JP2020189793A - Method for producing aromatic compound - Google Patents

Abstract

To provide a simple method for producing a DNTT intermediate that is a raw material for various DNTT derivatives.SOLUTION: Provided is a method for producing (3) that comprises a step of reacting (1) and (2). (R1 to R4, X1 are halogen atom, etc., R5 to R7 are alkyl group, X2 is S, etc.).SELECTED DRAWING: None

Description

The present invention relates to a method for producing an aromatic compound. More specifically, the present invention relates to a method for producing a dinaphtho [3,2-b: 2', 3'-f] thieno [3,2-b] thiophene (hereinafter abbreviated as "DNT") derivative.

In recent years, thin film devices using organic semiconductors such as organic FET (field effect transistor) devices and organic EL (electroluminescence) devices have attracted attention and have been put into practical use. Various compounds have been researched and developed as organic semiconductor materials used in these thin film devices. For example, in Patent Documents 1 and 2, DNT exhibits excellent charge mobility, and the thin film has organic semiconductor properties. Is shown. However, the DNT derivatives disclosed in Patent Documents 1 and 2 have a problem that they have poor solubility in an organic solvent and an organic semiconductor layer cannot be produced by a solution process such as a coating method.
To solve this problem, Patent Document 3 and Non-Patent Document 1 show that the solubility in an organic solvent is improved by introducing a branched chain alkyl group into the DNT skeleton.

As described above, DNT derivatives that are useful as these organic semiconductors have been developed, but the conventional production methods have restrictions on the method for constructing the thienothiophene structural portion, and have a particularly asymmetric substituent. It was difficult to produce DNTT. Under such circumstances, various studies have been conducted on methods for synthesizing DNTT derivatives, and three main methods are currently known.

The first method is a method for producing the following synthetic flow in which tetrabromothienothiophene, which has a thienothiophene structure from the beginning, is used as a starting material (Patent Document 4).

According to this production method, there is no problem when unsubstituted benzaldehyde is used, but when benzaldehyde having a substituent is used, the obtained DNTT derivative becomes a mixture of various compounds having different substitution positions of the substituent. Was the problem.

The second method is a method for producing the following synthetic flow using an acetylene derivative (A), which has been known for a long time, as a starting material (Patent Document 5).

According to this synthesis method, it is possible to selectively synthesize asymmetric DNTT, but it cannot be said that an industrial method for producing Br, which is a raw material for the acetylene derivative (A), has been established yet. The cyclization reaction of an acetylene derivative with iodine has a problem that the yield is generally low (in Patent Document 5, the yield is about 10% to 40%).

The third method is a production method using an ethylene derivative as a starting material, and most of the DNTT derivatives have been synthesized by this method (Patent Document 1, Patent Document 2, Patent Document 5, Patent Document 6).
For example, Patent Document 3 and Non-Patent Document 1 describe two different 3-methylthio-2-trifluoromethanesulfonyloxy) naphthalenes (B) and (C) and trans-1,2-bis (tributylstanyl) ethylene. It has been disclosed that asymmetric trans-1,2-bis (3-methylthionaphthalene-2-yl) ethylene can be obtained by coupling with, and then by closing the ring, the target compound, asymmetric DNTT. (See synthetic flow below).

However, in this synthetic method, the yield of compound (D) is low, and purification may be difficult depending on the structure of the by-product.

Further, in Patent Document 7, a method of introducing a target substituent by directly adding a halogen atom to the DNT skeleton and then performing a coupling reaction is known, but the substitution positions are limited to the 5th and 12th positions. It is difficult to introduce it to other locations.

WO2008 / 050726 WO2010 / 098372 Gazette WO2014 / 115479 KR2008100982 Gazette JP-A-2009-196975 WO2009 / 09790 WO2014 / 027685

ACS Appl. Mater. Interfaces, 8, 3810-3824 (2016)

An object of the present invention is to provide a method for producing various DNTT derivatives, particularly DNTT intermediates useful as raw material compounds for producing asymmetric DNTT derivatives, by a simpler method.

