JP2000281636A - Production of active methylene-substituted arene derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To simply produce the subject compound important as an intermediate for a tetracyanoquinodimethane derivative which is an electron acceptor in a high yield by condensing an active methylene compound with an aryl halide in the presence of a base and a specific catalyst. SOLUTION: (A) An active methylene compound represented by formula I (X and Y are each a substituent group having >=0.2 value of Hammet σp constant) (preferably malononitrile) is condensed with (B) an aryl halide represented by formula II (R1 is a halogen; R2 is a substituent group; m is 1-6; n is 0-5) in the presence of (C) a base (preferably sodium hydroxide or an alkali metal alkoxide) and (D) a catalyst of [1,1-bis(diphenylphosphino) ferrocene]palladium (II) chloride to synthesize a compound represented by formula III. Furthermore, in the above reaction, the amount of the catalyst of the component D is preferably 0.01-100 mol% based on the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an active methylene-substituted arene compound. In particular, the present invention relates to a method for producing a 1,4-bis (dicyanomethyl) benzene derivative which is an important material as a tetracyanoquinodimethane (TCNQ) derivative intermediate which is an electron acceptor used in the field of organic conductors.

[0002]

2. Description of the Related Art In recent years, research and development of organic conductors using a charge transfer complex have been actively conducted. In particular, tetracyanoquinodimethane (TCNQ) and derivatives thereof have been used as electron acceptors. The synthesis of these TCNQ derivatives is described in Tetrahedron Lett. , 2
As described in US Pat. No. 6,1553 (1985), it is synthesized via a 1,4-bis (dicyanomethyl) benzene derivative as an intermediate. The 1,4-bis (dicyanomethyl) benzene derivative is synthesized by condensing the corresponding diiodo compound with malononitrile in the presence of a catalytic amount of bis (triphenylphosphine) palladium (II) chloride, but generally the diiodo compound is generally used. Is difficult to synthesize. On the other hand, a 1,4-bis (dicyanomethyl) benzene derivative is not obtained even when an inexpensive and easily synthesized dibromo compound is condensed with malononitrile in the presence of a catalytic amount of bis (triphenylphosphine) palladium (II) chloride, and the TCNQ derivative is not obtained. At present, an industrial production method that is commonly used as a synthesis condition of is problematic in terms of versatility and economy.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the above-mentioned problems relating to the versatility and economical efficiency of the conventional methods, and to provide a simple and high-yield method for producing an active methylene-substituted arene compound. In particular, it is an object of the present invention to provide a method for producing a 1,4-bis (dicyanomethyl) benzene derivative.

[0004]

The above object has been attained by the following items which specify the present invention and preferred embodiments thereof. (1) An active methylene compound represented by the following general formula (I) and an aryl halide represented by the following general formula (II) are combined with a base and [1,1-bis (diphenylphosphino) ferrocene] palladium (II) chloride Condensation in the presence of a catalyst,
A method for producing an active methylene-substituted arene compound, comprising synthesizing an active methylene-substituted arene compound represented by the general formula (III).

[0005]

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[Wherein, X and Y each independently represent a substituent having a Hammett σ _p value of 0.2 or more. ]

[0007]

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[Wherein, R ₁ represents a halogen atom, and R ₂ represents a substituent. m represents an integer of 1 to 6, and n is 0
Represents an integer of 5 or more, and m + n ≦ 6. When m is 2 or more, R ₁ may be the same or different. When n is 2 or more, R ₂ may be the same or different, and R ₂ may be linked together to form an unsaturated condensed ring. ]

[0009]

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Wherein X, Y, R ₂ and m have the same meanings as in formulas (I) and (II). (2) The method for producing an active methylene-substituted arene compound according to the above (1), wherein R ₂ is a substituent having a Hammett σ _p value of 0 or less. (3) The method for producing an active methylene-substituted arene compound according to the above (1) or (2), wherein m = 2. (4) the active methylene compound is malononitrile,
And producing the active methylene-substituted arene compound of the above (1) or (2), wherein the aryl halide is a compound represented by the following general formula (IV), wherein the compound is represented by the following general formula (V): Method.

