JP5742500B2 - Method for producing biaryl compound - Google Patents

Description

  The present invention relates to a method for producing a biaryl compound and the like.

  Biaryl compounds, particularly biaryl compounds having an electron-attracting group such as a sulfo group, are useful compounds as pharmaceuticals, agricultural chemicals, liquid crystal materials, organic electro-luminescence materials, and synthetic intermediates thereof. As a method for producing such a compound, for example, after reacting 2,2′-benzidinedisulfonic acid with sodium nitrite, the resulting reaction product is reacted with hydrochloric acid containing copper chloride and neutralized with sodium hydroxide. Thus, Patent Document 1 discloses a method for producing disodium 4,4′-dichloro-2,2′-biphenyldisulfonate.

JP 2009-161493 A ([0046] [Production Example 1])

  The production method of Patent Document 1 has a problem that it is not always easy to obtain 2,2'-benzidinedisulfonic acid as a raw material.

As a result of intensive studies on a method for producing a biaryl compound using a raw material different from 2,2′-benzidinedisulfonic acid, the present inventors have reached the present invention described below.
<1> Formula (1) in the presence of an amine compound containing at least two tertiary amino groups in the molecule, metallic copper and a copper salt.
Ar-Cl (1)
(In formula (1), Ar represents an aromatic group which may have a substituent.)
Comprising the step of coupling an aryl chloride compound represented by formula (2):
Ar-Ar (2)
(In the formula (2), Ar has the same meaning as described above.)
The manufacturing method of biaryl compound shown by these.

<2> The method according to <1>, wherein the nitrogen atom constituting the tertiary amine group contained in the amine compound is a nitrogen atom bonded to three carbon atoms.
<3> The copper salt is a salt composed of a Bronsted base obtained by removing hydrogen ions from a Bronsted acid having an acid dissociation constant (pKa) of 10 or less and a copper cation <1> or <2 > The production method described.
<4> Bronsted acid is hydrogen halide, sulfuric acid, thiocyanic acid, phosphoric acid, carbonic acid, nitric acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, acetic acid, trifluoroacetic acid, pentafluoropropionic acid, acetylacetone, <2> or <3>, wherein the production method is at least one selected from the group consisting of phenol, pentafluorophenol and thiophenol.
<5> Copper salt is copper halide, copper sulfate, copper thiocyanate, copper phosphate, copper carbonate, copper nitrate, copper methanesulfonate, copper trifluoromethanesulfonate (I) -benzene complex, copper trifluoromethanesulfonate ( I) -toluene complex, copper (II) trifluoromethanesulfonate, copper benzenesulfonate, copper acetate, copper trifluoroacetate, copper pentafluoropropionate, copper (II) acetylacetonate, copper phenolate, copper pentafluorophenol <1> or <2>, wherein the production method is at least one selected from the group consisting of a rate and copper thiophenolate.
<6> The method according to <1> or <2>, wherein the copper salt is copper halide.
<7> The method according to any one of <1> to <6>, wherein the amount of copper salt used is in the range of 0.01 mol to 10 mol with respect to 1 mol of the amine compound.

<8> The amine compound is 2,2′-bipyridyl, 1,10-phenanthroline, 1,4,7-trimethyl-1,4,7-triazacyclononane, N, N, N ′, N′-tetra The production method according to any one of <1> to <7>, which is at least one amine compound selected from the group consisting of methylethylenediamine and N, N, N ′, N′-tetraethylethylenediamine.
<9> The production method according to any one of <1> to <8>, wherein the amount of the amine compound used is in the range of 0.0001 mol to 0.5 mol with respect to 1 mol of the aryl chloride compound. .

（式（３）中、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に、水素原子、ハロゲン原子、下記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルキル基、下記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルコキシ基、下記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリール基、下記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリールオキシ基、下記Ｇ群より選ばれる基を有していてもよい炭素数７〜２０のアラルキル基、下記Ｇ群より選ばれる基を有していてもよい炭素数７〜２０のアラルキルオキシ基又は下記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０の炭化水素基を有するアミノ基を表し、
Ｒ^４は、水素原子、下記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルキル基、下記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルコキシ基、下記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリール基、下記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリールオキシ基、下記Ｇ群より選ばれる基を有していてもよい炭素数７〜２０のアラルキル基、下記Ｇ群より選ばれる基を置換基として有していてもよい炭素数７〜２０のアラルキルオキシ基又は下記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０の炭化水素基を有するアミノ基を表す。なお、隣接する炭素原子にそれぞれ結合している、Ｒ^１及びＲ^２の組み合わせ、Ｒ^２及びＲ^３の組み合わせ、並びに、Ｒ^３及びＲ^４の組み合わせは、各々が結合している炭素原子と一緒になって環を形成していてもよい。Ｅは電子求引性基を表す。）
で示されるアリールクロライド化合物であり、
ビアリール化合物が、式（４）

（式（４）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＥは前記と同義である。）
で示されるビアリール化合物であることを特徴とする＜１＞〜＜１０＞のいずれか記載の製造方法。
〔Ｇ群〕
フッ素原子；シアノ基；炭素数１〜１２のアルコキシ基；炭素数６〜１２のアリール基；炭素数６〜１２のアリールオキシ基 <10> Ar is an aromatic group having at least one electron-withdrawing group, The production method according to any one of <1> to <9>.
<11> The aryl chloride compound is represented by the formula (3)

(In Formula (3), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms which may have a group selected from the following group G; From an alkoxy group having 1 to 20 carbon atoms which may have a group selected from the following G group, an aryl group having 6 to 20 carbon atoms which may have a group selected from the following G group, from the following G group An aryloxy group having 6 to 20 carbon atoms which may have a selected group, an aralkyl group having 7 to 20 carbon atoms which may have a group selected from the following G group, and a group selected from the following G group An aralkyloxy group having 7 to 20 carbon atoms which may have an amino group having a hydrocarbon group having 1 to 20 carbon atoms which may have a group selected from the following group G;
R ⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a group selected from the following G group, or a group having 1 to 20 carbon atoms which may have a group selected from the following G group. An alkoxy group, an aryl group having 6 to 20 carbon atoms which may have a group selected from the following G group, an aryloxy group having 6 to 20 carbon atoms which may have a group selected from the following G group, Aralkyl group having 7 to 20 carbon atoms which may have a group selected from the following G group, Aralkyloxy group having 7 to 20 carbon atoms which may have a group selected from the following G group as a substituent, or The amino group which has a C1-C20 hydrocarbon group which may have the group chosen from the following G group is represented. The combination of R ¹ and R ² , the combination of R ² and R ³ , and the combination of R ³ and R ⁴ that are bonded to adjacent carbon atoms are the same as the carbon atom to which each is bonded. To form a ring. E represents an electron withdrawing group. )
An aryl chloride compound represented by:
The biaryl compound is of the formula (4)

(In the formula (4), R ¹ , R ² , R ³ , R ⁴ and E are as defined above.)
The production method according to any one of <1> to <10>, which is a biaryl compound represented by the formula:
[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; an aryloxy group having 6 to 12 carbon atoms

（式（５）中、Ｙは、水素原子、アルカリ金属イオン、式（６）

（式（６）中、Ｙ^１、Ｙ^２、Ｙ^３及びＹ^４は、それぞれ独立に、水素原子又は炭素数１〜１０の炭化水素基を表す。）
で示されるアンモニウムイオン、下記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルキル基、または、下記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリール基を表す。
〔Ｇ群〕
フッ素原子；シアノ基；炭素数１〜１２のアルコキシ基；炭素数６〜１２のアリール基；炭素数６〜１２のアリールオキシ基）
で示される基であることを特徴とする＜１０＞又は＜１１＞記載の製造方法。 <12> The electron withdrawing group is represented by the formula (5)

(In Formula (5), Y is a hydrogen atom, an alkali metal ion, Formula (6)

(In formula (6), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.)
Or an alkyl group having 1 to 20 carbon atoms which may have a group selected from the following G group, or 6 to 20 carbon atoms which may have a group selected from the following G group. Represents an aryl group.
[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; an aryloxy group having 6 to 12 carbon atoms)
<10> or <11>, wherein the method is a group represented by the formula:

（式（１０）中、Ｙは、水素イオン、アルカリ金属イオン、式（６）

（式（６）中、Ｙ^１、Ｙ^２、Ｙ^３及びＹ^４は、それぞれ独立に、水素原子又は炭素数１〜１０の炭化水素基を表す。）
で示されるアンモニウムイオン、下記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルキル基、または、下記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリール基を表す。Ｒ^１０は、それぞれ独立に、フッ素原子、下記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルキル基、下記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルコキシ基、下記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリール基、下記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリールオキシ基、下記Ｇ群より選ばれる基を有していてもよい炭素数２〜２０のアシル基又はシアノ基を表わす。ｋは０〜３の整数を表わす。また、隣接する炭素原子にそれぞれ結合している２つのＲ^１０同士は結合し、それらが結合している炭素原子と一緒になって環を形成していてもよい。
〔Ｇ群〕
フッ素原子；シアノ基；炭素数１〜１２のアルコキシ基；炭素数６〜１２のアリール基；炭素数１〜１２のアリールオキシ基）
で示されるアリールクロライド化合物であり、ビアリール化合物が式（１１）

（式中、Ｒ^１0、Ｙ及びｋは前記と同義である。）
で示されるビアリール化合物であることを特徴とする＜１＞〜＜９＞のいずれか記載の製造方法。 <13> The aryl chloride compound has the formula (10)

(In Formula (10), Y is a hydrogen ion, an alkali metal ion, Formula (6)

(In formula (6), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.)
Or an alkyl group having 1 to 20 carbon atoms which may have a group selected from the following G group, or 6 to 20 carbon atoms which may have a group selected from the following G group. Represents an aryl group. R ¹⁰ is independently a fluorine atom, an alkyl group having 1 to 20 carbon atoms that may have a group selected from the following G group, or a carbon number that may have a group selected from the following G group. An alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms which may have a group selected from the following group G, and a 6 to 20 carbon atom which may have a group selected from the following group G An aryloxy group, an acyl group having 2 to 20 carbon atoms and a cyano group which may have a group selected from Group G below. k represents an integer of 0 to 3. Further, two R ¹⁰ bonded to adjacent carbon atoms may be bonded to each other to form a ring together with the carbon atoms to which they are bonded.
[G group]
A fluorine atom; a cyano group; an alkoxy group having 1 to 12 carbon atoms; an aryl group having 6 to 12 carbon atoms; an aryloxy group having 1 to 12 carbon atoms)
And the biaryl compound is represented by the formula (11):

(Wherein R ¹⁰ , Y and k are as defined above.)
The production method according to any one of <1> to <9>, which is a biaryl compound represented by the formula:

<14> The method according to <12> or <13>, wherein Y is an alkali metal ion.
<15> The method according to <10> or <11>, wherein the electron withdrawing group is a nitro group (—NO ₂ ).