As a result of diligent studies, the present inventors have found that a simple production method including a step of reacting a raw material compound having a specific structure solves the above-mentioned problems, and have completed the present invention.
That is, the present invention
[1] General formula (1)

(In the formula (1), _one of R ₁ and R ₂ represents a halogen atom, and the other represents a hydrogen atom, a halogen atom or a substituent. X ₁ represents a halogen atom or a trifluoromethanesulfonate group.)
And the compound represented by
General formula (2)

(In formula (2), R ₃ and R ₄ independently represent a hydrogen atom, an alkyl group, an alkoxy group or an aromatic group, respectively. X ₂ represents a sulfur atom or a selenium atom. R _{5 to} R ₇ are independent of each other. Represents an alkyl group.)
Including the step of reacting the compound represented by
General formula (3)

(In the formula (3), _{R 1} and _{R 2} are _.R 3, _{R 4} and _{X 2} is _R 3 in the formula (2) representing the same meaning as _{R 1} and _{R 2} in Formula (1), _{R 4} and X It has the same meaning as _2. )
Method for producing aromatic compound represented by,
[2] The method for producing an aromatic compound according to the preceding item [1], wherein R ₁ and / or R ₂ is a chlorine atom, a bromine atom or an iodine atom.
[3] The method for producing an aromatic compound according to the above item [1] or [2], wherein X ₁ is an iodine atom or a trifluoromethanesulfonate group.
[4] The method for producing an aromatic compound according to any one of the above items [1] to [3], wherein X ₂ is a sulfur atom.
[5] The method for producing an aromatic compound according to any one of the above items [1] to [4], wherein R _{5 to} R ₇ is a methyl group, and [6] R ₃ and R ₄ are hydrogen atoms. The method for producing an aromatic compound according to any one of the above items [1] to [5].
Regarding.

According to the present invention, it is possible to highly selectively produce a DNTT intermediate which is a raw material for producing a DNTT derivative, particularly an asymmetric DNTT derivative, which has been difficult to produce by a conventional method, and has various structures. DNT intermediates that can be used to make DNT derivatives of

Hereinafter, the production method of the present invention will be described in detail.
The method for producing an aromatic compound represented by the general formula (3) of the present invention includes a step of reacting the compound represented by the general formula (1) with the compound represented by the general formula (2). ..

In the general formula (1), _one of R ₁ and R ₂ represents a halogen atom, and the other represents a hydrogen atom, a halogen atom or a substituent.
Examples of the halogen atom represented by R ₁ and R ₂ of the general formula (1) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom, a bromine atom or an iodine atom is preferable.

The substituents represented by R ₁ and R ₂ of the general formula (1) are not particularly limited as long as they do not affect the reaction with the compound represented by the formula (2). Examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aromatic group, an alkoxy group, an alkylthio group and the like.

The alkyl group as a substituent represented by R ₁ and R _{2 in} the general formula (1) is limited to any of linear type, branched chain type and cyclic type as long as it is a saturated hydrocarbon group consisting of a carbon atom and a hydrogen atom. Not done. Further, the number of carbon atoms is not particularly limited, but is preferably 1 to 20, more preferably 1 to 16. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and the like.
The alkenyl group as a substituent represented by R ₁ and R ₂ of the general formula (1) is a substituent composed of a carbon atom and a hydrogen atom and having only one carbon-carbon double bond in the saturated hydrocarbon group. If there is, it is not limited to any of linear type, branched chain type and cyclic type. Further, the number of carbon atoms is not particularly limited, but is preferably 2 to 20, more preferably 2 to 16. Specific examples of the alkenyl group include an ethylene group, a propylene group, a butene group and a pentene group.

The alkynyl group as a substituent represented by R ₁ and R _{2 in} the general formula (1) is a substituent composed of a carbon atom and a hydrogen atom and having only one carbon-carbon triple bond in the saturated hydrocarbon group. If there is, it is not limited to any of linear type, branched chain type and cyclic type. Further, the number of carbon atoms is not particularly limited, but is preferably 2 to 20, more preferably 2 to 16. Specific examples of the alkenyl group include an acetylene group, a propyne group, a butin group, a pentyne group and the like.

The aromatic group as a substituent represented by R ₁ and R ₂ of the general formula (1) is a hydrogen atom from the aromatic ring of an aromatic compound such as an aromatic hydrocarbon compound, a fused ring aromatic compound and a heteroaromatic compound. The residue is not particularly limited as long as it is a residue excluding one. The number of carbon atoms is not particularly limited, but is preferably about 6 to 18. Specific examples of the aromatic group include a phenyl group, a naphthyl group, an anthranyl group, a frill group, a thienyl group, a selenofryl group, a thienotienyl group and the like.

