JP2008031090A - Organotin compound and its manufacturing method, and manufacturing method of aromatic compound derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method that enables efficient acquisition of an aromatic compound derivative bearing a reactive functional group such as a carboxylate group by a synthetic route via a reaction forming a carbon-carbon bond. <P>SOLUTION: The manufacturing method of an organotin compound comprises a step for forming an organotin compound represented by general formula (3) by a reaction of an aromatic compound represented by general formula (1) with a bis(trialkyltin) compound represented by general formula (2). Z-Ar-X<SP>1</SP>(1). R<SP>1</SP><SB>3</SB>-SnSn-R<SP>1</SP><SB>3</SB>(2). Z-Ar-SnR<SP>1</SP><SB>3</SB>(3). In formulae (1)-(3), Ar is an optionally substituted aromatic group; Z is a reactive functional group selected from among a carboxylate group and the like; and X<SP>1</SP>is a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an organotin compound, a method for producing the same, and a method for producing an aromatic compound derivative.

  As an important method for synthesizing a derivative of an aromatic compound, there is a method through a coupling reaction that generates a carbon-carbon bond. In this case, a method is generally performed in which an aromatic compound is converted into an organometallic compound such as an organotin compound and this is reacted with another reaction substrate. In order to obtain an organic tin compound, conventionally, a method of reacting a halogenated aromatic compound with a trialkyltin chloride compound has been widely used.

On the other hand, there are examples in which a coupling reaction using a bistrialkyltin compound has been studied (Non-Patent Documents 1 and 2).
Tetrahedron Letters, 2001, 42, p. 5327-5329 Tetrahedron Letters, 2002, 43, p. 4565-4567

  However, in the case of an aromatic compound having a highly reactive functional group such as a carboxylic acid ester group, it may be difficult to convert it into an organometallic compound such as an organotin compound. For example, according to the knowledge of the present inventors, in the case of a pyridine derivative substituted with a functional group such as a carboxylic acid ester group, it is extremely difficult to convert it into an organotin compound by a method using a trialkyltin chloride compound. .

  Therefore, the present invention provides a method that enables an aromatic compound derivative having a reactive functional group such as a carboxylic acid ester group to be efficiently obtained by a synthetic route through a reaction that generates a carbon-carbon bond. The main purpose is to do.

  The present invention provides an organotin compound represented by the following general formula (3) by a reaction between an aromatic compound represented by the following general formula (1) and a bistrialkyltin compound represented by the following general formula (2). It is a manufacturing method of an organotin compound provided with the step which produces | generates.

Z-Ar-X ¹ (1)
R ¹ ₃ -SnSn-R ¹ ₃ (2)
Z-Ar-SnR ¹ ₃ (3)

In the formulas (1), (2) and (3), Ar represents an aromatic group which may have a substituent, and Z may have a carboxylic acid ester group, a carboxyl group or a substituent. A reactive functional group selected from the group consisting of a vinyl group, a phosphate ester group, a sulfonate ester group, an acid amide group, an imino group and a thioester group, and X ¹ is a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group R ¹ represents an alkyl group, and a plurality of R ¹ in the same molecule may be the same or different.

  According to the present invention, the organotin compound of the formula (3) can be efficiently obtained from the aromatic compound of the formula (1) having a reactive functional group such as a carboxylate group. This makes it possible to efficiently obtain a derivative of an aromatic compound having a reactive functional group such as a carboxylic acid ester group by a synthetic route that undergoes a reaction that generates a carbon-carbon bond.

  The above reaction is preferably performed in the presence of a transition metal catalyst in order to increase the reaction rate.

The reaction is preferably carried out at a ratio of the bistrialkyltin compound to 2 equivalents or more relative to 1 equivalent of X ¹ in the aromatic compound. When this ratio is less than 2 equivalents, a dimer of the aromatic compound of the formula (1) is generated, and the yield of the organotin compound tends to decrease.

