JP2003095995A - Method for producing aromatic compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method by which an objective biaryl can be obtained in good yield without forming harmful by-products, especially the method suitable for the mass-production of the biaryl. SOLUTION: An aryl halide represented by formula (I) (wherein, Ar1 is a monovalent aryl group; X is a halogen atom) is reacted with an alcohol compound represented by formula (II) (wherein, Ar2 is a monovalent aryl group; R1 and R2 are each independently hydrogen atom, an alkyl group or an aryl group same as the Ar2 ; R1 and R2 may bond to each other to form a divalent group; with the proviso that the case of forming an indenylidene group from the R1 in combination with the R2 is omitted) to provide the objective aromatic compound represented by formula (III) (wherein, Ar1 and Ar2 have the same meanings as the above).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an aromatic compound, and more specifically, it produces a new aromatic carbon-carbon bond by a cross coupling reaction to produce various aromatic compounds including biaryls. To a new way to do.

[0002]

2. Description of the Related Art Generally, a biaryl skeleton has a wide range of applications because it is included not only in physiologically active compounds such as various natural products but also in liquid crystals, polymers, ligands, functional materials and the like. In addition, there is great interest in developing a production method by which the intended biaryls can be easily obtained.

Hitherto, biaryls have been produced by various methods by forming a new aromatic carbon-carbon bond, but as a general method having a wide range of application, asymmetric biaryls can be produced. However, only a known one is one in which an aromatic halogen compound or its analog is cross-coupled with an aryl metal reagent using a nickel or palladium catalyst.

As such a method, for example, a method using an arylmagnesium reagent (Grignard reagent) (K. Tamao, K. Sumitani, M. Kumada, J. Am. Chem. S.
oc., 1972, 94, 4374-4376; RJP Corriu, JP M
asse, J. Chem. Soc., Chem. Commun., 1972, 144; A.
Sekiya, N. lshikawa, J. 0rganomet. Chem., 1976, 11
8, 349-354) is known, but the Grignard reagent has a high polarity and cannot use a substrate having a carbonyl group or a nitro group.

Method Using Aryl Tin Reagent (JK St
ille, Angew. Chem., Int. Ed. Engl. 1986, 25, 508-5
24; TN Mitchell, Synthesis, 1992, 803-815) is also known, but in this method, not only the aryltin reagent itself, but also the by-products produced by the reaction are highly toxic. In addition, a method using an arylboron reagent (N. Miyaura, A. Suzuki, Chem. Rev., 1995, 95, 245
7-2483; A. Suzuki, J. 0rganomet. Chem., 1999, 576,
147-168) is known.

However, in the reaction using such an aryl metal reagent, the problem that a large amount of metal-containing by-product is produced after the reaction is unavoidable.

[0007]

The present invention has been made to solve the above-mentioned problems in the production of biaryls by forming a new aromatic carbon-carbon bond,
It is intended to provide a method by which a desired biaryl, including those having an asymmetric structure, can be obtained in good yield without producing harmful by-products, and particularly, a method suitable for large-scale production of biaryls. With the goal.

[0008]

According to the present invention, as a first method, the general formula (I) is used.

[0009]

[Chemical 7]

(Wherein Ar ₁ represents a monovalent aryl group and X represents a halogen atom), in the presence of a palladium compound, a tertiary phosphine and a base, an aryl halide represented by the general formula (II )

[0011]

[Chemical 8]

(In the formula, Ar ₂ represents a monovalent aryl group, R ₁ and R ₂ independently represent a hydrogen atom, an alkyl group or the same monovalent aryl group as Ar ₂ above, and R ₁ and R 2 ₂ may combine with each other to form a divalent group, provided that
Except when R ₁ and R ₂ together form an indenylidene group. ) By reacting an alcohol compound represented by
General formula (III)

[0013]

[Chemical 9]

A method for producing an aromatic compound represented by the formula (wherein Ar ₁ and Ar ₂ are the same as above) is provided.