[0011]

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[Wherein R ₁ , R ₂ and n represent the general formula (II)
Is synonymous with ]

[0013]

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[Wherein, R ₂ and n have the same meanings as in formula (II). (5) The method for producing an active methylene-substituted arene compound according to any one of the above (1) to (4), wherein R ₁ is a bromine atom or an iodine atom. (6) The method for producing an active methylene-substituted arene compound according to any one of the above (1) to (5), wherein the base is sodium hydride or an alkali metal alkoxide. (7) The method for producing an active methylene-substituted arene compound according to any one of the above (1) to (4), wherein R ₁ is a bromine atom and the base is sodium hydride. (8) The method for producing an active methylene-substituted arene compound according to any one of (1) to (4), wherein R ₁ is an iodine atom and the base is an alkali metal alkoxide. (9) Any of the above (1) to (8), wherein the catalytic amount of [1,1-bis (diphenylphosphino) ferrocene] palladium (II) chloride is from 0.01 mol% to 100 mol% of the aryl halide. A method for producing such an active methylene-substituted arene compound. (10) The catalyst according to any one of the above (1) to (8), wherein the catalytic amount of [1,1-bis (diphenylphosphino) ferrocene] palladium (II) chloride is 1 mol% to 10 mol% of the aryl halide. A method for producing an active methylene-substituted arene compound.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below.
The gist of the present invention is to condense an active methylene compound and an aryl halide in the presence of a base and a catalytic amount of [1,1-bis (diphenylphosphino) ferrocene] palladium (II) chloride to form an active methylene-substituted arene compound Is to synthesize. As the active methylene compound, a compound represented by the following general formula (I) is preferable.

[0016]

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In the formula, X and Y each independently represent a substituent having a Hammett σ _p value of 0.2 or more. Hammett's σ _p value is described in, for example, Chem. Rev .. , 91.165 (199
1). The upper limit of the σ _p value is not particularly limited, but is generally 2 or less. Hammett's σ _p value is 0.
Examples of the two or more substituents include a halogen atom (eg, chlorine, bromine, etc.), a cyano group, a nitro group, a halogen atom-substituted alkyl group (eg, a trifluoromethyl group,
A halogen atom-substituted aryl group (e.g., pentafluorobenzene, etc.), a halogen atom-substituted alkoxy group (e.g., a trifluoromethoxy group, etc.), a halogen atom-substituted alkylthio group (e.g.,
Trifluoromethylthio group), acyloxy group (eg, acetoxy group, benzoyloxy group, etc.), sulfonyloxy group (eg, methanesulfonyloxy group, etc.), acyl group (eg, acetyl group, etc.), oxycarbonyl group (eg, Methoxycarbonyl group, phenoxycarbonyl group, etc.), carbamoyl group (eg, unsubstituted carbamoyl group), thiocarbamoyl group (eg, unsubstituted thiocarbamoyl group), sulfonyl group (eg, methanesulfonyl group, P-toluenesulfonyl group) And the like, a sulfinyl group (eg, a methanesulfinyl group), a sulfamoyl group (eg, an unsubstituted sulfamoyl group, a methylsulfamoyl group, and the like). Particularly preferred are a halogen atom, a cyano group, an alkyl group substituted with a halogen atom, an acyl group, an oxycarbonyl group or a sulfonyl group, and most preferred is a cyano group.

The aryl halide is represented by the following general formula (I)
Compounds represented by I) are preferred.

[0019]