  The present invention also includes an aromatic compound derivative comprising a step of generating a carbon-carbon bond at the position of the carbon atom bonded to the trialkylstannyl group of the organotin compound represented by the general formula (3). It is a manufacturing method.

  When the aromatic compound is a compound represented by the following general formula (1a) or (1b) and the organotin compound is a compound represented by the following general formula (3a) or (3b) It is particularly useful. In this case, a pyridine derivative such as a pyridinecarboxylic acid derivative can be easily synthesized.

In the formulas (1a), (1b), (3a) and (3b), X ¹ represents a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group, R ¹ represents an alkyl group, and a plurality of R ¹ may be the same or different, R ¹⁰ represents an alkyl group which may have a substituent, and R ¹¹ has an aryl group or a substituent which may have a substituent. Or a good alkyl group.

In the manufacturing method of the said aromatic compound derivative, it is preferable to produce | generate a carbon-carbon bond by reaction of the organotin compound and the compound represented by following General formula (10).
R ² -X ² (10)

In Formula (10), R ² represents a hydrocarbon group which may have a substituent, and X ² represents a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group.

The present invention is also represented by the following general formula (5) from the aromatic compound represented by the above general formula (1) by the reaction in the presence of the bistrialkyltin compound represented by the above general formula (2). A method for producing an aromatic compound derivative, comprising the step of producing an aromatic compound derivative.
Z-Ar-Ar-Z (5)

  In the formula (5), Ar represents an aromatic group which may have a substituent, a plurality of Ar in the same molecule may be the same or different, and Z represents a carboxylic acid ester group, a carboxyl group, a substituted group A reactive functional group selected from the group consisting of a vinyl group, a phosphate ester group, a sulfonate ester group, an acid amide group, an imino group and a thioester group, which may have a group, and a plurality of Z in the same molecule; May be the same or different.

  According to the said manufacturing method, aromatic compound derivatives, such as a bipyridine compound, can be obtained simply and efficiently with a high yield.

  In the said manufacturing method, even if an aromatic compound is a compound represented by the following general formula (1-2), and the aromatic compound derivative to produce | generate is a compound represented by the following general formula (5-2). Good.

Ar in formula (1-2) and (5-2), Z and ^{X 1} is Ar in formula (1), and Z and ^{X 1} synonymous. A plurality of Ar in the same molecule may be the same or different, a plurality of Z in the same molecule may be the same or different, and a plurality of X ¹ in the same molecule may be the same or different. n represents an integer of 0 or more.

The reaction for producing the aromatic compound derivative of the formula (5) or (5-2) is preferably carried out with the ratio of the bistrialkyltin compound to 1 equivalent of X ¹ in the aromatic compound being 1/3 to 1 equivalent. When the ratio of the bistrialkyltin compound is not within this range, the production of the organic tin compound increases, and the yield of the aromatic compound derivative of the formula (5) or (5-2) tends to decrease.

  The present invention is also an organotin compound represented by the general formula (3a) or (3b). The organotin compound according to the present invention is suitably used for synthesizing an aromatic compound derivative by a coupling reaction or the like.

  According to the present invention, there is provided a method capable of efficiently obtaining a derivative of an aromatic compound having a reactive functional group such as a carboxylic acid ester group by a synthetic route through a reaction for generating a carbon-carbon bond. Is done.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

In the present embodiment, organotin represented by the following general formula (3) is obtained by the reaction of the aromatic compound represented by the following general formula (1) and the bistrialkyltin compound represented by the following general formula (2). A step of generating a compound, and a carbon-carbon bond is generated at the position of the carbon atom bonded to the trialkylstannyl group (—SnR ¹ ₃ ) of the organotin compound represented by the following general formula (3) Steps. According to this embodiment, useful aromatic compound derivatives such as pyridinecarboxylic acid derivatives are efficiently synthesized.

