JP2011006325A - Method for producing conjugated aromatic compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a conjugated aromatic compound in high yield.SOLUTION: The method for producing the conjugated aromatic compound includes a step for mixing the following compounds (a), (b), (c) and (d) with an aromatic compound represented by formula (1) (wherein, Aris an aromatic group; and Xis a leaving group) to condense the aromatic compound by using the compounds (a), (b), (c) and (d): (a) a nickel compound such as a zero-valence nickel compound; (b): a 2,2'-bipyridine derivative represented by formula (2) (wherein, two Rs are the same or different, and two Rs are the same or different); (c) tricyclohexylphosphine; and (d) a metal reducing agent.

Description

  The present invention relates to a method for producing a conjugated aromatic compound.

  It is known that conjugated aromatic compounds are useful compounds as organic device materials represented by pharmaceuticals, agricultural chemicals or liquid crystal materials, or synthetic intermediates thereof. The conjugated aromatic compound is produced by condensing an aromatic compound having a halogeno group. For example, Non-Patent Document 1 discloses a method for producing dimethoxybiphenyl (conjugated aromatic compound) by condensing chloroanisole using nickel chloride, triphenylphosphine, 2,2′-bipyridine and zinc. .

J. Org. Chem. 1986, 51, 2627-2637

However, the production method disclosed in Non-Patent Document 1 cannot be said to have a sufficient yield of the target conjugated aromatic compound, and improvement has been demanded in terms of such yield.

（式中、Ａｒ^１は、ベンゼン環、ビフェニル環、ナフタレン環、フルオレン環、アントラセン環、フェナントレン環、チオフェン環、ピロール環及びピリジン環からなる群より選ばれる芳香環を有する芳香族基を表わす。Ｘ^１は、ヨウ素原子、臭素原子又は塩素原子である脱離基であり、該脱離基は前記芳香環に直接結合している。）

（式中、Ａｒ^１は前記と同じ意味であり、２つのＡｒ^１は同じでも異なっていてもよい。）

（ａ）ゼロ価ニッケル化合物、ハロゲン化ニッケル、２−エチルヘキサン酸ニッケル、ニッケルアセチルアセトナート、（ジメトキシエタン）塩化ニッケル及び（ジメトキシエタン）臭化ニッケルからなる群より選ばれるニッケル化合物；
（ｂ）下記式（２）

（式中、Ｒ¹及びＲ²はそれぞれ独立に、水素原子、フッ素原子、フッ素原子を置換基として有していてもよい炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数１〜２０のアルコキシ基、炭素数２〜２０のアシル基、炭素数１〜２０のアルコキシカルボニル基、又は炭素数１〜２０のジアルキルアミノ基を表わし、２つのＲ^１は同じでも異なっていてもよく、２つのＲ^２は同じでも異なっていてもよい。）
で示される２，２’−ビピリジン誘導体；
（ｃ）トリシクロヘキシルホスフィン
（ｄ）金属還元剤 As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, this invention provides the manufacturing method of the following conjugated aromatic compounds.
(A), (b), (c), (d) and a step of mixing the aromatic compound represented by the formula (1), and by condensing the aromatic compound, the formula (3) A process for producing the conjugated aromatic compound shown;

(In the formula, Ar ¹ represents an aromatic group having an aromatic ring selected from the group consisting of a benzene ring, biphenyl ring, naphthalene ring, fluorene ring, anthracene ring, phenanthrene ring, thiophene ring, pyrrole ring and pyridine ring. X ¹ is a leaving group which is an iodine atom, a bromine atom or a chlorine atom, and the leaving group is directly bonded to the aromatic ring.)

(In the formula, Ar ¹ has the same meaning as described above, and two Ar ¹ may be the same or different.)

(A) a nickel compound selected from the group consisting of a zero-valent nickel compound, nickel halide, nickel 2-ethylhexanoate, nickel acetylacetonate, (dimethoxyethane) nickel chloride and (dimethoxyethane) nickel bromide;
(B) The following formula (2)

(Wherein R ¹ and R ² are each independently a hydrogen atom, a fluorine atom, a C 1-20 alkyl group optionally having a fluorine atom as a substituent, a C 6-20 aryl group, Represents an alkoxy group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, or a dialkylamino group having 1 to 20 carbon atoms, and two R ^{1 s} are the same or different. And two R ² may be the same or different.)
A 2,2′-bipyridine derivative represented by:
(C) Tricyclohexylphosphine (d) metal reducing agent

According to the present invention, a conjugated aromatic compound can be produced in high yield.

The production method of the present invention includes a step of mixing the above-mentioned (a), (b), (c), (d) and the aromatic compound. Examples of such mixing method include: a method in which (a), (b), (c), (d) and the aromatic compound are mixed substantially simultaneously in a reaction vessel;
A method in which (a), (b) and (c) are introduced into a reaction vessel and mixed, and (d) and the aromatic compound are mixed into the resulting mixture;
-The aromatic compound and (d) are charged into a first reaction vessel, and (a), (b) and (c) are charged into a second reaction vessel to prepare a mixture, A method of mixing (a), (b), (c) and (d) with the aromatic compound by charging the mixture into the first reaction vessel;
Can be mentioned. Among these, a preferable mixing method will be described later.

<Aromatic compounds>
First, the aromatic compound represented by the formula (1) (hereinafter referred to as “aromatic compound (1)”) will be described. The aromatic compound (1) is a compound having at least one aromatic ring and having at least one leaving group of iodine atom, bromine atom or chlorine atom bonded to the aromatic ring.
This aromatic ring is an aromatic heterocycle such as an aromatic hydrocarbon ring such as a benzene ring, biphenyl ring, naphthalene ring, fluorene ring and anthracene ring, thiophene ring, pyrrole ring and pyridine ring.

