is directly bonded to the carbon atom to which the chlorine atom is bonded (that is, the electron withdrawing group is adjacent to the chlorine atom). In this case, the reactivity of the compound (1) in the coupling reaction tends to be remarkably improved, which is preferable. Therefore, the compound (1) is preferably a compound having an electron withdrawing group in the ortho position to the chlorine atom. The compound represented by the formula (1) in the ortho position of the chlorine atom has a tendency to undergo a coupling reaction under milder conditions, specifically, at a lower reaction temperature, to obtain a corresponding biaryl compound. The so-called "pull-on-base" in this manual is the basis for the definition of the substituents σ/値 defined in the basics of the chemical handbook revision 5 edition 11-3 79~11-3 80 (edited by the Chemical Society of Japan, issued by Jiushan Co., Ltd.). The electron-donating group is preferably a group having a substituent constant σ/値 in the range of 0.3 to 1, more preferably a group in the range of 〇.5 to 1, preferably in the range of 0.7 to 1. In terms of nitro (-Ν02), formazan (-CHO), carboxyl (-COOH), a group represented by formula (5), 0 I. —S—〇· Υ (5) Medium ' Υ denotes hydrogen ion, alkali metal ion, ammonium ion represented by formula (6), -23- 201223930 Υ2 u Υ1—Ν—Υ3 (6) Υ4 (wherein Υ1, Υ2, Υ3, and Υ4 are independent representations a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms), an alkyl group having 1 to 20 carbon atoms selected from the group of the G group, or a carbon number 6 to 2 0 which may be selected from the group G base),