（式中、Ｒ^１１及びＲ^１２は、それぞれ独立に、水素原子、ハロゲン原子、下記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルキル基、下記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルコキシ基、下記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリール基、下記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリールオキシ基、下記Ｇ群より選ばれる基を有していてもよい炭素数７〜２０のアラルキル基、下記Ｇ群より選ばれる基を有していてもよい炭素数７〜２０のアラルキルオキシ基又は下記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０の炭化水素基を有するアミノ基を表し、
Ｒ^１４は、水素原子、下記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルキル基、下記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルコキシ基、下記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリール基、下記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリールオキシ基、下記Ｇ群より選ばれる基を有していてもよい炭素数７〜２０のアラルキル基、下記Ｇ群より選ばれる基を置換基として有していてもよい炭素数７〜２０のアラルキルオキシ基又は下記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０の炭化水素基を有するアミノ基を表す。なお、隣接する炭素原子にそれぞれ結合している、Ｒ^１１及びＲ^１２の組み合わせ、並びに、Ｒ^１２及びＲ^１４の組み合わせは、各々が結合している炭素原子と一緒になって環を形成していてもよい。Ａは、酸素原子または硫黄原子を表す。
〔Ｇ群〕
フッ素原子；シアノ基；炭素数１〜１２のアルコキシ基；炭素数６〜１２のアリール基；炭素数１〜１２のアリールオキシ基）
で示される化合物であり、
ビアリール化合物が式（８）

（式中、Ａ、Ｒ^１１、Ｒ^１２およびＲ^１４は前記と同義である。）
で示されるビアリール化合物であることを特徴とする＜１＞〜＜１０＞のいずれか記載の製造方法。
＜１９＞ カップリングさせる工程が、非プロトン性極性溶媒の存在下で行う工程であることを特徴とする＜１＞〜＜１８＞のいずれか記載の製造方法。 <16> Ar is a heterocyclic group having aromaticity (however, the heterocyclic group may have a substituent). Any one of <1> to <10> Manufacturing method.
<17> The production method according to <16>, wherein Ar is a heterocyclic group in which a hetero atom contained in Ar and a carbon atom bonded to Cl of Ar are directly bonded.
<18> The aryl chloride compound has the formula (7)

Wherein R ¹¹ and R ¹² are each independently selected from 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 the following G group. An alkoxy group having 1 to 20 carbon atoms which may have a group, an aryl group having 6 to 20 carbon atoms which may have a group selected from the following G group, and a group selected from the following G group An aryloxy group having 6 to 20 carbon atoms which may be present, an aralkyl group having 7 to 20 carbon atoms which may have a group selected from the following G group, and a group selected from the following G group. Represents an amino group having a C1-C20 hydrocarbon group which may have a good C7-20 aralkyloxy group or a group selected from the following G group;
R ¹⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that may have a group selected from the following G group, or a C 1 to 20 carbon group that may have a group selected from the following G group. An alkoxy group, an aryl group having 6 to 20 carbon atoms which may have a group selected from the following G group, an aryloxy group having 6 to 20 carbon atoms which may have a group selected from the following G group, Aralkyl group having 7 to 20 carbon atoms which may have a group selected from the following G group, Aralkyloxy group having 7 to 20 carbon atoms which may have a group selected from the following G group as a substituent, or The amino group which has a C1-C20 hydrocarbon group which may have the group chosen from the following G group is represented. The combination of R ¹¹ and R ^{12 and} the combination of R ¹² and R ¹⁴ that are bonded to adjacent carbon atoms, respectively, form a ring together with the carbon atoms to which they are bonded. May be. A represents an oxygen atom or a sulfur atom.
[G group]
A fluorine atom; a cyano group; an alkoxy group having 1 to 12 carbon atoms; an aryl group having 6 to 12 carbon atoms; an aryloxy group having 1 to 12 carbon atoms)
A compound represented by
Biaryl compounds are represented by formula (8)

(In the formula, A, R ¹¹ , R ¹² and R ¹⁴ are as defined above.)
The production method according to any one of <1> to <10>, which is a biaryl compound represented by the formula:
<19> The method according to any one of <1> to <18>, wherein the coupling step is a step performed in the presence of an aprotic polar solvent.

  According to the present invention, a biaryl compound can be produced from an easily available aryl chloride compound.

  The method for producing a biaryl compound represented by formula (2) of the present invention (hereinafter sometimes referred to as compound (2)) comprises an amine compound containing at least two tertiary amino groups in the molecule, metallic copper and a copper salt. In the presence of, an aryl chloride compound represented by formula (1) (hereinafter sometimes referred to as aryl chloride compound (1)) is coupled. In the following description, this process may be simply referred to as “coupling reaction”.

Hereinafter, the production method of the present invention will be described in detail.
First, metal copper and copper salt used for the coupling reaction will be described.
The amount of metallic copper used is, for example, in the range of 0.5 to 20 moles, preferably in the range of 1 to 5 moles with respect to 1 mole of the substance amount of the aryl chloride compound (1) used. is there. If the amount of metallic copper used is 0.5 mol or more, the yield of the resulting compound (2) tends to improve, and if the amount of metallic copper used is 20 mol or less, the compound The post-treatment for removing (2) from the reaction system is preferable because the operation tends to be simple. Examples of the shape of the metallic copper include a powder shape, a wire shape, a foil shape, a shaving shape, a particle shape, and the like. From the viewpoint of operability of the metallic copper, a powder shape is preferable. Such copper metal is readily available from the market. A part of the surface of such commercially available metallic copper may be oxidized by oxygen in the environment to become copper oxide. Thus, metallic copper containing a very small amount of copper oxide can be used for the coupling reaction as it is, for example, tetramethylammonium hydroxide, monoethanolamine, ethylenediaminetetraacetic acid, hydroxyethanediphosphonic acid, catechol, garlic acid. In addition, a very small amount of copper oxide can be removed with a cleaning agent such as oxalic acid, citric acid, hydroxylamine, 2-mercaptoethanol, thioglycerol, etc., and then subjected to a coupling reaction.

A copper salt consists of a copper cation and an anion. The copper salt which consists of a monovalent copper cation and an anion may be sufficient, and the copper salt which consists of a bivalent copper cation and an anion may be sufficient.
As the anion, a Bronsted base obtained by removing a hydrogen ion from a Bronsted acid having an acid dissociation constant (pKa) of 10 or less is preferable. The acid dissociation constant (pKa) is a value in water at 25 ° C., and is calculated by the method described in Chemical Handbook Basic Revised Edition II-331 to II-343 (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.). be able to. When the Bronsted acid is a polybasic acid, the acid dissociation constant (pKa ₁ ) in the first stage is preferably 10 or less.
As an anion, a Bronsted base obtained by removing hydrogen ions from a Bronsted acid having an acid dissociation constant (pKa) of 6 or less is more preferred, and a Bronsted base obtained by removing hydrogen ions from a Bronsted acid having 3 or less is particularly preferred. Moreover, as an anion, the Bronsted base which removed the hydrogen ion from the Bronsted acid whose acid dissociation constant (pKa) is -10 or more is preferable.
Specific examples of preferred anions as Bronsted acids include 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), methanesulfonic 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 thiophenol (pKa: 6.4).

  As a copper salt, for example, copper halide, copper sulfate, copper thiocyanate, copper phosphate, copper carbonate, copper nitrate, copper methanesulfonate, copper p-toluenesulfonate, copper trifluoromethanesulfonate (I) -benzene complex , Copper (I) trifluoromethanesulfonate-toluene complex, copper (II) trifluoromethanesulfonate, copper benzenesulfonate, copper acetate, copper trifluoroacetate, copper pentafluoropropionate, copper (II) acetylacetonate, copper Examples include phenolate, copper pentafluorophenolate, and copper thiophenolate. Examples of the copper halide include copper fluoride, copper chloride, copper bromide, and copper iodide, and two or more selected from these may be mixed. Such copper salts may be hydrates, but anhydrides are preferred.

  A commercially available copper salt may be used as it is, or a copper salt prepared by mixing a monovalent or divalent copper compound and an acid may be used. As the monovalent or divalent copper compound, usually, copper oxide, copper hydroxide, or the like is preferably used, and the above-mentioned Bronsted acid is used as the acid.

Preferred copper salts include, for example, copper halide, copper sulfate, copper thiocyanate, copper nitrate, copper (I) trifluoromethanesulfonate-benzene complex, copper (I) trifluoromethanesulfonate-toluene complex, copper trifluoromethanesulfonate (II), copper (II) acetylacetonate, copper thiophenolate, etc. can be mentioned, More preferably, for example, copper halide, copper sulfate, copper nitrate, copper trifluoromethanesulfonate (I) -benzene complex , Copper (II) trifluoromethanesulfonate, copper (II) acetylacetonate and the like.
The amount of copper salt used is, for example, in the range of 0.01 mol to 10 mol, preferably in the range of 0.02 mol to 1 mol, and more preferably, with respect to 1 mol of the amine compound used. For example, it is the range of 1/3 mol-1/30 mol.
Moreover, the lower limit of the usage-amount of copper salt is 0.00001 mol with respect to 1 mol of aryl chloride compounds (1) to be used, for example, Preferably, it is 0.0001 mol, More preferably, for example, 0.001 mol. On the other hand, the upper limit of the amount of copper salt used is, for example, 0.5 mol, preferably, for example, 0.3 mol, more preferably, with respect to 1 mol of the aryl chloride compound (1) to be used. For example, 0.1 mol. Therefore, the amount of copper salt used is, for example, in the range of 0.001 mol% to 50 mol% with respect to the substance amount of the aryl chloride compound (1) to be used (that is, as 100 mol%), preferably For example, it is in the range of 0.01 mol% to 50 mol%, more preferably in the range of 0.1 mol% to 50 mol%, for example, the yield of the desired compound (2) and after completion of the reaction From the viewpoint of the operability of removing the copper salt, it is in the range of 0.1 mol% to 30 mol%, preferably 0.5 mol% to 10 mol%, for example.

Next, an amine compound containing at least two tertiary amino groups in the molecule (hereinafter sometimes referred to as an amine compound) will be described.
The tertiary amino group contained in the amine compound means a substituent consisting of a nitrogen atom bonded to three carbon atoms, and the nitrogen atom constituting the tertiary amine group contained in the amine compound has three carbon atoms. It means a nitrogen atom bonded to an atom. The carbon atom may have aromaticity.
The two tertiary amino groups contained in the amine compound are preferably bonded via two carbon atoms.
Examples of the amine compound include 2,2′-bipyridyl, 1,10-phenanthroline, 1,4,7-trimethyl-1,4,7-triazacyclononane, N, N, N ′, N′-tetra. Mention may be made of methylethylenediamine and N, N, N ′, N′-tetraethylethylenediamine.
As the usage-amount of an amine compound, it is the range of 0.1 mol-100 mol with respect to 1 mol of copper salts to be used, Preferably, it is the range of 1 mol-50 mol, More preferably, For example, it is in the range of 3 mol to 30 mol. When the amount of the amine compound used is 0.1 mol or more with respect to 1 mol of the copper salt, the yield of the compound (2) tends to be improved, and when it is 100 mol or less, the reaction rate tends to be improved. This is preferable.
Moreover, as an upper limit of the usage-amount of an amine compound, it is 50 mol with respect to 1 mol of aryl chloride compounds (1) to be used, for example, Preferably, it is 20 mol, More preferably, for example, it is 5 Mol, particularly preferably, for example, 0.5 mol. On the other hand, the lower limit of the amount of the amine compound used is, for example, 0.00001 mol, preferably, for example, 0.0001 mol with respect to 1 mol of the aryl chloride compound (1) used. Therefore, the usage-amount of an amine compound is the range of 0.00001 mol-50 mol with respect to 1 mol of aryl chloride compounds (1) to be used, Preferably, it is the range of 0.0001 mol-20 mol, for example. More preferably, it is the range of 0.0001 mol-5 mol, for example, Most preferably, it is the range of 0.0001 mol-0.5 mol, for example.
Further, a more preferable lower limit of the amount of the amine compound used is, for example, 0.001 mol, particularly preferably, for example, 0.01 mol with respect to 1 mol of the aryl chloride compound (1) to be used. Therefore, the usage-amount of an amine compound is the range of 0.001 mol-20 mol with respect to 1 mol of aryl chloride compounds (1) to be used, Preferably, it is the range of 0.01 mol-5 mol, for example. It is.

  The coupling reaction is preferably performed in the presence of a solvent. Examples of the solvent include aprotic polar solvents such as dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and hexamethylphosphoric triamide, such as hexane, Aliphatic hydrocarbon solvents such as heptane and octane, for example, aromatic hydrocarbon solvents such as toluene and xylene, for example, ether solvents such as tetrahydrofuran, 1,4-dioxane and diethylene glycol dimethyl ether, such as ethyl acetate, butyl acetate and carbonic acid Examples thereof include ester solvents such as dimethyl and diethyl carbonate. Such a solvent may be used independently and may be used in mixture of 2 or more types. Of these, N-methyl-2-pyrrolidone, toluene, diethylene glycol dimethyl ether, and ethyl acetate are more preferable. The amount of the solvent used may be, for example, in the range of 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, with respect to 1 part by weight of the aryl chloride compound (1) to be used. Part range.

The coupling reaction is preferably performed in an atmosphere of an inert gas such as nitrogen gas or argon gas.
The reaction temperature of the coupling reaction is, for example, in the range of 0 ° C. to 300 ° C., and can be appropriately adjusted depending on the type and amount of the aryl chloride compound (1) used, the amount of metal copper and copper halide used, and the like. Preferably, it is the range of 50 to 250 degreeC, for example, More preferably, it is the range of 100 to 200 degreeC, Most preferably, it is the range of 140 to 180 degreeC. When the reaction temperature is 0 ° C. or higher, the rate at which the compound (2) is generated is improved and the reaction time tends to be shortened. When the reaction temperature is 300 ° C. or lower, the generated compound (2) is It is preferable because side reactions such as decomposition tend to be suppressed.
The reaction time of the coupling reaction is, for example, in the range of 1 hour to 48 hours, and can be adjusted as appropriate. In addition, the reaction mixture in the reaction system is sampled every predetermined time, and the sampled reaction solution is analyzed for the degree of disappearance of the aryl chloride compound (1) by an analysis means such as liquid chromatography analysis or gas chromatography analysis, Alternatively, the reaction time can be adjusted by obtaining the degree of formation of the compound (2).