（式中、Ａ^１は、炭素数１〜２０の炭化水素基を置換基として有するアミノ基又は炭素数１〜２０のアルコキシ基を表わす。ここで、前記炭化水素基及びアルコキシ基は、フッ素原子、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基及びシアノ基からなる群より選ばれる少なくとも一つの基で置換されていてもよい。）
で示される基；
（ｉ１）シアノ基；
（ｊ１）フッ素原子 Such an aromatic ring may have a substituent other than X ¹ , and when it has a substituent, this substituent does not affect the progress of the reaction according to the production method of the present invention. Specific examples of such a substituent include the following (a1), (b1), (c1), (d1), (e1), (f1), (g1), (h1), and (j1) [below , “(A1) to (j1)” may be used. ].
(A1): having as a substituent a group selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. An optionally substituted alkyl group having 1 to 20 carbon atoms;
(B1): having as a substituent a group selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. An optionally substituted alkoxy group having 1 to 20 carbon atoms;
(C1): a carbon atom having 6 to 20 carbon atoms which may have a substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms An aryl group of
(D1): a carbon atom having 6 to 20 carbon atoms which may have a substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms An aryloxy group of
(E1): having as a substituent a group selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. An optionally substituted acyl group having 2 to 20 carbon atoms;
(F1): having a group selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms as a substituent. An optionally substituted acyloxy group having 2 to 20 carbon atoms;
(G1): having a group selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms as a substituent. An optionally substituted arylsulfonyl group having 6 to 20 carbon atoms;
(H1): The following formula:

(In the formula, A ¹ represents an amino group having a hydrocarbon group having 1 to 20 carbon atoms as a substituent or an alkoxy group having 1 to 20 carbon atoms. Here, the hydrocarbon group and the alkoxy group are fluorine atoms. , At least one group selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and a cyano group May be substituted with.)
A group represented by:
(I1) a cyano group;
(J1) Fluorine atom

  As the “alkyl group having 1 to 20 carbon atoms” in (a1), a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, n-pentyl group, 2,2-dimethylpropyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, 2-methylpentyl 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-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group and Examples thereof include an n-icosyl group. As (a1), part or all of the hydrogen atoms in the alkyl group exemplified here are substituted with a group selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group, an aryl group and an aryloxy group. It may be. When it has a substituent, an alkyl group having 1 to 20 carbon atoms in total including the carbon number of the substituent is more preferable as (a1). Specific examples of the alkoxy group, the aryl group, and the aryloxy group will be described later.

  Examples of the “C1-C20 alkoxy group” in (b1) include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n- Pentyloxy group, 2,2-dimethylpropoxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy 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-heptadecyloxy group, n-octadecyloxy group, n- Examples include nonadecyloxy group and n-icosyloxy group. As (b1), part or all of the hydrogen atoms in the alkoxy group exemplified here are substituted with a group selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group, an aryl group and an aryloxy group It may be. When it has a substituent, an alkoxy group having 1 to 20 carbon atoms in total including the carbon number of the substituent is more preferable as (b1). Specific examples of the alkoxy group are the same as described above, and specific examples of the aryl group and the aryloxy group will be described later.

  Examples of the “aryl group having 6 to 20 carbon atoms” in the above (c1) include a phenyl group, a 4-methylphenyl group, a 2-methylphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 3-phenanthryl group, and 2- An anthryl group etc. are illustrated. (C1) is one in which some or all of the hydrogen atoms in the aryl group exemplified herein are substituted with a group selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group, an aryl group and an aryloxy group It may be. When it has a substituent, an aryl group having 6 to 20 carbon atoms in total including the carbon number of the substituent is more preferable as (c1). Specific examples of the alkoxy group and the aryl group are the same as described above, and specific examples of the aryloxy group will be described later.

  Examples of the “aryloxy group having 6 to 20 carbon atoms” in the above (d1) include a phenoxy group, 4-methylphenoxy group, 2-methylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 3-phenane. Examples thereof include those composed of the aryl group having 6 to 20 carbon atoms such as tolyloxy group and 2-anthryloxy group and an oxygen atom. As (d1), part or all of the hydrogen atoms in the aryloxy group exemplified herein are substituted with a group selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group, an aryl group and an aryloxy group. It may be a thing. When it has a substituent, an aryloxy group having a total of 6 to 20 carbon atoms including the carbon number of the substituent is more preferable as (d1). Specific examples of the alkoxy group, the aryl group, and the aryloxy group are the same as described above.

  Examples of the “acyl group having 2 to 20 carbon atoms” in (e1) include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a benzoyl group, a 1-naphthoyl group, and a 2-naphthoyl group. (E1) is one in which part or all of the hydrogen atoms in the acyl group exemplified here are substituted with a group selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group, an aryl group and an aryloxy group It may be. When it has a substituent, an acyl group having 2 to 20 carbon atoms in total including the carbon number of the substituent is more preferable as (e1). Specific examples of the alkoxy group, the aryl group, and the aryloxy group are the same as described above.

  Examples of the “acyloxy group having 2 to 20 carbon atoms” in (f1) include groups composed of any one of the acyl groups having 2 to 20 carbon atoms exemplified above and an oxygen atom. Examples thereof include acetyloxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, benzoyloxy group, 1-naphthoyloxy group and 2-naphthoyloxy group. (F1) is one in which part or all of the hydrogen atoms in the acyloxy group exemplified herein are substituted with a group selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group, an aryl group and an aryloxy group It may be. When it has a substituent, an acyloxy group having 2 to 20 carbon atoms in total including the carbon number of the substituent is more preferable as (f1). Specific examples of the alkoxy group, the aryl group, and the aryloxy group are the same as described above.

