JP2011256144A - Production method of thiophene compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new method for producing [1]benzothieno[3,2-b][1]benzothiophene derivative in high yield.SOLUTION: The target compound is produced by reacting a compound represented by formula (2-1) and formula (2-48) with an acid, preferably protonic acid or further trifluoromethane sulfonic acid.

Description

The present invention relates to a method for producing a thiophene compound having a specific structure.

Conventionally, a thin film transistor (TFT) made of amorphous silicon or polycrystalline silicon has been widely used as a switching element for flat panel display such as a liquid crystal display device. However, a CVD apparatus used for manufacturing a thin film transistor using silicon is expensive, and manufacturing a large-sized thin film transistor element has a drawback of increasing manufacturing cost.
In addition, since amorphous silicon and polycrystalline silicon are formed at a high temperature, there is a problem that a plastic material that is lightweight and flexible but has poor heat resistance cannot be used as a substrate. .
In order to solve the above problem, an organic transistor (also referred to as an organic thin film transistor or an organic TFT) using an organic compound for a channel semiconductor layer (hereinafter referred to as an organic semiconductor layer) instead of amorphous silicon or polycrystalline silicon is proposed. (Non-Patent Document 1).

As a method for forming the organic semiconductor layer, for example, a vacuum deposition method or a coating method is known. According to these film formation methods, it is easy to increase the size of the organic transistor element while suppressing the manufacturing cost. .
Furthermore, the temperature required for film formation can be lowered, and organic transistors using organic compounds can use plastic materials for the substrate, which can be applied to flexible display elements. Expectations are gathered for the transformation.

A practical organic transistor needs to have characteristics such as high charge mobility and a large current on / off ratio. Here, the term “on / off ratio” means the ratio of the current between the source electrode and the drain electrode when the organic transistor is on to the current between the source electrode and the drain electrode when the organic transistor is off. To do.
Furthermore, excellent storage stability is required for practical application of organic transistors.

To date, organic transistors using, for example, pentacene as the organic semiconductor layer have been proposed (Non-Patent Document 2).
However, an organic transistor using pentacene has a problem that it has a low function as an organic transistor in the atmosphere and low storage stability.
Furthermore, an organic transistor using a thiophene oligomer (α-hexathienylene) as an organic semiconductor layer has been proposed (Non-patent Document 3). However, the organic transistor also has a drawback that its storage stability in air is low.

In order to improve these storage stability, an organic transistor using a [1] benzothieno [3,2-b] [1] benzothiophene derivative as an organic semiconductor layer has been proposed. For example, an organic transistor using 2,7-diphenyl [1] benzothieno [3,2-b] [1] benzothiophene as an organic semiconductor layer has been proposed (Non-Patent Document 4). An organic transistor using 2,7-dialkyl [1] benzothieno [3,2-b] [1] benzothiophene for an organic semiconductor layer has been proposed (Non-patent Document 5). For example, an organic transistor using 2,7-dialkoxyalkyl [1] benzothieno [3,2-b] [1] benzothiophene as an organic semiconductor layer has been proposed (Patent Document 1). Further, an organic transistor using dinaphtho [2,3-b: 2 ′, 3′-f] thieno [3,2-b] thiophene as an organic semiconductor layer has been proposed (Non-Patent Document 6).

Several methods for producing these thiophene derivatives or intermediates for producing these thiophene derivatives have been reported. For example, 2,7-diethylcarboxylate [1] benzothieno [3,2-b] [1] benzothiophene is produced by allowing bromine to act on compound (A) (Non-patent Document 7).

2,7-nitro [1] benzothieno [3,2-b] [1] benzothiophene is produced by reacting compound (B) with perbrominated pyridine (Patent Document 2).

Dinaphtho [2,3-b: 2 ′, 3′-f] thieno [3,2-b] thiophene is produced by allowing iodine to act on compound (C) (Non-patent Document 6).

これらの製造方法は、必ずしも高収率で［１］ベンゾチエノ［３，２−ｂ］［１］ベンゾチオフェン誘導体を製造することができるものではなく、現在では、実用化に向け、［１］ベンゾチエノ［３，２−ｂ］［１］ベンゾチオフェン誘導体の一層改良された製造方法が求められている。
Further, dinaphtho [1,2-b: 1 ′, 2′-f] thieno [3,2-b] thiophene is produced by allowing iodine to act on the compound (D) (Non-patent Document 8).

These production methods are not necessarily capable of producing [1] benzothieno [3,2-b] [1] benzothiophene derivatives with high yield, and at present, [1] benzothieno for practical use. There is a need for a further improved process for the preparation of [3,2-b] [1] benzothiophene derivatives.