According to the production method of the present invention, it is possible to produce the corresponding compound (2) using the aryl chloride compound (1) which is easily available as a starting material.
The aryl chloride compound (1) generally tends to have low reactivity of the coupling reaction. However, according to the production method of the present invention, the aryl chloride compound (1) having low reactivity is used as a starting material. It is also possible to produce the corresponding compound (2).
As the aryl chloride compound (1), a plurality of types of aryl chloride compounds (1) may be used. For example, when two types of aryl chloride compounds (1) of Ar ₁ -Cl and Ar ₂ -Cl are used, Ar Three types of compounds (2) of _1- Ar ₁ , Ar ₁ -Ar ₂ , and Ar ₂ -Ar ₂ can be produced.
Preferably, the production method of the present invention uses one kind of aryl chloride compound (1).

Ar in the aryl chloride compound (1) is an aromatic group which may have a substituent. “Aromatic group optionally having substituent (s)” means a group obtained by removing one hydrogen atom bonded to the aromatic ring of an aromatic compound optionally having substituent (s). .
Examples of the aromatic compound having no substituent include aromaticity such as benzene, naphthalene, anthracene, pyrene, biphenyl, fluorene, 9, 9′-bifluorene, phenanthrene, perylene, chrysene, naphthacene, pentacene, and triptycene. Compounds that give cyclic hydrocarbon groups, such as pyridine, furan, thiophene, benzothiadiazole, pyrrole, quinoline, quinoxaline, pyrimidine and pyrazine compounds that give aromatic heterocyclic groups, such as ferrocene it can.

  Examples of the substituent include an electron withdrawing group, an alkyl group having 1 to 20 carbon atoms that may have a group selected from the following G group, and a group selected from the following G group. An alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms that may have a group selected from the following group G, and a carbon number 6 to 6 that may have a group selected from the following group G 20 aryloxy groups, an aralkyl group having 7 to 20 carbon atoms which may have a group selected from the following G group, and an aralkyl group having 7 to 20 carbon atoms which may have a group selected from the following G group The amino group etc. which have a C1-C20 hydrocarbon group which may have an oxy group or the group chosen from the following G group etc. can be mentioned.

[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; an aryloxy group having 6 to 12 carbon atoms

  Examples of the “alkyl group having 1 to 20 carbon atoms” in the alkyl group having 1 to 20 carbon atoms that may have a group selected from the group G include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 2,2-dimethylpropyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, 2-methyl Pentyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n- Linear, branched or cyclic alkyl groups such as hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group and n-icosyl group are listed. It is. The alkyl group optionally having a group selected from the G group as a substituent is a group in which part or all of the hydrogen atoms in the alkyl group exemplified herein are replaced with a group selected from the G group In the case of having a substituent, the total number of carbon atoms in the substituent is in the range of 1-20. Among these, an alkyl group having no substituent is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable.

  Examples of the “alkoxy group having 1 to 20 carbon atoms” of the alkoxy group which may have a group selected from the group G include, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and n-butoxy. Group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, 2,2-dimethylpropoxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, 2 -Methylpentyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n- Tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyl group Shi group, n- octadecyl group, n- nonadecyloxy group, n- icosyloxy group of straight, such branched or cyclic alkoxy group having 1 to 20 carbon atoms can be mentioned. The alkoxy group optionally having a group selected from the G group as a substituent is a group in which part or all of the hydrogen atoms in the alkoxy group exemplified herein are replaced with a group selected from the G group In the case of having a substituent, the total number of carbon atoms in the substituent is in the range of 1-20. Among these, an alkoxy group having no substituent is preferable, and an alkoxy group having 1 to 10 carbon atoms is more preferable.

Examples of the “aryl group having 6 to 20 carbon atoms” of the aryl group which may have a group selected from the group G include, for example, a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl Group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5- Tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-Butyl Nyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, An n-tetradecylphenyl group, a naphthyl group, an anthracenyl group, etc. are mentioned. The aryl group optionally having a group selected from the G group as a substituent is a group in which part or all of the hydrogen atoms in the aryl group exemplified herein are replaced with a group selected from the G group And having a substituent, the total number of carbon atoms is in the range of 6 to 20, including the number of carbon atoms in the substituent. Among these, an aryl group having no substituent is preferable, an aryl group having 6 to 10 carbon atoms is more preferable, and a phenyl group is particularly preferable.
Examples of the aryloxy group having 6 to 20 carbon atoms which may have a group selected from Group G as a substituent include, for example, phenoxy group, n-butylphenyloxy group, 2-naphthyloxy group and 2-an Examples include those composed of the aryl group exemplified above and an oxygen atom such as a tolyloxy group.

  Examples of the “aralkyl group having 7 to 20 carbon atoms” which may have a group selected from Group G include, for example, benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) Methyl group, (3,4-dimethylphenyl) methyl group, (4,6-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group , (2,3,6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-te Lamethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) ) Methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n- Pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-decylphenyl) methyl group, A naphthylmethyl group, an anthracenylmethyl group, etc. are mentioned. The aralkyl group optionally having a group selected from the G group as a substituent is a group in which part or all of the hydrogen atoms in the aralkyl group exemplified herein are replaced with a group selected from the G group. And having a substituent, the total number of carbon atoms is in the range of 7 to 20, including the number of carbon atoms in the substituent. Among these, an aralkyl group having no substituent is preferable, an aryl group having 7 to 10 carbon atoms is more preferable, and a benzyl group is particularly preferable.

  Examples of the “aralkyloxy group having 7 to 20 carbon atoms” of the C7 to C20 aralkyloxy group which may have a group selected from the group G include, for example, a benzyloxy group and (2-methylphenyl) Methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) ) Methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) me Xyl group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3, 4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group , (Isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) Before methoxy group, (n-decylphenyl) methoxy group, naphthylmethoxy group, anthracenylmethoxy group, etc. And the like composed of the exemplified aralkyl group and an oxygen atom.

  Examples of the amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms which may have a group selected from the group G include, for example, dimethylamino group, diethylamino group, di-n-propylamino group, diisopropyl Amino group, di-n-butylamino group, di-sec-butylamino group, di-tert-butylamino group, di-isobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di- Examples thereof include an n-octylamino group, a di-n-decylamino group, and a diphenylamino group, and among these, a dimethylamino group and a diethylamino group are preferable.

When an electron withdrawing group is substituted for Ar contained in the aryl chloride compound (1), the carbon atom to which the electron withdrawing group is bonded and the carbon atom to which the chlorine atom is bonded are Direct bonding (that is, the electron-withdrawing group is in the ortho position of the chlorine atom) is preferable because the reactivity in the coupling reaction tends to be extremely high.
Therefore, as the aryl chloride compound (1), as in the aryl chloride compound represented by the formula (3) (hereinafter sometimes referred to as the aryl chloride compound (3)), an electron withdrawing group is located at the ortho position of the chlorine atom. The thing which has is preferable. Thus, the aryl chloride compound (3) having an electron-attracting group at the ortho position of the chlorine atom has a coupling reaction caused by milder production conditions, specifically, a lower reaction temperature. There is a tendency to produce a compound represented by the formula (4) which is a corresponding biaryl compound (hereinafter sometimes referred to as a biaryl compound (4)).

（式（５）中、Ｙは、水素原子、アルカリ金属イオン、式（６）

（式（６）中、Ｙ^１、Ｙ^２、Ｙ^３及びＹ^４はそれぞれ独立に、水素原子又は炭素数１〜１０の炭化水素基を表す。）
で示されるアンモニウムイオン、下記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルキル基、または、下記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリール基を表す。Ｒ^１０はそれぞれ独立に、フッ素原子、下記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルキル基、下記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルコキシ基、下記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリール基、下記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリールオキシ基、下記Ｇ群より選ばれる基を有していてもよい炭素数２〜２０のアシル基又はシアノ基を表わす。ｋは０〜３の整数を表わす。また、隣接する炭素原子にそれぞれ結合している２つのＲ^１０同士は結合し、それらが結合している炭素原子と一緒になって環を形成していてもよい。）で示される基、
−ＣＯ_２−Ｙ
（式中、Ｙは前記Ｙと同一の意味を表わす。）
で示される基およびトリフルオロメチル基が挙げられ、
好ましくは、式（５）で示される基およびニトロ基である。 In this specification, “electron-withdrawing group” means a substituent constant σ _p ⁰ defined in Chemical Handbook Basic Edition, Rev. 5 II-379 to II-380 (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.). A group whose value is positive. The electron withdrawing group is preferably a group having a substituent constant σ _p ⁰ value in the range of 0.3 to 1, more preferably a group in the range of 0.5 to 1, and a range of 0.7 to 1. Is particularly preferred.
Specifically, nitro group (—NO ₂ ), formyl group (—CHO), carboxyl group (—COOH), formula (5)

(In Formula (5), Y is a hydrogen atom, an alkali metal ion, Formula (6)

(In formula (6), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.)
Or an alkyl group having 1 to 20 carbon atoms which may have a group selected from the following G group, or 6 to 20 carbon atoms which may have a group selected from the following G group. Represents an aryl group. R ¹⁰ each independently has a fluorine atom, an alkyl group having 1 to 20 carbon atoms that may have a group selected from the following group G, or a carbon number 1 that may have a group selected from the following group G. An alkoxy group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms which may have a group selected from the following group G, and an aryl having 6 to 20 carbon atoms which may have a group selected from the following group G An oxy group, an acyl group having 2 to 20 carbon atoms or a cyano group which may have a group selected from the following group G is represented. k represents an integer of 0 to 3. Further, two R ¹⁰ bonded to adjacent carbon atoms may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. Group represented by
-CO ₂ -Y
(In the formula, Y represents the same meaning as Y.)
And a group represented by trifluoromethyl group,
A group represented by formula (5) and a nitro group are preferable.

[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; an aryloxy group having 1 to 12 carbon atoms

Here, examples of the alkali metal ion include lithium ion (Li ⁺ ), sodium ion (Na ⁺ ), potassium ion (K ⁺ ), and cesium ion (Cs ⁺ ), and sodium ion is preferable.
In the formula (6), examples of the hydrocarbon group having 1 to 10 carbon atoms of Y ¹ , Y ² , Y ³ and Y ⁴ include carbon numbers such as a methyl group, an ethyl group, a propyl group, a butyl group and an octyl group. C6-C10 aryl groups, such as a 1-10 alkyl group and a phenyl group, etc. are mentioned. Examples of the ammonium ion represented by the formula (6) include ammonium ion (NH ₄ ⁺ ), methyl ammonium ion (N (CH ₃ ) H ₃ ⁺ ), and diethyl ammonium ion (N (C ₂ H ₅ ) ₂ H _2. ⁺ ), Dipropylammonium ion (N (C ₃ H ₇ ) ₂ H ₂ ⁺ ), tripropylammonium ion (N (C ₃ H ₇ ) ₃ H ⁺ ), tetrabutylammonium ion (N (C ₄ H ₉ ) ₄ ⁺ ), diisopropyldiethylammonium ion (N (CH (CH ₃ ) ₂ ) ₂ (C ₂ H ₅ ) ₂ ⁺ ), tetraoctyl ammonium ion (N (C ₈ H ₁₇ ) ₄ ⁺ ), tetradecyl ammonium ion ( N (C ₁₀ H ₂₁ ) ₄ ⁺ ) and triphenylammonium ion (N (C ₆ H ₅ ) ₃ H ⁺ ) and the like.