  Examples of the “arylsulfonyl group having 6 to 20 carbon atoms” in the above (g1) include a phenylsulfonyl group and a p-toluenesulfonyl group. As (g1), part or all of the hydrogen atoms in the arylsulfonyl group exemplified herein are substituted with a group selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group, an aryl group and an aryloxy group. It may be a thing. When it has a substituent, an arylsulfonyl group having a total of 6 to 20 carbon atoms including the carbon number of the substituent is more preferable as (g1). Specific examples of the alkoxy group, the aryl group, and the aryloxy group are the same as described above.

The amino group having a hydrocarbon group having 1 to 20 carbon atoms in (h1) is
-N (R) ₂
[In formula, R represents a hydrogen atom or a hydrocarbon group each independently. At least one of the two R is a hydrocarbon group, and the total number of carbon atoms of the two R is 1-20. Two Rs may be bonded together to form a ring together with the nitrogen atom to which they are bonded. ]
Means a group represented by

  Examples of the amino group substituted with such a hydrocarbon group include a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, an n-propylamino group, a di-n-propylamino group, an isopropylamino group, a diisopropylamino group, n-butylamino group, di-n-butylamino group, sec-butylamino group, di-sec-butylamino group, tert-butylamino group, di-tert-butylamino group, n-pentylamino group, 2, 2-dimethylpropylamino group, n-hexylamino group, cyclohexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, n-undecylamino group, n-dodecylamino group Group, n-tridecylamino group, n-tetradecylamino group, n-pentadecylamino group n-hexadecylamino group, n-heptadecylamino group, n-octadecylamino group, n-nonadecylamino group, n-icosylamino group, pyrrolyl group, pyrrolidinyl group, piperidinyl group, carbazolyl group, dihydroindolyl group and dihydroisoin A drill group etc. are mentioned.

Hereinafter, in (a1) to (h1), each suitable group will be described.
Among the groups (a1), preferred groups include an alkyl group having 1 to 20 carbon atoms having no substituent; a fluorinated alkyl group having 1 to 20 carbon atoms having a fluorine atom such as a trifluoromethyl group as a substituent; And an alkyl group having 1 to 20 carbon atoms having an alkoxy group such as a methoxymethyl group as a substituent; and an alkyl group having 1 to 20 carbon atoms having a cyano group such as a cyanomethyl group as a substituent. Particularly, an alkyl group having 1 to 6 carbon atoms having no substituent; an alkyl group having 1 to 6 carbon atoms having a fluorine atom, an alkoxy group, or a cyano group as a substituent is preferable.
Preferred examples of the group (b1) include a C 1-20 alkoxy group having no substituent; a C 1-20 alkoxy group having an alkoxy group as a substituent, such as a methoxymethoxy group; It is done. In particular, an alkoxy group having 1 to 6 carbon atoms having no substituent; an alkoxy group having an alkoxy group as a substituent and having 1 to 6 carbon atoms is preferable.
Preferred examples of the group (c1) include an aryl group having 6 to 20 carbon atoms having no substituent, and an aryl group having 6 to 10 carbon atoms having no substituent is particularly preferable.
Preferred examples of the group (d1) include C6-C20 aryloxy groups having no substituent, and C6-C10 aryloxy groups having no substituent are particularly preferable.
Preferred examples of the group (e1) include an acyl group having 2 to 20 carbon atoms having no substituent; an acyl group having 2 to 20 carbon atoms having an aryloxy group such as a phenoxybenzoyl group as a substituent. In particular, an acyl group having 2 to 10 carbon atoms having no substituent; an acyl group having an aryloxy group as a substituent and having 2 to 10 carbon atoms is preferable.
Among the above (f1), preferred groups include an acyloxy group having 2 to 20 carbon atoms having no substituent; an acyloxy group having 2 to 20 carbon atoms having an aryloxy group such as a phenoxybenzoyloxy group as a substituent; In particular, an acyl group having 2 to 10 carbon atoms having no substituent; an acyl group having an aryloxy group as a substituent and having 2 to 10 carbon atoms is preferable.
Preferred examples of the group (g1) include an arylsulfonyl group having 6 to 20 carbon atoms which has no substituent, and an arylsulfonyl group having 6 to 10 carbon atoms is particularly preferable.
Preferred examples of the group (h1) include groups in which A ¹ is an isopropoxy group, a 2,2-dimethylpropoxy group, a cyclohexyloxy group, a diethylamino group, or an n-dodecylamino group. Specific examples include isopropoxysulfo group, 2,2-dimethylpropoxysulfo group, cyclohexyloxysulfo group, diethylaminosulfo group, and n-dodecylaminosulfo group. Among these, a group in which A ¹ is an isopropoxy group, a 2,2-dimethylpropoxy group, or a cyclohexyloxy group is more preferable.

  Among the above (a1) to (j1), the reaction according to the production method of the present invention is selected from the group consisting of (a1), (b1), (e1) and (h1). Groups are preferred. Therefore, the aromatic compound (1) having these groups as a substituent can be preferably used in the production method of the present invention.

X ^{1 in the} aromatic compound (1) is a leaving group that can be removed in the reaction according to the production method of the present invention, and is preferably a chlorine atom or a bromine atom.