Further, according to the present invention, as the second method, the general formula (I) is used.

[0016]

[Chemical 10]

(Wherein Ar ₁ represents a monovalent aryl group and X represents a halogen atom), the aryl halide represented by the general formula (IIa) in the presence of a palladium compound, a tertiary phosphine and a base. )

[0018]

[Chemical 11]

(Wherein R ₃ represents a hydrogen atom, an alkyl group or a monovalent aryl group) is reacted to give a compound of the general formula (IIIa)

[0020]

[Chemical 12]

A method for producing an aromatic compound represented by the formula (wherein Ar ₁ and R ₃ are the same as above) is provided.

[0022]

According to the present invention, in any of the first and second methods, one of the starting materials represented by the general formula (I)

[0023]

[Chemical 13]

An aryl halide represented by the formula (wherein Ar ₁ represents a monovalent aryl group and X represents a halogen atom) is used.

The aryl group Ar ₁ is not particularly limited, but preferably, a phenyl group, a naphthyl group or a biphenyl group can be mentioned. Substituents inert to the reaction may be substituted on these aryl groups. Examples of the substituent inert to such a reaction include an alkyl group, an alkoxy group, an alkoxycarbonyl group and a nitro group. The alkyl group in the above alkyl group, alkoxy group or alkoxycarbonyl group preferably comprises 1 to 4 carbon atoms.

The halogen atom is preferably
It is a chlorine atom, a bromine atom or an iodine atom, but a bromine atom is particularly preferable from the viewpoint of reactivity.

Therefore, specific examples of the above aryl halides include, for example, bromobenzene, 2-bromotoluene, 4-bromotoluene, 2-bromo-m-xylene, 1-bromonaphthalene, depending on the intended biaryls. , 2-bromonaphthalene, 1-bromo-2-methylnaphthalene, 1-bromo-2-methoxynaphthalene, p-
Methyl bromobenzoate, ethyl p-bromobenzoate, 5
-Bromo-6-methoxytetralin, 5-bromo-6-
Examples thereof include, but are not limited to, methyltetralin.

According to the first method of the present invention, the general formula (II) is used as another starting material for cross-coupling with the above aryl halide.

[0029]

[Chemical 14]

(In the formula, Ar ₂ represents a monovalent aryl group, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group or the same monovalent aryl group as Ar ₂ above, and R ₁ and R 2 ₂ may combine with each other to form a divalent group, provided that
Except when R ₁ and R ₂ together form an indenylidene group. ) Is used as the first alcohol compound.

Also in the first alcohol compound,
The aryl group Ar ₂ is not particularly limited, but preferably a phenyl group, a naphthyl group or a biphenyl group can be mentioned. Substituents inert to the reaction may be substituted on these aryl groups. Examples of the substituent inert to such a reaction include an alkyl group, an alkoxy group, an alkoxycarbonyl group and a nitro group. The alkyl group in the above alkyl group, alkoxy group or alkoxycarbonyl group preferably comprises 1 to 4 carbon atoms.

In the first alcohol compound, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group or the same monovalent aryl group as Ar ₂ and R ₁ and R ₂ are bonded to each other. To form a divalent group. However,
Except when R ₁ and R ₂ together form an indenylidene group. However, according to the present invention, R ₁ and R ₂ are preferably both alkyl groups or the same monovalent aryl groups as Ar ₂ above, or are bonded together to form a divalent group. (However, except when R ₁ and R ₂ together form an indenylidene group.) Therefore, the first alcohol compound is preferably a tertiary alcohol.

When R ₁ or R ₂ is an alkyl group, the alkyl group is not particularly limited, but usually preferably has 1 to 4 carbon atoms. R ₁ and R ₂ may be bonded to each other to form a divalent group. Examples of such a divalent group include a trimethylene group, a tetramethylene group, a pentamethylene group and a 9-xanthenylidene group. Etc. can be mentioned. Above all,
A tetramethylene group and a 9-xanthenylidene group are preferred.