Examples of the aryl chloride compound (1) include 2-chloro-1-nitrobenzene, 2-chlorobenzene-1-sulfonic acid, lithium 2-chlorobenzene-1-sulfonate, sodium 2-chlorobenzene-1-sulfonate, 2- Potassium chlorobenzene-1-sulfonate, methyl 2-chlorobenzene-1-sulfonate, ethyl 2-chlorobenzene-1-sulfonate, propyl 2-chlorobenzene-1-sulfonate, isobutyl 2-chlorobenzene-1-sulfonate, 2- Chlorobenzene-1-sulfonic acid (2,2-dimethylpropyl), cyclohexyl 2-chlorobenzene-1-sulfonate, 2-chlorobenzene-1-carboxylic acid, methyl 2-chlorobenzene-1-carboxylate, 2-chlorobenzene-1- Ethyl carboxylate, 2-chloro 1-formyl benzene, 2-chloro-1-acetyl benzene, 2-chloro-1-benzoyl, 2,5-dichloro-1-benzoyl benzene, 2-chloro-1-trifluoromethylbenzene,
2-chloro-1-benzoic acid, methyl 2-chloro-1-benzoate, ethyl 2-chloro-1-benzoate,
2-chloro-1-nitronaphthalene, 2-chloronaphthalene-1-sulfonic acid, lithium 2-chloronaphthalene-1-sulfonate, sodium 2-chloronaphthalene-1-sulfonate, 2-chloronaphthalene-1-sulfonic acid Potassium, methyl 2-chloronaphthalene-1-sulfonate, ethyl 2-chloronaphthalene-1-sulfonate, propyl 2-chloronaphthalene-1-sulfonate, isobutyl 2-chloronaphthalene-1-sulfonate, 2-chloronaphthalene -1-sulfonic acid (2,2-dimethylpropyl), cyclohexyl 2-chloronaphthalene-1-sulfonate, 2-chloro-1-naphthoic acid, methyl 2-chloro-1-naphthoate, 2-chloro-1- Ethyl naphthoate, 2-chloro-1-formylnaphthalene, 2-chloro-1-acetyl Naphthalene, 2-chloro-1-benzoyl naphthalene, 2,5-dichloro-1-benzoyl naphthalene, 2-chloro-1-trifluoromethyl-naphthalene,

2-chloro-1-nitroanthracene, 2-chloroanthracene-1-sulfonic acid, lithium 2-chloroanthracene-1-sulfonate, sodium 2-chloroanthracene-1-sulfonate, 2-chloroanthracene-1-sulfonic acid Potassium, methyl 2-chloroanthracene-1-sulfonate, ethyl 2-chloroanthracene-1-sulfonate, propyl 2-chloroanthracene-1-propyl sulfonate, isobutyl 2-chloroanthracene-1-sulfonate, 2-chloroanthracene -1-sulfonic acid (2,2-dimethylpropyl), cyclohexyl 2-chloroanthracene-1-sulfonate, 2-chloroanthracene-1-carboxylic acid, methyl 2-chloroanthracene-1-carboxylate, 2-chloroanthracene -1-ethyl carboxylate, - chloro-1-formyl-anthracene, 2-chloro-1-acetyl-anthracene, 2-chloro-1-benzoyl-anthracene, 2,5-dichloro-1-benzoyl-anthracene, 2-chloro-1-trifluoromethyl anthracene,
2-chloro-1-nitropyrene, 2-chloropyrene-1-sulfonic acid, lithium 2-chloropyrene-1-sulfonate, sodium 2-chloropyrene-1-sulfonate, potassium 2-chloropyrene-1-sulfonate, 2-chloropyrene Methyl-1-sulfonate, ethyl 2-chloropyrene-1-sulfonate, propyl 2-chloropyrene-1-sulfonate, isobutyl 2-chloropyrene-1-sulfonate, 2-chloropyrene-1-sulfonate (2,2- Dimethylpropyl), cyclohexyl 2-chloropyrene-1-sulfonate, 2-chloropyrene-1-carboxylic acid, methyl 2-chloro-1-pyrenecarboxylate, ethyl 2-chloro-1-pyrenecarboxylate, 2-chloro-1 -Formylpyrene, 2-chloro-1-acetylpyrene, 2-chloro-1-be Zoirupiren, 2-chloro-1-trifluoromethyl pyrene,

2-chloro-1-nitrofluorene, 2-chlorofluorene-1-sulfonic acid, lithium 2-chlorofluorene-1-sulfonate, sodium 2-chlorofluorene-1-sulfonate, 2-chlorofluorene-1-sulfonic acid Potassium, methyl 2-chlorofluorene-1-sulfonate, ethyl 2-chlorofluorene-1-sulfonate, propyl 2-chlorofluorene-1-sulfonate, isobutyl 2-chlorofluorene-1-sulfonate, 2-chlorofluorene -1-sulfonic acid (2,2-dimethylpropyl), 2-chlorofluorene-1-sulfonic acid cyclohexyl, 2-chlorofluorene-1-carboxylic acid, methyl 2-chlorofluorene-1-carboxylate, 2-chlorofluorene -1-ethyl carboxylate, 2-chloro-1-formylfur Ren, 2-chloro-1-acetyl fluorene, 2-chloro-1-benzoyl-fluorene, 2-chloro-1-trifluoromethyl fluorene,
2-chloro-1-nitro-9,9′-bifluorene, 2-chloro-1-sulfo-9,9′-bifluorene, 2-chloro-9,9′-bifluorene-lithium sulfonate, 2-chloro-9 , 9'-bifluorene-sulfonate sodium, 2-chloro-9,9'-bifluorene-potassium sulfonate, methyl 2-chloro-9,9'-bifluorene-sulfonate, 2-chloro-9,9'-bifluorene -Ethyl sulfonate, 2-chloro-9,9'-bifluorene-propyl sulfonate, 2-chloro-9,9'-bifluorene-isobutyl sulfonate, 2-chloro-9,9'-bifluorene-sulfonic acid (2 , 2-dimethylpropyl), 2-chloro-9,9′-bifluorene-sulfonic acid cyclohexyl, 2-chloro-1-carboxy-9,9′-bifluorene, 2- Loro-1-formyl-9,9′-bifluorene, 2-chloro-1-acetyl-9,9′-bifluorene, 2-chloro-1-benzoyl-9,9′-bifluorene, 2-chloro-1-tri Fluoromethyl-9,9′-bifluorene,

2-chloro-1-nitrophenanthrene, 2-chlorophenanthrene-1-sulfonic acid, lithium 2-chlorophenanthrene-1-sulfonate, sodium 2-chlorophenanthrene-1-sulfonate, 2-chlorophenanthrene-1-sulfonic acid Potassium, methyl 2-chlorophenanthrene-1-sulfonate, ethyl 2-chlorophenanthrene-1-sulfonate, propyl 2-chlorophenanthrene-1-sulfonate, isobutyl 2-chlorophenanthrene-1-sulfonate, 2-chlorophenanthrene -1-sulfonic acid (2,2-dimethylpropyl), 2-chlorophenanthrene-1-sulfonic acid cyclohexyl, 2-chlorophenanthrene-1-carboxylic acid, 2-chloro-1-formylphenanthrene, 2-chloro-1- Acetylfe Ntoren, 2-chloro-1-benzoyl-phenanthrene, 2-chloro-1-trifluoromethyl-phenanthrene,
2-chloro-1-nitroperylene, 2-chloroperylene-1-sulfonic acid, lithium 2-chloroperylene-1-sulfonate, sodium 2-chloroperylene-1-sulfonate, 2-chloroperylene-1-sulfonic acid Potassium, methyl 2-chloroperylene-1-sulfonate, ethyl 2-chloroperylene-1-sulfonate, propyl 2-chloroperylene-1-sulfonate, isobutyl 2-chloroperylene-1-sulfonate, 2-chloroperylene -1-sulfonic acid (2,2-dimethylpropyl), 2-chloroperylene-1-sulfonic acid cyclohexyl, 2-chloroperylene-1-carboxylic acid, 2-chloro-1-formylperylene, 2-chloro-1- Acetylperylene, 2-chloro-1-benzoylperylene, 2-chloro-1-trifluoromethylpe Ren,
2-chloro-1-nitrochrysene, 2-chlorochrysene-1-sulfonic acid, lithium 2-chlorochrysene-1-sulfonate, sodium 2-chlorochrysene-1-sulfonate, 2-chlorochrysene-1-sulfonic acid Potassium, methyl 2-chlorochrysene-1-sulfonate, ethyl 2-chlorochrysene-1-sulfonate, propyl 2-chlorochrysene-1-sulfonate, isobutyl 2-chlorochrysene-1-sulfonate, 2-chlorochrysene -1-sulfonic acid (2,2-dimethylpropyl), 2-chlorochrysene-1-sulfonic acid cyclohexyl, 2-chlorochrysene-1-carboxylic acid, methyl 2-chlorochrysene-1-carboxylate, 2-chlorochrysene -1-ethyl carboxylate, 2-chloro-1-formyl licene, 2-chloro-1-acetyl Chrysene, 2-chloro-1-benzoyl chrysene, 2-chloro-1-trifluoromethyl chrysene,

2-chloro-1-nitronaphthacene, 2-chloronaphthacene-1-sulfonic acid, lithium 2-chloronaphthacene-1-sulfonate, sodium 2-chloronaphthacene-1-sulfonate, 2-chloronaphthacene -1-potassium sulfonate, methyl 2-chloronaphthacene-1-sulfonate, ethyl 2-chloronaphthacene-1-sulfonate, propyl 2-chloronaphthacene-1-propyl sulfonate, 2-chloronaphthacene-1 -Isobutyl sulfonate, 2-chloronaphthacene-1-sulfonic acid (2,2-dimethylpropyl), cyclohexyl 2-chloronaphthacene-1-sulfonate, 2-chloronaphthacene-1-carboxylic acid, 2-chloro Naphthacene-1-carboxylate methyl, ethyl 2-chloronaphthacene-1-carboxylate, 2-chloro-1-formylnaphth Sen, 2-chloro-1-acetyl naphthacene, 2-chloro-1-benzoyl naphthacene, 2-chloro-1-trifluoromethyl naphthacene,
2-chloro-1-nitropentacene, 2-chloropentacene-1-sulfonic acid, lithium 2-chloropentacene-1-sulfonate, sodium 2-chloropentacene-1-sulfonate, 2-chloropentacene-1-sulfonic acid Potassium, methyl 2-chloropentacene-1-sulfonate, ethyl 2-chloropentacene-1-sulfonate, propyl 2-chloropentacene-1-sulfonate, isobutyl 2-chloropentacene-1-sulfonate, 2-chloropentacene -1-sulfonic acid (2,2-dimethylpropyl), cyclohexyl 2-chloropentacene-1-sulfonate, 2-chloropentacene-1-carboxylic acid, methyl 2-chloropentacene-1-carboxylate, 2-chloropentacene -1-ethyl carboxylate, 2-chloro-1-formylpen Sen, 2-chloro-1-acetyl pentacene, 2-chloro-1-benzoyl pentacene, 2-chloro-1-trifluoromethyl pentacene,
2-chloro-1-nitrotriptycene, 2-chlorotriptycene-1-sulfonic acid, lithium 2-chlorotriptycene-1-sulfonate, sodium 2-chlorotriptycene-1-sulfonate, 2 -Potassium chlorotriptycene-1-sulfonate, methyl 2-chlorotriptycene-1-sulfonate, ethyl 2-chlorotriptycene-1-sulfonate, propyl 2-chlorotriptycene-1-sulfonate 2-chlorotriptycene-1-sulfonic acid isobutyl, 2-chlorotriptycene-1-sulfonic acid (2,2-dimethylpropyl), cyclohexyl 2-chlorotriptycene-1-sulfonic acid, 2-chloro Triptycene-1-carboxylic acid, methyl 2-chlorotriptycene-1-carboxylate, ethyl 2-chlorotriptycene-1-carboxylate, - chloro-1-formyl-tri Petit Sen, 2-chloro-1-acetyl tri Petit Sen, 2-chloro-1-benzoyl-tri Petit Sen, 2-chloro-1-trifluoromethyl-tri Petit Sen,

2-chloro-3-nitropyridine, 2-chloropyridine-3-sulfonic acid, lithium 2-chloropyridine-3-sulfonate, sodium 2-chloropyridine-3-sulfonate, 2-chloropyridine-3-sulfonic acid Potassium, methyl 2-chloropyridine-3-sulfonate, ethyl 2-chloropyridine-3-sulfonate, propyl 2-chloropyridine-3-sulfonate, isobutyl 2-chloropyridine-3-sulfonate, 2-chloropyridine -3-sulfonic acid (2,2-dimethylpropyl), 2-chloropyridine-3-cyclohexyl sulfonate, 2-chloropyridine-3-carboxylic acid, methyl 2-chloropyridine-3-carboxylate, 2-chloropyridine Ethyl-3-carboxylate, 2-chloro-3-formylpyridine, 2-chloro-3-acetyl Pyridine, 2-chloro-3-benzoyl pyridine, 2-chloro-3-trifluoromethylpyridine,
2-chloro-3-nitrofuran, 2-chlorofuran-3-sulfonic acid, lithium 2-chlorofuran-3-sulfonate, sodium 2-chlorofuran-3-sulfonate, 2-chlorofuran-3-sulfonic acid Potassium, methyl 2-chlorofuran-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), cyclohexyl 2-chlorofuran-3-sulfonate, 2-chlorofuran-3-carboxylic acid, methyl 2-chlorofuran-3-carboxylate, 2-chlorofuran Ethyl 3-carboxylate, 2-chloro-3-formylfuran, 2-chloro-3-acetylfuran, 2-chloro-3-ben Irufuran, 2-chloro-3-trifluoromethyl furan,

