JP7241346B2 - Method for producing aromatic compound - Google Patents

Description

The present invention relates to a method for producing aromatic compounds. 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 "DNTT") 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 to practical use. Various compounds have been researched and developed as organic semiconductor materials used in these thin film devices. is shown. However, the DNTT derivatives disclosed in Patent Literatures 1 and 2 have poor solubility in organic solvents, and the problem is that an organic semiconductor layer cannot be produced by a solution process such as a coating method.
Regarding this problem, Patent Document 3 and Non-Patent Document 1 show that the solubility in organic solvents is improved by introducing a branched alkyl group into the DNTT skeleton.

As described above, DNTT derivatives useful as these organic semiconductors have been developed. It has been difficult to manufacture DNTT. Under such circumstances, various methods for synthesizing DNTT derivatives have also been studied, and three methods are currently known.

The first method is a production method according to the following synthesis 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 resulting DNTT derivative is a mixture of various compounds having different substituent positions. was the problem.

The second method is a manufacturing method according to the following synthesis flow using a long-known acetylene derivative (A) as a starting material (Patent Document 5).

According to this synthesis method, it is possible to selectively synthesize an asymmetric DNTT. The cyclization reaction of an acetylene derivative with iodine generally has a low yield (approximately 10% to 40% yield in Patent Document 5) and other problems.

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 Documents 1, 2, 5 and 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(tributylstannyl)ethylene. to give the asymmetric trans-1,2-bis(3-methylthionaphthalen-2-yl)ethylene, which is then ring-closed to give the desired compound, the asymmetric DNTT (see synthesis flow below).

However, in this synthesis 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 DNTT skeleton and then performing a coupling reaction is known, but the substitution positions are limited to the 5- and 12-positions. and difficult to introduce to other locations.

WO2008/050726 publication WO2010/098372 publication WO2014/115749 publication KR2008100982 publication JP 2009-196975 A WO2009/009790 publication WO2014/027685 publication

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

An object of the present invention is to provide a more convenient method for producing DNTT intermediates useful as starting compounds for producing various DNTT derivatives, particularly asymmetric DNTT derivatives.

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

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

(In formula (2), R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group, an alkoxy group or an aromatic group. 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 formula (3), R ₁ and R ₂ have the same meanings as R ₁ and R ₂ in formula (1). R ₃ , R ₄ and X ₂ are R ₃ , R ₄ and X in formula (2). has the same meaning as _2. )
A method for producing an aromatic compound represented by
[2] The method for producing an aromatic compound according to [1] above, 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 preceding 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 [1] to [3] above, wherein _X2 is a sulfur atom;
[ ₅ ] The method for producing an aromatic compound according to any one of [1] to [4] above, wherein R 5 to R ₇ are methyl groups, and [6] R ₃ and R ₄ are hydrogen atoms. A method for producing the aromatic compound according to any one of [1] to [5] above,
Regarding.

According to the present invention, it is possible to highly selectively produce DNTT intermediates, which are raw materials for producing DNTT derivatives, in particular asymmetric DNTT derivatives, which have been difficult to produce by conventional methods. can provide a DNTT intermediate that can be used to make a DNTT derivative of

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

In 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.
Halogen atoms represented by R ₁ and R ₂ in general formula (1) include fluorine, chlorine, bromine and iodine atoms, with chlorine, bromine and iodine atoms being preferred.

The substituent represented by R ₁ and R ₂ in general formula (1) is not particularly limited as long as it does not affect the reaction with the compound represented by formula (2). Examples of substituents include alkyl groups, alkenyl groups, alkynyl groups, aromatic groups, alkoxy groups and alkylthio groups.

