JP5467676B2 - Method for producing aromatic compound - Google Patents

Description

  The present invention relates to a method for producing an aromatic compound. More specifically, the present invention relates to a method for producing [1] benzothieno [3,2-b] [1] benzothiophene derivatives.

  Conventionally, the synthesis of [1] benzothieno [3,2-b] [1] benzothiophene (compound 50 described later, hereinafter abbreviated as BTBT) has been attempted in many ways.

  As a method of synthesizing BTBT, a method of synthesizing BTBT from the reaction of α, α-dichlorotoluene and sulfur is known, and the yield is 39%, but generally a compound having a dichloromethyl group is used. There are many problems in availability and storage stability (Patent Document 1). Although a method for synthesizing BTBT from α, α, α-trichlorotoluene is known (Patent Document 1, Patent Document 2), although the target product is obtained, the yield is as low as about 12% and practical. Not right. Thereafter, the reaction of Reaction Formula 1 is known as a developed synthesis method, but there is a problem that the reaction route is long and the production cost becomes very high (Patent Document 3).

  Recently, a method has been developed in which 2,2′-dibromodiphenylacetylene and tert-butyllithium are reacted at an extremely low temperature, and then a desired product is obtained by adding sulfur, but reacts with moisture in the air. Since tert-butyllithium that ignites is used, there is a problem in safety and industrial properties (Patent Document 4, Non-Patent Document 1).

As the latest synthesis method, there is a method in which 2,7-diaminoBTBT is synthesized by diazolysis from diazotization as a starting material (Patent Document 5), but 2,7-diaminoBTBT (in Reaction Scheme 1, R = NH ₂ ) requires several steps, and starting from it is very expensive and is not an efficient production method.

  Further, BTBT is further condensed with a benzene ring, for example, Dinaphtho [2,3-b: 2 ′, 3′-f] thieno [3,2-b] thiophene (hereinafter, abbreviated as DNTT, compound) 91) is known.

This compound has been reported to have excellent properties as an organic semiconductor, and its mobility exceeds 3.0 cm ² / Vs and has a low threshold value. Therefore, industrial production of these DNTT derivatives The establishment of the law is expected.

  Currently, this compound is synthesized by the following route.

  However, in this synthesis route, (1) Step 1 uses dimethyl disulfide, which is a malodorous substance, (2) Uses n-butyllithium, which is a water-inhibiting substance, and (3) Step 3 uses iodine. There are various problems such as the reaction efficiency is extremely low, such as the use of 32 mol times, and (4) environmental problems such as the production of MeI as a by-product as a by-product ( Patent Literature 6, Non-Patent Literature 2, 3).

  As described above, it has been very difficult to industrially produce BTBT derivatives (including DNTT derivatives, for example).

  Under such circumstances, a technique capable of synthesizing BTBT using an aromatic aldehyde as a starting material has been developed (Patent Document 7). This method is a very effective synthesis method in which a BTBT derivative (including a DNTT derivative, for example) can be easily synthesized in one step from an easily available aromatic aldehyde.

  Recently, a technique capable of synthesizing BTBT from a stilbene derivative has been developed (Patent Document 8). In this method, (1) synthesis is easy and stilbene derivatives having various substituents can be used as starting materials, and (2) “S” (ion atom) is selectively added to the leaving group X of the stilbene derivative. This is a very effective synthesis method such as the ability to determine the condensed ring position because it can be introduced, and (3) the ability to easily synthesize asymmetric BTBT derivatives (including DNTT derivatives). Reference 8).

  As described above, BTBT derivatives (for example, including DNTT derivatives) can be easily estimated to be a group of compounds having excellent characteristics, and the establishment of industrial production methods continues even today.

US Pat. No. 3,278,552 US Pat. No. 3,433,874 SU755785 gazette WO2006 / 0777888 A1 JP 2008-239987 A WO2008 / 050726 JP 2008-290963 A Japanese Patent Application No. 2009-046477

Journal of Heterocyclic Chemistry (1998), 35 (3), 725-726. Journal of the American Chemical Society (2007), 129 (8), 2224-2225. Science and Technology of Advanced Materials (2007), 8 (4), 273-276.

  The present invention relates to a method for producing an aromatic compound derivative. More specifically, the present invention relates to the production of [1] benzothieno [3,2-b] [1] benzothiophene derivatives, which are highly selective and yielded compared to conventional synthesis techniques, and [1] benzothieno [3,2-b] [1] A benzothiophene derivative (general formula (2)) can be synthesized by a simpler technique.