JP 2009-267132 A JP 2009-62302 A

Appl.Phys.Lett., 63,1372 (1993) Appl.Phys.Lett., 72,1854 (1998) Science, 268,270 (1995) J. Amer. Chem. Soc., 128, 12604 (2006) J. Amer. Chem. Soc., 129, 15732 (2007) J. Amer. Chem. Soc., 129, 2224 (2007) J. Org. Chem. Soc., 58, 5209 (1993) Bull.Chem.Soc.Jpn., 83,120 (2010)

To date, various methods for producing [1] benzothieno [3,2-b] [1] benzothiophene derivatives have been proposed, but it is difficult to say that the method is sufficiently satisfactory for practical use.
In view of the above, the present invention is to provide a novel production method capable of producing a [1] benzothieno [3,2-b] [1] benzothiophene derivative in a high yield.

As a result of intensive studies to solve the above problems, the present inventors have found a novel method for producing a [1] benzothieno [3,2-b] [1] benzothiophene derivative.
That is, the present invention
(i) In the method for producing the compound represented by the general formula (1), the compound represented by the general formula (2) or the general formula (3) is allowed to act with an acid, and then the resulting compound is used as a base. This is a method for producing a compound represented by the general formula (1) by acting.

〔式中、Ｘ_１〜Ｘ_８はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、シアノ基、ニトロ基、直鎖、分岐または環状のアルキル基、直鎖、分岐または環状のアルコキシ基、直鎖、分岐または環状のアルコキシアルキル基、直鎖、分岐または環状のアルコキシアルコキシ基、あるいは置換または未置換のアリール基を表し、さらに、Ｘ_１〜Ｘ_４および／またはＸ_５〜Ｘ_８の組み合わせより選ばれる隣接する２個の置換基が互いに結合して、置換している炭素原子と共に置換または未置換のベンゼン環、あるいは置換または未置換のナフタレン環を形成していてもよく、Ｒ_１およびＲ_２はそれぞれ独立に、アルキル基を表す〕

[Wherein, X _{1 to} X ₈ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, or a linear chain. Represents a branched or cyclic alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxy group, or a substituted or unsubstituted aryl group, and further selected from a combination of X _{1 to} X ₄ and / or X _{5 to} X ₈ Two adjacent substituents may be bonded to each other to form a substituted or unsubstituted benzene ring or a substituted or unsubstituted naphthalene ring together with the substituted carbon atom, and R ₁ and R ₂ Each independently represents an alkyl group.

According to the present invention, it has become possible to provide a novel method for producing a compound useful for various functional materials (for example, materials for organic transistors).

Hereinafter, the present invention will be described in detail.
In the present invention, the compound represented by the general formula (2) or the general formula (3) is allowed to act with an acid, and then the resulting compound is allowed to act with a base to obtain the compound represented by the general formula (1). It is a manufacturing method.

〔式中、Ｘ_１〜Ｘ_８はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、シアノ基、ニトロ基、直鎖、分岐または環状のアルキル基、直鎖、分岐または環状のアルコキシ基、直鎖、分岐または環状のアルコキシアルキル基、直鎖、分岐または環状のアルコキシアルコキシ基、あるいは置換または未置換のアリール基を表し、さらに、Ｘ_１〜Ｘ_４および／またはＸ_５〜Ｘ_８の組み合わせより選ばれる隣接する２個の置換基が互いに結合して、置換している炭素原子と共に置換または未置換のベンゼン環、あるいは置換または未置換のナフタレン環を形成していてもよく、Ｒ_１およびＲ_２はそれぞれ独立に、アルキル基を表す〕

[Wherein, X _{1 to} X ₈ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, or a linear chain. Represents a branched or cyclic alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxy group, or a substituted or unsubstituted aryl group, and further selected from a combination of X _{1 to} X ₄ and / or X _{5 to} X ₈ Two adjacent substituents may be bonded to each other to form a substituted or unsubstituted benzene ring or a substituted or unsubstituted naphthalene ring together with the substituted carbon atom, and R ₁ and R ₂ Each independently represents an alkyl group.

In the compounds represented by general formula (1) to general formula (3), X _{1 to} X ₈ are each independently a hydrogen atom, halogen atom, hydroxyl group, cyano group, nitro group, linear, branched or cyclic alkyl. Represents a group, a linear, branched or cyclic alkoxy group, a linear, branched or cyclic alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxy group, or a substituted or unsubstituted aryl group.

In the present specification, the aryl group represents a carbocyclic aromatic group such as a phenyl group or a naphthyl group, for example, a heterocyclic aromatic group such as a furyl group, a thienyl group or a pyridyl group. In addition, the substituent of the aryl group includes a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, or a carbon number of 4 to The aryl group which may be substituted by 20 said halogen atoms, an alkyl group, and an alkoxy group etc. are mentioned.