Alkyl groups as substituents represented by R ₁ and R ₂ in general formula (1) are limited to any of linear, branched and cyclic as long as they are saturated hydrocarbon groups consisting of carbon and hydrogen atoms. not. The number of carbon atoms is also not particularly limited, but preferably 1 to 20, more preferably 1 to 16. Specific examples of alkyl groups include methyl, ethyl, propyl, butyl and pentyl groups.
The alkenyl group as a substituent represented by R ₁ and R ₂ in general formula (1) is a substituent consisting of a carbon atom and a hydrogen atom and having only one carbon-carbon double bond in a saturated hydrocarbon group. It is not limited to any of linear, branched, and cyclic types, if any. The number of carbon atoms is also not particularly limited, but preferably 2 to 20, more preferably 2 to 16. Specific examples of alkenyl groups include ethylene, propylene, butene and pentene groups.

The alkynyl group as a substituent represented by R ₁ and R ₂ in general formula (1) is a substituent consisting of a carbon atom and a hydrogen atom and having only one carbon-carbon triple bond in a saturated hydrocarbon group. It is not limited to any of linear, branched, and cyclic types, if any. The number of carbon atoms is also not particularly limited, but preferably 2 to 20, more preferably 2 to 16. Specific examples of alkenyl groups include acetylene, propyne, butyne and pentyne groups.

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

The alkoxy group as a substituent represented by R ₁ and R ₂ in 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 straight chain type, branched chain type and cyclic type as long as it is a saturated hydrocarbon group consisting of carbon atoms and hydrogen atoms. The number of carbon atoms is also not particularly limited, but preferably 1 to 20, more preferably 1 to 16. Specific examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and n-pentyloxy groups.
The alkylthio group as a substituent represented by R ₁ and R ₂ in 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 any of straight chain type, branched chain type and cyclic type as long as it is a saturated hydrocarbon group consisting of carbon atoms and hydrogen atoms. The number of carbon atoms is also not particularly limited, but preferably 1 to 20, more preferably 1 to 16. Specific examples of alkylthio groups include methylthio, ethylthio, n-propylthio and n-pentylthio groups.

The carbon atoms of the alkyl group, alkenyl group, alkynyl group, aryl group, alkyloxy group and alkylthio group may be substituted with an oxygen atom and/or a sulfur atom. In addition, one or more hydrogen atoms contained in the substituent may be partially substituted with a halogen atom, and the molecular structure is not particularly limited. However, the aryl group excludes the same halogen atoms as R ₁ to R ₄ in the general formula (3). Furthermore, some of the substituents may be substituted with aryl groups.

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

In general formula (1), _X1 represents a halogen atom or a trifluoromethanesulfonate group.
The halogen atom represented by X ₁ in formula (1) includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom, a bromine atom or an iodine atom, more preferably a bromine atom or an iodine atom.
X ₁ in general formula (1) is preferably an iodine atom or a trifluoromethanesulfonate group.

In general formula (2), _R3 and _R4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an aryl group. Also, R ₃ and R ₄ may combine with each other to form a ring such as a benzene ring.
The halogen atoms represented by R ₃ and R ₄ in formula (2) include the same halogen atoms as those represented by R ₁ and R ₂ in formula (1), and the preferred ones are also the same.

Examples of alkyl groups represented by R ₃ and R ₄ in general formula (2) include the same alkyl groups as substituents represented by R ₁ and R ₂ in general formula (1).
The alkoxy groups represented by R ₃ and R ₄ in general formula (2) include the same alkoxy groups as substituents represented by R ₁ and R ₂ in general formula (1).
The aromatic groups represented by R ₃ and R ₄ in general formula (2) include the same aromatic groups as the substituents represented by R ₁ and R ₂ in general formula (1).
A hydrogen atom is preferable as R ₃ and R ₄ in the general formula (1).

In general formula (2), _X2 represents a sulfur atom or a selenium atom, preferably a sulfur atom.
In general formula (2), R ₅ to R ₇ each independently represent an alkyl group.
Examples of the alkyl groups represented by R ₅ to R ₇ in general formula (2) include the same alkyl groups as the substituents represented by R ₁ and R ₂ in general formula (1).
The number of carbon atoms in the alkyl group represented by R ₅ to R ₇ in general formula (2) is usually 1 to 8, preferably 1 to 4. Specific examples of linear alkyl groups include methyl group, ethyl group, n-propyl group, n-butyl group, iso-butyl group, n-pentyl group and n-hexyl group, and specific examples of branched chain alkyl groups. Examples include i-propyl group, iso-butyl group, sec-butyl group, tert-butyl group, iso-pentyl group and iso-hexyl group.
A methyl group is more preferable as R ₅ to R ₇ in the general formula (2).