  As a result of intensive studies to solve the above problems, the present inventors have succeeded in developing a simple production method of [1] benzothieno [3,2-b] [1] benzothiophene derivatives (general formula (2)). did.

（式中、Ｘはハロゲン原子、Ｒは置換基を表す。ｍは、置換基Ｒの置換基の数を表し、０〜４の整数を表す。ｍが２以上の場合、置換基Ｒは同一でも異なっていてもよく、また互いに連結して環を形成してもよい。）
で表される芳香族化合物と、硫黄、硫化水素、金属水硫化物及び金属硫化物からなる群から選ばれる少なくとも一種の硫黄化合物とを反応させ、一般式（２）

（式中、Ｒ、ｍは、それぞれ一般式（１）のＲ、ｍと同じ意味を示す。）
で表される芳香族化合物を製造する、芳香族化合物の製造方法。
（２）一般式（１）で表される芳香族化合物の置換基Ｘのハロゲン原子が、フッ素原子、塩素原子、臭素原子又はヨウ素原子であり、Ｒが、水素原子、ハロゲン原子、アミノ基、シアノ基、ニトロ基、炭素数１〜１８のアルキル基、カルボニル基、アルコキシ基（ＯＣ１〜Ｃ１８）、アルキルチオ基（ＳＣ１〜Ｃ１８）、エステル基、アリール基、又は炭素数１〜１８のアルキル基を有するシリル基、である、（１）に記載の芳香族化合物の製造方法。
（３）前記硫黄化合物が、硫黄、硫化水素、含水又は無水の水硫化ナトリウム、含水又は無水の硫化ナトリウム、及び含水又は無水の多硫化ナトリウムからなる群から選ばれる、（１）又は（２）に記載の芳香族化合物の製造方法。
（４）複数種の前記硫黄化合物を混合して用いる、（１）乃至（３）のいずれかに記載の芳香族化合物の製造方法。
（５）前記硫黄化合物として、硫黄と含水又は無水の水硫化ナトリウムとの混合物、硫黄と含水又は無水の硫化ナトリウムとの混合物、又は、硫黄と含水又は無水の水硫化ナトリウムと含水又は無水の硫化ナトリウムとの混合物を用いる、（１）乃至（４）のいずれかに記載の芳香族化合物の製造方法。
（６）銅含有化合物を含む金属触媒の存在下で反応を行う、（１）乃至（５）のいずれかに記載の芳香族化合物の製造方法。
（７）反応溶媒として、少なくとも一種の沸点１００℃以上の高沸点溶媒を使用する、（１）乃至（６）のいずれかに記載の芳香族化合物の製造方法。
（８）前記沸点１００℃以上の高沸点溶媒がＮ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、１，３−ジメチル−２−イミダゾリンジノン、エチレングリコール、プロピレングリコール、ポリエチレングリコール及びジメチルスルホキシドからなる群から選ばれる、（７）に記載の芳香族化合物の製造方法。 That is, (1) General formula (1)

(In the formula, X represents a halogen atom and R represents a substituent. M represents the number of substituents of the substituent R and represents an integer of 0 to 4. When m is 2 or more, the substituents R are the same. However, they may be different from each other and may be linked to each other to form a ring.)
Is reacted with at least one sulfur compound selected from the group consisting of sulfur, hydrogen sulfide, metal hydrosulfides and metal sulfides.

(In the formula, R and m have the same meaning as R and m in the general formula (1), respectively).
The manufacturing method of the aromatic compound which manufactures the aromatic compound represented by these.
(2) The halogen atom of the substituent X of the aromatic compound represented by the general formula (1) is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and R is a hydrogen atom, a halogen atom, an amino group, A cyano group, a nitro group, an alkyl group having 1 to 18 carbon atoms, a carbonyl group, an alkoxy group (OC1 to C18), an alkylthio group (SC1 to C18), an ester group, an aryl group, or an alkyl group having 1 to 18 carbon atoms. The manufacturing method of the aromatic compound as described in (1) which is a silyl group which has.
(3) The sulfur compound is selected from the group consisting of sulfur, hydrogen sulfide, hydrous or anhydrous sodium hydrosulfide, hydrous or anhydrous sodium sulfide, and hydrous or anhydrous sodium polysulfide, (1) or (2) A method for producing the aromatic compound according to 1.
(4) The method for producing an aromatic compound according to any one of (1) to (3), wherein a plurality of types of the sulfur compounds are mixed and used.
(5) As the sulfur compound, a mixture of sulfur and hydrous or anhydrous sodium hydrosulfide, a mixture of sulfur and hydrous or anhydrous sodium sulfide, or sulfur and hydrous or anhydrous sodium hydrosulfide and hydrous or anhydrous sulphide The method for producing an aromatic compound according to any one of (1) to (4), wherein a mixture with sodium is used.
(6) The method for producing an aromatic compound according to any one of (1) to (5), wherein the reaction is performed in the presence of a metal catalyst containing a copper-containing compound.
(7) The method for producing an aromatic compound according to any one of (1) to (6), wherein at least one high-boiling solvent having a boiling point of 100 ° C. or higher is used as the reaction solvent.
(8) The high boiling point solvent having a boiling point of 100 ° C. or higher is N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolinedinone, ethylene glycol, propylene The method for producing an aromatic compound according to (7), selected from the group consisting of glycol, polyethylene glycol and dimethyl sulfoxide.