The alkoxy group as a substituent represented by R ₁ and R ₂ of the general formula (1) is a substituent in which an alkyl group and an oxygen atom are bonded. The alkyl group in the alkoxy group is not limited to any of linear type, branched chain type and cyclic type as long as it is a saturated hydrocarbon group consisting of a carbon atom and a hydrogen atom. Further, the number of carbon atoms is not particularly limited, but is preferably 1 to 20, more preferably 1 to 16. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an n-pentyloxy group and the like.
The alkylthio group as a substituent represented by R ₁ and R ₂ of the general formula (1) is a substituent in which an alkyl group and a sulfur atom are bonded. The alkyl group in the alkylthio group is not limited to a linear type, a branched chain type or a cyclic type as long as it is a saturated hydrocarbon group consisting of a carbon atom and a hydrogen atom. Further, the number of carbon atoms is not particularly limited, but is preferably 1 to 20, more preferably 1 to 16. Specific examples of the alkylthio group include a methylthio group, an ethylthio group, an n-propylthio group, an n-pentylthio group and the like.

The carbon atoms of the alkyl group, alkenyl group, alkynyl group, aryl group, alkyloxy group and alkylthio group may be substituted with oxygen atom and / or sulfur atom. Further, one or more hydrogen atoms contained in the above-mentioned substituent may be partially substituted with a halogen atom, and the molecular structure thereof is not particularly limited. However, the aryl group excludes the case of the same halogen atom as R _{1 to} R ₄ in the general formula (3). Further, a part of the above substituents may be substituted with an aryl group.

As R ₁ and R ₂ in the general formula (1), it is preferable that at least one of R ₁ and R ₂ is a chlorine atom, a bromine atom or an iodine atom.

In the general formula (1), X ₁ represents a halogen atom or a trifluoromethanesulfonate group.
Examples of the halogen atom represented by X ₁ of the general formula (1) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom, a bromine atom or an iodine atom is preferable, and a bromine atom or an iodine atom is more preferable.
The X ₁ in the general formula (1) is preferably an iodine atom or a trifluoromethanesulfonate group.

In the general formula (2), R ₃ and R ₄ independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an aryl group, respectively. Further, R ₃ and R ₄ may be bonded to each other to form a ring such as a benzene ring.
Examples of the halogen atom represented by R ₃ and R ₄ of the general formula (2) include the same halogen atoms represented by R ₁ and R ₂ of the general formula (1), and the same is preferable.

Examples of the alkyl group represented by R ₃ and R ₄ of the general formula (2) include the same alkyl group as the substituent represented by R ₁ and R ₂ of the general formula (1).
Examples of the alkoxy group represented by R ₃ and R ₄ of the general formula (2) include the same alkoxy group as the substituent represented by R ₁ and R ₂ of the general formula (1).
Examples of the aromatic group represented by R ₃ and R ₄ of the general formula (2) include the same aromatic group as the substituent represented by R ₁ and R ₂ of the general formula (1).
As R ₃ and R ₄ in the general formula (1), a hydrogen atom is preferable.

In the general formula (2), X ₂ represents a sulfur atom or a selenium atom, and a sulfur atom is preferable.
In the general formula (2), R _{5 to} R ₇ each independently represent an alkyl group.
Examples of the alkyl group represented by R _{5 to} R ₇ of the general formula (2) include the same alkyl group as the substituent represented by R ₁ and R ₂ of the general formula (1).
The number of carbon atoms in the alkyl group R ₅ or the R ₇ represents the general formula (2) is usually 1 to 8, preferably 1 to 4. Specific examples of the linear alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an iso-butyl group, an n-pentyl group and an n-hexyl group, and specific examples of the branched alkyl group. Examples thereof include i-propyl group, iso-butyl group, sec-butyl group, tert-butyl group, iso-pentyl group and iso-hexyl group.
The _{R 5} to _{R 7} in the general formula (2), more preferably a methyl group.

In the production method of the present invention, the step of reacting the compound represented by the formula (1) with the compound represented by the formula (2) involves the first-step reaction and the second-step reaction shown in the scheme below. Including.

The reaction temperature of the reaction in the first step is usually −10 to 200 ° C., preferably 40 to 180 ° C., more preferably 80 to 150 ° C. The reaction time is not particularly limited, but is usually 1 to 72 hours, preferably 6 to 48 hours.
By using the catalyst described later in combination, the reaction temperature can be lowered and the reaction time can be shortened.