The step of reacting the compound represented by the formula (1) and the compound represented by the formula (2) in the production method of the present invention includes the first-stage reaction and the second-stage reaction shown in the scheme below. include.

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

The reaction in the first step is preferably carried out under an inert gas atmosphere such as an argon atmosphere, nitrogen substitution, dry argon atmosphere, or dry nitrogen stream.

A catalyst is preferably used for the first-stage reaction. Examples of catalysts include tri-tert-butylphosphine, triadamantylphosphine, 1,3-bis(2,4,6-trimethylphenyl)imidazolidinium chloride, 1,3-bis(2,6-diisopropylphenyl) imidazolidinium chloride, 1,3-diadamantylimidazolidinium chloride, or mixtures thereof; metal Pd, Pd/C (hydrous or non-hydrous), 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) _Cl2 ), dibromobis(triphenylphosphine)nickel (Ni( _PPh3 ) _2Br2 ) _, bis(diphenylphosphino)propanenickel dichloride (Ni(dppp) _Cl2 ) and bis(diphenylphosphino) Ethane nickel dichloride (Ni(dppe)Cl ₂ ) is preferred, nickel-based catalysts or palladium-based catalysts are more preferred, and Pd/C (hydrous or non-hydrous) or Pd(PPh ₃ ) ₂ Cl ₂ , Pd(PPh ₃ ) ₄ is more preferred, and Pd(PPh ₃ ) ₂ Cl ₂ and Pd(PPh ₃ ) ₄ are particularly preferred.
A plurality of these catalysts may be used in combination, or these catalysts may be used in combination with other catalysts.

The amount of the catalyst used in the reaction in the first step is preferably 0.001 to 0.500 mol, more preferably 0.001 to 0.100 mol, per 1 mol of the compound represented by the general formula (1). It is preferably 0.001 to 0.050 mol.

An alkali metal salt may be used in combination in the first-stage reaction. By using an alkali metal salt together, 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. Examples thereof include lithium chloride, lithium bromide and lithium iodide, with lithium chloride being preferred.
The amount of the alkali metal salt to be added is preferably 0.001 to 5.0 mol per 1 mol of the compound represented by general formula (1).

The first step reaction may be carried out in a solvent. The solvent that can be used is any solvent that can dissolve the compound represented by the formula (1) and the compound represented by the formula (2), which are the starting materials, and the catalyst, alkali metal salt, etc. used if necessary. is also usable.
Specific examples of solvents include aromatic compounds such as chlorobenzene, o-dichlorobenzene, bromobenzene, nitrobenzene, toluene and xylene, and saturated aliphatic hydrocarbons such as n-hexane, n-heptane and n-pentane; Alicyclic hydrocarbons such as cyclohexane, cycloheptane, and cyclopentane; n-propyl bromide, n-butyl chloride, n-butyl bromide, dichloromethane, dibromomethane, dichloropropane, dibromopropane, dichlorobutane, chloroform, 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 Esters such as , butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate and butyl butyrate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; diethyl ether , dipropyl ether, dibutyl ether, cyclopentyl methyl ether, dimethoxyethane, tetrahydrofuran, 1,4-dioxane and 1,3-dioxane; N-methyl-2-pyrrolidone, N,N-dimethylformamide and N, 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 step reaction can be carried out in a manner similar to that detailed in WO2016/152889.

The aromatic compound represented by 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 formula (3). Specific examples include recrystallization, column chromatography, and sublimation purification.