As an aromatic compound (1), a commercially available thing may be used and what was manufactured according to the well-known method may be used.
When this aromatic compound (1) is specifically illustrated,
Chlorobenzene, bromobenzene, iodobenzene, 4-chlorofluorobenzene, 3-chlorofluorobenzene, 2-chlorofluorobenzene, 2-chlorotoluene, 2,5-dimethylchlorobenzene, 2-ethylchlorobenzene, 3-n-propylchlorobenzene, 4-isopropylchlorobenzene, 5-n-butylchlorobenzene, 2-isobutylchlorobenzene, 3-sec-butylchlorobenzene, 4-tert-butylchlorobenzene, 5- (2,2-dimethylpropyl) chlorobenzene, 2-n-hexylchlorobenzene, 4-cyclohexylchlorobenzene, 4-benzylchlorobenzene, 4-chlorobenzonitrile, 4-chlorobiphenyl, 2-chlorobiphenyl, 4-chlorobenzotrifluoride, 2-chlorobenzoto Fluoride, (4-chlorophenyl) acetonitrile,
3-chloroanisole, 4-chloroanisole, 2,3-dimethoxychlorobenzene, 2,4-dimethoxychlorobenzene, 2,5-dimethoxychlorobenzene, 2-ethoxychlorobenzene, 3-n-propoxychlorobenzene, 4-isopropoxychlorobenzene, 5 -N-butoxychlorobenzene, 4-tert-butoxychlorobenzene, 4-phenoxychlorobenzene, 4-benzyloxychlorobenzene, 4- (methoxymethyl) chlorobenzene, 4- (n-butoxymethyl) chlorobenzene, 4- (methoxymethoxy) chlorobenzene, 4- (benzyloxymethoxy) chlorobenzene, 4- {2- (n-butoxy) ethoxy} chlorobenzene,
4-chloroacetophenone, 2-chloroacetophenone, 4-chloropropiophenone, 1- (4-chlorophenyl) -2,2-dimethylpropanone, (4-chlorobenzoyl) cyclohexane, 4-chlorobenzophenone, p-chloroben Zalacetone, 1-chloro-4- (phenylsulfonyl) benzene, 4-chlorophenyl p-tolyl sulfone, methyl 4-chlorobenzenesulfonate, methyl 3-chlorobenzenesulfonate, methyl 2-chlorobenzenesulfonate, ethyl 4-chlorobenzenesulfonate 4-chlorobenzenesulfonic acid (2,2-dimethylpropyl), 3-chlorobenzenesulfonic acid (2,2-dimethylpropyl), 2-chlorobenzenesulfonic acid (2,2-dimethylpropyl),
N, N-dimethyl-4-chlorobenzenesulfonamide, N, N-dimethyl-3-chlorobenzenesulfonamide, N, N-dimethyl-2-chlorobenzenesulfonamide, N, N-diethyl-4-chlorobenzenesulfonamide,
1-chloronaphthalene, 2-bromothiophene, 5-bromo-3-hexylthiophene, 2-bromo-3-dodecylthiophene, 5-bromo-2,2′-bithiophene, 5-bromo-3-cyclohexylthiophene, 2- Chloro-3-octylthiophene, 5-chloro-3-phenylthiophene, 1-methyl-5-chloropyrrole, 1-hexyl-2-bromopyrrole, 1-octyl-5-chloropyrrole, 2-chloropyridine, 3- Chloropyridine, 5-bromopyridine, 3-methyl-2-chloropyridine, 3-hexyl-5-chloropyridine, 5-chloro-2,2′-bipyridine, 3,3′-dimethyl-5-chloro-2, Examples include 2'-bipyridine and 3,3'-dioctyl-5-bromo-2,2'-bipyridine. The aromatic compound (1) exemplified here has no substituent other than the leaving group X ¹ or has as a substituent a group that hardly affects the reaction according to the production method of the present invention. Therefore, it can be said to be particularly suitable for use in the production method of the present invention.

Next, the above (a) to (d) used in the present invention will be described with specific examples.
<Nickel compounds>
Examples of the nickel compound (a) (hereinafter sometimes referred to as “nickel compound (a)”) include zero-valent nickel compounds, nickel halides (eg, nickel fluoride, nickel chloride, nickel bromide, nickel iodide) ), Nickel 2-ethylhexanoate, nickel acetylacetonate, (dimethoxyethane) nickel chloride and (dimethoxyethane) nickel bromide. The zero-valent nickel compound is preferably a nickel complex (zero-valent nickel complex) in which the central metal nickel has a valence state of zero. Among the zero-valent nickel complexes, bis (1,5-cyclooctadiene) nickel (0 Is more preferable. As the nickel halide, nickel fluoride, nickel chloride and nickel bromide are preferable because they are easily available from the market, and nickel chloride and nickel bromide are more preferable.
The amount of the nickel compound (a) used is preferably in the range of 0.001 to 0.8 mol, more preferably in the range of 0.01 to 0.4 mol, with respect to 1 mol of the aromatic compound (1). If the amount used is too large, post-treatment after the reaction tends to be complicated. In addition, when using multiple types as this nickel compound (a), the total molar amount should just be the said range.

<Ligand compound>
Next, the bipyridine derivative (b) (hereinafter referred to as “bipyridine derivative (b)”) and (c) tricyclohexylphosphine will be described. Bipyridine derivative (b) and tricyclohexylphosphine are compounds having characteristics capable of coordinating to zero-valent nickel or nickel ions dissociated from the nickel compound (a) (hereinafter referred to as bipyridine derivative (b) and tricyclohexylphosphine). Are sometimes collectively referred to as “ligand compounds”.
First, the bipyridine derivative (b) will be described. In Formula (2), R ¹ and R ² are each independently a hydrogen atom, a fluorine atom, a C 1-20 alkyl group optionally having a fluorine atom as a substituent, or a C 6-20 carbon atom. An aryl group, an alkoxy group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms is represented.

Here, examples of the alkyl group having 1 to 20 carbon atoms are the same as those exemplified as the alkyl group of (a1), and a methyl group and a tert-butyl group are preferable.
Specific examples of the alkyl group having a fluorine atom as a substituent include monofluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, Examples include a fluoro-n-propyl group and a perfluoroisopropyl group, and a trifluoromethyl group is preferable.