Therefore, according to the present invention, as the first alcohol compound, depending on the target biaryl,
For example, 2-phenyl-2-propanol, 2- (1-
Naphthyl) -2-propanol, 2- (2-methoxy-)
1-naphthyl) -2-propanol, 9-phenylxanthen-9-ol, 9- (1-naphthyl) xanthen-9-ol, 2- (9-phenanthryl) -2-propanol, 2- (9-anthryl) 2-Propanol, triphenylmethyl alcohol, benzyl alcohol, diphenylmethyl alcohol, etc. may be used, but are not limited thereto.

According to the present invention, the first alcohol compound is usually used in an amount of 1 equivalent or more, preferably 1 to 10 equivalents, particularly preferably 1 to 5 equivalents, relative to the aryl halide. Used in a range.

According to the present invention, the reaction between the aryl halide and the alcohol compound is usually carried out in the reaction solvent in the presence of a catalyst composed of a palladium compound, a promoter composed of a tertiary phosphine, and a base.

Examples of the palladium compound include
Palladium acetate, palladium nitrate, palladium chloride, palladium bromide, palladium acetylacetonate, dibenzylideneacetone palladium (Pd (dba) ₂ or
It is represented by Pd ₂ (dba) ₃ . Here, dba represents a dibenzylideneacetone ligand. ) Etc. are used,
It is not limited to these. However, palladium is particularly preferably used in practical use.

Such a palladium compound is usually 0.0001 to 1 part by mole, preferably 0.001 in terms of palladium with respect to 1 part by mole of an aryl halide.
To 0.5 parts by mol, particularly preferably 0.01 to 0.1 parts by mol.

Examples of the tertiary phosphine include triethylphosphine, tricyclohexylphosphine, triisopropylphosphine, trialkylphosphine such as tri-n-butylphosphine, tri-t-butylphosphine, triphenylphosphine, and the like. Tertiary monophosphines such as triarylphosphines such as tri-o-tolylphosphine, 1,1'-bis (diphenylphosphino) ferrocene, (R)-(+)-2,2'-
Tertiary diphosphines such as bis (diphenylphosphino) -1,1′-binaphthyl are used.

Such a tertiary phosphine is usually used in an amount of 0.1 to 10 relative to 1 part by mole of the palladium compound used.
It is used in an amount of 0 mol part, preferably 1 to 10 mol part.

According to the present invention, as the tertiary phosphine, one having optical activity, for example, (R)-(+)
-2,2'-bis (diphenylphosphino) -1,1 '
The biaryls having axial asymmetry can be obtained by reacting 2-aryl-2-propanol with a halogenated benzene having an appropriate number of substituents at the ortho position using -binaphthyl.

Further, the above base used in the present invention is
Although not particularly limited, preferably, an alkali metal carbonate such as cesium carbonate and potassium carbonate, an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide, sodium t-butoxide, potassium t-butoxide. Alkali metal alkoxides such as
Such a base is not particularly limited as long as it is in the range of 0.5 mol site relative to 1 mol part of the aryl halide used, but usually 0.5 to 5 mol parts,
It is preferably used in the range of 1 to 2 parts by mole.

The reaction according to the present invention is usually carried out in the presence of a reaction solvent inert to the reaction. The reaction solvent used is not particularly limited, but aromatic hydrocarbons such as benzene, toluene, xylene, ethers such as diethyl ether, tetrahydrofuran, dioxane, acetonitrile, dimethylformamide, dimethylsulfoxide, etc. are used. Among them, aromatic hydrocarbons such as benzene, toluene and xylene are preferably used.

The reaction according to the present invention is preferably carried out under atmospheric pressure in an atmosphere of an inert gas such as nitrogen or argon. If necessary, the reaction can be performed under pressure.
Further, according to the present invention, the reaction temperature is usually 50 to 25.
It is in the range of 0 ° C, preferably in the range of 70 to 200 ° C. While the reaction time depends on the starting compound used, the palladium compound, the tertiary phosphine, the base, and the reaction temperature, it is usually in the range of 30 minutes to 48 hours.