2-chloro-3-nitrothiophene, 2-chlorothiophene-3-sulfonic acid, lithium 2-chlorothiophene-3-sulfonate, sodium 2-chlorothiophene-3-sulfonate, 2-chlorothiophene-3-sulfonic acid Potassium, methyl 2-chlorothiophene-3-sulfonate, ethyl 2-chlorothiophene-3-sulfonate, propyl 2-chlorothiophene-3-sulfonate, isobutyl 2-chlorothiophene-3-sulfonate, 2-chlorothiophene -3-sulfonic acid (2,2-dimethylpropyl), 2-chlorothiophene-3-sulfonic acid cyclohexyl, 2-chlorothiophene-3-carboxylic acid, 2-chlorothiophene-3-carboxylate methyl, 2-chlorothiophene -3-ethyl carboxylate, 2-chloro-3-formylthio E down, 2-chloro-3-acetyl thiophene, 2-chloro-3-benzoyl-thiophene, 2-chloro-3-trifluoromethyl-thiophene,
7-chloro-6-nitrobenzothiadiazole, 7-chlorobenzothiadiazole-6-sulfonic acid, 7-chlorobenzothiadiazole-6-sulfonic acid lithium, 7-chlorobenzothiadiazole-6-sulfonic acid sodium, 7-chlorobenzothiadiazole -6-sulfonic acid potassium, 7-chlorobenzothiadiazole-6-sulfonic acid methyl, 7-chlorobenzothiadiazole-6-sulfonic acid ethyl, 7-chlorobenzothiadiazole-6-sulfonic acid propyl, 7-chlorobenzothiadiazole-6 -Isobutyl sulfonate, 7-chlorobenzothiadiazole-6-sulfonic acid (2,2-dimethylpropyl), 7-chlorobenzothiadiazole-6-cyclohexyl sulfonate, 7-chlorobenzothiadiazole-6-carbon 7-chlorobenzothiadiazole-6-carboxylate methyl 7-chlorobenzothiadiazole-6-carboxylate, 7-chloro-6-formylbenzothiadiazole, 7-chloro-6-acetylbenzothiadiazole, 7-chloro-6- Benzoylbenzothiadiazole, 7-chloro-6-trifluoromethylbenzothiadiazole,

2-chloro-3-nitropyrrole, 2-chloropyrrole-3-sulfonic acid, lithium 2-chloropyrrole-3-sulfonate, sodium 2-chloropyrrole-3-sulfonate, 2-chloropyrrole-3-sulfonic acid Potassium, methyl 2-chloropyrrole-3-sulfonate, ethyl 2-chloropyrrole-3-sulfonate, propyl 2-chloropyrrole-3-sulfonate, isobutyl 2-chloropyrrole-3-sulfonate, 2-chloropyrrole -3-sulfonic acid (2,2-dimethylpropyl), 2-chloropyrrole-3-cyclohexyl sulfonate, 2-chloropyrrole-3-carboxylic acid, methyl 2-chloropyrrole-3-carboxylate, 2-chloropyrrole Ethyl-3-carboxylate, 2-chloro-3-formylpyrrole, 2-chloro-3-acetyl Pyrrole, 2-chloro-3-benzoyl-pyrrole, 2-chloro-3-trifluoromethyl pyrrole,
2-chloro-3-nitroquinoline, 2-chloroquinoline-3-sulfonic acid, lithium 2-chloroquinoline-3-sulfonate, sodium 2-chloroquinoline-3-sulfonate, 2-chloroquinoline-3-sulfonic acid Potassium, methyl 2-chloroquinoline-3-sulfonate, ethyl 2-chloroquinoline-3-sulfonate, propyl 2-chloroquinoline-3-sulfonate, isobutyl 2-chloroquinoline-3-sulfonate, 2-chloroquinoline -3-sulfonic acid (2,2-dimethylpropyl), 2-chloroquinoline-3-cyclohexyl sulfonate, 2-chloroquinoline-3-carboxylic acid, methyl 2-chloroquinoline-3-carboxylate, 2-chloroquinoline Ethyl-3-carboxylate, 2-chloro-3-formylquinoline, 2-chloro-3-acetyl Quinoline, 2-chloro-3-benzoyl quinoline, 2-chloro-3-trifluoromethyl quinoline,
2-chloro-3-nitroquinoxaline, 2-chloroquinoxaline-3-sulfonic acid, lithium 2-chloroquinoxaline-3-sulfonate, sodium 2-chloroquinoxaline-3-sulfonate, 2-chloroquinoxaline-3-sulfonic acid Potassium, methyl 2-chloroquinoxaline-3-sulfonate, ethyl 2-chloroquinoxaline-3-sulfonate, propyl 2-chloroquinoxaline-3-sulfonate, isobutyl 2-chloroquinoxaline-3-sulfonate, 2-chloroquinoxaline -3-sulfonic acid (2,2-dimethylpropyl), 2-chloroquinoxaline-3-cyclohexyl sulfonate, 2-chloroquinoxaline-3-carboxylic acid, methyl 2-chloroquinoxaline-3-carboxylate, 2-chloroquinoxaline -3-ethyl carboxylate, - chloro-3-Hol Miruki tetrahydroquinoxaline, 2-chloro-3-acetyl-Quinoxaline, 2-chloro-3-benzoyl Lucino quinoxaline, 2-chloro-3-trifluoromethyl-quinoxaline,

4-chloro-5-nitropyrimidine, 4-chloropyrimidine-5-sulfonic acid, lithium 4-chloropyrimidine-5-sulfonate, sodium 4-chloropyrimidine-5-sulfonate, 4-chloropyrimidine-5-sulfonic acid Potassium, methyl 4-chloropyrimidine-5-sulfonate, ethyl 4-chloropyrimidine-5-sulfonate, propyl 4-chloropyrimidine-5-sulfonate, isobutyl 4-chloropyrimidine-5-sulfonate, 4-chloropyrimidine -5-sulfonic acid (2,2-dimethylpropyl), 4-chloropyrimidine-5-sulfonic acid cyclohexyl, 4-chloropyrimidine-5-carboxylic acid, 4-chloropyrimidine-5-carboxylate methyl, 4-chloropyrimidine Ethyl-5-carboxylate, 4-chloro-5-formylpyri Jin, 4-chloro-5-acetyl pyrimidine, 4-chloro-5-benzoyl pyrimidine, 4-chloro-5-trifluoromethyl pyrimidine,
2-chloro-3-nitropyrazine, 2-chloropyrazine-3-sulfonic acid, lithium 2-chloropyrazine-3-sulfonate, sodium 2-chloropyrazine-3-sulfonate, 2-chloropyrazine-3-sulfonic acid Potassium, methyl 2-chloropyrazine-3-sulfonate, ethyl 2-chloropyrazine-3-sulfonate, propyl 2-chloropyrazine-3-sulfonate, isobutyl 2-chloropyrazine-3-sulfonate, 2-chloropyrazine -3-sulfonic acid (2,2-dimethylpropyl), 2-chloropyrazine-3-sulfonic acid cyclohexyl, 2-chloropyrazine-3-carboxylic acid, methyl 2-chloropyrazine-3-carboxylate, 2-chloropyrazine Ethyl-3-carboxylate, 2-chloro-3-formylpyrazine, 2-chloro-3-acetyl Pyrazine, 2-chloro-3-benzoyl pyrazine, 2-chloro-3-trifluoromethyl pyrazine and the like.

（式（３）中、Ｒ^１、Ｒ^２及びＲ^３はそれぞれ独立に、水素原子、ハロゲン原子、前記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルキル基、前記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルコキシ基、前記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリール基、前記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリールオキシ基、前記Ｇ群より選ばれる基を有していてもよい炭素数７〜２０のアラルキル基、前記Ｇ群より選ばれる基を有していてもよい炭素数７〜２０のアラルキルオキシ基又は前記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０の炭化水素基を有するアミノ基を表し、
Ｒ^４は、水素原子、前記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルキル基、前記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルコキシ基、前記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリール基、前記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリールオキシ基、前記Ｇ群より選ばれる基を有していてもよい炭素数７〜２０のアラルキル基、前記Ｇ群より選ばれる基を置換基として有していてもよい炭素数７〜２０のアラルキルオキシ基又は前記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０の炭化水素基を有するアミノ基を表す。なお、隣接する炭素原子にそれぞれ結合している、Ｒ^１及びＲ^２の組み合わせ、Ｒ^２及びＲ^３の組み合わせ、並びに、Ｒ^３及びＲ^４の組み合わせは、各々が結合している炭素原子と一緒になって環を形成していてもよい。Ｅは電子求引性基を表す。）
で示されるアリールクロライド化合物（以下、アリールクロライド化合物（３）と記すことがある）に該当するものが好ましい。 Further, among the aryl chloride compounds (1) exemplified here, the formula (3)

(In Formula (3), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms which may have a group selected from Group G, An alkoxy group having 1 to 20 carbon atoms which may have a group selected from group G, an aryl group having 6 to 20 carbon atoms which may have a group selected from group G, and the group G An aryloxy group having 6 to 20 carbon atoms which may have a group selected from the above, an aralkyl group having 7 to 20 carbon atoms which may have a group selected from the G group, and a group selected from the G group. Represents an amino group having an optionally substituted aralkyloxy group having 7 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms which may have a group selected from the group G;
R ⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that may have a group selected from the G group, or a C 1 to 20 carbon group that may have a group selected from the G group. An alkoxy group, an aryl group having 6 to 20 carbon atoms which may have a group selected from the G group, an aryloxy group having 6 to 20 carbon atoms which may have a group selected from the G group, An aralkyl group having 7 to 20 carbon atoms which may have a group selected from group G, an aralkyloxy group having 7 to 20 carbon atoms which may have a group selected from group G as a substituent, or The amino group which has a C1-C20 hydrocarbon group which may have the group chosen from the said G group is represented. The combination of R ¹ and R ² , the combination of R ² and R ³ , and the combination of R ³ and R ⁴ that are bonded to adjacent carbon atoms are the same as the carbon atom to which each is bonded. To form a ring. E represents an electron withdrawing group. )
The thing corresponding to the aryl chloride compound shown below (it may be described as an aryl chloride compound (3) hereafter) is preferable.

Preferable examples of E contained in the aryl chloride compound (3) include those having a nitro group (—NO ₂ ) or a group represented by the formula (5). Specific examples of the aryl chloride compound (3) include 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. Examples thereof include methyl -1-benzenesulfonate and methyl 2-chloro-benzoate.

（式（１０）中、Ｙは、前記と同義を表す。Ｒ^１０はそれぞれ独立に、フッ素原子、前記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルキル基、前記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルコキシ基、前記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリール基、前記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリールオキシ基、前記Ｇ群より選ばれる基を有していてもよい炭素数２〜２０のアシル基又はシアノ基を表わす。ｋは０〜３の整数を表わす。また、隣接する炭素原子にそれぞれ結合している２つのＲ^１０同士は結合し、それらが結合している炭素原子と一緒になって環を形成していてもよい。）
で示されるアリールクロライド化合物（以下、アリールクロライド化合物（１０）と記すことがある）等を挙げることができる。 In the coupling reaction of the present invention, as described above, when the aryl chloride compound (1) having a chlorine atom at the ortho position of the electron withdrawing group is used, the chlorine atom is coupled even at a relatively low temperature. There are features. By utilizing such characteristics, the compound (2) can be produced regioselectively. Examples of the aryl chloride compound (1) exhibiting such effects include, for example, the formula (10)

(In Formula (10), Y represents the same meaning as described above. R ¹⁰ each independently represents a fluorine atom or an alkyl group having 1 to 20 carbon atoms which may have a group selected from Group G, An alkoxy group having 1 to 20 carbon atoms which may have a group selected from group G, an aryl group having 6 to 20 carbon atoms which may have a group selected from group G, and the group G Represents an aryloxy group having 6 to 20 carbon atoms which may have a group selected from the above, an acyl group having 2 to 20 carbon atoms which may have a group selected from the group G, or a cyano group, where k is 0. Represents an integer of ˜3, and two R ¹⁰ bonded to adjacent carbon atoms may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. )
And the like (hereinafter, may be referred to as an aryl chloride compound (10)).