Z-Ar-X ¹ (1)
R ¹ ₃ -SnSn-R ¹ ₃ (2)
Z-Ar-SnR ¹ ₃ (3)

In these formulas, Ar is an aromatic group which may have a substituent. Examples of the aromatic ring constituting Ar include nitrogen-containing aromatic rings such as a pyridine ring, a pyridazine ring, a quinoline ring, and an isoquinoline ring. Ar may further have the same or different substituents in addition to Z and X ¹ .

  Z is a reactive functional group selected from the group consisting of a carboxylic acid ester group, a carboxyl group and an optionally substituted vinyl group, a phosphoric acid ester group, a sulfonic acid ester group, an acid amide group, an imino group and a thioester group. It is a group. It is thought that it has been difficult to obtain a desired organotin compound by the side reaction in which these reactive functional groups react with alkyllithium, a trialkyltin chloride compound or the like.

When Z is a carboxylic acid ester group, the aromatic compound of the formula (1) is represented by, for example, the general formula (1a). When Z is a carboxyl group, it is preferably converted to a carboxylic acid ester group before the reaction with the bistrialkyltin compound. In the formula (1a), R ¹⁰ represents an alkyl group which may have a substituent. Examples of R ¹⁰ include a methyl group, an ethyl group, a propyl group, a butyl group, and a benzyl group.

When Z is a vinyl group which may have a substituent, the aromatic compound of the formula (1) is represented by, for example, the general formula (1b). In the formula (1b), R ¹¹ is an aryl group which may have a substituent or an alkyl group which may have a substituent. R ¹¹ includes a phenyl group, an alkylphenyl group (4-ethylphenyl group, etc.), a thienyl group, a pyridyl group, a naphthyl group, an anthranyl group, a phenanthryl group, a furanyl group, and a carbonyl group, a carboxylic acid ester group, etc. And the like.

When the aromatic compound represented by the formula (1a) or (1b) is used, the organotin compound represented by the general formula (3a) or (3b) is obtained. ^{R 1, R 10} and ^{R 11} in the formula (3a) and (3b), the formula (2), interchangeably, including preferred embodiments thereof and ^{R 1, R 10} and ^{R 11} in (1a) and (1b) is there.

X ¹ is a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group. Typically, X ¹ is a bromine atom, a chlorine atom or a trifluoromethylsulfonyloxy group.

R ¹ in the formula (2) is an alkyl group. Examples of R ¹ include a methyl group, an ethyl group, a butyl group, and a propyl group. As the bistrialkyltin compound of the formula (2), hexabutylditin or the like is commercially available.

  The reaction between the aromatic compound and the bistrialkyltin compound is carried out by heating to about 50 to 200 ° C. in an organic solvent such as toluene if necessary. This reaction is preferably performed in the presence of a transition metal catalyst. Suitable transition metal catalysts include Pd (0) complexes such as tetrakistriphenylphosphinopalladium. After the reaction, the desired organotin compound is isolated by a usual method such as a method using silica gel column chromatography.

Regarding the charge ratio of the reaction when the organic tin compound is isolated, the ratio of the bistrialkyltin compound is preferably about 2 equivalents or more with respect to 1.0 equivalent of X ¹ in the aromatic compound. More preferably. The upper limit of the ratio of the bistrialkyltin compound is preferably about 10 equivalents.

  In the step of generating a carbon-carbon bond, preferably in the presence of a Pd (0) complex, for example, an organotin compound of the formula (3) and a compound represented by the following general formula (10) or (11) The cross-coupling reaction proceeds by the reaction. By using the compound of the formula (10) or (11), an aromatic compound derivative represented by the following general formula (4a) or (4b) is obtained.

R ² -X ² (10)
R ³ —CO—X ³ (11)
Z-Ar-R ² (4a)
Z-Ar-CO-R ³ (4b)

In the formulas (10) and (4a), R ² is a hydrocarbon group that may have a substituent. R ² is preferably an aryl group or an alkenyl group. X ² is a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group.