The first-stage reaction is preferably carried out in an inert gas atmosphere such as an argon atmosphere, nitrogen substitution, a dry argon atmosphere, and a dry nitrogen stream.

It is preferable to use a catalyst for the reaction in the first step. Examples of the catalyst include tri-tert-butylphosphine, triadamantylphosphine, 1,3-bis (2,4,6-trimethylphenyl) imidazolidinium chloride, 1,3-bis (2,6-diisopropylphenyl). Imidazolidinium chloride, 1,3-diadamantyl imidazolidinium chloride, or a mixture thereof; metal Pd, Pd / C (hydrated or non-hydrated), bis (triphenylphosphino) palladium dichloride (Pd (PPh ₃ ) ₂ ) Cl ₂ ), palladium (II) acetate (Pd (OAc) ₂ ), (1,1'-bis (diphenylphosphino) ferrocene) palladium dichloride (Pd (dppf) Cl ₂ ), tetrakis (triphenylphosphine) palladium ( Pd (PPh ₃ ) ₄ ), tetrakis (triphenylphosphine) nickel (Ni (PPh ₃ ) ₄ ), nickel (II) acetylacetonate (Ni (acac) ₂ ), dichloro (2,2'-bipyridine) nickel ( Ni (bpy) Cl ₂ ), dibromobis (triphenylphosphine) nickel (Ni (PPh ₃ ) ₂ Br ₂ ), bis (diphenylphosphino) propanenickel dichloride (Ni (dpppp) Cl ₂ ) and bis (diphenylphosphino) Ethan nickel dichloride (Ni (dppe) Cl ₂ ) and the like are preferable, nickel-based catalysts or palladium-based catalysts are more preferable, and Pd / C (hydrous or non-hydrated) or Pd (PPh ₃ ) ₂ Cl ₂ , Pd (PPh). ₃ ) ₄ is more preferable, and Pd (PPh ₃ ) ₂ Cl ₂ and Pd (PPh ₃ ) ₄ are particularly preferable.
A plurality of types of these catalysts may be mixed and used, or other catalysts may be mixed and used with these catalysts.

The amount of the catalyst used in the first-stage reaction is preferably 0.001 to 0.500 mol, more preferably 0.001 to 0.100 mol, and further, with respect to 1 mol of the compound represented by the general formula (1). It is preferably 0.001 to 0.050 mol.

Alkali metal salts may be used in combination with the first stage reaction. By using an alkali metal salt in combination, the selectivity of the reaction can be improved.
Any alkali metal salt that can be used in combination can be used as long as it contains an alkali metal, and examples thereof include lithium chloride, lithium bromide, and lithium iodide, and lithium chloride is preferable.
The amount of the alkali metal salt added is preferably 0.001 to 5.0 mol with respect to 1 mol of the compound represented by the general formula (1).

The first step reaction may be carried out in a solvent. Any solvent can be used as long as it can dissolve the raw material compound represented by the formula (1), the compound represented by the formula (2), and the catalyst, alkali metal salt, etc. used as necessary. But it can be used.
Specific examples of the solvent include aromatic compounds such as chlorobenzene, o-dichlorobenzene, bromobenzene, nitrobenzene, toluene and xylene, and saturated aliphatic hydrocarbons such as n-hexane, n-heptan and n-pentane; Alicyclic hydrocarbons such as cyclohexane, cycloheptan and cyclopentane; n-propyl bromide, n-butyl chloride, n-butyl bromide, dichloromethane, dibromomethane, dichloropropane, dibromopropane, dichlorobutane, chloroform, bromoform, tetra Saturated aliphatic halogenated hydrocarbons such as carbon chloride, carbon tetrabromide, trichloroethane, tetrachloroethane and pentachloroethane; halogenated cyclic hydrocarbons such as chlorocyclohexane, chlorocyclopentane and bromocyclopentane; ethyl acetate, propyl acetate , Butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate and butyl butyrate and other esters; acetone, methyl ethyl ketone and methyl isobutyl ketone and other ketones; diethyl ether , Dipropyl ether, dibutyl ether, cyclopentylmethyl ether, dimethoxyethane, tetrahydrofuran, 1,4-dioxane and ethers such as 1,3-dioxane; N-methyl-2-pyrrolidone, N, N-dimethylformamide and N, Examples thereof include amides such as N-dimethylacetamide; glycols such as ethylene glycol, propylene glycol and polyethylene glycol; and sulfoxides such as dimethylsulfoxide. These solvents may be used alone or in combination of two or more.