-COOY (wherein Υ represents the same meaning as defined above), and a trifluoromethyl group, preferably a group represented by the formula (5) and a nitro group. The alkali metal ions are exemplified by lithium ions (Li + ), sodium ions (Na + ), potassium ions (K + ), and planing ions (Cs + ), preferably sodium ions. The hydrocarbon group having 1 to 10 carbon atoms of Y1, Y2, Y3 and Y4 is exemplified by a carbon number of 1 to 10 such as a methyl group, an ethyl group, a propyl group, a butyl group or an octyl group, and a carbon number of a phenyl group or the like 6~ 10 aryl. The ammonium ion represented by the formula (6) is exemplified by ammonium ion (NH4 + ), methylammonium ion (N(CH3)H3 + ), diethylammonium ion (N(C2H5)2H2 + ), dipropylammonium ion. (N(C3H7)2H2 + ) 'Tripropylammonium ion (n(c3h7)3h + ), tetrabutylammonium ion (n(c4h9)4+), diisopropyldiethylammonium ion (n(ch) (ch3)2)2(c2h5)2 + ), tetraoctylammonium ion (N(c8Hl7)4 + ), tetradecylammonium ion (N(c1QH21)4 + ) and triphenylammonium ion (N(c6H5) ) 3H+). As the compound (1), it is exemplified by 2-chloro-1·nitrobenzene, 2·chlorobenzene-1-sulfonic acid, lithium chlorobenzene-1-sulfonate, sodium 2-chlorobenzene-1-sulfonate, 2-Chlorobenzene-1-sulfonic acid-24- 201223930 Potassium, methyl 2-chlorobenzene-1-sulfonate, ethyl 2-chlorobenzene-1-sulfonate, 2-chlorobenzene-1-sulfonic acid propyl ester , 2-chlorobenzene-1-sulfonic acid isobutyl ester, 2-chlorobenzene-1-sulfonic acid (2,2-dimethylpropyl ester), 2-chlorobenzene-1-sulfonic acid cyclohexyl ester, 2- Chlorobenzene-1-carboxylic acid, methyl 2-chlorobenzene-1-carboxylate, ethyl 2-chlorobenzene-1-carboxylate, 2-chloro-1-methylnonylbenzene, 2-chloro-1-B Nonylbenzene, 2-chloro-p-benzoylbenzene, 2,5-dichloro-1-benzhydrylbenzene, 2-chloro-1-trifluoromethylbenzene, 2-chloro-1-benzoic acid , 2-chloro-1-benzoic acid methyl ester, 2-chloro-1-benzoic acid ethyl ester, 2-chloro-1-nitronaphthalene, 2-chloronaphthalene-1-sulfonic acid, 2-chloronaphthalene-1- Lithium sulfonate, sodium 2-chloronaphthalene-1-sulfonate, potassium 2-chloronaphthalene-1-sulfonate, methyl 2-chloronaphthalene-1-sulfonate, ethyl 2-chloronaphthalene-1-sulfonate, 2-chloronaphthalene-1-sulfonate propyl ester, 2-chloronaphthalene-1-sulfonic acid isobutyl ester, 2-chloronaphthalene-1-sulfonic acid (2,2-dimethylpropyl ester), 2_·chloronaphthalene Cyclohexyl-1-sulfonate, 2-chloro-1-naphthoic acid, methyl 2-chloro-1-naphthoate, ethyl 2-chloro-1-naphthoate, 2- -1-Minylnaphthalene, 2-chloro-b-ethenylnaphthalene, 2-chloro-1-benzoylnaphthalene, 2,5-dichloro-1-benzylidene naphthalene, 2-chloro-1 -trifluoromethylnaphthalene, 2-chloro-l-nitroguanidine, 2-chloroindole-1-sulfonic acid, lithium 2-chloroindole-1-sulfonate, sodium 2-chloroindole-1-sulfonate, Potassium 2-chloroindole-1-sulfonate, methyl 2-chloroindole-1-sulfonate, ethyl 2-chloroindole-1-sulfonate, propyl 2-chloroindole-1-sulfonate, 2-chloro蒽-1_ isobutyl sulfonate, 2-chloroindole-1-sulfonic acid (2,2-dimethylpropyl), 2-chloroindole-1-sulfonic acid cyclohexyl ester, 2-chloroindole-1 -carboxylic acid, methyl 2-chloroindole-1-carboxylate, ethyl 2-chloroindole-1-carboxylate, 2-chloro-1-methylindenylhydrazine, 2-chloro-1-ethylindenylhydrazine, 2-Chloro-1-benzylidene hydrazide, 2,5-dichloro-1-benzylidene hydrazine, 2-chloro-1-trifluoromethyl hydrazine, 2-chloro-1-nitroindole, 2 -Chloroindole-1-sulfonic acid, lithium 2-chloroindole-1-sulfonate·· -25- 201223930 Sodium 2-chloroindole-1-sulfonate, potassium 2-chloroindole-1-sulfonate, 2-chloro Methyl 芘-1-sulfonate, ethyl 2-chloroindole-1-sulfonate, propyl 2-chloroindole-1-sulfonate, isobutyl 2-chloroindole-1-sulfonate, 2-chloroindole 1-sulfonic acid (2,2-dimethylpropyl), 2-chloroindole-1-sulfonic acid cyclohexyl ester, 2-chloroindole-1-carboxylic acid, 2-chloro-1-indolecarboxylic acid A Ester, 2-chloro-1-pyrene Ethyl acetate, 2-chloro-1-methylindenyl hydrazine, 2-chloro-1-ethenyl hydrazine, 2-chloro-1-benzylidene hydrazine, 2-chloro-1-trifluoromethyl hydrazine, 2-Chloro-1-nitroindole, 2-chloroindole-.1-sulfonic acid, lithium 2-chloroindole-1-sulfonate, sodium 2-chloroindole-1-sulfonate, 2-chloroindole- 1- Potassium sulfonate, methyl 2-chloroindole-1-sulfonate, ethyl 2-chloroindole-1-sulfonate, propyl 2-chloroindole-1-sulfonate, 2-chloroindole-1-sulfonic acid Butyl ester, 2-chloroindole-1-sulfonic acid (2,2-dimethylpropyl), 2-chloroindole-1-sulfonic acid cyclohexyl ester, 2-chloroindole-1-carboxylic acid, 2-chloro Methyl thin-1-carboxylate, ethyl 2-chloroindole-1-carboxylate, 2-chloro-1-methylindenyl hydrazine, 2-chloro-1-ethylindenyl hydrazine, 2-chloro-1-benzene Methyl hydrazide, 2-chloro-1-trifluoromethyl hydrazine, 2-chloro-1-nitro-9,9'- hydrazine, 2-chloro-1-sulfo-9,9'- hydrazine , 2-Chloro-9,9'-bifluorene-sulfonic acid lithium, 2-chloro-9,9'-biindole-sodium sulfonate, 2-chloro-9,9'-bi-p-sulfonic acid potassium, 2 -Chloro-9,9'-biindole-sulfonic acid methyl ester, 2-chloro-9,9'-bifluorene-sulfonic acid ethyl ester, 2-chloro-9,9'-bifluorene-sulfonic acid propyl ester, 2-Chloro-9,9'-biindole-isobutyl sulfonate, 2-chloro-9,9'-biindole-sulfonic acid (2,2-dimethylpropyl), 2-chloro-9, 9'-bifluorene-cyclohexyl sulfonate, 2-chloro-1-carboxy-9,9'-linked , 2-chloro-1-methylindolyl-9,9'-biguanidine, 2-chloro-1-ethenyl-9,9'-biguanidine, 2-chloro-1-benzhydryl-yl, 9'-biguanidine, 2-chloro-1-trifluoromethyl_9,9,-bifluorene, 2-chloro-1-nitrophenanthrene, 2-chlorophenan-1-sulfonic acid, 2-chlorophenanol- Lithium 1-sulfonate, sodium 2-chlorophenanthrene-1-sulfonate, potassium 2-chlorophenan-1-sulfonate, methyl 2-chlorophenan-1-sulfonate, 2-chlorophenan-1-sulfonic acid Ester, 2-chlorophenanthrene-1-sulfonate, 2-chlorophenan-1-sulfo-26- 201223930 isobutyl acrylate, 2-chlorophenan-1-sulfonic acid (2,2-dimethylpropyl ester) ), 2-chlorophenan-1-sulfonic acid cyclohexyl ester, 2-chlorophenan-1-carboxylic acid, 2-chloro-1-methylpyridyl phenanthrene, 2-chloro-1-ethenyl phenanthrene, 2-chloro 1-benzylidene phenanthrene, 2-chloro-1-trifluoromethylphenanthrene, 2-chloro-1-nitroindole, 2-chloroindole-1-sulfonic acid, 2-chloroindole-1-sulfonic acid Lithium, sodium 2-chloroindole-1-sulfonate, potassium 2-chloroindole-1-sulfonate, methyl 2-chloroindole-1-sulfonate, ethyl 2-chloroindole-1-sulfonate, 2- Propyl chlorophenan-1-sulfonate, 2-chloroindole-]-isobutyl sulfonate, 2-chloroindole-1-sulfonic acid (2,2-dimethylpropyl), 2-chloroindole-1 - cyclohexyl sulfonate, 2-chloroindole-1-carboxylic acid, 2-chloro-1-methylindenyl hydrazine, 2-chloro-1-ethylindenyl hydrazine, 2-chloro-1-benzhydryl hydrazine 2-chloro-1-trifluoromethyl hydrazine, 2-chloro 1-nitrobenzophenanthrene, 2-chlorobenzophenanthrene-1-sulfonic acid, lithium 2-chlorobenzophenanthrene-1-sulfonate, sodium 2-chlorobenzophenanthrene-1-sulfonate, 2-chloro Potassium benzophenanthrene-1-sulfonate, methyl 2-chlorobenzophenan-1-sulfonate, ethyl 2-chlorobenzophenan-1-sulfonate, 2-chlorobenzophenanthrene-1-sulfonate Ester, isobutyl 2-chlorobenzophenanthrene-1-sulfonate 2-chlorobenzophenanthrene-1-sulfonic acid (2,2-dimethylpropyl), 2-chlorobenzophenanthrene-1-sulfonate Cyclohexyl ester, 2-chlorobenzophenan-1-carboxylic acid, methyl 2-chlorobenzophenan-1-carboxylate, ethyl 2-chlorobenzophenan-1-carboxylate, 2-chloro-1 -Methylmercaptobenzophenanthrene, 2-chloro-1-ethinylbenzophenanthrene, 2-chloro-1-benzoguanidinobenzophenanthrene, 2-chloro-1-trifluoromethylbenzophenanthrene, 2 -Chloro-1-nitronaphthacene, 2-chloronaphthene-1-sulfonic acid, lithium 2-chloronaphthene-1-sulfonate, sodium 2-chloronaphthene-1-sulfonate, 2 - Potassium chloronaphthyl-1-sulfonate, methyl 2-chloronaphthyridin-1-sulfonate, ethyl 2-chloronaphthoquinone-1-sulfonate, 2-chloronaphthene-1-sulfonate Acid propyl ester, 2-chloronaphthene-1-sulfonate isobutyl ester, 2-chloronaphthene-1-sulfonic acid (2,2-dimethylpropyl), 2-chloronaphthene-1 - cyclohexyl sulfonate, 2-chloronaphthene-1-carboxylic acid, methyl 2-chloronaphthacene-1-carboxylate, 2--27-20122 3930 ethyl chloronaphthyl-1-carboxylate, 2-chloro-1-methylindolyl benzophenone, 2-chloro-1-ethenylnaphthacene, 2-chloro-1-benzylidene naphthalene Acetylene, 