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In the formula, R ₁ represents a halogen atom, and R ₂ represents a substituent. m represents an integer of 1 or more and 6 or less, and n represents an integer of 0 or more and 5 or less. However, m + n is 6 or less. When m is 2 or more, R ₁ may be different halogen atoms. As the halogen atom for R ₁ ,
Bromine and iodine are particularly preferred. m is preferably 1, 2 or 3, and particularly preferably 2. When m is 2, it is particularly preferred that two halogen atoms are substituted at the para-position to each other. R ₂
Examples of the substituent represented by are, for example, an alkyl group (for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, cyclohexyl, methoxyethyl, ethoxycarbonylethyl, cyanoethyl, diethylaminoethyl , Hydroxyethyl, chloroethyl, acetoxyethyl, etc.), aralkyl groups (eg, benzyl, etc.), alkenyl groups (eg, vinyl, etc.), alkynyl groups (eg, ethynyl, etc.), aryl groups (eg, phenyl, 4-methylphenyl, Methoxyphenyl, 4-carboxyphenyl, etc.), acyl group (eg, acetyl, propionyl, butanoyl, chloroacetyl, etc.), sulfonyl group (eg, methanesulfonyl, p-toluenesulfonyl, etc.), sulfinyl Group (eg, methanesulfinyl, ethanesulfinyl, etc.), alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl, 4-methoxyphenylcarbonyl, etc.), alkoxy group (eg, methoxy , Ethoxy, n
-Butoxy, methoxyethoxy, hydroxyethoxy, etc.), an aryloxy group (eg, phenoxy, 4-methoxyphenoxy, etc.), an alkylthio group (eg, methylthio, ethylthio, etc.), an arylthio group (eg, phenylthio, etc.), an acyloxy group (eg, , Acetoxy, ethylcarbonyloxy, cyclohexylcarbonyloxy, benzoyloxy, chloroacetyloxy, etc.), sulfonyloxy group (eg, methanesulfonyloxy etc.), carbamoyloxy group (eg,
Methylcarbamoyloxy, diethylcarbamoyloxy, etc.), amino group (for example, unsubstituted amino, methylamino, dimethylamino, diethylamino, anilino, methoxyphenylamino, chlorophenylamino, morpholino, piperidino, pyrrolidino, pyridylamino, methoxycarbonylamino, phenoxycarbonyl) amino,
Ethylthiocarbonylamino, methylcarbamoylamino, phenylcarbamoylamino, methylsulfamoylamino, phenylsulfamoylamino, acetylamino, ethylcarbonylamino, ethylthiocarbonylamino, benzoylamino, chloroacetylamino, methanesulfonylamino, benzenesulfonyl Carbamoyl groups (eg, unsubstituted carbamoyl,
Methylcarbamoyl, dimethylcarbamoyl, etc.), sulfamoyl group (eg, unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl, etc.), hydroxyl group, nitro group, cyano group, carboxy group, sulfo group and the like. These substituents may further have a halogen atom or the above substituent. Preferably, it is a substituent having a Hammett σ _p value not exceeding 0, for example,
Alkyl groups such as methyl (-0.17), ethyl (-0.15) and propyl (-0.13), methoxy (-0.
27), ethoxy (-0.24), butoxy (-0.3
2) and the like, a hydroxyl group (−0.37), a thioalkyl group such as methylthio (0.00), dimethylamino (−0.83), acylamino (0.00), ethoxycarbonylamino (−0.15). ) And the like. Particularly preferred is an alkoxy group.

When n represents an integer of 2 or more, R ₂ may be different from each other and may be linked to form an unsaturated condensed ring (eg, a naphthalene derivative, an anthracene derivative, etc.). When n is 2 or more, a combination of substituents whose sum of Hammett's immediate σ _p values for each substituent does not exceed 0 is preferable, and particularly preferable is a combination of σ of Hammett's rule.
It is a combination of substituents whose _p value does not exceed 0. Particularly preferred is a combination of alkoxy groups. When n is 2, it is preferred that they are mutually substituted at the para position.

The compound represented by the general formula (II) is particularly preferably a compound represented by the following general formula (IV).

[0023]

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In the formula, R ₁ , R ₂ and n have the same meanings as in the above formula (II), and their preferred embodiments are also the same.

The active methylene-substituted arene compound synthesized in the present invention is represented by the following general formula (III).

[0026]

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In the formula, X and Y represent X in the above-mentioned general formula (I).
And Y, R _2, m and n are each and R _2, m and n in the general formula (II) synonymous preferred embodiments thereof are also the same.

The compound represented by the general formula (III) is
The compound represented by the following general formula (V) is particularly preferred.

[0029]

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[0030] In the formula, R ₂ and n are each and R ₂ and n in the general formula (III) synonymous preferred embodiments thereof are also the same.

Hereinafter, specific examples of the compounds represented by formulas (I) to (III) are shown, but the present invention is not limited thereto.

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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The base used in the present invention includes:
Examples include sodium carbonate, sodium hydroxide, triethylamine, alkali metal alkoxides (eg, sodium methoxide, sodium ethoxide, potassium ^t- butoxide), sodium hydride and the like. Particularly preferred are sodium hydride and alkali metal alkoxides.

The catalyst amount of [1,1-bis (diphenylphosphino) ferrocene] palladium (II) chloride used in the present invention is preferably from 0.01 mol% to 100 mol% of the aryl halide, particularly preferably from 0.1 mol% to 100 mol%. 1 mol%
It is preferably at least 100 mol% and at most 1 mol% and at most 10 mol%. The order of adding [1,1-bis (diphenylphosphino) ferrocene] palladium (II) chloride is not particularly limited. That is, the base, the aryl halide and the active methylene compound may be added after dissolving in a solvent, or [1,1-bis (diphenylphosphino) ferrocene] palladium (II) chloride may be added after the base and the aryl halide are added. After the addition, an active methylene compound may be added. The temperature at the time of addition is not particularly limited as long as it is lower than the boiling point of the reaction solution, but is preferably lower than room temperature (eg, 20 ° C.).