  According to the present invention, [1] benzothieno [3,2-b] [1] benzothiophene derivatives can be easily produced. In addition, a BTBT skeleton can be constructed with high selectivity by providing a halogen atom which is a leaving group at the 2-position relative to the aldehyde group in the starting material.

  Hereinafter, the production method of the present invention will be described in detail. The scheme of the production method of the present invention is as follows.

  In the present invention, examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom, a bromine atom, and an iodine atom are preferable. More preferably, they are a chlorine atom and a bromine atom.

  R represented by the general formula (1) represents a substituent. R is usually a hydrogen atom, a halogen atom, an amino group, a cyano group, a nitro group, an alkyl group having 1 to 18 carbon atoms, a carbonyl group, an alkoxy group (OC1 to C18), an alkylthio group (SC1 to C18), an ester group, An aryl group or a silyl group having an alkyl group having 1 to 18 carbon atoms is shown. In the formula (1), when there are a plurality of Rs (when m is 2 or more), each R may be the same or different, and may be connected to each other to form a ring such as a benzene ring. .

  Here, as the alkyl group having 1 to 18 carbon atoms, methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group. Group, cyclobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, An n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, and the like can be given, and one or more of these may be dehydrogenated.

  Preferably, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n An alkyl group such as an undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, and one or more thereof. More preferably, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group , And one or more of these are dehydrogenated.

  An aryl group is an aromatic hydrocarbon group such as phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, benzopyrenyl group, pyridyl group, pyrazyl group, pyrimidyl group, quinolyl group, isoquinolyl group, pyrrolyl group, indolenyl group. , Heterocyclic groups such as imidazolyl group, carbazolyl group, thienyl group, furyl group, pyranyl group, pyridonyl group, and the like, and condensed heterocyclic groups such as benzoquinolyl group, anthraquinolyl group, benzothienyl group, and benzofuryl group. These substituents may be condensed with a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, furan ring, pyrrole ring, thiophene ring, pyridine ring, or the like. Of these, preferred aryl groups are a phenyl group, a naphthyl group, a pyridyl group, and a thienyl group.

  The alkoxy group (OC1 to C18) means an alkoxy group having an alkyl group having 1 to 18 carbon atoms, an aryloxy group, etc., and the alkyl group in the alkoxy group (OC1 to C18) is preferably a methyl group , Ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n -Dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group and phenyl group, more preferably n-pentyl group, n -Hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, and phenyl group.

  The alkylthio group (SC1 to C18) means an alkylthio group having an alkyl group having 1 to 18 carbon atoms, an arylthio group, and the like, and the alkyl group in the alkylthio group (SC1 to C18) is preferably a methyl group. , Ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n Alkyldo groups such as -dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group and phenyl group, more preferably n- Pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, and An alkylthio group having a phenyl group.

  When R represents an alkyl group having 1 to 18 carbon atoms, an alkoxy group (OC1 to C18), an alkylthio group or an aryl group, these groups may have a substituent, and as the substituent, a halogen atom , Alkyl group, aryl group, heterocyclic group, hydroxy group, alkoxy group, acyloxy group, alkylthio group, cyano group, nitro group, acyl group, alkoxycarbonyl group, carbamoyl group, formyl group, and acylamino group It is.

  The ester group refers to an ester group having a carboxylic acid, an alkyl group having 1 to 18 carbon atoms (CO2-alkyl group) or an aryl group (CO2-aryl group).