In the compounds represented by the general formula (1) to the general formula (3), more preferably, X _{1 to} X ₈ are a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, A linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a linear, branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, a linear, branched or cyclic alkoxyalkoxy group having 2 to 20 carbon atoms, Alternatively, it represents a substituted or unsubstituted aryl group having 4 to 20 carbon atoms.

Specific examples of X _{1 to} X _{8 in} the general formula (1) to the general formula (3) include, for example, a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and iodine; a hydroxyl group, a cyano group, Nitro group,
For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, cyclohexylmethyl group, n- Octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 2,6-dimethyl-4-heptyl group, 3 , 5,5-trimethylhexyl group, n-decyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group Group, 1-hexylheptyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-eicosyl group, cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, Linear, branched or cyclic alkyl groups such as 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group;

For example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, n-pentyloxy group, neopentyloxy group, cyclopentyloxy group, n-hexyloxy group 3,3-dimethylbutyloxy group, 2-ethylbutyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, n -Undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyl group Linear, branched or cyclic alkoxy groups such as oxy group and n-eicosyloxy group

For example, methoxymethyl group, ethoxymethyl group, n-butoxymethyl group, n-pentyloxymethyl group, n-hexyloxymethyl group, (2-ethylbutyloxy) methyl group, n-heptyloxymethyl group, n-octyl Oxymethyl group, n-decyloxymethyl group, n-dodecyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-isopropoxyethyl group, 2-n-butoxy Ethyl group, 2-n-pentyloxyethyl group, 2-n-hexyloxyethyl group, 2- (2′-ethylbutyloxy) ethyl group, 2-n-heptyloxyethyl group, 2-n-octyloxyethyl group Group, 2- (2′-ethylhexyloxy) ethyl group, 2-n-decyloxyethyl group, 2-n-dodecyloxyethyl group 2-n-tetradecyloxyethyl group, 2-cyclohexyloxyethyl group, 2-methoxypropyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-n-propoxypropyl group, 3-isopropoxypropyl group, 3-n-butoxypropyl group, 3-n-pentyloxypropyl group, 3-n-hexyloxypropyl group, 3- (2′-ethylbutoxy) propyl group, 3-n-octyloxypropyl group, 3- ( 2'-ethylhexyloxy) propyl group, 3-n-decyloxypropyl group, 3-n-dodecyloxypropyl group, 3-n-tetradecyloxypropyl group, 3-cyclohexyloxypropyl group, 4-methoxybutyl group, 4-ethoxybutyl group, 4-n-propoxybutyl group, 4-isopropoxybutyl group, 4-n-butyl group Xylbutyl group, 4-n-hexyloxybutyl group, 4-n-octyloxybutyl group, 4-n-decyloxybutyl group, 4-n-dodecyloxybutyl group, 5-methoxypentyl group, 5-ethoxypentyl group 5-n-propoxypentyl group, 5-n-pentyloxypentyl group, 6-methoxyhexyl group, 6-ethoxyhexyl group, 6-isopropoxyhexyl group, 6-n-butoxyhexyl group, 6-n-hexyl Oxyhexyl group, 6-n-decyloxyhexyl group, 4-methoxycyclohexyl group, 7-methoxyheptyl group, 7-ethoxyheptyl group, 7-isopropoxyheptyl group, 8-methoxyoctyl group, 8-ethoxyoctyl group, 9-methoxynonyl group, 9-ethoxynonyl group, 10-methoxydecyl group, 10-ethoxyde Group, 10-n-butoxydecyl group, 11-methoxyundecyl group, 11-ethoxyundecyl group, 12-methoxydodecyl group, 12-ethoxydodecyl group, 12-isopropoxide decyl group, 14-methoxytetradecyl group A linear, branched or cyclic alkoxyalkyl group such as a tetrahydrofurfuryl group;