In formulas (11) and (4b), R ³ is the same as R ² in formula (10), including preferred embodiments thereof. X ³ represents a halogen atom. That is, the compound of formula (11) is an organic acid halide.

  Carbon-carbon bonds can also be generated by reaction between organotin compounds of formula (3). In this case, as will be understood by those skilled in the art, an aromatic compound derivative can be produced in one step without isolating the organotin compound of formula (3) by appropriately adjusting the charge ratio of the reaction and the like. . That is, in the presence of the bistrialkyltin compound represented by the general formula (2), the coupling reaction of the aromatic compound represented by the general formula (1) is allowed to proceed. The aromatic compound derivative represented can be synthesized.

  Furthermore, in this case, a compound represented by the above general formula (5-2) may be obtained by using a compound represented by the above general formula (1-2) as an aromatic compound and subjecting it to a coupling reaction. it can. It is extremely difficult to synthesize an aromatic compound derivative represented by the formula (5-2) by another synthesis route, and this method is highly industrially useful.

This coupling reaction is suitably applied, for example, to synthesize an aromatic compound derivative represented by the following (5-2a) from an aromatic compound represented by the following general formula (1-2a).

The reaction for generating the aromatic compound derivative of the formula (5) or (5-2) in one stage is performed by setting the ratio of the bistrialkyltin compound to 1 equivalent of X ¹ in the aromatic compound as 1/3 to 1 equivalent. Is preferred.

When Ar is an aromatic group composed of a pyridine ring and Z is a carboxylic acid ester group or a carboxyl group, a pyridinecarboxylic acid derivative can be efficiently synthesized according to this embodiment. The pyridinecarboxylic acid derivative obtained in this case is represented by, for example, the following general formula (40a) or (40b). In the formula (40a) and ^(40b), R 2, ^{R 3} and ^{R 10} of formula (10), (11) or, including preferred embodiments thereof and ^R 2, ^{R 3} and ^{R 10} in (1a) synonymous It is. The carboxylic acid ester group possessed by the pyridinecarboxylic acid derivatives of the formulas (4a) and (4b) is appropriately converted into a carboxyl group.

  A pyridinecarboxylic acid derivative is a useful compound as an intermediate for synthesizing pharmaceutical ligands, electronic materials, complex ligands used in catalysts, and the like. In order to synthesize a pyridinecarboxylic acid derivative derivatized with various substituents, a method of linking pyridinecarboxylic acid derivatives by a coupling reaction is the simplest synthetic route. According to this embodiment, even when a reactive functional group such as a carboxylic acid ester group is present, a tin compound for performing a coupling reaction can be easily obtained without being consumed by the reactive functional group. it can. Thereby, it becomes possible to synthesize a desired pyridinecarboxylic acid derivative through various coupling reactions.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

Example 1: Synthesis of 4- (4-ethylstyryl) -2-tributylstannylpyridine 452 mg 4- (4-ethylstyryl) -2-bromopyridine (a1), 3.9 mL bistributyltin, and tetrakistriphenylphos 80 mg of finopalladium was dissolved in 8 mL of toluene and heated at 100 ° C. for 50 hours. The solvent was distilled off and the residue was purified by silica gel chromatography (hexane / ethyl acetate = 10/1) to obtain 250 mg of 4- (4-ethylstyryl) -2-tributylstannylpyridine (b1).
¹ H-NMR (δ (ppm) CDCl ₃ ): 8.60 (d, J = 5.2Hz, 1H), 7.24 (d, J = 1.8Hz, 1H), 7.15 (d, J = 7.9Hz, 2H), 7.07 (d, J = 8.0Hz, 2H), 6.98 (dd, J = 5.2,1.5Hz, 1H), 6.73 (d, J = 1.2Hz, 1H), 6.42 (d, J = 1.2Hz, 1H), 2.62 (q, J = 7.6Hz .2H), 1.48 (quint, J = 7.8Hz, 6H), 1.28 (sext, J = 7.3Hz, 6H), 1.22 (t, J = 7.6Hz, 3H), 1.02 (t , J = 8.1Hz, 6H), 0.86 (t, J = 7.2Hz, 9H)