The second stage reaction can be carried out in a manner similar to that detailed in WO 2016/152888.

The aromatic compound represented by the formula (3) obtained by the production method of the present invention is preferably used as a DNTT intermediate after purification. The purification method is not particularly limited, and a known purification method can be used depending on the physical properties of the aromatic compound represented by the formula (3). Specific examples thereof include a recrystallization method, a column chromatography method, and a sublimation purification method.

By converting the halogen atom of the compound represented by the formula (3) thus obtained into a substituent by a known method such as a coupling reaction using a metal catalyst, a DNTT derivative having a desired substituent can be obtained. Can be manufactured.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In the examples, the melting point is Optimelt MPA100 manufactured by Stand Research Systems, the nuclear magnetic resonance spectrum is Avance 500 manufactured by Bruker, the HR-MS is JMS-T100GCV manufactured by JEOL, and the elemental analysis is MT-6 CHN CORD manufactured by Yanaco. did.
In addition, "part" in an Example means a mass part.

Example 1 (Synthesis of an aromatic compound (DNTT intermediate) represented by the following formula 6)
(Step 1) Synthesis of compound represented by the following formula 1 In a 500 mL four-necked flask equipped with a dropping funnel and dried by heating, 2,2,6,6-tetramethylpiperidin (TMP) 15.3 mL (in a nitrogen atmosphere) 90 mmol) was dissolved in 90 mL of tetrahydrofuran (THF). After cooling to −80 ° C., 58 mL of a 1.55 M hexane solution of normal butyllithium (n-BuLi) (number of moles of normal butyllithium in the solution; 90 mmol) was slowly added dropwise. After stirring at −80 ° C. for 10 minutes, 8.30 parts (22.5 mmol) of zinc chloride-tetramethylethylenediamine complex was added, and the temperature was raised to 0 ° C. After stirring for 15 minutes, the mixture was cooled to −80 ° C. again, and 7.11 parts (30.0 mmol) of 2-bromo-6-methoxynaphthalene was added. The reaction mixture was heated to room temperature, stirred for 2 hours, and then 16.0 mL (180 mmol) of dimethyl disulfide (MeS-SMe) was added. After stirring for 17 hours, 2N hydrochloric acid was added, the reaction solution was extracted with ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, the reaction mixture was collected by filtration, and the solvent was distilled off with a rotary evaporator. The obtained reaction mixture was purified by silica gel chromatography using a mixed solvent of hexane: methylene chloride 8: 2 as a mobile phase, and 6.23 parts of the compound represented by the following formula 1 (22.0 mmol, yield 73%). Was obtained as a white solid.

The melting points, nuclear magnetic resonance spectra, HR-MS spectra, and elemental analysis results of the compounds represented by the following formula 1 were as follows.
mp 86.2 --86.8 ° C.
^{1 1} H NMR (CDCl ₃ , 400 MHz): d (ppm) 7.85 (d, 1H, J = 1.6 Hz), 7.56 (d, 1H, J = 8.8 Hz), 7.43 (dd, 1H, J = 8.8, 2.0 Hz), 7.32 (s, 1H), 7.03 (s, 1H), 3.99 (s, 3H), 2.53 (s, 3H).
¹³ C NMR (CDCl ₃ , 100 MHz): d (ppm) 154.63, 131.42, 130.40, 130.33, 128.52, 128.38, 128.07, 121.53, 117.59, 104.47, 55.93, 14.32.
HRMS (EI) m / z: Calcd for C ₁₂ H ₁₁ BrOS [M] ⁺ : 281.9714. Found: 281.9726.
Elemental analysis: Calcd for C ₁₂ H ₁₁ BrOS: C, 50.90; H, 3.92. Found: C, 50.73; H, 3.85.