（式中、Ｒ^１0、Ｙ及びｋは前記と同義を表す。）

に示されるビアリール化合物（以下、ビアリール化合物（１１）と記すことがある）を得ることができる。 Aryl chlorides Compound (10) is an electron withdrawing group chlorine atom ortho to the "-SO 3 _-Y" is - for the "SO 3 _-Y" to chlorine atoms in the meta position Thus, it has higher reactivity in the coupling reaction of the present invention. Along with this difference in reactivity, when the aryl chloride compound (10) is subjected to the coupling reaction of the present invention, the formula (11)

(Wherein R ¹⁰ , Y and k are as defined above.)

Can be obtained (hereinafter sometimes referred to as biaryl compound (11)).

  Table 1 below shows suitable examples of the aryl chloride compound (10) and biaryl compounds (11) obtained from these preferable aryl chloride compounds (10).

（式中、Ｒ^１0及びｋは前記と同義を表す。）
で示されるアリールクロライド化合物についてカップリング反応を行うと、式（１３）

（式中、Ｒ^１0及びｋは前記と同義を表す。）
に示されるビアリール化合物を製造することができる。 Moreover, Formula (12)

(In the formula, R ¹⁰ and k are as defined above.)
When the coupling reaction is performed on the aryl chloride compound represented by formula (13),

(In the formula, R ¹⁰ and k are as defined above.)
Can be produced.

（式中、Ｒ^１１及びＲ^１２は、それぞれ独立に、水素原子、ハロゲン原子、前記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルキル基、前記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルコキシ基、前記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリール基、前記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリールオキシ基、前記Ｇ群より選ばれる基を有していてもよい炭素数７〜２０のアラルキル基、前記Ｇ群より選ばれる基を有していてもよい炭素数７〜２０のアラルキルオキシ基又は前記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０の炭化水素基を有するアミノ基を表し、
Ｒ^１４は、水素原子、前記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルキル基、前記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０のアルコキシ基、前記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリール基、前記Ｇ群より選ばれる基を有していてもよい炭素数６〜２０のアリールオキシ基、前記Ｇ群より選ばれる基を有していてもよい炭素数７〜２０のアラルキル基、前記Ｇ群より選ばれる基を置換基として有していてもよい炭素数７〜２０のアラルキルオキシ基又は前記Ｇ群より選ばれる基を有していてもよい炭素数１〜２０の炭化水素基を有するアミノ基を表す。なお、隣接する炭素原子にそれぞれ結合している、Ｒ^１１及びＲ^１２の組み合わせ、並びに、Ｒ^１２及びＲ^１４の組み合わせは、各々が結合している炭素原子と一緒になって環を形成していてもよい。Ａは酸素原子もしくは硫黄原子を表す。）
で示される化合物等を挙げることができる。 According to the present invention, even if Ar contained in the aryl chloride compound (1) is a heterocyclic group having aromaticity (however, the heterocyclic group may have a substituent) is coupled. The reaction can be performed.
As the aryl chloride compound (1) containing a heterocyclic group having aromaticity (however, the heterocyclic group may have a substituent) as Ar, for example, a hetero atom contained in Ar and Ar A compound containing a heterocyclic group in which a carbon atom bonded to Cl is directly bonded is preferable. Specifically, equation (7)

(Wherein R ¹¹ and R ¹² are each independently selected from a hydrogen atom, a halogen atom, a C 1-20 alkyl group optionally having a group selected from the G group, and the G group. An alkoxy group having 1 to 20 carbon atoms which may have a group, an aryl group having 6 to 20 carbon atoms which may have a group selected from the G group, and a group selected from the G group An aryloxy group having 6 to 20 carbon atoms which may be present, an aralkyl group having 7 to 20 carbon atoms which may have a group selected from group G, and a group selected from group G. Represents an amino group having a C1-C20 hydrocarbon group which may have a good C7-20 aralkyloxy group or a group selected from the group G;
R ¹⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that may have a group selected from the G group, or a C 1 to 20 carbon group that may have a group selected from the G group. An alkoxy group, an aryl group having 6 to 20 carbon atoms which may have a group selected from the G group, an aryloxy group having 6 to 20 carbon atoms which may have a group selected from the G group, An aralkyl group having 7 to 20 carbon atoms which may have a group selected from group G, an aralkyloxy group having 7 to 20 carbon atoms which may have a group selected from group G as a substituent, or The amino group which has a C1-C20 hydrocarbon group which may have the group chosen from the said G group is represented. The combination of R ¹¹ and R ^{12 and} the combination of R ¹² and R ¹⁴ that are bonded to adjacent carbon atoms, respectively, form a ring together with the carbon atoms to which they are bonded. May be. A represents an oxygen atom or a sulfur atom. )
And the like.

（式中、Ａ、Ｒ^１１、Ｒ^１２およびＲ^１４は前記と同義である。）
で示されるビアリール化合物が製造可能である。 By coupling the compound represented by the formula (7), the formula (8)

(In the formula, A, R ¹¹ , R ¹² and R ¹⁴ are as defined above.)
The biaryl compound shown by can be manufactured.

  The compound (2) obtained by the present invention may be further purified. In the purification method of the compound (2), after the coupling reaction of the present invention is performed, the produced compound (2) is separated from unreacted metal copper, copper salt and aryl chloride compound (1), and a solvent. It can be obtained by purification. Such separation and purification can be performed from known purification operations such as filtration, extraction, concentration, recrystallization, reprecipitation, and chromatographic separation, or purification operations that combine these, and the types of the unreacted substances and the objects of separation and purification. What is necessary is just to select optimal operation suitably according to the kind of compound (2).

Hereinafter, the present invention will be described in more detail with reference to examples.
In the following examples, the compound (2) produced after the coupling reaction was analyzed by high performance liquid chromatography (LC) or gas chromatography (GC), and the reaction yield was calculated from the area value of the obtained chromatogram. .

The analysis conditions for LC analysis are as follows.
<Analysis conditions>
LC measuring device: LC-10AT (manufactured by Shimadzu Corporation)
Column: L-Column ODS (5 μm, 4.6 mmφ × 15 cm)
Column temperature: 40 ° C
Mobile phase: A: 0.1% n-tetrabutylammonium bromide aqueous solution B: 0.1% n-tetrabutylammonium bromide acetonitrile solution Gradient: 0 min B = 30%
20min B = 90%
35min B = 90%
35.1min B = 30%
45 min STOP TOTAL analysis time 45 minutes Flow rate: 1.0 mL / min Detection: UV absorption (wavelength: 254 nm)

The analysis conditions for GC analysis are as follows.
<Analysis conditions>
GC measuring device: GC-2010A (manufactured by Shimadzu Corporation)
Column: J & W DB-1701 (0.32mmφ × 30m, 1.0μm)
Column temperature: 50 ° C (0 min) → (10 ° C / min) → 150 ° C (0 min) → (20 ° C / min) → 280 ° C (8 min)
TOTAL analysis time 24.5 minutes Inlet temperature: 250 ° C, detector temperature: 250 ° C (FID, range 10 ¹ )
Carrier gas: He (flow rate approx. 2.3mL / min)
Inlet pressure: 75.2 kPa (Control mode pressure)
Split ratio: Total flow rate 55.9mL / min (split ratio approx. 1/22)
Injection volume: 1μL

２，５−ジクロロベンゼンスルホン酸ナトリウム０．８０ｇ、粉末状金属銅０．４１ｇ、ヨウ化銅（Ｉ）０．０３１、Ｎ，Ｎ，Ｎ’，Ｎ’，−テトラメチルエチレンジアミン０．０１９ｇ及びＮ−メチル−２−ピロリドン４．０ｇを混合し、得られた混合物を、窒素雰囲気を保持しつつ、１００℃まで昇温した。窒素雰囲気を保持したまま、１００℃で４時間、当該混合物を撹拌した。冷却後、反応混合物をサンプリングして、前記ＬＣ分析を行い、生成ビアリール化合物である４，４’−ジクロロ−２，２’−ビフェニルジスルホン酸ジナトリウムの収率を算出した。収率：９８％。 [Example 1]

Sodium 2,5-dichlorobenzenesulfonate 0.80 g, powdered metallic copper 0.41 g, copper (I) iodide 0.031, N, N, N ′, N ′,-tetramethylethylenediamine 0.019 g and N -4.0 g of methyl-2-pyrrolidone was mixed, and the resulting mixture was heated to 100 ° C while maintaining a nitrogen atmosphere. The mixture was stirred at 100 ° C. for 4 hours while maintaining the nitrogen atmosphere. After cooling, the reaction mixture was sampled and subjected to the LC analysis, and the yield of disodium 4,4′-dichloro-2,2′-biphenyldisulfonate, which is the resulting biaryl compound, was calculated. Yield: 98%.

２，５−ジクロロベンゼンスルホン酸ナトリウム０．８０ｇ、粉末状金属銅０．４１ｇ、ヨウ化銅（Ｉ）０．０３１ｇ、２，２’−ビピリジン０．０２５ｇ及びＮ−メチル−２−ピロリドン４．０ｇを混合し、得られた混合物を、窒素雰囲気を保持しつつ、１００℃まで昇温した。窒素雰囲気を保持したまま、１００℃で４時間、当該混合物を撹拌した。冷却後、反応混合物をサンプリングして、前記ＬＣ分析を行い、生成ビアリール化合物である４，４’−ジクロロ−２，２’−ビフェニルジスルホン酸ジナトリウムの収率を算出した。収率：９６％。 [Example 2]

Sodium 0.85-g, 2,5-dichlorobenzenesulfonate, 0.41 g of powdered metallic copper, 0.031 g of copper (I) iodide, 0.025 g of 2,2′-bipyridine and N-methyl-2-pyrrolidone 0 g was mixed, and the resulting mixture was heated to 100 ° C. while maintaining a nitrogen atmosphere. The mixture was stirred at 100 ° C. for 4 hours while maintaining the nitrogen atmosphere. After cooling, the reaction mixture was sampled and subjected to the LC analysis, and the yield of disodium 4,4′-dichloro-2,2′-biphenyldisulfonate, which is the resulting biaryl compound, was calculated. Yield: 96%.

２，５−ジクロロベンゼンスルホン酸ナトリウム０．５０ｇ、粉末状金属銅０．２５ｇ、ヨウ化銅（Ｉ）０．０１９ｇ、１，１０−フェナントロリン０．０１８ｇ及びＮ−メチル−２−ピロリドン２．５ｇを混合し、得られた混合物を、窒素雰囲気を保持しつつ、１００℃まで昇温した。窒素雰囲気を保持したまま、１００℃で４時間、当該混合物を撹拌した。冷却後、反応混合物をサンプリングして、前記ＬＣ分析を行い、生成ビアリール化合物である４，４’−ジクロロ−２，２’−ビフェニルジスルホン酸ジナトリウムの収率を算出した。収率：９５％。 [Example 3]

Sodium 2,5-dichlorobenzenesulfonate 0.50 g, powdered metal copper 0.25 g, copper (I) iodide 0.019 g, 1,10-phenanthroline 0.018 g and N-methyl-2-pyrrolidone 2.5 g The mixture was heated to 100 ° C. while maintaining a nitrogen atmosphere. The mixture was stirred at 100 ° C. for 4 hours while maintaining the nitrogen atmosphere. After cooling, the reaction mixture was sampled and subjected to the LC analysis, and the yield of disodium 4,4′-dichloro-2,2′-biphenyldisulfonate, which is the resulting biaryl compound, was calculated. Yield: 95%.

２，５−ジクロロベンゼンスルホン酸（２，２−ジメチルプロピル）０．５９ｇ、粉末状金属銅０．２５ｇ、ヨウ化銅（Ｉ）０．０１９ｇ、Ｎ，Ｎ，Ｎ’，Ｎ’，−テトラメチルエチレンジアミン０．０３５ｇ及びＮ−メチル−２−ピロリドン２．５ｇを混合し、得られた混合物を、窒素雰囲気を保持しつつ、１００℃まで昇温した。窒素雰囲気を保持したまま、１００℃で４時間、当該混合物を撹拌した。冷却後、反応混合物をサンプリングして、前記ＬＣ分析を行い、生成ビアリール化合物である４，４’−ジクロロビフェニル−２，２’−ジスルホン酸ジ（２，２−ジメチルプロピル）の収率を算出した。収率：５６％。 [Example 4]

2,5-dichlorobenzenesulfonic acid (2,2-dimethylpropyl) 0.59 g, powdered metal copper 0.25 g, copper iodide (I) 0.019 g, N, N, N ′, N ′,-tetra 0.035 g of methylethylenediamine and 2.5 g of N-methyl-2-pyrrolidone were mixed, and the resulting mixture was heated to 100 ° C. while maintaining a nitrogen atmosphere. The mixture was stirred at 100 ° C. for 4 hours while maintaining the nitrogen atmosphere. After cooling, the reaction mixture is sampled, the LC analysis is performed, and the yield of 4,4′-dichlorobiphenyl-2,2′-disulfonic acid di (2,2-dimethylpropyl), which is the resulting biaryl compound, is calculated. did. Yield: 56%.