  A carbonyl group refers to an aldehyde, a ketone group having an alkyl group having 1 to 18 carbon atoms (CO-alkyl group) or an aryl group (CO-aryl group).

  The amino group refers to an amino group that is unsubstituted or substituted with one or two of the alkyl group having 1 to 18 carbon atoms, the carbonyl group, or the aryl group.

  Many of the compounds represented by the general formula (1) are commercially available and are easily available. Moreover, it is also possible to synthesize | combine according to the synthesis method of the aromatic aldehyde conventionally used for McMurry reaction (McMurry reaction) (reaction formula 2, patent document 5, nonpatent literature 2, 3).

  Specific examples of the compound represented by the general formula (1) represented by the following compounds 1 to 40 as X = Cl are shown in the following Tables 1 and 2, but are limited thereto. is not. Unless otherwise specified, the blank represents a hydrogen atom, the methyl group is Me, the ethyl group is Et, the propyl group is Pr, the butyl group is Bu, the hexyl group is Hexyl, the acetyl group is Ac, and the phenyl group is Ph. , The tolyl group is represented by Tolyl, and the naphthyl group is represented by Nap.

  Furthermore, although the compound represented by General formula (1) is set to X = Cl, the specific example represented by the following compounds 41-49 is illustrated, However, It is not limited to these.

  The sulfur compound used in the reaction is usually used in an amount of 1 to 30 mol with respect to 1 mol of the starting material (general formula (1)). Preferably, it is 1.5-20 mol, More preferably, it is 1.5-6 mol.

  As the sulfur compound, any sulfur, hydrogen sulfide, metal hydrosulfide, and metal sulfide can be used, but easily available sulfur, hydrogen sulfide, hydrous or anhydrous sodium hydrosulfide, hydrous Or anhydrous sodium sulfide and hydrous or anhydrous sodium polysulfide are preferred. More preferred are sulfur, hydrous or anhydrous sodium hydrosulfide, hydrous or anhydrous sodium sulfide, and hydrous or anhydrous sodium polysulfide.

  In addition, the reaction proceeds even when a single sulfur compound is used, but the use of multiple sulfur compounds can improve the yield of the reaction and suppress tarring by post-treatment of the reaction. There may be.

  When a mixture of a plurality of sulfur compounds is used, the sulfur compound to be used may be sulfur, hydrogen sulfide, metal hydrosulfide, or metal sulfide. More preferably, a mixture of sulfur and hydrous or anhydrous sodium hydrosulfide, or a mixture of sulfur and hydrous or anhydrous sodium sulfide, or sulfur and hydrous or anhydrous sodium hydrosulfide and hydrous or anhydrous sodium sulfide. It is a mixture (a mixture of three).

  When mixing and using a some sulfur compound, it is desirable to mix so that a sulfur compound total amount may be 1-30 mol with respect to 1 mol of starting materials. More preferably, it is 1.5-20 mol, More preferably, it is 1.5-6 mol.

  The reaction temperature is usually 0 to 300 ° C., and the reaction temperature can be varied or can be kept constant. The preferred reaction temperature is 100 to 250 ° C, more preferably 120 to 250 ° C.

  When carrying out the reaction, a solvent may or may not be used. When a solvent is used, any solvent can be used as long as it is a solvent used in ordinary organic synthesis. For example, aromatic compounds having no methyl group such as chlorobenzene, o-dichlorobenzene, bromobenzene, nitrobenzene, saturated aliphatic hydrocarbons such as n-hexane, n-heptane, n-pentane, cyclohexane, cycloheptane, cyclo Cyclic hydrocarbons such as pentane, n-propyl bromide, n-butyl chloride, n-butyl bromide, dichloromethane, dibromomethane, dichloropropane, dibromopropane, dichloroethane, dibromoethane, dichloropropane, dibromopropane, dichlorobutane, chloroform, bromoform Saturated aliphatic halogenated hydrocarbons such as carbon tetrachloride, carbon tetrabromide, trichloroethane, tetrachloroethane, pentachloroethane, chlorocyclohexane, chlorocyclopentane, bromocyclopenta Halogenated cyclic hydrocarbons such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, acetone, Mention may be made of ketones such as methyl ethyl ketone and methyl isobutyl ketone. These solvents may be used alone or in combination of two or more.

  Moreover, it is preferable to use at least one high boiling point solvent having a boiling point of 100 ° C. or higher as the reaction solvent because the reaction rate is greatly improved.