2-chloro-1-trifluoromethylnaphthacene, 2-chloro-1-nitropentacene, 2-chloropentacene-1-sulfonic acid, 2-chloropentacene-1- Lithium sulfonate, sodium 2-chloropentacene-1-sulfonate, potassium 2-chloropentacene-1-sulfonate, methyl 2-chloropentacene-1-sulfonate, 2-chloropentacene Ethyl-1-sulfonate, 2-chloropenta-benzene-1-sulfonate, 2-chloropentacene-1-sulfonate isobutyl ester, 2-chloropentacene-1-sulfonic acid (2 ,2-dimethylpropyl ester), 2-chloropentacene-1-sulfonic acid cyclohexyl ester, 2-chloropentacene-1-carboxylic acid, 2-chloropentacene-1-carboxylic acid methyl ester , 2-chloropentacene-1-carboxylic acid ethyl ester, 2-chloro-1-methylindolo pentacene, 2-chloro-1-ethenyl pentacene, 2-chloro-1-benzamide Pentacene, 2-chloro-1-trifluoromethyl pentacene, 2-chloro-1-nitrotripterin (triptycene), 2-chlorotripterin-1-acid, 2-chlorotri Lithium pterene-1-sulfonate, sodium 2-chlorotripycenes-1-sulfonate, potassium 2-chlorotripadene-1-sulfonate, methyl 2-chlorotripadene-1-sulfonate, 2 -Chloricopyran-1-sulfonate ethyl ester, 2-chlorotriptycee-1-sulfonate propyl ester, 2-chlorotripter Isobutyl 1-sulfonate, 2-chlorotriptycee-1-sulfonic acid (2,2-dimethylpropyl), 2·chlorotridecene-1-sulfonic acid cyclohexyl ester, 2-chloro Triptycene-1-carboxylic acid, methyl 2-chlorotripycenes-1-carboxylate, ethyl 2-chlorotripycenes-1-carboxylate, 2-chloro-1-methyldecyl triptycene, 2-Chloro-1-ethenyl triptycene, 2-chloro-1-benzylidene triptycene, 2-chloro-1-trifluoromethyl triptycene, 2-chloro-3-nitropyridine , 2-chloropyridine-3-sulfonic acid, lithium 2-chloropyridine-3-sulfonate, sodium 2-chloropyridine-3-sulfonate, potassium 2-chloropyridine-3-sulfonate, 2-chloropyridine-3 -methyl sulfonate, ethyl 2-chloropyridine-3-sulfonate, 2-chloropyridine-3-sulfonic acid -28-201223930 propyl ester, 2-chloropyridine-3-sulfonic acid isobutyl ester, 2-chloro Pyridine-3-sulfonic acid (2,2-dimethylpropyl), 2-chloropyridine-3-sulfonic acid cyclohexyl ester, 2-chloropyridine-3-carboxylic acid, 2-chloropyridine-3-carboxylic acid Methyl ester, ethyl 2-chloropyridine-3-carboxylate, 2-chloroindole-methylpyridylpyridine, 2-chloro-3-acetylpyridylpyridine, 2-chloro-3-benzylidenepyridine, 2- Chloro-3-trifluoromethylpyridine, 2-chloro-3.nitrofuran, 2-chlorofuran-3-sulfonic acid, lithium 2-chlorofuran-3-sulfonate, 2-chlorofuran-3-sulfonic acid Sodium, potassium 2-chlorofuran-3-sulfonate, 2-chlorofur Methyl m--3-sulfonate, ethyl 2-chlorofuran-3-sulfonate, propyl 2-chlorofuran-3-sulfonate, isobutyl 2-chlorofuran-3-sulfonate, 2-chlorofuran 3-sulfonic acid (2,2-dimethylpropyl), 2-chlorofuran-3-sulfonic acid cyclohexyl ester, 2-chlorofuran-3-carboxylic acid, 2-chlorofuran-3-carboxylic acid A Ester, ethyl 2-chlorofuran-3-carboxylate, 2-chloro-3-methylmercaptofuran, 2-chloro-3-ethylmercaptofuran, 2-chloro-3-benzylidenefuran, 2- Chloro-3-trifluoromethylfuran, 2-chloro-3-nitrothiophene, 2-chlorothiophene-3-sulfonic acid, lithium 2-chlorothiophene-3-sulfonate, 2-chlorothiophene-3-sulfonic acid Sodium, potassium 2-chlorothiophene-3-sulfonate, methyl 2-chlorothiophene-3-sulfonate, ethyl 2-chlorothiophene-3-sulfonate, propyl 2-chlorothiophene-3-sulfonate, 2 -chlorothiophene-3-sulfonate isobutyl ester, 2-chlorothiophene-3-sulfonic acid (2,2-dimethylpropyl), 2-chlorothiophene-3-sulfonic acid cyclohexyl ester, 2-chlorothiophene 3-carboxylic acid, methyl 2-chlorothiophene-3-carboxylate, ethyl 2-chlorothiophene-3-carboxylate, 2-chloro-3-methylsulfonylthiophene, 2-chloro-3-ethylhydrazine Thiophene, 2-chloro-3-benzylidenethiophene, 2-chloro-3-trifluoromethylthiophene, 7-chloro-6-nitrobenzothiadiazole, 7-chlorobenzothiadiazole-6 -sulfonic acid, 7-chlorobenzothiadiazole-6- Lithium acid, sodium 7-chlorobenzothiadiazole-6-sulfonate, potassium 7-chlorobenzothiadiazole-6-sulfonate, methyl 7-chlorobenzothiadiazole-6-sulfonate-29 - 201223930, ethyl 7-chlorobenzothiadiazole-6-sulfonate, propyl 7-chlorobenzothiadiazole-6-sulfonate, isobutyl 7-chlorobenzothiadiazole-6-sulfonate Ester, 7-chlorobenzothiadiazole-6-sulfonic acid (2,2-dimethylpropyl), 7-chlorobenzothiadiazole-6-sulfonic acid cyclohexyl ester, 7-chlorobenzothiazide Diazole-6-carboxylic acid, methyl 7-chlorobenzothiadiazole-6-carboxylate, ethyl 7-chlorobenzothiadiazole-6-carboxylate, 7-chloro-6-methylnonylbenzene Thiadiazole, 7-chloro-6-ethylmercaptobenzothiadiazole, 7-chloro-6-benzhydrylbenzothiadiazole, 7-chloro-6-trifluoromethylbenzothiazepine Oxazole, 2-chloro-3-nitropyrrole, 2-chloropyrrole-3-sulfonic acid, lithium 2-chloropyrrole-3-sulfonate, sodium 2-chloropyrrole-3-sulfonate, 2-chloropyrrole-3 - potassium sulfonate, methyl 2-chloropyrrole-3-sulfonate, ethyl 2-chloropyrrole-3-sulfonate, propyl 2-chloropyrrole-3-sulfonate, 2-chloropyrrole-3-sulfonate Isobutyl acrylate, 2-chloropyrrole-3-sulfonic acid (2,2-dimethylpropyl), 2-chloropyrrole-3-sulfonic acid cyclohexyl ester, 2-chloropyrrole-3-carboxylic acid, 2 -Chloropyrrol-3-carboxylate, 2-chloro Ethyl 3-carboxylic acid, 2-chloro-3-methylpyridylpyrrole, 2-chloro-3-ethinylpyrrole, 2-chloro-3-benzylidenepyrrole, 2-chloro-3-tri Fluoromethylpyrrole, 2-chloro-3-nitrosporphyrin, 2-chlorosporin-3-sulfonic acid, lithium 2-chloroquinoline-3-sulfonate, sodium 2-chloroquinoline-3-sulfonate, 2 - chloroquinoline-3-sulfonate potassium, 2-chloroquinoline-3-sulfonic acid methyl ester, 2-chloroquinoline-3-sulfonic acid ethyl ester, 2-chloroquinoline-3-sulfonic acid propyl ester, 2-chloroquinoline Isobutyl -3-sulfonate, 2-chloroquinoline-3-sulfonic acid (2,2-dimethylpropyl), 2-chloroquinoline-3-sulfonic acid cyclohexyl ester, 2-chloroquinoline-3- Carboxylic acid, methyl 2-chloroquinoline-3-carboxylate, ethyl 2-chloroquinoline-3-carboxylate, 2-chloro-3-methylindolylquinoline, 2-chloro-3-ethenylquinoline , 2-chloro-3-benzylidenequinoline, 2-chloro-3-trifluoromethylquinoline, 2-chloro-3-nitroindole, 2-chlorosporin-3-propionic acid , 2-Chloroindole-30- 201223930 Lithium phthalate-3-sulfonate, sodium 2-chloroquinoxaline-3-sulfonate, potassium 2-chloroquinoxaline-3-sulfonate, 2-chlorosporphyrin-3 - methyl sulfonate, ethyl 2-chloroquinoxaline-3-sulfonate, 2-chloroquinoxaline-3-sulfonate propyl ester, 2-chloroquinoxaline-3-sulfonate isobutyl ester, 2-chloroquinoline Porphyrin-3-sulfonic acid (2,2-dimethylpropyl) 2-Chloroporphyrin-3-sulfonic acid cyclohexyl ester, 2-chloroquinoxaline-3-carboxylic acid, 2-chlorosupporin-3-carboxylic acid methyl ester, 2-chloroquinoxaline-3-carboxylic acid Ethyl ester, 2-chloro-3-methylindolyl quinoxaline, 2-chloro-3-ethylhydrazinoquinoxaline, 2-chloro-3-benzylidene quinoxaline, 2-chloro-3-tri Fluoromethylquinoxaline, 4-chloro-5-nitropyrimidine, 4-chloropyrimidine-5-sulfonic acid, lithium 4-chloropyrimidine-5-sulfonate, sodium 4-chloropyrimidine-5-sulfonate, 4 - chloropyrimidine-5-sulfonate, 4-chloropyrimidine-5-sulfonic acid methyl ester, 4-chloropyrimidine-5-sulfonic acid ethyl ester, 4-chloropyrimidine-5-sulfonic acid propyl ester, 4-chloropyrimidine -5-isobutyl sulfonate, 4-chloropyrimidine-5-sulfonic acid (2,2-dimethylpropyl) ' 4-chloropyrimidine-5-sulfonic acid cyclohexyl ester, 4-chloropyrimidine-5- Carboxylic acid, methyl 4-chloropyrimidine-5-carboxylate, ethyl 4-chloropyrimidine-5-carboxylate, 4-chloro-5-methylpyridylpyrimidine, 4-chloro-5-ethenylpyrimidine, 4 -Chloro-5-benzimidylpyrimidine, 4-chloro-5-trifluoromethylpyrimidine, 2-chloro-3-nitropyrazine, 2-chloropyrazine-3-sulfonic acid, 2-chloropyrazine Lithium-3-sulfonate, sodium 2-chloropyrazine-3-sulfonate, potassium 2-chloropyrazine-3-sulfonate, methyl 2-chloropyrazin-3-sulfonate, 2-chloropyrazine- Ethyl 3-sulfonate, 2-chloropyrazine-3-sulfonate propyl 2-chloropyrazine-3- Isobutyl sulfonate, 2-chloropyrazine-3-sulfonic acid (2,2-dimethylpropyl), 2-chloropyrazine-3-sulfonic acid cyclohexyl ester, 2-chloropyrazine-3- Carboxylic acid, methyl 2-chloropyrazine-3-carboxylate, ethyl 2-chloropyrazine-3-carboxylate, 2-chloro-3.methylpyridylpyrazine, 2-chloro-3-ethenyl Pyrazine, 2-chloro-3-benzylidylpyrazine, 2-chloro-3-trifluoromethylpyrazine. -31 - 201223930 Among them, a compound represented by the formula (3) (hereinafter referred to simply as a compound (3)) is preferred:

Ci

(wherein R1, R2 and R3 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a group selected from the following G group, and may have a group selected from the following G group; An alkoxy group having a carbon number of 2, and an aryl group having a carbon number of 6 to 20 selected from the group of the following G group, and having a carbon number of 6 to 2 0 selected from the group of the following G group The oxy group may have an aralkyl group having 7 to 20 carbon atoms selected from the group consisting of the following group G, and an aralkyloxy group having 7 to 20 carbon atoms which may have a group selected from the group G below, or An amine group which may have a hydrocarbon group of a carbon number selected from the group G, and R4 represents a hydrogen atom, may have an alkyl group having a carbon number of 1 to 20 selected from the group of the following G group, and may have The alkoxy group having 1 to 20 carbon atoms selected from the group G, and the aryl group having 6 to 20 carbon atoms which may be selected from the group G, may be selected from the group G below. An aryloxy group having 6 to 20 carbon atoms, a aralkyl group having 7 to 20 carbon atoms which may be selected from the group G, and a carbon which may have a substituent selected from the group of the following groups a 7 to 20 aralkyloxy group, or having a group selected from the group G below The amine group of the hydrocarbon group having 1 to 20 carbon atoms is further bonded to the adjacent carbon atom, and R1 and R2, R2 and R3, or r3 and r4 may form a ring together with the carbon atom to be bonded, respectively. The electron-forming group '[G group] -32- 201223930 fluorine atom; cyano group; alkoxy group having 1 to 12 carbon atoms; aryl group having 6 to 12 carbon atoms; and aryloxy group having 6 to 12 carbon atoms). The electron withdrawing group represented by E in the compound (3) is preferably a nitro group (-N02) and a group represented by the formula (5). Specific examples of the compound (3) are 2-chloro-1-nitrobenzene, 2-chloro-1-benzenesulfonic acid or a metal salt thereof, 2-chloro-benzoic acid or a metal salt thereof, and 2-chloro-1- Methyl benzenesulfonate and methyl 2-chloro-benzoate. In the coupling reaction of the compound (1), as described above, the chlorine atom of the compound (1) having a chlorine atom in the ortho position of the electron withdrawing group is characterized in that it can participate in the coupling reaction even at a lower temperature. By utilizing this feature, a position-selective biaryl compound (2) can be produced. When the compound (1) is a compound represented by the formula (1) (hereinafter referred to simply as the compound (10)),