The reaction temperature is preferably between 20 ° C. and 150 ° C., particularly preferably between 40 ° C. and 100 ° C.

As a reaction system, a two-phase system of water-organic solvent,
Either a water-containing organic solvent or a homogeneous organic solvent may be used. Examples of the organic solvent include hydrocarbon solvents such as toluene, xylene, and hexane; amide solvents such as dimethylformamide; ether solvents such as tetrahydrofuran; alcohol solvents such as methanol and ethanol; nitrile solvents such as acetonitrile; and acetone. And an ester solvent such as ethyl acetate. Further, two or more organic solvents may be used in combination. Most preferably, it is tetrahydrofuran.

[0043]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but these examples do not limit the present invention.

Example 1 Synthesis of Compound (III-1) In a nitrogen atmosphere, 62 g of sodium hydride and compound (II-
1) 100 g (0.26 mol) and [1,1-bis (diphenylphosphino) ferrocene] palladium (I
I) 3.7 g of chloride (2 parts per compound (II-1))
mol.) was dissolved in 1.5 L of tetrahydrofuran, and 68 g (1 mol) of malononitrile was added dropwise under ice-cooling. After the reaction solution was refluxed for 8 hours, 120 ml of isopropyl alcohol was added to inactivate unreacted sodium hydride. After stirring at room temperature for 30 minutes, the reaction solution was
The mixture was poured into 2 L of normal hydrochloric acid and stirred at room temperature for 2 hours. The obtained white precipitate was collected by filtration, washed with water, and then recrystallized from acetonitrile to obtain 43 g of the desired product (III-1). Yield was 63%. Analytical value: H-NMR (CDCl ₃ ): 7.13 (s, 2H), 5.28 (s, 2H), 4.1
(s, 6H)

Example 2 Synthesis of Compound (III-1) In a nitrogen atmosphere, 6.2 g of sodium hydride and compound (II)
-2) 7.6 g (26 mmol) and [1,1-bis (diphenylphosphino) ferrocene] palladium (I
I) After dissolving 0.76 g (4 mol%) of chloride in 150 ml of tetrahydrofuran, 6.8 g (0.1 mol) of malononitrile was added dropwise under ice cooling. After refluxing the reaction solution for 8 hours, isopropyl alcohol 12m
1 was added to inactivate unreacted sodium hydride. After stirring at room temperature for 30 minutes, the reaction mixture was diluted with 200 ml of 1N hydrochloric acid.
Then, the mixture was stirred at room temperature for 2 hours. The obtained white precipitate was collected by filtration, washed with water, and then recrystallized from acetonitrile to obtain 6.0 g of the desired product (III-1). Yield 88
%. Analytical value: H-NMR (CDCl ₃ ): 7.13 (s, 2H), 5.28 (s, 2H), 4.1
(s, 6H)

Comparative Example 1 Under a nitrogen atmosphere, 6.2 g of sodium hydride and 7.6 g of compound (II-2) (26 mmol)
l) and 0.72 g (4 mol%) of (Ph ₃ P) ₂ PdCl ₂ were dissolved in 150 ml of tetrahydrofuran, and 6.8 g (0.1 mol) of malononitrile was added dropwise under ice cooling. After the reaction solution was heated to reflux for 8 hours, 12 ml of isopropyl alcohol was added to inactivate unreacted sodium hydride. After stirring at room temperature for 30 minutes, the reaction solution was poured into 200 ml of 1N hydrochloric acid and stirred at room temperature for 2 hours. The resulting white precipitate was collected by filtration and the structure was identified by H-NMR. As a result, the target compound (III-1) was not obtained, and only 6.7 g (yield: 91%) of the following compound (a) was obtained. . Analytical value: H-NMR (dmso-d ₆ ): 7.50 (s, 1H), 7.20 (s, 1H),
6.30 (s, 1H), 3.90 (s, 3H), 3.80 (s, 3H)

[0047]