After completion of the reaction, the desired biaryls may be separated from the obtained reaction mixture by an appropriate means, and purified if necessary. For example, after completion of the reaction, the obtained reaction mixture is extracted with diethyl ether-dilute hydrochloric acid,
The desired biaryls can be obtained by drying, removing the reaction solvent used, and then drying under reduced pressure. If necessary, this may be purified by an appropriate means.

According to the first method of the present invention, as described above, by reacting the aryl halide represented by the general formula (I) with the alcohol compound represented by the general formula (II), As shown in the following formula, the general formula (II
An aromatic compound represented by I) can be obtained. By-products are ketones.

[0047]

[Chemical 15]

However, according to the second method of the present invention, the alcohol compound as the starting material is represented by the general formula (IIa)

[0049]

[Chemical 16]

(In the formula, R ₃ represents a hydrogen atom, an alkyl group or a monovalent aryl group.) When a second alcohol compound, that is, fluorenyl alcohols, is used, other than the above, In the same manner as the first method described above, the compound represented by the general formula (IIIa)

[0051]

[Chemical 17]

An aromatic compound represented by the formula (wherein Ar ₁ and R ₃ are the same as above) can be obtained.

In the second alcohol compound, the fluorenylidene group may have a substituent inactive to the reaction. Examples of the substituent inert to such a reaction include an alkyl group, an alkoxy group, an alkoxycarbonyl group and a nitro group. The alkyl group in the above alkyl group, alkoxy group or alkoxycarbonyl group preferably comprises 1 to 4 carbon atoms.

According to the second method of the present invention, the reason is not yet clear, but when the second alcohol compound is 9-arylfluoren-9-ol, as shown in the following formula, Aryl halide is the second
By cross-coupling with an aromatic nucleus forming a fluorene skeleton, rather than an aryl group of the alcohol compound, the biaryls having an aryloyl group are obtained.

[0055]

[Chemical 18]

[0056]

The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

Example 1 (Synthesis of 1- (2-methylphenyl) naphthalene) 2-
Bromotoluene (103 mg), 2- (1-naphthyl)
-2-Propanol (93 mg), palladium acetate (5.6 mg), triphenylphosphine (26.2 m)
g) and cesium carbonate (195 mg) were added to o-xylene (2.5 mL), and the temperature of the oil bath was 160 under nitrogen atmosphere.
Heated at ° C for 4 hours. After cooling to room temperature and extracting the resulting reaction mixture with diethyl ether-dilute hydrochloric acid, the organic layer was dried over sodium sulfate. The solvent was removed using a rotary evaporator and then dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel chromatography to obtain 1- (2-methylphenyl) naphthalene (77 mg, yield 72%).

Melting point: 67-68 ° C. ¹ H-NMR spectrum (400 MHz, solvent CDC
l ₃ , δ (ppm)): 2.02 (s, 3H), 7.23-7.39 (m, 6
H), 7.44-7.48 (m, 2H), 7.51 (dt, 1H), J = 1.5, 7.7H
z), 7.85 (d, 1H, J = 8.3Hz), 7,89 (d, 1H, J = 8.0HZ). ¹³ C-NMR spectrum (δ (ppm)): 20.04, 12
5.35, 125.55, 125.68, 125.94, 126.08, 126.59, 127.
40, 127.54. 128.18, 129.84, 130.35, 131.99, 133.5
1, 136.79, 139.77, 140.21. Mass spectrum (m / s): 218 (M ⁺ ).