(wherein Y represents the same meaning as defined above, and R1() each independently represents a fluorine atom, may have an alkyl group having 1 to 20 carbon atoms selected from the group of the above G group, and may have a group selected from the aforementioned G group. An alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms which may be selected from the group G, and an aromatic oxygen having 6 to 20 carbon atoms which may be selected from the group G The base may have a fluorenyl group or a cyano group having a carbon number of 2 to 20 selected from the group G, and k represents an integer of 〇~3, and further, two R1Gs respectively bonded to adjacent carbon atoms may be bonded. , which forms a ring together with the carbon atom to which it is bonded, and is a meta atom relative to the "-S03-Y" which is an electron-based group. The chlorine atom has a higher reactivity in the coupling of the -33 to 201223930, and the biaryl compound represented by the formula (1 1) (hereinafter referred to as a biaryl compound) is obtained by the difference in reactivity. 11)): 〇~ γ :s=o

GI

(wherein 'R1(), γ, and k represent the same meaning as described above). Preferred examples of the compound (10) and the obtained biaryl compound (1 1) are shown in Table 1 below. [Table 1] Compound (10) Biaryl compound (11) Sodium 2,5-dichlorobenzenesulfonate 4,4'-Dichloro-2,2'-biphenyldisulfonic acid monosodium 2,5-di Lithium chlorobenzenesulfonate 4,4'-dichloro-2,2'-biphenyl monosulfonic acid monolithium 2,5-dichlorobenzenesulfonic acid (2,2-dimethylpropyl vinegar) 4,4'- Dichloro-2,2'-biphenyl monosulfonic acid mono(2,2-dimethylpropyl ester) Further, as for the compound (1), a compound represented by the formula (12) can be used:

(wherein R1() and k are the same as defined above), and a biaryl compound represented by the formula (13) is produced: -34- 201223930

(wherein R1Q and k represent the same meaning as described above). According to the present invention, the Ar contained in the compound (1) can be subjected to a coupling reaction even if it is an aromatic heterocyclic group (but the heterocyclic group may have a substituent). The compound (1) wherein Ar is an aromatic heterocyclic group (however, the heterocyclic group may have a substituent) is preferably a direct bond of a hetero atom contained in Ar to a carbon atom bonded to Ar of C1. A compound containing a heterocyclic group. Specifically, it is listed as a compound represented by the formula (7).

(wherein R11 and R12 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be selected from the group G, and may have a carbon number of 1 selected from the group G; An alkoxy group of 20, an aryl group having 6 to 20 carbon atoms which may be selected from the group G, and an aryloxy group having 6 to 20 carbon atoms which may be selected from the group G, may have the above-mentioned The aralkyl group having a carbon number of 7 to 20 selected from the group G, may have an aralkoxy group having 7 to 20 carbon atoms selected from the group of the G group, or may have a group selected from the group G The amine group of the hydrocarbon group having 1 to 20 carbon atoms| R14 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a group selected from the above G group, and a carbon number which may have a group selected from the above G group ~20-alkane-35-201223930 oxy group, an aryl group having 6 to 20 carbon atoms which may have a group selected from the above G group, and an aryloxy group having 6 to 20 carbon atoms which may have a group selected from the above G group And an aralkyl group having 7 to 20 carbon atoms selected from the group of the G group, an aralkoxy group having 7 to 20 carbon atoms which may be selected from the group G, or having the aforementioned The basis of the G group The amine group of a hydrocarbon group having 1 to 20 carbon atoms, and R11 and R12 respectively bonded to adjacent carbon atoms, or R12 and R14 may form a ring together with each bonded carbon atom, and A represents an oxygen atom or a sulfur atom. ). The biaryl compound represented by the formula (8) can be produced by subjecting a compound represented by the formula (7) to a coupling reaction:

(wherein, A, R11, R12 and R14 respectively have the same meanings as defined above). The biaryl compound (2) obtained by the coupling reaction can be further purified. The biaryl compound (2) can be obtained by separating and purifying the biaryl compound (2) formed from a copper metal, a copper salt, an unreacted compound (1), and the like, and a solvent, after the coupling reaction. obtain. The separation and purification can be carried out by filtration, extraction, concentration, recrystallization, reprecipitation, and chromatographic separation, depending on the type of the unreacted product or the type of the biaryl compound (2) to be isolated and purified. Choose the most suitable means. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples. In the following examples, the biaryl compound (2) formed after the coupling reaction was analyzed by means of liquid chromatography (L C) or gas chromatography 201223930 (G C), and the yield was calculated based on the obtained chromatographic area 値. The analysis conditions of the LC analysis were as follows: &lt;Analytical conditions&gt; LC measuring device: LC-10AT (manufactured by Shimadzu Corporation) Column: L-column ODS (5 pm, 4.6 mm &lt; ^ xl 5 cm)

Column temperature: 40 ° C Mobile phase: A : 0 · 1 % tetrabutylammonium bromide aqueous solution B : 〇 · 1 % tetrabutylammonium bromide solution gradient: Omin B = 3 0 % 20 min B = 9 Ο % 3 5min Β = 9 Ο % 3 5 . 1 mi η Β = 3 Ο % 45min Stop total analysis time 45 minutes Flow rate: 1.0 mL/min Detection: UV absorption (wavelength: 254 nm) The analytical conditions for GC analysis are as follows: &lt;Analytical conditions&gt; GC measuring device: GC-2010A (manufactured by Shimadzu Corporation: J&amp;W DB-17Ol (O.32mm0 x 30m, Ι.Ομηι) -37- 201223930 Column temperature: 50°C (keep 〇 minute) + (heating at l〇°C/min)&quot;&gt;150°C (keep 〇min)+ (warm at 20°C/min) 4280°C (for 8 minutes) Total analysis time 24.5 Minute inlet temperature: 2 5 0 〇 C, detector temperature: 2 5 0 ° C (FID, range 1 01) Carrier gas: He (flow rate about 2.3 mL / min) Injection pressure: 75.2 kPa (control mode pressure Split ratio: full flow 55.9mL / min (split ratio about 1/22)

Injection volume: 1 pL

[Example 1]

Mixing sodium 2,5-dichlorobenzenesulfonate 0.8 (^, powdered metal copper 0.41 §, copper iodide (I) 〇. 〇 31 g, N, N, N', N'-tetramethylethylenediamine 0.019 g and N-methyl-2-pyrrolidone 4. Og. The obtained mixture was heated to 100 ° C while maintaining a nitrogen atmosphere. The mixture was directly maintained under a nitrogen atmosphere, and the mixture was stirred at 100 ° C for 4 hours to obtain a content of 4, a reaction mixture of 4'-dichloro-2,2'-diphenyldisulfonic acid disodium. After cooling, a portion of the reaction mixture was sampled and subjected to the aforementioned LC analysis to calculate 4,4'-dichloro-2,2'- Yield of disodium diphenyl disulfonate. Yield: 98% [Example 2] -38- 201223930 2 Cl