  Examples of high-boiling solvents having a boiling point of 100 ° C. or higher include amides (N-methyl-2-pyrrolidone (hereinafter referred to as NMP), N, N-dimethylformamide (hereinafter referred to as DMF), N, N-dimethylacetamide (hereinafter referred to as DMAc), 1,3-dimethyl-2-imidazolinedinone), glycols (ethylene glycol, propylene glycol, polyethylene glycol), and sulfoxides (dimethyl sulfoxide (hereinafter, DMSO), sulfolane) are preferable, and N-methyl- 2-pyrrolidone (NMP), N, N-dimethylformamide (DMF), and N, N-dimethylacetamide (DMAc).

  The amount of the solvent used is usually 0.01 to 300 times by weight, preferably 0.1 to 300 times by weight, more preferably 2 to 50 times by weight with respect to the starting material 1 represented by the general formula (1). It is. At this time, a plurality of solvents may be used in combination.

  When performing the reaction, the use of a catalyst is not essential, but when the catalyst is used, the reaction may proceed smoothly.

  In some cases, this reaction can also proceed by using a metal catalyst.

  Examples of the metal catalyst used include copper, copper chloride (I), copper chloride (II), copper bromide (I), copper bromide (II), copper iodide (I), and copper iodide (II). A copper containing compound is mentioned, These 1 type or multiple can be used in combination. Copper, copper chloride (I), and copper bromide (I) are preferable.

  The amount of the metal catalyst used is usually 0.01 to 1 mol, preferably 0.05 to 0.6 mol, more preferably 0.1 to 0.6 mol, relative to 1 mol of the starting material.

  When a plurality of metal catalysts are used, the total amount of each metal catalyst is usually 0.01 to 1 mol, preferably 0.05 to 0.6 mol, more preferably 0.1 to 0.00 mol, per 1 mol of the starting material. 6 mol.

  The reaction time is usually 1 to 50 hours, but the reaction is completed within 24 hours.

  If necessary, the target compound can be obtained from the reaction product by an isolation / purification method used in ordinary organic synthesis reactions. In order to increase the purity, vacuum sublimation purification can also be performed.

  Moreover, although the specific example (compounds 50-89) of a compound represented by General formula (2) is illustrated in particular, it is not limited to these.

  Moreover, although the specific example represented by the following compounds 90-98 is illustrated as a compound represented by General formula (2), it is not limited to these.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated still in detail, this invention is not limited to these examples.

Example 1 Synthesis of benzothieno [3,2-b] benzothiophene (Compound 50)
70% NaSH · nH ₂ O (1.14 g, 14.2 mmol) and o-chlorobenzaldehyde (Compound 1,1.0 g, 7.1 mmol) were mixed with NMP (20 ml) and heated at 180 ° C. for 3 hours. The reaction solution was allowed to cool, added to a saturated aqueous ammonium chloride solution (100 ml), and the mixture was extracted with toluene (30 ml × 2 times). The organic layer was collected, dried over anhydrous MgSO ₄ , filtered and concentrated, and purified by column chromatography (silica gel, developing solvent hexane) to obtain the desired product (compound 50, 395 mg, yield 39%). .
¹ H NMR (400 MHz, CDCl ₃ ) d 7.95-7.85 (m, 4H), 7.50-7.39 (m, 4H); MS (70 eV, EI) m / z = 240 (M ⁺ )

Example 2 Synthesis of benzothieno [3,2-b] benzothiophene (Compound 50)
Copper chloride (0.1 g, 1 mmol) was added to the first NMP mixed solvent of Example 1, and the reaction was carried out in the same manner as in Example 1 to obtain the target product 50 in a yield of 42%. The spectrum of the obtained compound was the same as that of Example 1.

Example 3 Synthesis of benzothieno [3,2-b] benzothiophene (Compound 50)
Similar to Example 1 except that Na ₂ S · 5H ₂ O (2.38 g, 14.2 mmol) was used instead of 70% NaSH · nH ₂ O (1.14 g, 14.2 mmol) used in Example 1. The target product 50 was obtained in a yield of 5%. The spectrum of the obtained compound was the same as that of Example 1.

Example 4 Synthesis of benzothieno [3,2-b] benzothiophene (Compound 50)
Using o-bromobenzaldehyde (1.31 g, 7.1 mmol) instead of o-chlorobenzaldehyde used in Example 1, the reaction was carried out in the same manner as in Example 1, and the target product 50 was obtained in a yield of 15%. I was able to get it. The spectrum of the obtained compound was the same as that of Example 1.