For example, methoxymethoxy group, ethoxymexi group, n-butoxymethoxy group, n-pentyloxymethoxy group, n-hexyloxymethoxy group, (2-ethylbutoxy) methoxy group, n-heptyloxymethoxy group, n-octyloxy Methoxy group, n-decyloxymethoxy group, n-dodecyloxymethoxy group, 1-methoxyethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-n-propoxyethoxy group, 2-isopropoxyethoxy group, 2-n-butoxyethoxy group, 2-n-pentyloxyethoxy group, 2-n-hexyloxyethoxy group, 2- (2′-ethylbutyloxy) ethoxy group, 2-n-heptyloxyethoxy group, 2- n-octyloxyethoxy group, 2- (2′-ethylhexyloxy) ethoxy group, -N-decyloxyethoxy group, 2-n-dodecyloxyethoxy group, 2-n-tetradecyloxyethoxy group, 2-cyclohexyloxyethoxy group, 2-methoxypropoxy group, 3-methoxypropoxy group, 3-ethoxypropoxy group Group, 3-n-propoxypropoxy group, 3-isopropoxypropoxy group, 3-n-butoxypropoxy group, 3-n-pentyloxypropoxy group, 3-n-hexyloxypropoxy group, 3- (2′-ethyl) Butoxy) propoxy, 3-n-octyloxypropoxy, 3- (2′-ethylhexyloxy) propoxy, 3-n-decyloxypropoxy, 3-n-dodecyloxypropoxy, 3-n-tetradecyl Oxypropoxy group, 3-cyclohexyloxypropoxy group, 2-methoxy Toxyl group, 3-methoxybutoxy group, 4-methoxybutoxy group, 4-ethoxybutoxy group, 4-n-propoxybutoxy group, 4-isopropoxybutoxy group, 4-n-butoxybutoxy group, 4-n-hexyloxy Butoxy group, 4-n-octyloxybutoxy group, 4-n-decyloxybutoxy group, 4-n-dodecyloxybutoxy group, 5-methoxypentyloxy group, 5-ethoxypentyloxy group, 5-n-propoxypentyl Oxy group, 5-n-pentyloxypentyloxy group, 6-methoxyhexyloxy group, 6-ethoxyhexyloxy group, 6-isopropoxyhexyloxy group, 6-n-butoxyhexyloxy group, 6-n-hexyloxy Hexyloxy group, 6-n-decyloxyhexyloxy group, 4-methoxy Hexyloxy group, 7-methoxyheptyloxy group, 7-ethoxyheptyloxy group, 7-isopropoxyheptyloxy group, 8-methoxyoctyloxy group, 8-ethoxyoctyloxy group, 9-methoxynonyloxy group, 9-ethoxy Nonyloxy group, 10-methoxydecyloxy group, 10-ethoxydecyloxy group, 10-n-butoxydecyloxy group, 11-methoxyundecyloxy group, 11-ethoxyundecyloxy group, 12-methoxydodecyloxy group, Linear, branched or cyclic alkoxyalkoxy groups such as 12-ethoxydodecyloxy group, 12-isopropoxide decyloxy group, 14-methoxytetradecyloxy group, tetrahydrofurfuryloxy group;

For example, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-n-propylphenyl group, 4-isopropylphenyl group, 4-n-butylphenyl group 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-n-pentylphenyl group, 4-isopentylphenyl group, 4-tert-pentylphenyl group, 4-n-hexylphenyl group, 4-cyclohexylphenyl Group, 4-n-heptylphenyl group, 4-n-octylphenyl group, 4-n-nonylphenyl group, 4-n-decylphenyl group, 4-n-undecylphenyl group, 4-n-dodecylphenyl group 4-n-tetradecylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethyl An phenyl group, a 2,6-dimethylphenyl group, a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 3,4,5-trimethylphenyl group, a 2,3,5,6-tetramethylphenyl group, 5-indanyl group, 1,2,3,4-tetrahydro-5-naphthyl group, 1,2,3,4-tetrahydro-6-naphthyl group,
2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 3-ethoxyphenyl group, 4-ethoxyphenyl group, 4-n-propoxyphenyl group, 4-isopropoxyphenyl group, 4-n-butoxy Phenyl group, 4-isobutoxyphenyl group, 4-n-pentyloxyphenyl group, 4-n-hexyloxyphenyl group, 4-cyclohexyloxyphenyl group, 4-n-heptyloxyphenyl group, 4-n-octyloxy Phenyl group, 4-n-nonyloxyphenyl group, 4-n-decyloxyphenyl group, 4-n-undecyloxyphenyl group, 4-n-dodecyloxyphenyl group, 4-n-tetradecyloxyphenyl group, 2,3-dimethoxyphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,5-diethoxyphenyl group, 2-methoxy-4-methylphenyl group, 2-methoxy-5-methylphenyl group, 2-methyl- 4-methoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3-methyl-5-methoxyphenyl group,
2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 3-trifluoromethylphenyl group, 4-triphenyl Fluoromethylphenyl group, 2,4-difluorophenyl group, 2,4-dichlorophenyl group, 3,4-difluorophenyl group, 3,4-dichlorophenyl group, 3,5-difluorophenyl group, 3,5-dichlorophenyl group, 3,4,5-trifluorophenyl group, 2-methyl-4-chlorophenyl group, 2-chloro-4-methylphenyl group, 3-chloro-4-methylphenyl group, 2-chloro-4-methoxyphenyl group, 3-methoxy-4-fluorophenyl group, 3-methoxy-4-chlorophenyl group, 3-fluoro-4 Methoxyphenyl group, 2,3,4,5,6-pentafluorophenyl group, 4-phenylphenyl group, 3-phenylphenyl group, 4- (4′-methylphenyl) phenyl group, 4- (4′-methoxy) Phenyl) phenyl group, 1-naphthyl group, 2-naphthyl group, 4-methyl-1-naphthyl group, 4-ethoxy-1-naphthyl group, 6-n-butyl-2-naphthyl group, 6-methoxy-2- Naphthyl group, 7-ethoxy-2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 2-tetracenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, 9, 9-di-n-propyl-2-fluorenyl group, 2-furyl group, 2-thienyl group, 5-n-propyl-2-thienyl group, 5-n-butyl-2-thienyl group, 5- n-hexyl-2-thienyl group, 5-n-octyl-2-thienyl group, 5-n-decyl-2-thienyl group, 5-n-tridecyl-2-thienyl group, 5-phenyl-2-thienyl group 5- (2′-thienyl) -2-thienyl group, 5- (5′-n-butyl-2′-thienyl) -2-thienyl group, 5- (5′-n-hexyl-2′-thienyl) ) Substitution of 2-thienyl group, 5- (5′-n-decyl-2′-thienyl) -2-thienyl group, 3-thienyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, etc. Or an unsubstituted aryl group can be mentioned.