(Step 2) Synthesis of compound represented by the following formula 2 In a 500 mL four-necked flask, 5.66 parts (20.0 mmol) of the compound represented by formula 1 obtained in step 1 was dissolved in 150 mL of methylene chloride. It was. At 0 ° C., 25 mL of a 1.0 M molar concentration of boron tribromide (BBr ₃ ) (molar number of boron tribromide in the solution; 25 mmol) was slowly added dropwise. After stirring for 9 hours, the mixture was poured into ice water, the reaction solution was extracted with methylene chloride, the organic layer was dried over anhydrous magnesium sulfate, the reaction mixture was collected by filtration, and the solvent was distilled off with a rotary evaporator. The obtained reaction mixture was purified by recrystallization to obtain 5.28 parts (19.6 mmol, 98%) of the compound represented by the following formula 2 as a white solid.

The melting points, nuclear magnetic resonance spectra, HR-MS spectra, and elemental analysis results of the compounds represented by the following formula 2 were as follows.
mp 123.4 --123.7 ° C.
¹³ C NMR (CDCl ₃ , 100 MHz): d (ppm) 152.87, 133.25, 132.37, 130.18, 129.92, 129.18, 128.09, 125.92, 117.40, 109.29, 19.53.
HRMS (EI) m / z: Calcd for C ₁₁ H ₉ BrOS [M] ⁺ : 267,9558. Found: 267.9574.
Elemental analysis: Calcd for C ₁₁ H ₉ BrOS: C, 49.09; H, 3.37. Found: C, 48.99; H, 3.38.

(Step 3) Synthesis of compound represented by the following formula 3 In a 500 mL four-necked flask, 5.20 parts (19.3 mmol) of the compound represented by formula 2 obtained in step 2 was dissolved in 120 mL of methylene chloride. It was. After adding 6.4 mL (46 mmol) of triethylamine and cooling to 0 ° C., 3.9 mL (23 mmol) of trifluoromethanesulfonic anhydride was slowly added dropwise. After stirring for 1 hour, 1N hydrochloric acid was added, the reaction solution was extracted with methylene chloride, the organic layer was dried over anhydrous magnesium sulfate, the reaction mixture was collected by filtration, and the solvent was distilled off with a rotary evaporator. The obtained reaction mixture was purified by silica gel chromatography using a mixed solvent of hexane: methylene chloride 3: 7 as a mobile phase, and 7.59 parts of the compound represented by the following formula 3 (18.9 mmol, yield 98%). Was obtained as a white solid.

The melting points, nuclear magnetic resonance spectra, HR-MS spectra, and elemental analysis results of the compounds represented by the following formula 3 were as follows.
mp 73.2 --74.6 ° C.
^{1 1} H NMR (CDCl ₃ , 500 MHz): d (ppm) 7.95 (d, 1H, J = 1.5 Hz), 7.68 (s, 1H), 7.65 (d, 1H, J = 9.0 Hz), 7.55 (dd, dd, 1H, J = 8.5, 2.0 Hz), 7.53 (s, 1H), 2.59 (s, 3H).
HRMS (EI) m / z: Calcd for C ₁₂ H ₈ BrF ₃ O ₃ S ₂ [M] ⁺ : 399.9050. Found: 399.9065.
Elemental analysis: Calcd for C ₁₂ H ₈ BrF ₃ O ₃ S ₂ : C, 35.92; H, 2.01. Found: C, 35.76; H, 2.09.

(Step 4) Synthesis of compound represented by the following formula 4 In a 2 L four-necked flask, 22.47 parts (56.00 mmol) of the compound represented by formula 3 obtained in step 3 was dissolved in 1000 mL of methylene chloride. It was. After cooling to 0 ° C., 13.10 parts of a 20 mass% aqueous solution of meta-chloroperbenzoic acid (mCPBA) (number of moles of metachloroperbenzoic acid in the aqueous solution; 60.70 mmol) was slowly added. After stirring for 6 hours, the mixture was quenched with saturated aqueous sodium hydrogen carbonate solution, the organic layer was dried over anhydrous magnesium sulfate, the reaction mixture was collected by filtration, and the solvent was distilled off with a rotary evaporator. The obtained reaction mixture was purified by silica gel chromatography using a mixed solvent of methylene chloride: ethyl acetate = 19: 1 as a mobile phase, and 22.81 parts (54.67 mmol, 98%) of the compound represented by the following formula 4 was purified. Was obtained as a white solid.