Example 2 (Synthesis of (+)-2-methoxy-1,1'-binaphthyl) 1-Bromo-2-methoxynaphthalene (119 m
g), 2- (1-naphthyl), 2-propanol (14
0 mg), palladium acetate (5.6 mg), (R)-
(+)-2,2'-bis (diphenylphosphino)-
1,1′-Binaphtyl (31.1 mg) and cesium carbonate (163 mg) were added to o-xylene (2.5 mL), and the mixture was heated under a nitrogen atmosphere at an oil bath temperature of 160 ° C. for 4 hours. After cooling to room temperature and extracting the resulting reaction mixture with diethyl ether-dilute hydrochloric acid, the organic layer was dried over sodium sulfate. The solvent was removed using a rotary evaporator and then dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel chromatography,
(+)-2-Methoxy-1,1'-binaphthyl (118
mg, yield 83%) at room temperature as a viscous liquid. It became a white solid on standing. The enantiomer excess of this compound was 63% as measured in a tetrahydrofuran solution using a polarimeter.

¹ H-NMR spectrum (500 MHz,
Solvent CDCl ₃ , δ (ppm)): 3.75 (s, 3H), 7.14
(d, IH, J = 8.8Hz), 7.21 (dd, IH, J = 1.1, 5.5Hz), 7.2
7 (dd, IH, J = 1.1, 5.5Hz), 7.30-7.33 (m, 2H), 7.42-
7.47 (m, 3H), 7.61 (t, 1H, J = 7.7Hz), 7.86 (d, 1H,
J = 8.0Hz), 7.93 (d, 1H, J = 8.0Hz), 7.94 (d, 1H, J = 8.
0Hz), 7.97 (d, 1H, J = 8.8HZ). ¹³ C-NMR spectrum (δ (ppm)): 113.84, 12
3.24, 123.55, 125.49, 125.55, 125.66, 125.83, 126.
16, 126.36, 127.72, 127.78, 128.21, 128.42, 129.01,
129.45, 132.93, 133.68, 134.25, 134.52, 154.60. Mass spectrum (m / s): 284 (M ⁺ ).

Example 3 (Synthesis of 2,6-dimethylbiphenyl) 2-bromo-m
-Xylene (222 mg), 9-phenylxanthene-
9-ol (274 mg), palladium acetate (11.2
mg), triphenylphosphine (52.4 mg) and cesium carbonate (390 mg) in o-xylene (5 mL).
In addition, the mixture was heated for 6 hours at an oil bath temperature of 160 ° C. under a nitrogen atmosphere. After cooling to room temperature and extracting the resulting reaction mixture with diethyl ether-dilute hydrochloric acid, the organic layer was dried over sodium sulfate. The solvent was removed using a rotary evaporator and then dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel chromatography,
2,6-Dimethylbiphenyl (129 mg, yield 71
%) Was obtained.

¹ H-NMR spectrum of this product and
¹³ C-NMR spectra can be found in the literature (JP Wolfe, RA
Singer, BH Yang, SL Buchwald, J. Am. Chem.
Soc., 1999, 121, 9550-9561).

Example 4 (Synthesis of 2-benzoyl-1,1 ': 2', 1 "-terphenyl) Promobenzene (188 mg), 9-phenylfluoren-9-ol (258 mg), palladium acetate (11. 2 mg), triphenylphosphine (5
2.4 mg) and cesium carbonate (390 mg) were added to o-xylene (5 mL), and the temperature of the oil bath was 16 under a nitrogen atmosphere.
Heated at 0 ° C. for 2 hours. After cooling to room temperature and extracting the resulting reaction mixture with diethyl ether-dilute hydrochloric acid, the organic layer was dried over sodium sulfate. The solvent was removed using a rotary evaporator and then dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel chromatography to give 2-benzoyl-1,1 ′: 2 ′,
1 ″ -terphenyl (290 mg, yield 87%) was obtained.