Carbon in which two adjacent substituents selected from the combination of X _{1 to} X ₄ and / or the combination of X _{5 to} X _{8 in} the general formula (1) to the general formula (3) are bonded to each other and substituted. A substituted or unsubstituted benzene ring or a substituted or unsubstituted naphthalene ring may be formed together with the atoms.

When the formed benzene ring or naphthalene ring has a substituent, examples of the substituent include a halogen atom, a hydroxyl group, a cyano group, a nitro group, a linear, branched or cyclic alkyl group, a linear, branched or cyclic group. An alkoxy group, a linear, branched or cyclic alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxy group, or a substituted or unsubstituted aryl group,
Preferably, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a linear, branched or cyclic group having 2 to 20 carbon atoms An alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxy group having 2 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 4 to 20 carbon atoms.
Specific examples of the substituent that may be substituted on the benzene ring or naphthalene ring formed are exemplified by X _{1 to} X ₈ in the compounds represented by the general formula (1) to the general formula (3). Halogen atom, linear, branched or cyclic alkyl group, linear, branched or cyclic alkoxy group, linear, branched or cyclic alkoxyalkyl group, linear, branched or cyclic alkoxyalkoxy group, or substituted or unsubstituted Can be mentioned.
The formed naphthalene ring is a naphthalene ring condensed at the 2-position and 3-position, or at the 1-position and 2-position.

In the general formula (2) and the general formula (3), R ₁ and R ₂ each represents an alkyl group, preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert group Represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, such as a butyl group, an n-pentyl group, a cyclopentyl group, a cyclohexyl group, an n-octyl group or an n-decyl group, more preferably a methyl group Represents.

Specific examples of the compound represented by the general formula (1) according to the present invention include the following compounds, but the present invention is not limited thereto.

[Method for producing compounds of general formula (2) and general formula (3)]
The compound represented by the general formula (2) is, for example, a compound represented by the general formula (4) and a compound represented by the general formula (5), for example, a palladium catalyst [for example, bis ( Triphenylphosphine) palladium dichloride, tetrakis (triphenylphosphine) palladium, palladium acetate, palladium / carbon], and optionally, in the presence of a base, can be produced [see, for example, Chem. Rev. 95, 2457 (1995), Chem. Rev. , 102, 1359 (2002), Chem. Rev. 107, 133 (2007), Tetrahedron, 54, 263 (1998) can be referred to].

〔式中、Ｘ_１〜Ｘ_８、Ｒ_１は一般式（２）と同じ意味を表し、Ｍ_１はアルカリ金属、または金属含有基を表し、Ｚ_１はハロゲン原子または−ＯＳＯ_２−Ｒ_１０基を表す〕

同様に、一般式（３）で表される化合物は、例えば、一般式（６）で表される化合物と、一般式（７）で表される化合物を、触媒として、例えば、パラジウム触媒［例えば、ビス（トリフェニルフォスフィン）パラジウムジクロライド、テトラキス（トリフェニルフォスフィン）パラジウム、酢酸パラジウム、パラジウム／炭素］、および必要に応じて塩基の存在下で作用させることにより製造することができる。

[Wherein, X _{1 to} X ₈ and R ₁ represent the same meaning as in the general formula (2), M ₁ represents an alkali metal or a metal-containing group, and Z ₁ represents a halogen atom or —OSO ₂ —R ₁₀ group. Represents)

Similarly, the compound represented by the general formula (3) is, for example, a palladium catalyst [for example, a compound represented by the general formula (6) and a compound represented by the general formula (7) as a catalyst. , Bis (triphenylphosphine) palladium dichloride, tetrakis (triphenylphosphine) palladium, palladium acetate, palladium / carbon], and if necessary, in the presence of a base.