Example 5 Synthesis of benzothieno [3,2-b] benzothiophene (Compound 50)
Instead of 70% NaSH · nH ₂ O (1.14 g, 14.2 mmol) used in Example 1, 70% NaSH · nH ₂ O (375 mg, 4.7 mmol), Na ₂ S · 5H ₂ O (788 mg) , 4.7 mmol), and a mixture of sulfur (150 mg, 4.7 mmol), the reaction was carried out in the same manner as in Example 1, and the target product 50 could be obtained in a yield of 30%. The spectrum of the obtained compound was the same as that of Example 1.

Example 6 Dinaphtho [2,3-b: 2 ′, 3′-f] thieno [3,2-b] thiophene (Compound 91)
A mixture of 3-chloro-2-naphthaldehyde (compound 42, 3.81 g, 20 mmol) and 70% NaSH.nH ₂ O (3.20 g, 40 mmol) in NMP (56 ml) was attached to a Dean-Stark dehydration tube, and 180 ° Heat at 5 ° C. for 5 hours. The reaction solution was allowed to cool, filtered, washed with 200 ml of water and 200 ml of acetone, and dried to obtain DNTT (compound 91, 0.30 g, yield 8.8%).
Yellow crystal; mp> 300 ° C .; ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.54-7.57 (m, 4H, ArH), 7.96-7.98 (m, 2H, ArH), 8. 05-8.07 (m, 2H, ArH), 8.40 (s, 2H, ArH), 8.45 (s, 2H, ArH); IR (KBr) ν 1273, 872, 750, 739 cm ⁻¹ MS (70 eV, EI) m / z = 340 (M ⁺ ), 170 (M ⁺ / 2); Anal. Calcd for C22H12S2: C, 77.61; H, 3.55%. Found: C, 77.40; H, 3.38%.

As described above, according to the present invention, the selective and selective [1] benzothieno [3,2-b] [1] benzothiophene derivative (general formula (2)), which is a BTBT derivative which is a group of compounds having excellent characteristics, is provided. Efficient production is possible.
Therefore, the method for producing an aromatic compound derivative of the present invention is extremely useful.

Claims (8)

General formula (1)

(In the formula, X is a halogen atom , and R is a hydrogen atom, an amino group, a cyano group, a nitro group, an alkyl group having 1 to 18 carbon atoms, an alkoxy group (OC1 to C18), an alkylthio group (SC1 to C18)). , An aryl group, or a silyl group having an alkyl group having 1 to 18 carbon atoms, m represents the number of substituents of substituent R, and represents an integer of 0 to 4. When m is 2 or more, groups R may be the same or different.)
Is reacted with at least one sulfur compound selected from the group consisting of sulfur, hydrogen sulfide, metal hydrosulfides and metal sulfides.

(In the formula, R and m have the same meaning as R and m in the general formula (1), respectively).
The manufacturing method of the aromatic compound which manufactures the aromatic compound represented by these. Halogen atom of the substituents X of the aromatic compound represented by the general formula (1) is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a manufacturing method of an aromatic compound according to claim 1.   The aromatic according to claim 1 or 2, wherein the sulfur compound is selected from the group consisting of sulfur, hydrogen sulfide, hydrous or anhydrous sodium hydrosulfide, hydrous or anhydrous sodium sulfide, and hydrous or anhydrous sodium polysulfide. Compound production method.   The manufacturing method of the aromatic compound as described in any one of Claims 1 thru | or 3 which mixes and uses the said multiple types of said sulfur compound.   As the sulfur compound, a mixture of sulfur and hydrous or anhydrous sodium hydrosulfide, a mixture of sulfur and hydrous or anhydrous sodium sulfide, or sulfur and hydrous or anhydrous sodium hydrosulfide and hydrous or anhydrous sodium sulfide. The manufacturing method of the aromatic compound as described in any one of Claims 1 thru | or 4 using a mixture.   The method for producing an aromatic compound according to any one of claims 1 to 5, wherein the reaction is carried out in the presence of a metal catalyst containing a copper-containing compound.   The method for producing an aromatic compound according to any one of claims 1 to 6, wherein at least one high-boiling solvent having a boiling point of 100 ° C or higher is used as the reaction solvent. The high boiling point solvent having a boiling point of 100 ° C. or higher is N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolinedinone, ethylene glycol, propylene glycol, polyethylene The method for producing an aromatic compound according to claim 7, which is selected from the group consisting of glycol and dimethyl sulfoxide.