  Examples of the aryl group are the same as those exemplified above in the description of (c1) and those having no substituent, and preferably a phenyl group.

  Examples of the alkoxy group are the same as those exemplified above in the description of (b1) and those having no substituent, and preferably a methoxy group.

  Illustrative examples of the acyl group are the same as those exemplified above in the description of (e1) and those having no substituent, preferably an acyl group and a benzoyl group.

  Examples of the alkoxycarbonyl group having 1 to 20 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, and an isopropyloxycarbonyl group, and a methoxycarbonyl group is preferable.

The dialkylamino group having 2 to 20 carbon atoms is
-N (R ') ₂
[Wherein, R ′ represents a hydrocarbon group, and the total number of carbon atoms of two R ′ is 2-20. Two R's may be bonded together to form a ring together with the nitrogen atom to which they are bonded. ]
Means a group represented by
Examples thereof include dimethylamino group, diethylamino group, di (n-propyl) amino group, diisopropylamino group, di (n-butyl) amino group and di (2,2-dimethylpropyl) amino group, preferably dimethylamino group. It is an amino group.

  Specific examples of the bipyridine derivative (b) include 4,4′-difluoro-2,2′-bipyridine, 4,4′-dimethyl-2,2′-bipyridine, 4,4′-diphenyl-2, 2'-bipyridine, 4,4'-dimethoxy-2,2'-bipyridine, 4,4'-diacetyl-2,2'-bipyridine, methyl 2,2'-bipyridine-4,4'-dicarboxylate, 4 4,4′-ditrifluoromethyl-2,2′-bipyridine, 4,4′-di-tert-butyl-2,2-bipyridine, 4,4′-dimethylamino-2,2′-bipyridine, and the like. Can do.

  The amount of the bipyridine derivative (b) used is preferably in the range of 0.1 to 2 mol, more preferably in the range of 0.3 to 0.8 mol, with respect to 1 mol of the nickel compound (a). In addition, when using multiple types as this bipyridine derivative (b), the total molar amount should just be the said range.

As the (c) tricyclohexylphosphine, those easily available from the market can be used.
The amount of tricyclohexylphosphine used is preferably in the range of 0.2 to 4 mol, more preferably in the range of 0.5 to 1.5 mol, per 1 mol of the nickel compound (a).

  The above-mentioned range is preferable for the amount of each of the bipyridine derivative (b) and tricyclohexylphosphine. When the ratio of the amount of tricyclohexylphosphine used to the total amount of the ligand compound is expressed in molar ratio, A range of 0.01 to 0.99 is preferable, and a range of 0.1 to 0.9 is more preferable.

<Metal reducing agent>
In the production method of the present invention, even when a zero-valent nickel compound is used as the nickel compound (a), it is zero in the reaction system in which the aromatic compound (1) is condensed to produce a conjugated aromatic compound. Nickel valence itself may be oxidized to monovalent, divalent or trivalent nickel ions (1 to 3 valent nickel ions). If the 1-3 valent nickel ions can be reduced in the reaction system, the production of the conjugated aromatic compound proceeds more efficiently. For such reduction, it is preferable to use a metal reducing agent (d) (hereinafter referred to as “metal reducing agent (d)”). Therefore, the process of condensing the aromatic compound (1) is performed using a metal reducing agent. The presence of (b) is preferred. This metal reducing agent (d) has a reducing ability capable of reducing 1-3 valent nickel ions in the reaction system, and for example, metals such as zinc, magnesium, manganese, aluminum and sodium are preferably used. In terms of easy handling, the metal reducing agent (d) is preferably zinc, magnesium and manganese, and more preferably zinc. Further, in terms of easy handling, the shape of the metal reducing agent (d) is preferably in the form of powder or shaving.
Although the usage-amount of a metal reducing agent (d) should just be 1 mol or more with respect to 1 mol of aromatic compounds (1), when too large, the post-process after reaction will become complicated and economically. Since it becomes disadvantageous, the range of 10 mol or less is preferable with respect to 1 mol of the aromatic compound (1), and the range of 5 mol or less is more preferable. In addition, when using multiple types as this metal reducing agent (b), the total molar amount should just be the said range.

<Preparation of nickel complex>
The production method of the present invention includes a step of mixing a nickel compound (a), a ligand compound (bipyridyl derivative (b) and tricyclohexylphosphine), a metal reducing agent (d) and an aromatic compound (1). The nickel complex may be prepared in advance by mixing the nickel compound (a) and the ligand compound.
Examples of the method for preparing the nickel complex include (a), (b), (c) or (d) [(a) to (d)] shown below.
(A) Preparation of preparing a complex prepared from a nickel compound (a) and a bipyridine derivative (b) and a complex prepared from a nickel compound (a) and tricyclohexylphosphine, and mixing these in a solvent Method;
(B) Preparation in which a solution containing a complex is prepared using a nickel compound (a) and a bipyridine derivative (b) or tricyclohexylphosphine in a solvent, and the other ligand compound is added to the solution. Method;
(C) a preparation method of preparing a nickel complex by adding a nickel compound and two ligand compounds to a solution;
(D) A ligand compound and a nickel compound are mixed in the solid state to prepare a nickel complex. A nickel complex prepared by any of the preparation methods shown in (a) to (d) In some cases, not only one kind but also several kinds of nickel complexes have been prepared.

Among the exemplified examples, the nickel complex is preferably prepared in a solution, and the preparation of the nickel complex in the solution is easy to determine that the nickel complex has been prepared by changing the hue of the solution. . Moreover, when the nickel complex is prepared in a solution, the nickel complex has an advantage that it can be prepared in a shorter time. In order to prepare the nickel complex in a solution, a solvent may be used during the preparation.