Comparative Example 1
4- (4-Ethylstyryl) -2-bromopyridine (a1) (452 mg) was dissolved in 10 mL of THF with stirring, and 1.0 mL of 1.6 M butyllithium was added dropwise at -70 ° C. 7 mL was added. After 30 minutes, the reaction mixture was allowed to warm to room temperature and stirred for 1 hour, 20 mL of water was added, and the mixture was extracted twice with 10 mL of ethyl acetate. After drying with sodium sulfate, the solvent was distilled off, and the main product was purified by silica gel chromatography (hexane / ethyl acetate = 10/1). 4- (4-Ethylstyryl) -2-tributylstannylpyridine (b1) was not obtained, and 4- (1- (4-ethylphenyl) -2-hexyl) -2-bromopyridine (c1) and 4- (2- (4-Ethylphenyl) -1-hexyl) -2-bromopyridine (c2) was obtained.

Example 2: Synthesis of 4- (methoxycarbonyl) -2-tributylstannylpyridine 339 mg 4- (methoxycarbonyl) -2-bromopyridine (a2), 3.9 mL bistributyltin, and 80 mg tetrakistriphenylphosphinopalladium. Dissolved in 8 mL of toluene and heated at 100 ° C. for 50 hours. The solvent was distilled off and the residue was purified by silica gel chromatography (hexane / ethyl acetate = 10/1) to obtain 220 mg of 4- (methoxycarbonyl) -2-tributylstannylpyridine.
¹ H-NMR (δ (ppm) CDCl ₃ ): 8.16 (d, J = 5.2Hz, 1H), 7.21 (d, J = 1.8Hz, 1H), 6.94 (dd, J = 5.2, 1.8Hz, 1H) , 4.02 (S, 3H), 1.56 (quint, J = 7.8Hz, 6H), 1.32 (sext, J = 7.6Hz, 6H), 1.10 (t, J = 8.1Hz, 6H), 0.87 (t, J = (7.3Hz, 9H)

Comparative Example 2
339 mg of 4- (methoxycarbonyl) -2-bromopyridine (a2) was dissolved in 10 mL of THF with stirring, and 1.0 mL of 1.6 M butyllithium was added dropwise at −70 ° C. After 30 minutes, 0.7 mL of tributyltin chloride was added. added. After 30 minutes, the reaction mixture was allowed to warm to room temperature and stirred for 1 hour, 20 mL of water was added, and the mixture was extracted twice with 10 mL of ethyl acetate. After drying with sodium sulfate, the solvent was distilled off. The product was analyzed, but no significant material could be isolated or identified from the mixture.

Example 3: Synthesis of 4,4'-di (methoxycarbonyl) -2,2'-bipyridine 8.68 g of 4- (methoxycarbonyl) -2-bromopyridine (a2), 2.3 g of bistributyltin, and tetrakistri 650 mg of phenylphosphinopalladium was dissolved in 100 mL of toluene and heated at 100 ° C. for 39 hours. The solvent was distilled off, and recrystallization from ethyl acetate gave 4.2 g of 4,4′-di (methoxycarbonyl) -2,2′-bipyridine (d1).
¹ H-NMR (δ (ppm) CDCl ₃ ): 8.96 (S, 2H), 8.87 (d, 2H, J = 4.3Hz), 7.91 (d, 2H, J = 4.3Hz), 4.00 (S, 6H)

Comparative Example 3
678 mg of 4- (methoxycarbonyl) -2-bromopyridine (a2) is dissolved in 10 mL of THF with stirring, and 1.0 mL of 1.6 M butyllithium is added dropwise at −70 ° C. After 30 minutes, 0.7 mL of tributyltin chloride is added. Was added. After 30 minutes, the reaction mixture was allowed to warm to room temperature and stirred for 1 hour, 20 mL of water was added, and the mixture was extracted twice with 10 mL of ethyl acetate. It dried with sodium sulfate and the solvent was distilled off. The product was analyzed, but no significant material could be isolated or identified from the mixture.