Melting point: 119 to 120 ° C. ¹ H-NMR spectrum (400 MHz, solvent CDC
l ₃ , δ (ppm)): 7.03-7.09 (m, 5H), 7.25-7.39
(m, 11H), 7.42-7.47 (m, 2H). ¹³ C-NMR spectrum (δ (ppm)): 125.97, 12
6,42, 127.15, 127.74, 127.80, I27.84, 129.35, 130.
02, 130.07, 130.19, 130.26, 130.59, 132.15, 132.36,
137,23, 138.48, 139.22, 140.41,140.94, 142,32, 19
6.59. Mass spectrum (m / s): 334 (M ⁺ ).

Examples 5 to 26 In the presence of a tertiary phosphine (L), the aryl halide (bromobenzene or its derivative) represented by the general formula (1) and the general formula (II ) Represented by
The aromatic compound represented by the general formula (2) was obtained by reacting with the alcohol compound according to the present invention.

[0066]

[Chemical 19]

W, X, Y and Z in the aryl halide used in each example, Ar ₂ , R ₁ and R ₂ in the first alcohol compound used, phosphine used, reaction time and aromatics obtained The compound yields are shown in Tables 1 and 2.

In the table, a, b, c and d in the reaction method column
Indicates that the same method as in Examples 1, 2, 3 and 4 was used. In the column of Ar ₂ , Ph represents a phenyl group, and H represents a hydrogen atom. In the column of phosphine, PPh ₃ is triphenylphosphine, (R)
-BINAP is (R) - (+) - 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl, PCy ₃
Is tricyclohexylphosphine, P (o-Toly
l) ₃ represents tris-o-tolylphosphine.

[0069]

[Table 1]

[0070]

[Table 2]

[0071]

[Table 3]

[0072]

[Table 4]

Of the reaction products obtained, biphenyl,
2-methylbiphenyl, 1-phenylnaphthalene, 4-
Methylbiphenyl and 2-methoxybiphenyl were identified by comparison with authentic samples. The melting point and ¹ H-NMR spectrum of 1- (4-methylphenyl) naphthalene are shown in the literature (CC Lezoff, RJ Hayward, Can.
J. Chem., 1970, 48, 1842).

Further, ethyl 4- (1-naphthyl) benzoate obtained in Example 11, 2-methoxy-1-phenylnaphthalene obtained in Examples 13 and 14, Example 15
Melting point of 9-phenylphenanthrene obtained in Example 1, 9-phenylanthracene obtained in Example 16 and 5- (2-methyl-1-naphthyl) tetralin obtained in Example 23 (when there is a melting point) , Mass spectrometry and ¹ H-NMR spectrum (400 MHz, solvent CDCl ₃ , δ (pp
m)) is shown below.

Ethyl 4- (1-naphthyl) benzoate (viscous liquid at room temperature) ¹³ C-NMR spectrum (δ (ppm)): 1.44 (t, 3)
H, J = 7.1Hz), 4.43 (q, 2H, J = 7.1Hz), 7.42-7.46 (m, 2
H), 7.49-7.54 (m, 2H), 7.57 (d, 2H, J = 8.4Hz), 7.83
(d, 1H, J = 8.1Hz), 7.88 (d, 1H, J = 8.8Hz), 7.91 (d,
1H, J = 8.8Hz), 8.17 (d, 2H, J = 8.4Hz). Mass spectrometry (m / s): 276 (M ⁺ ).

2-Methoxy-1-phenylnaphthalene Melting point: 50 to 51 ° C. ¹³ C-NMR spectrum (δ (ppm)): 3.73 (s, 3)
H), 7.17-7.34 (m, 6H), 7.38-7.42 (m, 3H), 7.71-7.73
(m, 1H), 7.77 (d, 1H, J = 9.2Hz). Mass spectrum (m / s): 234 (M ⁺ ).

9-Phenylphenanthrene Melting point: 104-105 ° C. ¹³ C-NMR spectrum (δ (ppm)): 7.42-7.46
(m, 1H), 7.48-7.55 (m, 5H), 7.58-7.68 (m, 4H), 7.87
(dd, 1H, J = 1.4, 7.7Hz), 7.91 (dd, 1H, J = 1.1, 8.1H
z), 8.70 (d, 1H, J = 8.1Hz), 8.77 (d, 1H, J = 8.4Hz). Mass spectrum (m / s): 254 (M ⁺ ).