〔式中、Ｘ_１〜Ｘ_８、Ｒ_２は一般式（３）と同じ意味を表し、Ｍ_２はアルカリ金属、または金属含有基を表し、Ｚ_２はハロゲン原子または−ＯＳＯ_２−Ｒ_１０基を表す〕

尚、一般式（４）および一般式（７）において、Ｚ_１〜Ｚ_２で表されるハロゲン原子は、好ましくは、塩素原子、臭素原子、ヨウ素原子を表し、より好ましくは、臭素原子、ヨウ素原子を表す。

[Wherein, X _{1 to} X ₈ and R ₂ represent the same meaning as in the general formula (3), M ₂ represents an alkali metal or a metal-containing group, and Z ₂ represents a halogen atom or —OSO ₂ —R ₁₀ group. Represents)

In general formula (4) and general formula (7), the halogen atom represented by Z _{1 to} Z ₂ preferably represents a chlorine atom, a bromine atom or an iodine atom, more preferably a bromine atom or iodine. Represents an atom.

In the general formula (4) and the general formula _(7), in -OSO ₂ -R ₁₀ group represented by Z 1 ~Z _{2, R 10} is substituted with a substituted or unsubstituted aryl group or a halogen atom, Represents a linear, branched or cyclic alkyl group, more preferably a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a linear chain having 1 to 10 carbon atoms which may be substituted with a halogen atom. Represents a branched or cyclic alkyl group, and more preferably represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom.

Specific examples of the substituted or unsubstituted aryl group represented by R ₁₀ of the —OSO ₂ —R ₁₀ group include a phenyl group, a 4-methylphenyl group, and a 4-chlorophenyl group. .
In addition, specific examples of the linear, branched or cyclic alkyl group which may be substituted with the halogen atom represented by R ₁₀ of the —OSO ₂ —R ₁₀ group include, for example, a methyl group, an ethyl group, n- Alkyl groups such as propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, cyclopentyl group, cyclohexyl group, n-octyl group, n-decyl group, trifluoromethyl group, chloro Examples thereof include an alkyl group substituted with a halogen atom such as a difluoromethyl group, a dichlorofluoromethyl group, a pentafluoroethyl group, and an n-nonafluorobutyl group.
The —OSO ₂ —R ₁₀ group represented by Z _{1 to} Z ₄ is more preferably a benzenesulfonyloxy group, a p-toluenesulfonyloxy group, a methanesulfonyloxy group, or a trifluoromethanesulfonyloxy group.

Moreover, in General Formula (5) and General Formula (6), the alkali metal represented by M _{1 to} M ₂ preferably represents Li, Na, and K.
In general formula (5) and general formula (6), the metal-containing group represented by M _{1 to} M ₂ is preferably a boron metal-containing group, a tin metal-containing group, a magnesium metal-containing group, a zinc metal-containing group, Represents a manganese metal-containing group, a zirconium metal-containing group, an indium metal-containing group, a germanium metal-containing group, a lead metal-containing group, a bismuth metal-containing group, or a copper metal-containing group, more preferably a boron metal-containing group or a tin metal-containing group Represents a group, a magnesium metal-containing group, or a zinc metal-containing group.

The boron metal-containing group is preferably a group represented by the general formula (M-1).
_{-B (OR 0) (OR 00} ) (M-1)
(Wherein R ₀ and R ₀₀ represent a hydrogen atom or an alkyl group, and R ₀ and R ₀₀ may be bonded to each other to form a cyclic alkylene group or an arylene group)
In General Formula (M-1), R ₀ and R ₀₀ each represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
When R ₀ and R ₀₀ are bonded to each other to represent a cyclic alkylene group, it preferably represents a cyclic alkylene group having 2 to 10 carbon atoms.
In addition, when R ₀ and R ₀₀ are bonded to each other to represent an arylene group, it preferably represents a 1,2-phenylene group having 6 to 10 carbon atoms which may be substituted with an alkyl group.