A DNTT derivative having a desired substituent is obtained 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. can be manufactured.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
In the examples, the melting point was measured using Optimelt MPA100 manufactured by Stanford Research Systems, the nuclear magnetic resonance spectrum was measured using Avance500 manufactured by Bruker, the HR-MS was JMS-T100GCV manufactured by JEOL, and the elemental analysis was measured using MT-6 CHN CORDER manufactured by Yanaco. bottom.
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 a compound represented by the following formula 1 In a 500 mL four-necked flask equipped with a dropping funnel and heated and dried, under a nitrogen atmosphere, 2,2,6,6-tetramethylpiperidine (TMP) 15.3 mL ( 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 n-BuLi in molarity (number of moles of n-butyllithium in 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. After heating the reaction solution to room temperature and stirring for 2 hours, 16.0 mL (180 mmol) of dimethyldisulfide (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 using 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 (22.0 mmol, yield 73%) of a compound represented by the following formula 1 was obtained. was obtained as a white solid.

The results of melting point, nuclear magnetic resonance spectrum, HR-MS spectrum and elemental analysis of the compound represented by Formula 1 below were as follows.
mp 86.2 - 86.8 °C.
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).
^13C NMR ( _CDCl3 , 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 _C12H11BrOS [M] ⁺ : 281.9714. _Found : 281.9726.
Elemental analysis: Calcd for _{C12H11BrOS :} C, 50.90; H, 3.92. Found: C, 50.73; H, 3.85.

(Step 2) Synthesis of a 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 the formula 1 obtained in step 1 was dissolved in 150 mL of methylene chloride. rice field. At 0° C., 25 mL of a 1.0 M methylene chloride solution 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 using 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 results of melting point, nuclear magnetic resonance spectrum, HR-MS spectrum and elemental analysis of the compound represented by Formula 2 below were as follows.
mp 123.4 - 123.7 °C.
^13C NMR ( _CDCl3 , 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 _C11H9BrOS [M] ⁺ : 267,9558. _Found : 267.9574.
Elemental analysis: Calcd for _C11H9BrOS : C, 49.09; H, 3.37. Found: C, 48.99; H, 3.38 _.

(Step 3) Synthesis of a 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 the formula 2 obtained in step 2 was dissolved in 120 mL of methylene chloride. rice field. 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 using 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 (18.9 mmol, yield 98%) of the compound represented by the following formula 3 was obtained as a white solid.

The results of melting point, nuclear magnetic resonance spectrum, HR-MS spectrum and elemental analysis of the compound represented by Formula 3 below were as follows.
mp 73.2 - 74.6 °C.
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, 1H, J = 8.5, 2.0 Hz), 7.53 (s, 1H), 2.59 (s, 3H).
HRMS ₍ EI) m/ _z : Calcd for _{C12H8BrF3O3S2} [M _] ⁺ : 399.9050. _Found : 399.9065.
Elemental analysis: Calcd for _{C12H8BrF3O3S2} : C, _35.92 ; H _{, 2.01} . Found: _C , 35.76; H, 2.09.

(Step 4) Synthesis of a 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 the formula 3 obtained in step 3 was dissolved in 1000 mL of methylene chloride. rice field. After cooling to 0° C., 13.10 parts of a 20 mass % aqueous solution of meta-chloroperbenzoic acid (mCPBA) (number of moles of meta-chloroperbenzoic acid in aqueous solution: 60.70 mmol) was slowly added. After stirring for 6 hours, the mixture was quenched with a saturated aqueous sodium hydrogencarbonate solution, the organic layer was dried over anhydrous magnesium sulfate, the reaction mixture was collected by filtration, and the solvent was distilled off using a rotary evaporator. The resulting 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 obtained. was obtained as a white solid.

The results of melting point, nuclear magnetic resonance spectrum, HR-MS spectrum and elemental analysis of the compound represented by Formula 4 below 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 = 8.5Hz, 2.0Hz), 2.90 (s, 3H).
HRMS (EI) m/ _z : _Calcd for _{C12H8BrF3O4S2} [M _] ⁺ : 415.9000. _Found : 415.9023.
Elemental analysis: Calcd for _{C12H8BrF3O4S2} : C, _34.55 ; _H , 1.93. _Found : _C , 34.40; H, 1.98.