The production method of the present invention is preferably carried out by mixing the aromatic compound (1), the nickel compound (a), the metal reducing agent (b) and the ligand compound. These mixing orders are
(I) When preparing a nickel complex beforehand, after mixing nickel compound (a), a ligand compound, and a solvent and preparing a nickel complex, aromatic compound (1) and metal reducing agent are added to this reaction liquid. A form in which (b) is mixed with a solvent if necessary;
(Ii) A form in which the aromatic compound (1) is added to the resulting mixture after mixing the nickel compound (a), the ligand compound and the metal reducing agent (d), and the solvent;
(Iii) A form in which a nickel compound (a), a ligand compound, a metal reducing agent (d), an aromatic compound (1), and a solvent are charged into a reaction vessel almost simultaneously and mixed;
Etc., not particularly limited. When the nickel complex is prepared in advance, the mixing order of (i) or (ii) may be selected, and when the operation is simplified, the mixing order of (iii) may be selected. .
Thus, after mixing aromatic compound (1) and said (a)-(d), the manufacturing method of this invention can be performed by heat-retaining at predetermined reaction temperature. The said reaction temperature can be adjusted from the range of 0-250 degreeC by the kind etc. of the aromatic compound (1), nickel compound (a), and metal reducing agent (d) to be used, Preferably it is the range of 30-100 degreeC. It is. The reaction time is in the range of 0.5 to 48 hours, and the degree of consumption of the aromatic compound (1) and the degree of formation of the conjugated aromatic compound are determined every predetermined time by performing chromatography analysis and the like. The reaction end point can also be determined. Moreover, it is preferable to perform the manufacturing method of this invention in the atmosphere of inert gas, such as nitrogen, and when preparing nickel complex beforehand, the said preparation is also preferably performed in the atmosphere of inert gas. In the production method of the present invention, stirring is preferably performed to such an extent that the metal reducing agent (d) is sufficiently dispersed in the reaction solution during the reaction. When this stirring is performed, the reaction time can be further shortened.

  Here, the solvent used in the production method of the present invention will be described. As the solvent, those in which the aromatic compound (1) to be used and the conjugated aromatic compound to be produced are soluble are preferable, and aromatic hydrocarbon solvents such as toluene and xylene; ethers such as tetrahydrofuran and 1,4-dioxane Solvents; aprotic polar solvents such as dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and hexamethylphosphoric triamide; halogenated hydrocarbons such as dichloromethane and dichloroethane A solvent is mentioned. These solvents may be used alone or in combination of two or more. Of these, ether solvents and aprotic polar solvents are preferred, and tetrahydrofuran, dimethyl sulfoxide, N-methyl-2-pyrrolidone and N, N-dimethylacetamide are more preferred. As for the usage-amount of a solvent, 1-200 weight part is preferable with respect to 1 weight part of an aromatic compound (1), and 5-100 weight part is more preferable.

  From the reaction mixture after the reaction, for example, a purification operation such as extraction, recrystallization, reprecipitation, or chromatography, or a purification operation combining these, is performed to purify or isolate the target conjugated aromatic compound. be able to. Moreover, before performing such a purification operation, it is preferable that the reaction mixture after the reaction is cooled or heated to a temperature of about room temperature (about 23 ° C.).

（Ａｒ^１は前記と同じ意味である。）
上述のとおり、式（４）において２つのＡｒ^１は異なっていてもよいが、２つのＡｒ^１が同じである共役芳香族化合物、いわゆる対称型の共役芳香族化合物が好ましい。その理由は、このような対称型の共役芳香族化合物が、医薬、農薬又は液晶材料等の用途に特に有用であるからである。また、この対称型の共役芳香族化合物は、本発明の製造方法において、１種の芳香族化合物（１）のみを用いることで製造できるため、製造がより簡便であり、また精製し易くなるという利点もある。
式（４）で示される共役芳香族化合物の中で、好適な対称型の共役芳香族化合物としては、例えば、
ビフェニル、４，４’−ジフルオロビフェニル、３，３’−ジフルオロビフェニル、２，２’−ジフルオロビフェニル、２，２’−ジメチルビフェニル、２，２’，５，５’−テトラメチルビフェニル、２，２’−ジエチルビフェニル、３，３’−ジ−ｎ−プロピルビフェニル、４，４’−ジイソプロピルビフェニル、５，５’−ジ−ｎ−ブチルビフェニル、２，２’−ジイソブチルビフェニル、３，３’−ジ−ｓｅｃ−ブチルビフェニル、４，４’−ジ−ｔｅｒｔ−ブチルビフェニル、５，５’−ビス（２，２−ジメチルプロピル）ビフェニル、２，２’−ジ−ｎ−ヘキシルビフェニル、４，４’−ジシクロヘキシルビフェニル、４，４’−ジベンジルビフェニル、４，４’−ジシアノビフェニル、４，４’−ビス（トリフルオロメチル）ビフェニル、２，２’−ビス（トリフルオロメチル）ビフェニル、４，４’−ビス（シアノメチル）ビフェニル、
３，３’−ジメトキシビフェニル、４，４’−ジメトキシビフェニル、２，２’，３，３’−テトラメトキシビフェニル、２，２’，４，４’−テトラメトキシビフェニル、２，２’，５，５’−テトラメトキシビフェニル、２，２’−ジエトキシビフェニル、３，３’−ジ−ｎ−プロポキシビフェニル、４，４’−ジイソプロポキシビフェニル、５，５’−ジ−ｎ−ブトキシビフェニル、４，４’−ジ−ｔｅｒｔ−ブトキシビフェニル、４，４’−ジフェノキシビフェニル、４，４’−ジベンジルオキシビフェニル、４，４’−ビス（メトキシメチル）ビフェニル、４，４’−ビス（ｎ−ブトキシメチル）ビフェニル、４，４’−ビス（メトキシメトキシ）ビフェニル、４，４’−ビス（ベンジルオキシメトキシ）ビフェニル、４，４’−ビス｛２−（ｎ−ブトキシ）エトキシ｝ビフェニル、
４，４’−ジアセチルビフェニル、４，４’−ジベンゾイルビフェニル、４，４’−ビス（フェニルスルホニル）ビフェニル、ビフェニル−４，４’−ジスルホン酸ジメチル、ビフェニル−４，４’−ジスルホン酸ジエチル、ビフェニル−４，４’−ジスルホン酸ジ（２，２−ジメチルプロピル）、ビフェニル−３，３’−ジスルホン酸ジ（２，２−ジメチルプロピル）、１，１’−ビナフタレン、２，２’−ビチオフェン、３，３’−ジヘキシル−５，５’−ビチオフェン、１，１’−ジメチル−５，５’−ビピロ−ル、２，２’−ビピリジン、３，３’−ジメチル−２，２’−ビピリジン、３，３’−ジヘキシル−５，５’−ビピリジン、２，２’−ビピリミジン、５，５’−ビキノリン、１，１’−ビイソキノリン、４，４’−ビス（２，１，３−ベンゾチアジアゾ−ル）及び７，７’−ビス（ベンゾイミダゾ−ル）等が挙げられる。 Thus, a conjugated aromatic compound represented by the following formula (4) is obtained.