Mixing sodium 2,5-dichlorobenzenesulfonate 0.8 (^, powdered metal copper 0.41 §, copper iodide (I) 〇.031 g, 2,2'-bipyridine 0.025 g and N-methyl-2-pyrrolidone 4.0 g. The obtained mixture was heated to 10 ° C while maintaining a nitrogen atmosphere. The mixture was directly maintained under a nitrogen atmosphere, and the mixture was stirred at 100 ° C for 4 hours to obtain 4,4'-dichloro-2,2'. - a reaction mixture of disodium diphenyl disulfonate. After cooling, sample one part of the reaction mixture and perform the aforementioned LC analysis' to calculate the yield of disodium 4,4'-dichloro-2,2'-biphenyldisulfonate Yield: 96% [Example 3]

2 C1~^~C1 S03Na mixed sodium 2,5-dichlorobenzenesulfonate 0.5 (^, powdered metal copper ruthenium. 25 §, copper iodide (I) 0.019 g, l,l porphyrin 0.018 g and N-methyl-2-pyrrolidone 2 · 5 g. The mixture was heated to 1 Torr while maintaining a nitrogen atmosphere. The mixture was stirred at 100 ° C for 4 hours while maintaining the nitrogen atmosphere. a reaction mixture of '-dichloro-2,2'-diphenyldisulfonic acid disodium. After cooling, 'sampling one part of the reaction mixture, performing the aforementioned LC analysis to calculate 4,4'-dichloro-2,2' - yield of disodium diphenyl disulfonate. Yield: 95% - 39 - 201223930 [Example 4]

Mixing 2,5-dichlorobenzenesulfonic acid (2,2-dimethylpropyl) 0.59 g, powdered metal copper 0.25 g, copper iodide (I) 0.019 g, hydrazine, hydrazine, hydrazine, Ν'- Tetramethylethylenediamine oxime. 35 g and N-methyl-2-pyrrolidone 2.5 g. The resulting mixture was heated to l ° ° C while maintaining a nitrogen atmosphere. The mixture was stirred under nitrogen for a period of 4 hours at 10 ° C to obtain bis(2,2-dimethylpropyl) 4,4'-dichlorobiphenyl-2,2'-disulfonate. The reaction mixture. After cooling, a part of the reaction mixture was sampled, and the above LC analysis was carried out to calculate the yield of 4,4'-dichlorobiphenyl-2,2'-disulfonic acid bis(2,2-dimethylpropyl). Yield: 56%

120.0 g of 2,5-dichlorobenzenesulfonic acid (2,2-dimethylpropyl), 28.2 g of powdered metallic copper, and 300.0 g of toluene were added. The resulting mixture was concentrated to 290 g, and the water mixture of the concentrated mixture was confirmed to be 2 1 ppm. Among them, 3.60 g of copper (II) fluorocarbonate and 2.35 g of N,N,N,N,-tetramethylethylenediamine were added thereto. The resulting mixture was heated to 1001 ^ while maintaining the nitrogen atmosphere. The mixture was stirred at 100 ° C for 24 hours to obtain 4,4'-dichlorobiphenyl-2,2'-disulfonic acid. A reaction mixture of bis(2,2-dimethylpropyl). A portion of the reaction mixture was sampled and subjected to the aforementioned LC analysis to calculate the yield of 4,4'-dichlorobiphenyl-2,2'-disulfonic acid bis(2,2-dimethylpropyl). Yield: 8 6 %. After adding toluene 4 8 0.0 g to the obtained reaction mixture, it was added dropwise to 8 8 8.2 g of 1 8 · 9 % hydrochloric acid. The resulting mixture was at 75. (: After stirring for 10 minutes, the aqueous layer was removed at 75 ° C. The obtained oil layer was washed with water until pH 4, and cooled to 5 ° C to precipitate a solid. The precipitated solid was collected by filtration and dried to obtain 4, 4' - 72.4 g of dichlorobiphenyl-2,2'-disulfonic acid bis(2,2-dimethylpropyl). Yield: 68%. [Example 6]

CH

CH^ CH.

Cu.r

0.95 g of 2-chlorothiophene, 1.02 g of powdered metal copper, 0.029 g of copper (II) trifluoromethanesulfonate, &gt;^, &gt;1 mountain', :^'-tetramethylethylenediamine 〇.〇 93§ and 1^-methyl-2-pyrrolidone l.Og»The obtained mixture was heated to 150 ° C while maintaining a nitrogen atmosphere. The mixture was stirred at 150 ° C for 4 hours while maintaining a nitrogen atmosphere to obtain a reaction mixture containing 2,2'-bithiophene. After cooling, a part of the reaction mixture was sampled, and the above GC analysis was carried out to calculate the yield of 2,2,-bithiophene. Yield: 20%. -41 - 201223930 [Embodiment 7]

Mixed 2-chloronitrophenylhydrazine.95g, powdered metal copper 0.77g, copper iodide (I) 0.05 7g, N,N,N',N'-tetramethylethylenediamine 〇.〇35g and N- Methyl-2-pyrrolidone 7.5 g. The resulting mixture was heated to 150 ° C while maintaining a nitrogen atmosphere. The mixture was directly maintained under a nitrogen atmosphere, and the mixture was stirred at 150 ° C for 4 hours to obtain a reaction mixture containing 2,2'-dinitrobiphenyl. After cooling, a part of the reaction mixture was sampled, and the above GC analysis was carried out to calculate the yield of 2,2'-dinitrobiphenyl. Yield: 54%. [Embodiment 8]

Methyl 2-chlorobenzoate 1.36 g, powdered metal copper l. 〇 2 g, copper (II) trifluoromethanesulfonate 0.029 g, N, N, N', N'-tetramethylethylenediamine oxime. 〇93g and N-methyl-2-pyrrolidone l.Og. The resulting mixture was heated to 150 ° C while maintaining a nitrogen atmosphere. Directly maintained under a nitrogen atmosphere, the mixture was stirred at 15 (TC for 4 hours to obtain a reaction mixture containing 2,2'-bis(methoxycarbonyl)biphenyl. After cooling, a portion of the reaction mixture was sampled, -42-201223930 The GC analysis was carried out to calculate the yield of 2,2'-bis(methoxycarbonyl)biphenyl. Yield: 29%. [Example 9]