Example 4: Synthesis of 4,4'-di (methoxycarbonyl) -3,3'-dibromo-2,2'-bipyridine 20 g of 4- (methoxycarbonyl) -2,6-dibutylpyridine (a3), bistributyltin 11.8 g and tetrakistriphenylphosphinopalladium 1.1 g were dissolved in 400 mL of toluene and heated at 100 ° C. for 50 hours. The solvent was distilled off, washed with cold hexane, washed with cold ether and then distilled under reduced pressure to 4.6 g of 4,4′-di (methoxycarbonyl) -3,3′-dibromo-2,2′-bipyridine ( d2) and 4,4 ′, 4 ″ -tetramethoxycarbonyl-6,6 ″ -dibromo-2,2 ′, 6 ′, 2 ″ -terpyridine (d3) 1.4 g were obtained.
¹ H-NMR (δ (ppm) CDCl ₃ ): 8.87 (d, J = 1.2Hz, 2H), 8.09 (d, J = 1.2Hz, 2H), 4.02 (s, 6H) (4,4′-di (Methoxycarbonyl) -3,3′-dibromo-2,2′-bipyridine),
¹ H-NMR (δ (ppm) CDCl ₃ ): 9.03 (d, J = 1.2Hz, 2H), 9.00 (s, 2H), 8.11 (d, J = 1.2Hz, 2H), 4.06 (s, 3H) , 4.05 (s, 6H) (4,4 ′, 4 ″ -tetramethoxycarbonyl-6,6 ″ -dibromo-2,2 ′, 6 ′, 2 ″ -terpyridine)

Comparative Example 4
926 mg of 4- (methoxycarbonyl) -2,6-dibutylpyridine (a3) was suspended in 10 mL of THF with stirring, and 1.0 mL of 1.6 M butyllithium was added dropwise at −70 ° C. 7 mL was added. After 30 minutes, the reaction mixture was returned to room temperature and stirred for 1 hour, 20 mL of water was added, and the mixture was extracted twice with 40 mL of chloroform. After drying with sodium sulfate, the solvent was distilled off. The product was analyzed, but no significant material could be isolated or identified from the mixture.

Claims (11)

A step of producing an organotin compound represented by the following general formula (3) by a reaction between an aromatic compound represented by the following general formula (1) and a bistrialkyltin compound represented by the following general formula (2): A method for producing an organotin compound.
Z-Ar-X ¹ (1)
R ¹ ₃ -SnSn-R ¹ ₃ (2)
Z-Ar-SnR ¹ ₃ (3)
[In the formulas (1), (2) and (3)
Ar represents an aromatic group which may have a substituent,
Z is a reactive functional group selected from the group consisting of a carboxylic acid ester group, a carboxyl group, an optionally substituted vinyl group, a phosphoric acid ester group, a sulfonic acid ester group, an acid amide group, an imino group, and a thioester group. Group,
X ¹ represents a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group,
R ¹ represents an alkyl group, and a plurality of R ¹ in the same molecule may be the same or different. ] The said aromatic compound is a compound represented by the following general formula (1a) or (1b), and the said organotin compound is a compound represented by the following general formula (3a) or (3b). Manufacturing method.