The tin metal-containing group is preferably a group represented by the general formula (M-2).
_{-Sn (R 000) 3 (M} -2)
(In the formula, R ₀₀₀ represents an alkyl group)
In General Formula (M-2), _R000 represents an alkyl group, and preferably represents an alkyl group having 1 to 8 carbon atoms.

The magnesium metal-containing group is preferably a group represented by the general formula (M-3).
-MgZ ₀ (M-3)
(In the formula, Z ₀ represents a halogen atom)
In General Formula (M-3), Z ₀ represents a halogen atom, preferably a chlorine atom, a bromine atom, or an iodine atom.

The zinc metal-containing group is preferably a group represented by the general formula (M-4).
-ZnZ ₀₀ (M-4)
(In the formula, Z ₀₀ represents a halogen atom)
In General Formula (M-4), Z ₀₀ represents a halogen atom, preferably a chlorine atom, a bromine atom, or an iodine atom.

In the production method of the present invention, first, the compound represented by the general formula (2) or the general formula (3) is allowed to act with an acid.
The acid is preferably a protonic acid, for example, an alkyl carboxylic acid such as acetic acid, chloroacetic acid, fluoroacetic acid, trifluoroacetic acid, such as methanesulfonic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, n -An alkyl sulfonic acid such as nonafluorobutane sulfonic acid, more preferably an alkyl sulfonic acid, and still more preferably trifluoromethane sulfonic acid.

The amount of the acid used is not particularly limited, but it is sufficient if there is a necessary amount for the reaction. In general, it is 1 mole per mole of the compound represented by the general formula (2) or the general formula (3). It is preferable to use the above.
Moreover, an acid can also be used as a reaction solvent. In general, the amount of the acid used is more preferably 1 to 10000 times mol of the compound represented by the general formula (2) or the general formula (3). Use about.

The reaction temperature when the compound represented by the general formula (2) or the general formula (3) is allowed to act with an acid is not particularly limited, but is generally about -20 ° C to 150 ° C, preferably, It implements at about 0 degreeC-100 degreeC.
The reaction with the acid can be carried out under atmospheric pressure or under pressure.
The reaction time is not particularly limited, and the reaction process is carried out for a desired time by determining the remaining amount of the compound represented by the general formula (2) or the general formula (3) as a raw material by various analytical methods. In general, when the reaction temperature is about −20 ° C. to 150 ° C., the reaction is performed in about 30 minutes to 100 hours.

After reacting the compound represented by the general formula (2) or the general formula (3) with an acid, the reaction mixture can be reacted with water or ice water to obtain a precipitated solid.
In the production method of the present invention, the compound represented by the general formula (1) can be produced by further reacting this solid with a base.

In addition, after reacting the compound represented by the general formula (2) or the general formula (3) with an acid, the reaction mixture obtained is subsequently reacted with a base, thereby being represented by the general formula (1). Can be produced.
The base is not particularly limited, but is preferably a nitrogen-containing organic base such as pyridine, quinoline, picoline, ammonia, triethylamine, diisopropylethylamine, and more preferably pyridine.

The amount of the base to be used is not particularly limited, but it is sufficient if there is a necessary amount for the reaction. In general, the amount of the base is 1 mol per mol of the compound represented by the general formula (2) or the general formula (3) It is preferable to use the above.
In addition, a base can also be used as a reaction solvent. In general, the amount of the base used is more preferably 1 to 10,000-fold mol with respect to the compound represented by the general formula (2) or the general formula (3). Use about.
Moreover, when making it act with a base, it can also implement by coexistence of water if desired.

Although it does not specifically limit regarding the reaction temperature at the time of making it act with a base, Generally, it implements at about 10 to 150 degreeC, Preferably it is about 50 to 100 degreeC.
The reaction with the base can be carried out under atmospheric pressure or under pressure.
The reaction time is not particularly limited, and the progress of the reaction can be carried out for a desired time by obtaining the amount of the compound represented by the general formula (1) as a product by various analysis methods. Generally, when the reaction temperature is about 10 ° C to 150 ° C, the reaction is carried out in about 10 minutes to 50 hours.

Furthermore, in the production method of the present invention, an organic solvent may be used in combination when desired to react with an acid or a base.
Examples of the organic solvent include organic solvents such as ether solvents such as diethyl ether, dioxane, tetrahydrofuran and anisole, and hydrocarbon solvents such as hexane and octane.
These organic solvents may be used alone or in combination.

The compound represented by the general formula (1) thus produced can be purified by a recrystallization method, a column chromatography method, a purification method such as a sublimation purification method, or a combination of these methods.

The compound represented by the general formula (1) can be used as various functional materials.