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Example 3 Synthesis of Compound (III-1) In a nitrogen atmosphere, 3.4 g of potassium ^t- butoxide (30 m
mol), 2.0 g (5 mmol) of compound (II-1),
And 0.16 g of [1,1-bis (diphenylphosphino) ferrocene] palladium (II) chloride (4 mol
%) Was dissolved in 30 ml of tetrahydrofuran, and then 1.3 g (20 mmol) of malononitrile was added dropwise under ice cooling. After the reaction solution was heated to reflux for 8 hours, 2 ml of isopropyl alcohol was added to inactivate unreacted sodium hydride. After stirring at room temperature for 30 minutes, the reaction mixture was poured into 50 ml of 1N hydrochloric acid and stirred at room temperature for 2 hours. The obtained white precipitate was collected by filtration, washed with water, and then recrystallized from acetonitrile to obtain 1.0 g of the desired product (III-1). Yield 80%. Analytical value: H-NMR (CDCl ₃ ): 7.13 (s, 2H), 5.28 (s, 2H), 4.1
(s, 6H)

Comparative Example 2 In a nitrogen atmosphere, 3.4 g (30 mmol) of potassium ^t- butoxide, compound (II-1)
2.0 g (5 mmol) and (Ph ₃ P) ₂ PdCl ₂ 0.14
g (4 mol%) was dissolved in 30 ml of tetrahydrofuran, and then 1.3 g of malononitrile (20 mm) under ice-cooling.
ol) was added dropwise. After the reaction solution was heated to reflux for 8 hours, 2 ml of isopropyl alcohol was added to inactivate unreacted sodium hydride. After stirring at room temperature for 30 minutes, the reaction solution was poured into 50 ml of 1N aqueous hydrochloric acid and allowed to stand at room temperature for 2 minutes.
Stirred for hours. The resulting white precipitate was collected by filtration and extracted with H-NM.
When the structure was identified by R, the target compound (III-1) was not obtained, and the compound (II-1) as a raw material was almost recovered.

Example 4 Synthesis of Compound (III-2) Under a nitrogen atmosphere, 1.2 g of sodium hydride and 2.1 g (5 mmol) of compound (II-3) were dissolved in 30 ml of tetrahydrofuran, and then ice-cooled. Below, 1.3 g (20 mmol) of malononitrile was added dropwise. After completion of the dropwise addition, [1,1-bis (diphenylphosphino) ferrocene] palladium (II) chloride 73 mg (2 mol) was added at room temperature.
%) And the reaction was heated at reflux for 8 hours. After completion of the reaction, 2.5 ml of isopropyl alcohol was added to inactivate unreacted sodium hydride. After stirring at room temperature for 30 minutes, the reaction solution was poured into 1N hydrochloric acid (80 ml) and stirred under ice cooling for 2 hours. The resulting white precipitate was collected by filtration, washed with water, and then recrystallized from acetonitrile to give the desired product (III-
2) 1.3 g was obtained. Yield 92%. Analytical value: H-NMR (CDCl ₃ ): 7.18 (s, 2H), 5.25 (s, 2H), 4.1
5 (q, 4H), 1.52 (t, 6H)

Example 5 Synthesis of Compound (III-3) Under a nitrogen atmosphere, 1.9 g of sodium hydride and compound (II)
-5) 3.8 g (8 mmol) and 0.12 g (2 mol%) of [1,1-bis (diphenylphosphino) ferrocene] palladium (II) chloride are dissolved in 50 ml of tetrahydrofuran and then malononitrile under ice-cooling. 2.1 g (32 mmol) were added dropwise. After the reaction solution was heated to reflux for 8 hours, 2 ml of isopropyl alcohol was added to inactivate unreacted sodium hydride. 3 at room temperature
After stirring for 0 minutes, the reaction solution was poured into 100 ml of 1N hydrochloric acid and stirred at room temperature for 2 hours. The obtained white precipitate was collected by filtration, washed with water, and then recrystallized from acetonitrile to obtain 2.4 g of the desired product (III-3). Yield 85%. Analysis: H-NMR (dmso-d 6): 7.4 (s, 2H), 6.3 (s, 2H), 3.7
3 (dd, 4H), 3.5 (dd, 4H), 3.35 (s, 6H)

Example 6 Synthesis of Compound (III-4) Under a nitrogen atmosphere, 1.6 g of sodium hydride and compound (II)
-6) 2.3 g (5 mmol) and 0.15 g (4 mol%) of [1,1-bis (diphenylphosphino) ferrocene] palladium (II) chloride are dissolved in 30 ml of tetrahydrofuran and then malononitrile under ice cooling. 1.3 g (20 mmol) were added dropwise. After the reaction solution was heated to reflux for 8 hours, 2 ml of isopropyl alcohol was added to inactivate unreacted sodium hydride. 3 at room temperature
After stirring for 0 minutes, the reaction solution was poured into 150 ml of 1N hydrochloric acid and stirred at room temperature for 2 hours. The obtained white precipitate was collected by filtration, washed with water, and then recrystallized from acetonitrile to obtain 1.6 g of the desired product (III-4). Yield 98%. Analysis: H-NMR (dmso-d 6): 7.4 (s, 2H), 6.3 (s, 2H), 4.1
5 (dd, 4H), 3.8 (dd, 4H)