9-Phenylanthracene Melting point: 153-154 ° C. ¹³ C-NMR spectrum (δ (ppm)): 7.42-7.36
(m, 2H), 7.41-7.47 (m, 4H), 7.50-7.60 (m, 3H), 7.65
(d, 2H, J = 8.8Hz), 8.04 (d, 2H, J = 8.4Hz), 8.49 (s,
1H). Mass spectrum (m / s): 254 (M ⁺ ) 5- (2-methyl-1-naphthyl) tetralin (viscous liquid at room temperature) ¹³ C-NMR spectrum (δ (ppm)): 2.10 ( s, 3
H), 7.14 (d, 1H, J = 7.4Hz), 7.19-7.28 (m, 3H), 7.36
-7.40 (m, 2H), 7.44-7.49 (m, 2H), 7.60 (t, 1H, J =
7.5Hz), 7.86-7.95 (m, 4H). Mass spectrometry (m / s): 268 (M ⁺ ).

[0079]

INDUSTRIAL APPLICABILITY As described above, according to the present invention, by using easily available starting materials, catalysts, etc., and selecting those starting materials, it is possible to obtain the objects including those having an asymmetric structure. Biaryls can be obtained easily and in high yields without the formation of harmful by-products. Therefore,
The process according to the invention is suitable for large-scale production of biaryls.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07C 27/00 C07C 27/00 41/30 41/30 43/20 43/20 D 45/29 45/29 49/08 49/08 A 49/784 49/784 49/786 49/786 67/343 67/343 69/76 69/76 A C07D 311/86 C07D 311/86 // C07C 15/27 C07C 15/27 (72) Inventor Masahiro Miura 6-8-1-418 Makamicho, Takatsuki City, Osaka Prefecture (72) Inventor Tetsuya Sato 4-37-29-6 Yamada Higashi, Suita City, Osaka Prefecture (72) Inventor Masakatsu Nomura Hyogo Prefecture 1-21-18 F-term, Hanayashiki, Kawanishi-shi (reference) 4C062 HH25 4H006 AA02 AC24 AC44 BA25 BA32 BA53 BA82 BJ50 GP03 KA31 4H039 CA41 CA62 CC20

Claims (5)

[Claims] 1. A compound represented by the general formula (I): (In the formula, Ar ₁ represents a monovalent aryl group and X represents a halogen atom.) In the presence of a palladium compound, a tertiary phosphine, and a base, an aryl halide represented by the general formula (II) 2] (In the formula, Ar ₂ represents a monovalent aryl group, and R ₁ and R ₂
Are each independently a hydrogen atom, an alkyl group or the above Ar ₂
And R ₁ and R ₂ may be bonded to each other to form a divalent group. However, the case where R ₁ and R ₂ jointly form an indenylidene group is excluded. ) Is reacted with an alcohol compound represented by the general formula (III) (In the formula, Ar ₁ and Ar ₂ are the same as the above.) A method for producing an aromatic compound. 2. A compound represented by the general formula (I): (In the formula, Ar ₁ represents a monovalent aryl group and X represents a halogen atom.) In the presence of a palladium compound, a tertiary phosphine and a base, an aryl halide represented by the general formula (IIa) 5] (In the formula, R ₃ represents a hydrogen atom, an alkyl group or a monovalent aryl group.) The alcohol compound represented by the formula is reacted to give a compound represented by the general formula (IIIa): (In the formula, Ar ₁ and R ₃ are the same as the above.) A method for producing an aromatic compound. 3. The method according to claim 1, wherein the palladium compound is palladium acetate. 4. The method according to claim 1, wherein the tertiary phosphine is monophosphine or diphosphine. 5. The method according to claim 1, wherein the base is a carbonate of an alkali metal.