(Step 5) Synthesis of the compound represented by the following formula 5 In a 500 mL four-necked flask, 4.17 parts (10.0 mmol) of the compound represented by the formula 4 obtained in step 4, 2-trimethylstannyl ( Naphtho[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) were added to 1, It was dissolved in 125 mL of 4-dioxane. The mixed solution obtained above was stirred at 50° C. for 48 hours, then quenched with water, the reaction solution was extracted with methylene chloride, the organic layer was dried over anhydrous magnesium sulfate, and the reaction mixture was 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 results of melting point, nuclear magnetic resonance spectrum, HR-MS spectrum and elemental analysis of the compound represented by Formula 5 below were as follows.
mp 262.9 - 264.9 °C.
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, 132.92, 131.81, 131.42, 131.31, 130.58, 130.58, 130.58 , 123.95, 122.72, 122.14, 120.47, 42.14.
HRMS (EI) m/z: Calcd for _C23H15BrOS2 [M] ⁺ : 449.9748. _{Found :} 449.9753.
Elemental analysis: _Calcd for _C23H15BrOS2 : C, 61.20; H, 3.35. Found: C, 61.19; H, 3.36 _.

(Step 6) Synthesis of compound represented by Formula 6 below 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, it was poured into ice water and filtered to obtain a yellow solid. This 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 obtain a yellow solid. The resulting reaction mixture was purified by silica gel chromatography using heated chloroform as a mobile phase, and further purified by sublimation to give 140 mg (0.343 mmol, yield 69%) of the compound represented by the following formula 6 as a pale yellow solid. Obtained as crystals.

The results of the melting point, nuclear magnetic resonance spectrum, HR-MS spectrum and elemental analysis of the compound represented by Formula 6 below 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 _C22H11BrS2 [M] ⁺ : _417.9486 . _Found : 417.9495.
Elemental analysis: Calcd for _C22H11BrS2 : C, 63.01; H, 2.64. _Found : C, 62.90; H, 2.71 _.

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

The results of melting point, nuclear magnetic resonance spectrum, HR-MS spectrum and elemental analysis of the compound represented by Formula 7 below were as follows.
m.p. > 350°C.
¹H-NMR (CDCl₃, 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).
¹³C NMR (C₂D.₂Cl_Four, 120 ° C, 100 MHz): δ (PPM) 141.77, 141.03, 134.52, 133.93, 133.93, 132.40, 131.53, 131.33, 131.03 , 121.05, 120.24, 119.93, 105.67, 96.01, 0.04.
HRMS (EI) m/z: Calcd for C₂₇H.₂₀S.₂Si[M]⁺: 436.0776. Found: 436.0779.
Elemental analysis: Calcd for C₂₇H.₂₀S.₂Si: 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 DNTT intermediates, which are raw materials for producing DNTT derivatives, in particular asymmetric DNTT derivatives, which have been difficult to produce by conventional methods. can provide a DNTT intermediate that can be used to make a DNTT derivative of

Claims (6)

General formula (1)

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

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

(In formula (3), R ₁ and R ₂ have the same meanings as R ₁ and R ₂ in formula (1). R ₃ , R ₄ and X ₂ are R ₃ , R ₄ and X in formula (2). has the same meaning as _2. )
A method for producing an aromatic compound represented by. 2. The method for producing an aromatic compound according to claim 1, wherein _R1 and/or _R2 is a chlorine atom, a bromine atom or an iodine atom. 3. The method for producing an aromatic compound according to claim 1, wherein _X1 is an iodine atom or a trifluoromethanesulfonate group. 4. The method for producing an aromatic compound according to any one of claims 1 to 3, wherein _X2 is a sulfur atom. _5. The method for producing an aromatic compound according to any one of claims 1 to 4, wherein R5 to _R7 are methyl groups. 6. The method for producing an aromatic compound according to any one of claims 1 to 5, wherein _R3 and _R4 are hydrogen atoms.