２，５−ジクロロベンゼンスルホン酸（２，２−ジメチルプロピル）１２０．０ｇ、粉末状金属銅２８．２ｇ及びトルエン３００．０ｇを加え、混合物が２９０ｇになるまで濃縮し、水分値が２１ｐｐｍであることを確認した。ここにトリフルオロメタンスルホン酸銅（II）１．４６ｇ及びＮ，Ｎ，Ｎ’，Ｎ’，−テトラメチルエチレンジアミン２．３５ｇを加え、得られた混合物を、窒素雰囲気を保持しつつ、１００℃まで昇温した。窒素雰囲気を保持したまま、１００℃で２４時間、当該混合物を撹拌した。反応混合物をサンプリングして、前記ＬＣ分析を行い、生成ビアリール化合物である４，４’−ジクロロビフェニル−２，２’−ジスルホン酸ジ（２，２−ジメチルプロピル）の収率を算出した。収率：８６％。
得られた反応マスにトルエン４８０．０ｇを加え、１８．９％塩酸３８８．２ｇに滴下し、７５℃で１０分間攪拌した。７５℃のまま水層を除去し、得られた油層をｐＨ４になるまで水で洗浄し、５℃まで冷却して固体を析出させた。得られた固体を濾過し、乾燥することによって４，４’−ジクロロビフェニル−２，２’−ジスルホン酸ジ（２，２−ジメチルプロピル）７２．４ｇを単離した（収率６８％）。 [Example 5]

Add 120.0 g of 2,5-dichlorobenzenesulfonic acid (2,2-dimethylpropyl), 28.2 g of powdered metallic copper and 300.0 g of toluene, concentrate until the mixture is 290 g, and have a moisture value of 21 ppm. It was confirmed. To this, 1.46 g of copper (II) trifluoromethanesulfonate and 2.35 g of N, N, N ′, N ′,-tetramethylethylenediamine were added, and the resulting mixture was maintained at 100 ° C. while maintaining a nitrogen atmosphere. The temperature rose. The mixture was stirred at 100 ° C. for 24 hours while maintaining the nitrogen atmosphere. The reaction mixture was sampled and subjected to the LC analysis, and the yield of the resulting biaryl compound 4,4′-dichlorobiphenyl-2,2′-disulfonic acid di (2,2-dimethylpropyl) was calculated. Yield: 86%.
To the obtained reaction mass, 480.0 g of toluene was added, added dropwise to 388.2 g of 18.9% hydrochloric acid, and stirred at 75 ° C. for 10 minutes. The aqueous layer was removed at 75 ° C., and the resulting oil layer was washed with water until pH 4 and cooled to 5 ° C. to precipitate a solid. The obtained solid was filtered and dried to isolate 72.4 g of 4,4′-dichlorobiphenyl-2,2′-disulfonic acid di (2,2-dimethylpropyl) (yield 68%).

２−クロロチオフェン０．９５ｇ、粉末状金属銅１．０２ｇ、トリフルオロメタンスルホン酸銅（II）０．０２９ｇ、Ｎ，Ｎ，Ｎ’，Ｎ’，−テトラメチルエチレンジアミン０．０９３ｇ及びＮ−メチル−２−ピロリドン１．０ｇを混合し、得られた混合物を、窒素雰囲気を保持しつつ、１５０℃まで昇温した。窒素雰囲気を保持したまま、１５０℃で４時間、当該混合物を撹拌した。冷却後、反応混合物をサンプリングして、前記ＧＣ分析を行い、生成ビアリール化合物である２，２’−ビチオフェンの収率を算出した。収率：２０％。 [Example 6]

0.95 g of 2-chlorothiophene, 1.02 g of powdered metallic copper, 0.029 g of copper (II) trifluoromethanesulfonate, 0.093 g of N, N, N ′, N ′,-tetramethylethylenediamine and N-methyl- 1.0 g of 2-pyrrolidone was mixed, and the resulting mixture was heated to 150 ° C. while maintaining a nitrogen atmosphere. The mixture was stirred at 150 ° C. for 4 hours while maintaining the nitrogen atmosphere. After cooling, the reaction mixture was sampled and subjected to the GC analysis, and the yield of 2,2′-bithiophene, which was the resulting biaryl compound, was calculated. Yield: 20%.

２−クロロニトロベンゼン０．９５ｇ、粉末状金属銅０．７７ｇ、ヨウ化銅（Ｉ）０．０５７ｇ、Ｎ，Ｎ，Ｎ’，Ｎ’，−テトラメチルエチレンジアミン０．０３５ｇ及びＮ−メチル−２−ピロリドン７．５ｇを混合し、得られた混合物を、窒素雰囲気を保持しつつ、１５０℃まで昇温した。窒素雰囲気を保持したまま、１５０℃で４時間、当該混合物を撹拌した。冷却後、反応混合物をサンプリングして、前記ＧＣ分析を行い、生成ビアリール化合物である２，２’−ジニトロビフェニルの収率を算出した。収率：５４％。 [Example 7]

0.95 g of 2-chloronitrobenzene, 0.77 g of powdered metallic copper, 0.057 g of copper (I) iodide, 0.035 g of N, N, N ′, N ′,-tetramethylethylenediamine and N-methyl-2- 7.5 g of pyrrolidone was mixed, and the resulting mixture was heated to 150 ° C. while maintaining a nitrogen atmosphere. The mixture was stirred at 150 ° C. for 4 hours while maintaining the nitrogen atmosphere. After cooling, the reaction mixture was sampled and subjected to the GC analysis, and the yield of 2,2′-dinitrobiphenyl, which was the resulting biaryl compound, was calculated. Yield: 54%.

２−クロロ安息香酸メチル１．３６ｇ、粉末状金属銅１．０２ｇ、トリフルオロメタンスルホン酸銅（II）０．０２９ｇ、Ｎ，Ｎ，Ｎ’，Ｎ’，−テトラメチルエチレンジアミン０．０９３ｇ及びＮ−メチル−２−ピロリドン１．０ｇを混合し、得られた混合物を、窒素雰囲気を保持しつつ、１５０℃まで昇温した。窒素雰囲気を保持したまま、１５０℃で４時間、該混合物を撹拌した。冷却後、反応混合物をサンプリングして、前記ＧＣ分析を行い、生成ビアリール化合物である２，２’−ビス(メトキシカルボニル)ビフェニルの収率を算出した。収率：２９％。 [Example 8]

1.36 g of methyl 2-chlorobenzoate, 1.02 g of powdered metallic copper, 0.029 g of copper (II) trifluoromethanesulfonate, 0.093 g of N, N, N ′, N ′,-tetramethylethylenediamine and N— 1.0 g of methyl-2-pyrrolidone was mixed, and the resulting 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. After cooling, the reaction mixture was sampled and subjected to the GC analysis, and the yield of 2,2′-bis (methoxycarbonyl) biphenyl, which was the resulting biaryl compound, was calculated. Yield: 29%.

２，５−ジクロロベンゼンスルホン酸（２，２−ジメチルプロピル）２．３８ｇ、粉末状金属銅０．５６ｇ、トリフルオロメタンスルホン酸銅（II）０．０２９ｇ、１，４，７−トリメチル−１，４，７−トリアザシクロノナン０．２１ｇ及びトルエン２．３８ｇを混合し、得られた混合物を、窒素雰囲気を保持しつつ、１００℃まで昇温した。窒素雰囲気を保持したまま、１００℃で４時間、当該混合物を撹拌した。冷却後、反応混合物をサンプリングして、前記ＬＣ分析を行い、生成ビアリール化合物である４，４’−ジクロロビフェニル−２，２’−ジスルホン酸ジ（２，２−ジメチルプロピル）の収率を算出した。収率：８２％。 [Example 9]

2.38 g of 2,5-dichlorobenzenesulfonic acid (2,2-dimethylpropyl), 0.56 g of powdered metal copper, 0.029 g of copper (II) trifluoromethanesulfonate, 1,4,7-trimethyl-1, 4,7-Triazacyclononane 0.21 g and toluene 2.38 g were mixed, and the resulting mixture was heated to 100 ° C. while maintaining a nitrogen atmosphere. The mixture was stirred at 100 ° C. for 4 hours while maintaining the nitrogen atmosphere. After cooling, the reaction mixture is sampled, the LC analysis is performed, and the yield of 4,4′-dichlorobiphenyl-2,2′-disulfonic acid di (2,2-dimethylpropyl), which is the resulting biaryl compound, is calculated. did. Yield: 82%.

２−クロロピリジン０．９１ｇ、粉末状金属銅１．０２ｇ、トリフルオロメタンスルホン酸銅（II）０．０２９ｇ、Ｎ，Ｎ，Ｎ’，Ｎ’，−テトラメチルエチレンジアミン０．０９３ｇ及びＮ−メチル−２−ピロリドン１．０ｇを混合し、得られた混合物を、窒素雰囲気を保持しつつ、１５０℃まで昇温した。窒素雰囲気を保持したまま、１５０℃で４時間、当該混合物を撹拌した。冷却後、反応混合物をサンプリングして、前記ＧＣ分析を行い、生成ビアリール化合物である２，２’−ビピリジンの収率を算出した。収率：１０％。 [Example 10]

0.91 g of 2-chloropyridine, 1.02 g of powdered metallic copper, 0.029 g of copper (II) trifluoromethanesulfonate, 0.093 g of N, N, N ′, N ′,-tetramethylethylenediamine and N-methyl- 1.0 g of 2-pyrrolidone was mixed, and the resulting mixture was heated to 150 ° C. while maintaining a nitrogen atmosphere. The mixture was stirred at 150 ° C. for 4 hours while maintaining the nitrogen atmosphere. After cooling, the reaction mixture was sampled and subjected to the GC analysis, and the yield of 2,2′-bipyridine, which was the resulting biaryl compound, was calculated. Yield: 10%.

２，５−ジクロロベンゾフェノン２．０ｇ、粉末状金属銅１．０２ｇ、トリフルオロメタンスルホン酸銅（II）０．０２９ｇ、Ｎ，Ｎ，Ｎ’，Ｎ’，−テトラメチルエチレンジアミン０．０９３ｇ及びＮ−メチル−２−ピロリドン１．０ｇを混合し、得られた混合物を、窒素雰囲気を保持しつつ、１５０℃まで昇温した。窒素雰囲気を保持したまま、１５０℃で４時間、当該混合物を撹拌した。冷却後、反応混合物をサンプリングして、前記ＧＣ分析を行い、生成ビアリール化合物である４，４’−ジクロロ−２，２’−ビス(ベンゾイル)ビフェニルの収率を算出した。収率：２１％。 [Example 11]

2.0 g of 2,5-dichlorobenzophenone, 1.02 g of powdered metal copper, 0.029 g of copper (II) trifluoromethanesulfonate, 0.093 g of N, N, N ′, N ′,-tetramethylethylenediamine and N— 1.0 g of methyl-2-pyrrolidone was mixed, and the resulting mixture was heated to 150 ° C. while maintaining a nitrogen atmosphere. The mixture was stirred at 150 ° C. for 4 hours while maintaining the nitrogen atmosphere. After cooling, the reaction mixture was sampled and subjected to the GC analysis, and the yield of 4,4′-dichloro-2,2′-bis (benzoyl) biphenyl, which was the resulting biaryl compound, was calculated. Yield: 21%.

ｐ−トルエンスルホン酸・１水和物１．１５ｇと酢酸銅（II）０．５５ｇ及びトルエン１３５ｇを加え、１１０℃で１時間加熱して、トルエンを５４ｇ留去した。濃縮マス内に生成したｐ−トルエンスルホン酸銅を含む混合物に、２，５−ジクロロベンゼンスルホン酸（２，２−ジメチルプロピル）４５．０ｇ、粉末状金属銅１０．６ｇを加え、１００℃で２０時間、当該混合物を撹拌した。反応混合物をサンプリングして、前記ＬＣ分析を行い、生成ビアリール化合物である４，４’−ジクロロビフェニル−２，２’−ジスルホン酸ジ（２，２−ジメチルプロピル）の収率を算出した。収率：７７％。 [Example 12]

1.15 g of p-toluenesulfonic acid monohydrate, 0.55 g of copper (II) acetate and 135 g of toluene were added, and the mixture was heated at 110 ° C. for 1 hour to distill off 54 g of toluene. To a mixture containing copper p-toluenesulfonate formed in the concentrated mass, 45.0 g of 2,5-dichlorobenzenesulfonic acid (2,2-dimethylpropyl) and 10.6 g of powdered metal copper are added, and the mixture is 100 ° C. The mixture was stirred for 20 hours. The reaction mixture was sampled and subjected to the LC analysis, and the yield of the resulting biaryl compound 4,4′-dichlorobiphenyl-2,2′-disulfonic acid di (2,2-dimethylpropyl) was calculated. Yield: 77%.