(Ar ¹ has the same meaning as described above.)
As described above, in the formula (4), two Ar ¹ may be different, but a conjugated aromatic compound in which two Ar ¹ are the same, that is, a so-called symmetric conjugated aromatic compound is preferable. This is because such a symmetric conjugated aromatic compound is particularly useful for uses such as pharmaceuticals, agricultural chemicals, and liquid crystal materials. In addition, since this symmetrical conjugated aromatic compound can be produced by using only one kind of aromatic compound (1) in the production method of the present invention, it is easier to produce and easier to purify. There are also advantages.
Among the conjugated aromatic compounds represented by the formula (4), suitable symmetric conjugated aromatic compounds include, for example,
Biphenyl, 4,4′-difluorobiphenyl, 3,3′-difluorobiphenyl, 2,2′-difluorobiphenyl, 2,2′-dimethylbiphenyl, 2,2 ′, 5,5′-tetramethylbiphenyl, 2, 2'-diethylbiphenyl, 3,3'-di-n-propylbiphenyl, 4,4'-diisopropylbiphenyl, 5,5'-di-n-butylbiphenyl, 2,2'-diisobutylbiphenyl, 3,3 ' -Di-sec-butylbiphenyl, 4,4'-di-tert-butylbiphenyl, 5,5'-bis (2,2-dimethylpropyl) biphenyl, 2,2'-di-n-hexylbiphenyl, 4, 4'-dicyclohexylbiphenyl, 4,4'-dibenzylbiphenyl, 4,4'-dicyanobiphenyl, 4,4'-bis (trifluoromethyl) biphenyl, 2,2'-bis Trifluoromethyl) biphenyl, 4,4'-bis (cyanomethyl) biphenyl,
3,3′-dimethoxybiphenyl, 4,4′-dimethoxybiphenyl, 2,2 ′, 3,3′-tetramethoxybiphenyl, 2,2 ′, 4,4′-tetramethoxybiphenyl, 2,2 ′, 5 , 5'-tetramethoxybiphenyl, 2,2'-diethoxybiphenyl, 3,3'-di-n-propoxybiphenyl, 4,4'-diisopropoxybiphenyl, 5,5'-di-n-butoxybiphenyl 4,4′-di-tert-butoxybiphenyl, 4,4′-diphenoxybiphenyl, 4,4′-dibenzyloxybiphenyl, 4,4′-bis (methoxymethyl) biphenyl, 4,4′-bis (N-butoxymethyl) biphenyl, 4,4′-bis (methoxymethoxy) biphenyl, 4,4′-bis (benzyloxymethoxy) biphenyl, 4,4′-bis {2- (n-butoxy) Butoxy} biphenyl,
4,4′-diacetylbiphenyl, 4,4′-dibenzoylbiphenyl, 4,4′-bis (phenylsulfonyl) biphenyl, dimethyl biphenyl-4,4′-disulfonate, diethyl biphenyl-4,4′-disulfonate Biphenyl-4,4′-disulfonic acid di (2,2-dimethylpropyl), biphenyl-3,3′-disulfonic acid di (2,2-dimethylpropyl), 1,1′-binaphthalene, 2,2 ′ -Bithiophene, 3,3'-dihexyl-5,5'-bithiophene, 1,1'-dimethyl-5,5'-bipyrrole, 2,2'-bipyridine, 3,3'-dimethyl-2,2 '-Bipyridine, 3,3'-dihexyl-5,5'-bipyridine, 2,2'-bipyrimidine, 5,5'-biquinoline, 1,1'-biisoquinoline, 4,4'-bis (2,1 , 3-Benzothiadiazo And 7,7′-bis (benzimidazole) and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. For the obtained conjugated aromatic compound, the concentration of the conjugated aromatic compound in the reaction mixture was determined by gas chromatography (GC) internal standard analysis, and the yield was calculated from the result. The measurement conditions for the GC internal standard method analysis are shown below.

GC measuring device manufactured by SHIMADZU GC-2010
DB-1 made by J & W
(Film thickness 0.25μm, length 30m, inner diameter 0.2mm) Connected injection mode Split (split ratio 63)
Vaporization chamber temperature 250 ℃
Detector (FID) Temperature 250 ℃
Measurement column temperature After holding at 100 ° C. for 10 minutes, the temperature is raised to 260 ° C. at a rate of 10 ° C./min.
did.