The melting points, nuclear magnetic resonance spectra, HR-MS spectra, and elemental analysis results of the compounds represented by the following formula 4 were as follows.
mp 122.0 --122.4 ° C.
¹ H NMR (CDCl ₃ , 500 MHz): d (ppm) 8.42 (s, 1H), 8.19 (d, 1H, J = 1.5 Hz), 7.83 (s, 1H), 7.81 (d, 1H, J = 9.0) Hz), 7.76 (dd, 1H, J = 8.5 Hz, 2.0 Hz), 2.90 (s, 3H).
HRMS (EI) m / z: Calcd for C ₁₂ H ₈ BrF ₃ O ₄ S ₂ [M] ⁺ : 415.9000. Found: 415.9023.
Elemental analysis: Calcd for C ₁₂ H ₈ BrF ₃ O ₄ S ₂ : C, 34.55; H, 1.93. Found: C, 34.40; H, 1.98.

(Step 5) Synthesis of compound represented by the following formula 5 4.17 parts (10.0 mmol) of the compound represented by formula 4 obtained in step 4 in a 500 mL four-necked flask, 2-trimethylstanyl (2. Naft [2,3-b] thiophene) 3.61 parts (10.4 mmol), lithium chloride 1.27 parts (30.0 mmol) and Pd (PPh ₃ ) ₄ 0.14 parts (0.20 mmol) 1, It was dissolved in 125 mL of 4-dioxane. The mixed solution obtained above is stirred at 50 ° C. for 48 hours, quenched with water, the reaction solution is extracted with methylene chloride, the organic layer is dried over anhydrous magnesium sulfate, and the reaction mixture is collected by filtration and rotary. The solvent was distilled off with an evaporator. The obtained reaction mixture was purified by recrystallization to obtain 4.27 parts (94.5 mmol, yield 95%) of the compound represented by the following formula 5 as a yellow solid.

The melting points, nuclear magnetic resonance spectra, HR-MS spectra, and elemental analysis results of the compounds represented by the following formula 5 were as follows.
mp 262.9 --264.9 ° C.
^{1 1} H NMR (CDCl ₃ , 500 MHz): d (ppm) 8.56 (s, 1H), 8.37 (s, 1H), 8.36 (s, 1H), 8.20 (d, 1H, J = 1.5 Hz), 8.06 ( s, 1H), 8.01-7.99 (m, 1H), 7.95-7.93 (m, 1H), 7.82 (d, 1H, J = 8.5 Hz), 7.71 (dd, 1H, J = 8.5, 1,5 Hz) , 7.61 (s, 1H), 7.55-7.49 (m, 2H), 2.55 (s, 3H)
¹³ C NMR (CDCl ₃ , 100 MHz): d (ppm) 143.62, 139.89, 139.08, 138.18, 133.92, 132.29, 131.81, 131.42, 131.31, 130.83, 130.58, 129.62, 128.58, 128.33, 127.31, 125.97, 125.49, 124.17 , 123.95, 122.72, 122.14, 120.47, 42.14.
HRMS (EI) m / z: Calcd for C ₂₃ H ₁₅ BrOS ₂ [M] ⁺ : 449.9748. Found: 449.9753.
Elemental analysis: Calcd for C ₂₃ H ₁₅ BrOS ₂ : C, 61.20; H, 3.35. Found: C, 61.19; H, 3.36.

(Step 6) Synthesis of compound represented by the following formula 6 226 mg (0.500 mmol) of the compound represented by formula 5 obtained in step 5 and 10 mL of Eaton's reagent were added to a 50 mL flask. After stirring at room temperature for 4 days, the mixture was poured into ice water and filtered to obtain a yellow solid. The yellow solid was suspended in 35 mL of pyridine and refluxed for 20 hours. The reaction solution was cooled to room temperature, poured into methanol and filtered to give a yellow solid. The obtained reaction mixture was purified by silica gel chromatography using heated chloroform as a mobile phase, and further sublimated and purified to obtain 140 mg (0.343 mmol, yield 69%) of the compound represented by the following formula 6 in yellow. Obtained as crystals.

The melting points, nuclear magnetic resonance spectra, HR-MS spectra, and elemental analysis results of the compounds represented by the following formula 6 were as follows.
mp> 350 ° C.
_{^{1 H-NMR (CDCl 3,}} 500 MHz): δ (ppm) 8.46 (s, 1H), 8.42 (s, 1H), 8.37 (s, 2H), 8.14 (s, 1H), 8.10-8.00 (br, 2H), 7.93 (d, 1H, J = 8.5 Hz), 7.62 (dd, 1H, J = 9.0 Hz, 2.0 Hz) 7.58-7.56 (br, 2H).
HRMS (EI) m / z: Calcd for C ₂₂ H ₁₁ BrS ₂ [M] ⁺ : 417.9486. Found: 417.9495.
Elemental analysis: Calcd for C ₂₂ H ₁₁ BrS ₂ : C, 63.01; H, 2.64. Found: C, 62.90; H, 2.71.