２，５−ジクロロベンゼンスルホン酸（２，２−ジメチルプロピル）４５．０ｇ、粉末状金属銅１０．６ｇ、水酸化銅（II）０．３０ｇ、メタンスルホン酸０．５８ｇ及びトルエン９０ｇを加え、反応マス内に生成したメタンスルホン酸銅を含む混合物が１０４ｇになるまで濃縮し、水分値が２０ｐｐｍであることを確認した。ここにＮ，Ｎ，Ｎ’，Ｎ’，−テトラメチルエチレンジアミン３．５ｇを加え、得られた混合物を、窒素雰囲気を保持しつつ、１０５℃まで昇温した。窒素雰囲気を保持したまま、１０５℃で２６時間、当該混合物を撹拌した。反応混合物をサンプリングして、前記ＬＣ分析を行い、生成ビアリール化合物である４，４’−ジクロロビフェニル−２，２’−ジスルホン酸ジ（２，２−ジメチルプロピル）の収率を算出した。収率：７２％。 [Example 13]

Add 45.0 g of 2,5-dichlorobenzenesulfonic acid (2,2-dimethylpropyl), 10.6 g of powdered metal copper, 0.30 g of copper hydroxide (II), 0.58 g of methanesulfonic acid and 90 g of toluene, It concentrated until the mixture containing the copper methanesulfonate produced | generated in the reaction mass became 104g, and confirmed that the moisture value was 20 ppm. N, N, N ′, N ′,-tetramethylethylenediamine (3.5 g) was added thereto, and the resulting mixture was heated to 105 ° C. while maintaining a nitrogen atmosphere. The mixture was stirred at 105 ° C. for 26 hours while maintaining the nitrogen atmosphere. The reaction mixture was sampled and subjected to the LC analysis, and the yield of the resulting biaryl compound 4,4′-dichlorobiphenyl-2,2′-disulfonic acid di (2,2-dimethylpropyl) was calculated. Yield: 72%.

  According to the present invention, a biaryl compound can be produced from an easily available aryl chloride compound.

Claims (15)

In the presence of an amine compound containing at least two tertiary amino groups in the molecule, metallic copper and a copper salt,
(The copper salt is a Bronsted acid having an acid dissociation constant (pKa) of 10 or less (the Bronsted acid is hydrogen halide, sulfuric acid, thiocyanic acid, phosphoric acid, carbonic acid, nitric acid, methanesulfonic acid, trifluoromethanesulfone). A Bronsted base from which hydrogen ions are removed from acid, benzenesulfonic acid, acetic acid, trifluoroacetic acid, pentafluoropropionic acid, acetylacetone, phenol, pentafluorophenol and thiophenol. (Salt consisting of copper cations.)
Formula (1)
Ar-Cl (1)
(In the formula (1), Ar represents at least one electron-withdrawing group at the ortho position of the chlorine atom (the substituent constant σ _p ⁰ value of the electron-withdrawing group is in the range of 0.3 to 1). The aromatic group may have a substituent other than the electron-withdrawing group.
Comprising the step of coupling an aryl chloride compound represented by formula (2):
Ar-Ar (2)
(In the formula (2), Ar has the same meaning as described above.)
The manufacturing method of biaryl compound shown by these.   2. The production method according to claim 1, wherein the nitrogen atom constituting the tertiary amino group contained in the amine compound is a nitrogen atom bonded to three carbon atoms. Copper salt is copper halide, copper sulfate, copper thiocyanate, copper phosphate, copper carbonate, copper nitrate, copper methanesulfonate, copper trifluoromethanesulfonate (I) -benzene complex, copper trifluoromethanesulfonate (I)- Toluene complex, copper (II) trifluoromethanesulfonate, copper benzenesulfonate, copper acetate, copper trifluoroacetate, copper pentafluoropropionate, copper (II) acetylacetonate, copper phenolate, copper pentafluorophenolate and copper the process according to claim 1 Symbol mounting, characterized in that at least one selected from the group consisting of thiophenolate.   The method according to claim 1 or 2, wherein the copper salt is a copper halide. The manufacturing method according to any one of claims 1 to 4 , wherein the amount of copper salt used is in the range of 0.01 mol to 10 mol with respect to 1 mol of the amine compound. The amine compound is 2,2′-bipyridyl, 1,10-phenanthroline, 1,4,7-trimethyl-1,4,7-triazacyclononane, N, N, N ′, N′-tetramethylethylenediamine and N, N, N ', the method according to any one of claims 1-5, characterized in that at least one amine compound selected from the group consisting of N'- tetraethyl ethylenediamine. The production method according to any one of claims 1 to 6 , wherein the amount of the amine compound used is in the range of 0.0001 mol to 0.5 mol with respect to 1 mol of the aryl chloride compound. The aryl chloride compound has the formula (3)

(In Formula (3), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms which may have a group selected from the following group G; From an alkoxy group having 1 to 20 carbon atoms which may have a group selected from the following G group, an aryl group having 6 to 20 carbon atoms which may have a group selected from the following G group, from the following G group An aryloxy group having 6 to 20 carbon atoms which may have a selected group, an aralkyl group having 7 to 20 carbon atoms which may have a group selected from the following G group, and a group selected from the following G group An aralkyloxy group having 7 to 20 carbon atoms which may have an amino group having a hydrocarbon group having 1 to 20 carbon atoms which may have a group selected from the following group G;
R ⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a group selected from the following G group, or a group having 1 to 20 carbon atoms which may have a group selected from the following G group. An alkoxy group, an aryl group having 6 to 20 carbon atoms which may have a group selected from the following G group, an aryloxy group having 6 to 20 carbon atoms which may have a group selected from the following G group, Aralkyl group having 7 to 20 carbon atoms which may have a group selected from the following G group, Aralkyloxy group having 7 to 20 carbon atoms which may have a group selected from the following G group as a substituent, or The amino group which has a C1-C20 hydrocarbon group which may have the group chosen from the following G group is represented. The combination of R ¹ and R ² , the combination of R ² and R ³ , and the combination of R ³ and R ⁴ that are bonded to adjacent carbon atoms are the same as the carbon atom to which each is bonded. To form a ring. E represents an electron withdrawing group (the substituent constant σ _p ⁰ value of the electron withdrawing group is in the range of 0.3 to 1) . )
An aryl chloride compound represented by:
The biaryl compound is of the formula (4)

(In the formula (4), R ¹ , R ² , R ³ , R ⁴ and E are as defined above.)
The method according to any one of claims 1-7, characterized in that in a biaryl compound represented.
[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; an aryloxy group having 6 to 12 carbon atoms The electron withdrawing group has the formula (5)

(In Formula (5), Y is a hydrogen ion, an alkali metal ion, Formula (6)

(In formula (6), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.)
Or an alkyl group having 1 to 20 carbon atoms which may have a group selected from the following G group, or 6 to 20 carbon atoms which may have a group selected from the following G group. Represents an aryl group.
[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; an aryloxy group having 6 to 12 carbon atoms)
The production method according to claim 1, wherein the group is a group represented by the formula : The aryl chloride compound has the formula (10)

(In Formula (10), Y is a hydrogen ion, an alkali metal ion, Formula (6)

(In formula (6), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.)
Or an alkyl group having 1 to 20 carbon atoms which may have a group selected from the following G group, or 6 to 20 carbon atoms which may have a group selected from the following G group. Represents an aryl group. R ¹⁰ is independently a fluorine atom, an alkyl group having 1 to 20 carbon atoms that may have a group selected from the following G group, or a carbon number that may have a group selected from the following G group. An alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms which may have a group selected from the following group G, and a 6 to 20 carbon atom which may have a group selected from the following group G An aryloxy group, an acyl group having 2 to 20 carbon atoms and a cyano group which may have a group selected from Group G below. k represents an integer of 0 to 3. Further, two R ¹⁰ bonded to adjacent carbon atoms may be bonded to each other to form a ring together with the carbon atoms to which they are bonded.
[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; an aryloxy group having 1 to 12 carbon atoms)
And the biaryl compound is represented by the formula (11):

(Wherein R ¹⁰ , Y and k are as defined above.)
The method according to any one of claims 1-7, characterized in that in a biaryl compound represented. The method according to claim 9 or 10 , wherein Y is an alkali metal ion. Electron withdrawing group, The method according to any one of claims 1-8, characterized in that a nitro group (-NO _2). In the presence of an amine compound containing at least two tertiary amino groups in the molecule, metallic copper and a copper salt,
(The copper salt is a Bronsted acid having an acid dissociation constant (pKa) of 10 or less (the Bronsted acid is hydrogen halide, sulfuric acid, thiocyanic acid, phosphoric acid, carbonic acid, nitric acid, methanesulfonic acid, trifluoromethanesulfone). A Bronsted base from which hydrogen ions are removed from acid, benzenesulfonic acid, acetic acid, trifluoroacetic acid, pentafluoropropionic acid, acetylacetone, phenol, pentafluorophenol and thiophenol. (Salt consisting of copper cations.)
Formula (1)
Ar-Cl (1)
(In formula (1), Ar is a heterocyclic group having aromaticity (however, the heterocyclic group may have a substituent), and a nitrogen atom, oxygen atom or sulfur atom contained in Ar) Represents a heterocyclic group in which the carbon atom bonded to Cl of Ar is directly bonded .)
Comprising the step of coupling an aryl chloride compound represented by formula (2):
Ar-Ar (2)
(In the formula (2), Ar has the same meaning as described above.)
The manufacturing method of biaryl compound shown by these. In the presence of an amine compound containing at least two tertiary amino groups in the molecule, metallic copper and a copper salt,
(The copper salt is a Bronsted acid having an acid dissociation constant (pKa) of 10 or less (the Bronsted acid is hydrogen halide, sulfuric acid, thiocyanic acid, phosphoric acid, carbonic acid, nitric acid, methanesulfonic acid, trifluoromethanesulfone). A Bronsted base from which hydrogen ions are removed from acid, benzenesulfonic acid, acetic acid, trifluoroacetic acid, pentafluoropropionic acid, acetylacetone, phenol, pentafluorophenol and thiophenol. (Salt consisting of copper cations.)
Formula (7)

Wherein R ¹¹ and R ¹² are each independently selected from 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 the following G group. An alkoxy group having 1 to 20 carbon atoms which may have a group, an aryl group having 6 to 20 carbon atoms which may have a group selected from the following G group, and a group selected from the following G group May have an aryloxy group having 6 to 20 carbon atoms, a group selected from the following G group, an aralkyl group having 7 to 20 carbon atoms, or a group selected from the following G group. Represents an amino group having a C1-C20 hydrocarbon group which may have a good C7-20 aralkyloxy group or a group selected from the following G group;
R ¹⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that may have a group selected from the following G group, or a C 1 to 20 carbon group that may have a group selected from the following G group. An alkoxy group, an aryl group having 6 to 20 carbon atoms which may have a group selected from the following G group, an aryloxy group having 6 to 20 carbon atoms which may have a group selected from the following G group, Aralkyl group having 7 to 20 carbon atoms which may have a group selected from the following G group, Aralkyloxy group having 7 to 20 carbon atoms which may have a group selected from the following G group as a substituent, or The amino group which has a C1-C20 hydrocarbon group which may have the group chosen from the following G group is represented. The combination of R ¹¹ and R ^{12 and} the combination of R ¹² and R ¹⁴ that are bonded to adjacent carbon atoms, respectively, form a ring together with the carbon atoms to which they are bonded. May be. A represents an oxygen atom or a sulfur atom.
[G group]
A fluorine atom; a cyano group; an alkoxy group having 1 to 12 carbon atoms; an aryl group having 6 to 12 carbon atoms; an aryloxy group having 1 to 12 carbon atoms)
A compound represented by
Comprising the step of coupling an aryl chloride compound represented by formula (8):

(In the formula, A, R ¹¹ , R ¹² and R ¹⁴ are as defined above.)
The manufacturing method of biaryl compound shown by these. The process according to any one of claims 1 to 14 , wherein the coupling step is a step performed in the presence of an aprotic polar solvent.