Example 1
The atmosphere in a glass reaction vessel equipped with a stirrer and a cooling device was sufficiently replaced with nitrogen, and then the reaction vessel was charged with 7.6 mg of nickel bromide and 2,2′- at room temperature (about 23 ° C.). 4.8 mg of methyl bipyridine-4,4′-dicarboxylate, 9.8 mg of tricyclohexylphosphine, 96.2 mg of zinc powder, 118.8 mg (0.70 mmol) of 4-chloroacetophenone and 5 mL of N, N′-dimethylacetamide It is. The internal temperature was raised to 70 ° C., and the reaction was carried out for 4 hours while maintaining the same temperature to obtain a reaction mixture containing 4,4′-diacetylbiphenyl as a product. As a result of GC internal standard method analysis, it was found that 4,4′-diacetylbiphenyl was obtained almost quantitatively (yield: about 100%).

Comparative Example 1
In Example 1, 9.2 mg of triphenylphosphine was used instead of 9.8 mg of tricyclohexylphosphine, and 2,2 ′ instead of 4.8 mg of methyl 2,2′-bipyridine-4,4′-dicarboxylate. -The same reaction as Example 1 was performed except having used 2.7 mg of bipyridine, and the reaction mixture containing 4, 4'- diacetyl biphenyl was obtained. The yield of 4,4′-diacetylbiphenyl was 24.4 mg (0.10 mmol), and the yield was 29%.

Example 2
After the atmosphere in the glass reaction vessel equipped with a stirrer and a cooling device was sufficiently replaced with nitrogen, 7.6 mg of nickel bromide, 2.7 mg of 2,2′-bipyridine, 9.8 mg of tricyclohexylphosphine, 96.2 mg of zinc powder, 109.5 mg (0.77 mmol) of 2-chloroanisole and 5 mL of N, N′-dimethylacetamide were charged. The internal temperature was raised to 70 ° C., and the reaction was carried out for 4 hours while maintaining the same temperature to obtain a reaction mixture containing 2,2′-dimethoxybiphenyl as a product. The yield of 2,2′-dimethoxybiphenyl was 47.6 mg (0.22 mmol), and the yield was 57%.

Comparative Example 2
In Example 2, the same reaction as in Example 2 was performed except that 9.2 mg of triphenylphosphine was used instead of 9.8 mg of tricyclohexylphosphine. When the GC internal standard method analysis was performed, the production of 2,2′-dimethoxybiphenyl, which was the target product, could not be confirmed (yield about 0%).

Example 3
After the atmosphere in the glass reaction vessel equipped with a stirrer and a cooling device was sufficiently replaced with nitrogen, 7.6 mg of nickel bromide, 2.7 mg of 2,2′-bipyridine, 9.8 mg of tricyclohexylphosphine, 96.2 mg of zinc powder, 109.5 mg (0.77 mmol) of 4-chloroanisole, and 5 mL of N, N′-dimethylacetamide were charged. The internal temperature was raised to 70 ° C., and the reaction was carried out for 4 hours while maintaining the same temperature, whereby a reaction mixture containing 4,4′-dimethoxybiphenyl as a product was obtained. The yield of 4,4′-dimethoxybiphenyl was 56.3 mg (0.26 mmol), and the yield was 74%.

Comparative Example 5
In Example 3, the same reaction as in Example 3 was carried out except that 9.2 mg of triphenylphosphine was used instead of 9.8 mg of tricyclohexylphosphine to obtain a reaction mixture containing 4,4′-dimethoxybiphenyl. . The yield of 4,4′-dimethoxybiphenyl was 11.2 mg (0.047 mmol), and the yield was 13%.

  According to the present invention, a conjugated aromatic compound can be produced with a good yield. The conjugated aromatic compound obtained by the present invention can be used for pharmaceuticals, agricultural chemicals, organic device materials, etc., or synthetic intermediates thereof.

Claims (4)

(A), (b), (c), (d) and a step of mixing the aromatic compound represented by the formula (1), and by condensing the aromatic compound, the formula (3) A method for producing the conjugated aromatic compound shown.

(In the formula, Ar ¹ represents an aromatic group having an aromatic ring selected from the group consisting of a benzene ring, biphenyl ring, naphthalene ring, fluorene ring, anthracene ring, phenanthrene ring, thiophene ring, pyrrole ring and pyridine ring. X ¹ is a leaving group which is an iodine atom, a bromine atom or a chlorine atom, and the leaving group is directly bonded to the aromatic ring.)

(In the formula, Ar ¹ has the same meaning as described above, and two Ar ¹ may be the same or different.)

(A) a nickel compound selected from the group consisting of a zero-valent nickel compound, nickel halide, nickel 2-ethylhexanoate, nickel acetylacetonate, (dimethoxyethane) nickel chloride and (dimethoxyethane) nickel bromide;
(B) The following formula (2)

(Wherein R ¹ and R ² are each independently a hydrogen atom, a fluorine atom, a C 1-20 alkyl group optionally having a fluorine atom as a substituent, a C 6-20 aryl group, Represents an alkoxy group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms, and two R ^{1 s} are the same or different. And two R ² may be the same or different.)
A 2,2′-bipyridine derivative represented by:
(C) Tricyclohexylphosphine (d) metal reducing agent   The manufacturing method according to claim 1, wherein the (a) contains bis (1,5-cyclooctadiene) nickel (0).   The manufacturing method according to claim 1, wherein (a) includes a nickel halide selected from the group consisting of nickel fluoride, nickel chloride and nickel bromide. Production method wherein the conjugated aromatic compound, the two Ar ¹ in the formula (3) is according to claim 1 which is symmetrical conjugated aromatic compound are the same.