[In the formulas (1a), (1b), (3a) and (3b)
X ¹ represents a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group,
R ¹ represents an alkyl group, and a plurality of R ¹ in the same molecule may be the same or different,
R ¹⁰ represents an alkyl group which may have a substituent,
R ¹¹ represents an aryl group which may have a substituent or an alkyl group which may have a substituent. ]   The production method according to claim 1 or 2, wherein the reaction is carried out in the presence of a transition metal catalyst. The reaction is carried out with a ratio of X ^{1 1} wherein the bis trialkyltin compound to equivalents of the aromatic compound as above 2 equivalents, A process according to any one of claims 1 to 3. The manufacturing method of an aromatic compound derivative provided with the step which produces | generates a carbon-carbon bond in the position of the carbon atom couple | bonded with the said trialkylstannyl group of the organotin compound represented by following General formula (3).
Z-Ar-SnR ¹ ₃ (3)
[In Formula (3),
Ar represents an aromatic group which may have a substituent,
Z is a reactive functional group selected from the group consisting of a carboxylic acid ester group, a carboxyl group, an optionally substituted vinyl group, a phosphoric acid ester group, a sulfonic acid ester group, an acid amide group, an imino group, and a thioester group. Group,
R ¹ represents an alkyl group, and a plurality of R ¹ in the same molecule may be the same or different. ] The manufacturing method of Claim 5 whose said organic tin compound is a compound represented by the following general formula (3a) or (3b).

[In the formulas (3a) and (3b)
R ¹ represents an alkyl group, and a plurality of R ¹ in the same molecule may be the same or different,
R ¹⁰ represents an alkyl group which may have a substituent,
R ¹¹ represents an aryl group which may have a substituent or an alkyl group which may have a substituent. ] The manufacturing method of Claim 5 or 6 which produces | generates the said carbon-carbon bond by reaction with the compound represented with the said organic tin compound and following General formula (10).
R ² -X ² (10)
[In Formula (10),
R ² represents a hydrocarbon group which may have a substituent,
X ² represents a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group. ] An aromatic compound derivative represented by the following general formula (5) from an aromatic compound represented by the following general formula (1) by a reaction in the presence of the bistrialkyltin compound represented by the following general formula (2) The manufacturing method of an aromatic compound derivative provided with the step which produces | generates.
Z-Ar-X ¹ (1)
R ¹ ₃ -SnSn-R ¹ ₃ (2)
Z-Ar-Ar-Z (5)
[In the formulas (1), (2) and (5)
Ar represents an aromatic group which may have a substituent, and a plurality of Ar in the same molecule may be the same or different,
Z is a reactive functional group selected from the group consisting of a carboxylic acid ester group, a carboxyl group, an optionally substituted vinyl group, a phosphoric acid ester group, a sulfonic acid ester group, an acid amide group, an imino group, and a thioester group. A plurality of Z in the same molecule may be the same or different,
X ¹ represents a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group,
R ¹ represents an alkyl group, and a plurality of R ¹ in the same molecule may be the same or different. ] The manufacturing method according to claim 8, wherein the aromatic compound is a compound represented by the following general formula (1-2), and the aromatic compound derivative is a compound represented by the following general formula (5-2). .

[In the formulas (1-2) and (5-2)
Ar represents an aromatic group which may have a substituent, and a plurality of Ar in the same molecule may be the same or different,
Z is a reactive functional group selected from the group consisting of a carboxylic acid ester group, a carboxyl group, an optionally substituted vinyl group, a phosphoric acid ester group, a sulfonic acid ester group, an acid amide group, an imino group, and a thioester group. A plurality of Z in the same molecule may be the same or different,
X ¹ represents a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group, and a plurality of X ¹ in the same molecule may be the same or different,
n represents an integer of 0 or more. ] The reaction is carried out with a ratio of said bis trialkyltin compound to the X ^{1 1} equivalent of the aromatic compound as a 1 / 3-1 eq method according to claim 8 or 9, wherein. Organotin compounds represented by the following general formula (3a) or (3b).

[In the formulas (3a) and (3b)
R ¹ represents an alkyl group, and a plurality of R ¹ in the same molecule may be the same or different,
R ¹⁰ represents an alkyl group which may have a substituent,
R ¹¹ represents an aryl group which may have a substituent or an alkyl group which may have a substituent. ]