Mix 2,5-dichlorobenzenesulfonic acid (2,2-dimethylpropyl) 2.388, powdered metal copper 0.56 g, copper (II) trifluoromethanesulfonate 〇.〇29g, 1,4,7- Trimethyl-1,4,7-triazacyclononane.21 g and toluene 2.38 g. The resulting mixture was heated to 100 ° C while maintaining a nitrogen atmosphere. The mixture was directly maintained under a nitrogen atmosphere. The mixture was stirred at 1 ° C for 4 hours to obtain a 4,4'-dichlorobiphenyl-2,2'. a reaction mixture of di(2,2-dimethylpropyl) disulfonate. After cooling, a part of the reaction mixture was sampled, and the above LC analysis was carried out to calculate the yield of 4,4,-dichlorobiphenyl-2,2'-disulfonic acid bis(2,2-dimethylpropyl). Yield: 82%. [Embodiment 10] h3c.n^i!i

Mixing 0.91 g of 2-chloropyridine, powdered metal copper i.〇2g, copper (II) trifluoromethanesulfonate 0_029g, N,N,N',N'-tetramethylethylenediamine 0.093g and N-A Ke-2-pyrrolidone l.〇g. The resulting mixture was maintained under a nitrogen atmosphere and heated to 150 °C on 201223930. The mixture was stirred at 150 ° C for 4 hours while maintaining a nitrogen atmosphere to obtain a reaction mixture containing 2,2'-bipyridine. After cooling, a part of the reaction mixture was sampled, and the above GC analysis was carried out to calculate the yield of 2,2'-bipyridine. Yield: 1 〇 %. [Embodiment 1 1]

Mix 2,5-dichlorodiphenyl copper 2. (^, powdered metal copper 1. 〇 28, copper (II) trifluoromethanesulfonate 〇. 〇 29g, N, N, N', N'-four 0.093 g of methylethylenediamine and 1.0 g of N-methyl-2-pyrrolidone. The mixture was heated to 15 (TC) while maintaining a nitrogen atmosphere, and the mixture was stirred at 150 ° C directly under nitrogen atmosphere. After 4 hours, a reaction mixture containing 4,4'-dichloro-2,2'-bis(benzimidyl)biphenyl was obtained. After cooling, a part of the reaction mixture was sampled, and the above GC analysis was carried out to calculate 4, 4'. - yield of dichloro-2,2'-bis(benzimidyl)biphenyl. Yield: 21%. [Example 12]

-44 - 201223930 1.15 g of p-toluenesulfonic acid·1 hydrate and 0.55 g of copper (II) acetate and 1 35 g of toluene were mixed, and the obtained mixture was heated at 1 〇 ° C for 1 hour to distill off 54 g of toluene. A concentrate containing copper p-toluenesulfonate. 45.0 g of 2,5-dichlorobenzenesulfonic acid (2,2-dimethylpropyl) and 10.6 g of powdery metallic copper were added to the concentrate, and the resulting mixture was stirred at 10 ° C for 20 hours. A reaction mixture containing 4,4'-dichlorobiphenyl-2,2'-disulfonic acid bis(2,2-dimethylpropyl). A part of the reaction mixture was sampled, and the above LC analysis was carried out to calculate the yield of 4,4'-dichlorobiphenyl-2,2'-disulfonic acid bis(2,2-dimethylpropyl). Yield: 7 7%. [Example 13]

Add 2,5-dichlorobenzenesulfonic acid (2,2-dimethylpropyl) 4 5. (^, powdered metal copper l〇.6g, copper (II) hydroxide 0.30g, methanesulfonic acid 0.58g And 9 甲苯g of toluene, and the obtained mixture containing the produced copper methane sulfonate was concentrated to become 4 g. The water enthalpy of the concentrated mixture was confirmed to be 20 ppm, and N, N, N', N'-four was added thereto. 3.5 g of methylethylenediamine, and the mixture was heated to 105 ° C while maintaining a nitrogen atmosphere. The mixture was directly maintained under a nitrogen atmosphere, and the mixture was stirred at 10 ° C for 26 hours to obtain 4,4'- a reaction mixture of dichlorobiphenyl-2,2'. di(2,2-dimethylpropyl) disulfonate. Sampling reaction is mixed with one part of -45-201223930, and the above LC analysis is carried out to calculate disulfonic acid Yield of (2,2-dimethylpropyl). [Industrial Applicability] According to the present invention, a corresponding biaryl compound can be produced by easily obtaining it. 4,4'-Dichlorobiphenyl- 2,2'- rate: 72%. Compound of formula (1) -46 -

Claims (1)