Comparative Example 3 Under a nitrogen atmosphere, 1.6 g of sodium hydride and 2.3 g of compound (II-6) (5 mmol)
l) and 0.13 g (4 mol%) of (Ph ₃ P) ₂ PdCl ₂ were dissolved in 30 ml of tetrahydrofuran, and then cooled under ice-cooling.
1.3 g (20 mmol) of malononitrile were added dropwise.
After the reaction solution was heated to reflux for 8 hours, 2 ml of isopropyl alcohol was added to inactivate unreacted sodium hydride. After stirring at room temperature for 30 minutes, the reaction solution was poured into 150 ml of 1N hydrochloric acid and stirred at room temperature for 2 hours. The resulting white precipitate was collected by filtration, and the structure was identified by H-NMR. As a result, the target compound (III-4) was not obtained, and the compound (II-6) as a raw material was almost quantitatively recovered.

From the above results, it can be seen that the synthesis method of the present invention provides the desired active methylene-substituted arene derivative represented by the general formula (III) in good yield. In particular, as is clear from the comparison between Example 6 and Comparative Example 3, a compound that could not be synthesized by the conventional method can be synthesized in high yield. Further, as is clear from the comparison between Example 2 and Comparative Example 1, according to the synthesis method of the present invention, an active methylene-substituted arene compound can be derived at a higher yield than a dibromo compound which is inexpensive and easy to synthesize. Furthermore, as is clear from the comparison between Example 3 and Comparative Example 2, while the conventional method requires the use of sodium hydride having a high risk of ignition, the present invention synthesizes using an alkali metal alkoxide. This is advantageous in that it can be performed.

[0055]

According to the synthesis method of the present invention, an active methylene-substituted arene derivative can be produced at a high yield and at a low cost. In addition, since synthesis can be performed using an alkali metal alkoxide having a low risk of fire, a safe production method can be provided.

Claims (8)

[Claims] 1. An active methylene compound represented by the following general formula (I) and an aryl halide represented by the following general formula (II) are reacted with a base and [1,1-bis (diphenylphosphino) ferrocene] palladium (II) A) a method for producing an active methylene-substituted arene compound, which comprises condensing in the presence of a chloride catalyst to synthesize an active methylene-substituted arene compound represented by the general formula (III). Embedded image [Wherein, X and Y each independently represent a substituent having a Hammett σ _p value of 0.2 or more. ] [Wherein, R ₁ represents a halogen atom, and R ₂ represents a substituent. m represents an integer of 1 or more and 6 or less, n represents an integer of 0 or more and 5 or less, and m + n ≦ 6. When m is 2 or more, R ₁ may be the same or different. When n is 2 or more, R ₂ may be the same or different, and R ₂ may be linked together to form an unsaturated condensed ring. ] [Wherein, X, Y, R ₂ and m have the same meanings as in general formulas (I) and (II). ] 2. The method for producing an active methylene-substituted arene compound according to claim 1, wherein m = 2. 3. The compound according to claim 1, wherein the active methylene compound is malononitrile, and the aryl halide is a compound represented by the following general formula (IV), wherein the compound is represented by the following general formula (V). For producing an active methylene-substituted arene compound. Embedded image [Wherein, R ₁ , R ₂ and n have the same meanings as in formula (II). ] [Wherein, R ₂ and n have the same meanings as in formula (II). ] 4. The process according to claim 1, wherein R ₁ is a bromine atom or an iodine atom. 5. The method according to claim 1, wherein the base is sodium hydride or an alkali metal alkoxide. 6. The process for producing an active methylene-substituted arene compound according to claim 1, wherein R ₁ is a bromine atom and the base is sodium hydride. 7. The method according to claim 1, wherein R ₁ is an iodine atom and the base is an alkali metal alkoxide. 8. The method according to claim 1, wherein the catalytic amount of [1,1-bis (diphenylphosphino) ferrocene] palladium (II) chloride is from 0.01 mol% to 100 mol% of the aryl halide. For producing an active methylene-substituted arene compound.