Reference Example 1 (Synthesis of aromatic compound (DNTT derivative) represented by the following formula 7)
(Step 7) Synthesis of compound represented by the following formula 7 132 mg (0.315 mmol) of the compound represented by the formula 6 obtained in step 6 and 182 mg (0.469 mmol) of (trimethylsilylethynyl) tributyltin were placed in an argon-substituted pressure-resistant vial. _), Pd _(PPh 3) a 4 9.5 mg (0.0082 mmol) and toluene 19mL was added, and heated 180 ° C. 1 h in a microwave reactor. The reaction solution was purified by silica gel chromatography using methylene chloride as a mobile phase, and further sublimated to obtain 99 mg (0.228 mmol, yield 72%) of the compound represented by the following formula 7 as a yellow solid. ..

The melting points, nuclear magnetic resonance spectra, HR-MS spectra, and elemental analysis results of the compounds represented by the following formula 7 were as follows.
mp> 350 ° C.
_{^{1 H-NMR (CDCl 3,}} 500 MHz): δ (ppm) 8.43 (s, 1H), 8.39 (s, 1H), 8.36 (s, 1H), 8.32 (s, 1H), 8.10 (d, 1H) , 8.04 (dt, 1H, J = 4.5 Hz, 2.0 Hz), 7.96 (m, 1H), 7.95 (m, 1H) 7.55 ~ 7.35 (m, 3H), 0.311 (s, 9H).
¹³ C NMR (C ₂ D ₂ Cl ₄ , 120 ° C, 100 MHz): δ (ppm) 141.77, 141.03, 134.52, 133.93, 133.15, 132.40, 131.82, 131.53, 131.33, 131.03, 130.77, 128.56, 128.31, 128.10 , 127.33, 126.11, 125.08, 122.50, 122.26, 121.05, 120.24, 119.93, 105.67, 96.01, 0.04.
HRMS (EI) m / z: Calcd for C ₂₇ H ₂₀ S ₂ Si [M] ⁺ : 436.0776. Found: 436.0779.
Elemental analysis: Calcd for C ₂₇ H ₂₀ S ₂ Si: C, 74.27; H, 4.62. Found: C, 74.18; H, 4.71.

According to the present invention, it is possible to highly selectively produce a DNTT intermediate which is a raw material for producing a DNTT derivative, particularly an asymmetric DNTT derivative, which has been difficult to produce by a conventional method, and has various structures. DNT intermediates that can be used to make DNT derivatives of

Claims (6)

General formula (1)

(In the formula (1), _one of R ₁ and R ₂ represents a halogen atom, and the other represents a hydrogen atom, a halogen atom or a substituent. X ₁ represents a halogen atom or a trifluoromethanesulfonate group.)
And the compound represented by
General formula (2)

(In formula (2), R ₃ and R ₄ independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an aromatic group, respectively. X ₂ represents a sulfur atom or a selenium atom. R _{5 to} R ₇ Each independently represents an alkyl group.)
Including the step of reacting the compound represented by
General formula (3)

(In the formula (3), _{R 1} and _{R 2} are _.R 3, _{R 4} and _{X 2} is _R 3 in the formula (2) representing the same meaning as _{R 1} and _{R 2} in Formula (1), _{R 4} and X It has the same meaning as _2. )
A method for producing an aromatic compound represented by. The method for producing an aromatic compound according to claim 1, wherein R ₁ and / or R ₂ are chlorine atoms, bromine atoms or iodine atoms. The method for producing an aromatic compound according to claim 1 or 2, wherein X ₁ is an iodine atom or a trifluoromethanesulfonate group. The method for producing an aromatic compound according to any one of claims 1 to 3, wherein X ₂ is a sulfur atom. The method for producing an aromatic compound according to any one of claims 1 to 4, wherein R _{5 to} R ₇ is a methyl group. The method for producing an aromatic compound according to any one of claims 1 to 5, wherein R ₃ and R ₄ are hydrogen atoms.