201223930 VII. Patent application scope: 1. A method for producing a biaryl compound represented by formula (2), Ar-Ar (2) (wherein Ar represents an aromatic group which may have a substituent), and the method a step of coupling a compound represented by the formula (1) in the presence of an amine compound having at least two tertiary amino groups in the molecule, a metal copper and a copper salt: Ar-Cl (1) (wherein Ar and the foregoing Synonymous). 2. The production method according to the first aspect of the invention, wherein the nitrogen atom constituting the tertiary amino group contained in the amine compound is a nitrogen atom bonded to three carbon atoms. 3. The production method according to claim 1, wherein the amine compound having at least two tertiary amino groups in the molecule is a 2,2'-bipyridine compound which may have a substituent or a substituent which may have a substituent Anthraquinone-phenanthroline compound. 4. The method of claim 1, wherein the copper salt is a Bruce base and a copper cation formed by removing hydrogen ions from a Brucetin acid exhibiting an acid dissociation constant (pKa) of 10 or less. Salt into salt. 5. The manufacturing method of claim 4, wherein the Brucenic acid is hydrogen halide, sulfuric acid, thiocyanate, phosphoric acid, carbonic acid, nitric acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, acetic acid At least one selected from the group consisting of trifluoroacetic acid, pentafluoropropyl-47-201223930 acid, etidylacetone, phenol, pentafluorophenol and thiophenol. 6. The manufacturing method of claim 1, wherein the copper salt is copper halide, copper sulfate, copper thiocyanate, copper phosphate 'copper carbonate, copper nitrate, copper methanesulfonate, copper trifluoromethanesulfonate ( I)-benzene complex, copper (I)-toluene complex of trifluoromethanesulfonate, copper (II) trifluoromethanesulfonate, copper benzenesulfonate, copper acetate, copper trifluoroacetate, pentafluoropropyl At least one selected from the group consisting of copper acid, copper (II) acetylacetonate, copper phenate, copper pentoxide and copper thiophenolate. 7. The manufacturing method of claim 1, wherein the copper salt is copper. 8. The method of claim 1, wherein the copper salt is used in an amount of 0.01 mol to 10 mol relative to the amine compound 1 mol, 9. The method of manufacturing according to claim 1 wherein the amine The compound is composed of 2,2'-bipyridine, 1,10-morpholine, 1,4,7-trimethylq〆, 'triazacyclononane, N,N,N',N'-tetra At least one amine compound selected from the group consisting of ethylenediamine and &gt;1,\chuan, and 1^-tetraethylethylenediamine. 10. The method of manufacturing of the first aspect of the patent application, wherein the amine compound The amount of use relative to the aryl chloride compound 1 is in the range of 〇〇〇〇丨 耳 〇 〇 5 摩尔. The manufacturing method of claim 1, wherein Ar is an aromatic group having at least one electron-withdrawing group. 12. The manufacturing method according to the scope of the patent application, wherein the compound represented by the formula is a compound represented by the formula (3): -48- 201223930 (wherein R1, R2 and R3 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a group selected from the group G below, and a carbon which may have a group selected from the following group G An alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms which may be selected from the group G, and an aromatic oxygen having 6 to 20 carbon atoms which may be selected from the group G a aralkyl group having 7 to 20 carbon atoms which may be selected from the group consisting of the following G group, an aralkyloxy group having 7 to 20 carbon atoms which may have a group selected from the group G below, or may have The amine group of the hydrocarbon group having a carbon number of 1 to 2 0 selected from the group G below, and R4 represents a hydrogen atom, an alkyl group having 1 to 2 carbon atoms which may have a group selected from the group G below, and may have a lower group The alkoxy group having a carbon number of 1 to 20 selected from the group G, and an aryl group having 6 to 20 carbon atoms which may be selected from the group G, may have a group selected from the group G below. An aryloxy group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms which may be selected from the group G, and a carbon number which may have a substituent selected from the group G below: 20 aralkoxy, or having a group selected from the following group G The amine group of the hydrocarbon group of carbon number 20 is further bonded to the adjacent carbon atom, and R1 and R2, R2 and r3, or r3 and r4 may form a ring together with the carbon atoms respectively bonded, and E represents a pull. Electron-based '[G group] fluorine atom; cyano group; alkoxy group having 1 to 12 carbon atoms; aryl group having 6 to 12 carbon atoms; and aryloxy group having 6 to 12 carbon atoms), represented by formula (2) The biaryl compound is a compound represented by the formula (4) -49-201223930 compound: 13. The manufacturing method of claim i.2, wherein the electron withdrawing group is a group represented by the formula (5): - 丨 - 〇 ~ Y (5) • I: (wherein Y represents hydrogen ion, alkali Metal ion, ammonium ion represented by formula (6): Y2 - Φ - Y1 - N - Y3 (6) Y4 (wherein Y1, Y2, Y3 and Y4 each independently represent a hydrogen atom or a hydrocarbon group of carbon number 10) The alkyl group having a carbon number of 1 to 20 selected from the group G, or an aryl group having 6 to 20 carbon atoms which may be selected from the group G, [G group] fluorine atom a cyano group; an alkoxy group having a carbon number of from 1 to 12; an aryl group having a carbon number of 6 to U: and an aryloxy group having a carbon number of from 6 to 12). 14. A manufacturing method according to the first aspect of the patent application ' Formula (1) Table-50-201223930 The compound shown is a compound represented by the formula (10): (R10)k Ο- Y (wherein Y represents a hydrogen ion, an alkali metal ion, and an ammonium ion represented by the formula (6): Y2 Y1—ti—Y3 (6) Y4 (wherein, Y1, Y2, Y3, and Y4 are each independently represented a hydrogen atom or a hydrocarbon group having a carbon number of 1), an alkyl group having 1 to 20 carbon atoms which may be selected from the group G, or a carbon number 6 to 20 which may have a group selected from the following group G The aryl group, R1G each independently represents a fluorine atom, may have an alkyl group having 1 to 20 carbon atoms selected from the group G, and may have a carbon number of 1 to 2 0 selected from the group G below. The alkoxy group may have an aryl group having 6 to 20 carbon atoms selected from the group of the following G group, and may have an aryloxy group having 6 to 20 carbon atoms selected from the group of the following G group, and may have an The group selected from the group G has a carbon number of 2 to 20 or a cyano group, and k represents an integer of 0 to 3, and two R1() respectively bonded to adjacent carbon atoms may be bonded to each other. The bonded carbon atoms together form a ring, [G group] fluorine atom; cyano group; carbon number 12 alkoxy group; carbon number 6 to 12 aryl group; and carbon number 1 to 12 aryloxy group), The compound represented by the formula (2) is a combination of the formula (11) Yl -51--201223930 compound: (wherein Rie, Y and k represent the same meaning as described above). 15. The method of manufacture of claim 13 or 14, wherein γ is an alkali metal ion. 16. The method of manufacture of claim η or 12, wherein the electron withdrawing group is a nitro group (-Ν02). 17. The production method according to the first aspect of the invention, wherein Ar is an aromatic heterocyclic group (however, the heterocyclic group may have a substituent. 18. The production method of claim 17 wherein ^ A heterocyclic group in which a hetero atom contained in Ar is directly bonded to a carbon atom bonded to Ar of Cl. 19. A method of producing a compound represented by the formula (1), wherein the compound represented by the formula (1) For the compound represented by the formula (7): CI (7) The alkyl group of the carbon number selected from the group G below, which may have an alkoxy group having a carbon number of 1 to 2 selected from the group G, may have the following 0 The group selects an aryl group having a carbon number of 6 to 20 at the base of 52-201223930, and may have an aryloxy group having a carbon number of 6 to 20 selected from the group of the following G group, and may have a group selected by the following G group. An aralkyl group having 7 to 20 carbon atoms, a aralkyloxy group having 7 to 20 carbon atoms which may be selected from the group G, or a carbon number which may have a group selected from the group G below An amino group of a hydrocarbon group of 1 to 20, and R14 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a group selected from the group G below, and a carbon number which may have a group selected from the following G group 1~ 20 alkoxy group, an aryl group having 6 to 2 carbon atoms which may be selected from the group G, and an aryloxy group having 6 to 20 carbon atoms which may have a group selected from the group G below, and may have The aralkyl group having a carbon number of 7 to 20 selected from the group G, which may have a carbon number of 7 to 2 0 selected from the group of G below, or having the following The amine group of the hydrocarbon group having a carbon number of 1 to 20 selected from the group G, and respectively bonded to the adjacent R11 and R12' or R12 and R14 on the carbon atom may form a ring together with the carbon atoms respectively bonded, A represents an oxygen atom or a sulfur atom, [G group] fluorine atom; cyano group; carbon number 1 to 12 Alkoxy group; aryl group having 6 to 12 carbon atoms; and aryloxy group having 1 to 12 carbon atoms) The biaryl compound represented by the formula (2) is a biaryl compound represented by the formula (8): (wherein, A, R11, R12 and R14 respectively have the same meanings as described above). 2 〇 · The manufacturing method of claim 1 ' wherein the coupling step -53 - 201223930 is a step carried out in the presence of an aprotic polar solvent. -54- 201223930 IV. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the representative figure is a simple description: No 201223930 If there is a chemical formula in the case, please disclose the chemical formula that best shows the characteristics of the invention. :no