For example, when the compound represented by the general formula (1) is used in an organic transistor, the purity is increased by using a recrystallization method, a column chromatography method, a purification method such as a sublimation purification method, or a combination of these methods. It is preferred to use the compounds.
An organic transistor using a compound represented by the general formula (1) manufactured by the manufacturing method of the present invention for an organic semiconductor layer is, for example, a liquid crystal display element, an organic electroluminescent element, electronic paper, various sensors, RFIDs ( radio frequency identification cards).

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

(Example 1) Production of Compound of Example Compound No. 1 Under a nitrogen atmosphere, a compound represented by the formula (2-1) (544 mg, 2 mmol) was added to trifluoromethanesulfonic acid (10 ml), and at 25 ° C, Stir for 40 hours.

反応混合物を水（５０ｍｌ）に加えた後、析出した固体を濾別した。
この固体をピリジン（４０ｍｌ）に加えた後、７０℃で１０時間撹拌した。反応混合物に、塩化メチレン（１５０ｍｌ）を加え、有機層を分離した後、有機層を水（５０ｍｌ）で洗浄した。
有機層から塩化メチレンを留去した後、残渣をシリカゲルカラムクロマトグラフィー〔展開液：トルエン／ヘキサン（体積比：３／１）〕にて分離精製し、例示化合物番号１の化合物を４２２ｍｇ得た。収率８８％

The reaction mixture was added to water (50 ml), and the precipitated solid was filtered off.
This solid was added to pyridine (40 ml) and then stirred at 70 ° C. for 10 hours. Methylene chloride (150 ml) was added to the reaction mixture, the organic layer was separated, and the organic layer was washed with water (50 ml).
After distilling off methylene chloride from the organic layer, the residue was separated and purified by silica gel column chromatography [developing solution: toluene / hexane (volume ratio: 3/1)] to obtain 422 mg of the compound of Exemplary Compound No. 1. Yield 88%

Example 2 Production of Compound of Illustrative Compound No. 5 In Example 1, the compound (2 mmol) represented by the formula (2-5) was used instead of the compound represented by the formula (2-1). Except that, the compound of Exemplified Compound No. 5 was obtained according to the procedure described in Example 1. Yield 84%

Example 3 Production of Compound of Illustrative Compound No. 19 In Example 1, the compound represented by the formula (2-19) (2 mmol) was used instead of the compound represented by the formula (2-1). Except that, the compound of Exemplified Compound No. 19 was obtained according to the procedure described in Example 1. Yield 78%

Example 4 Production of Compound of Illustrative Compound No. 29 In Example 1, the compound (2 mmol) represented by the formula (2-29) was used instead of the compound represented by the formula (2-1). Except that, Exemplified Compound No. 29 was obtained according to the procedure described in Example 1. Yield 82%

Example 5 Production of Compound of Illustrative Compound No. 37 In Example 1, instead of the compound represented by Formula (2-1), the compound represented by Formula (3-37) (2 mmol) was used. Except that, the compound of Exemplified Compound No. 37 was obtained according to the procedures described in Example 1. Yield 80%

Example 6 Production of Compound of Illustrative Compound No. 48 In Example 1, instead of the compound represented by Formula (2-1), the compound represented by Formula (2-48) (2 mmol) was used. Except that, the compound of Exemplified Compound No. 48 was obtained according to the procedures described in Example 1. Yield 84%

Example 7 Production of Compound of Example Compound No. 57 In Example 1, the compound (2 mmol) represented by the formula (2-57) was used instead of the compound represented by the formula (2-1). Except that, the compound of Exemplified Compound No. 57 was obtained according to the procedures described in Example 1. Yield 76%

（実施例８） 例示化合物番号６９の化合物の製造
窒素雰囲気下、式（２−６９）で表される化合物（８４８ｍｇ、２ミリモル）を、トリフルオロメタンスルフォン酸（２０ｍｌ）に加え、２５℃で、１５時間撹拌した。

(Example 8) Production of Compound of Example Compound No. 69 Under a nitrogen atmosphere, a compound represented by the formula (2-69) (848 mg, 2 mmol) was added to trifluoromethanesulfonic acid (20 ml) at 25 ° C. Stir for 15 hours.

The reaction mixture was added to water (100 ml), and the precipitated solid was filtered off.
This solid was added to pyridine (50 ml) and then stirred at 70 ° C. for 5 hours. Water (150 ml) was added to the reaction mixture, and the precipitated solid was filtered off and washed with water (50 ml) and methanol (30 ml).
The washed solid was dried and purified by sublimation under vacuum (5 × 10 ⁻⁴ Pa) at 250 ° C. to obtain 610 mg of the compound of exemplified compound number 69. Yield 78%

Example 9 Production of Compound of Illustrative Compound No. 71 In Example 1, the compound represented by the formula (2-71) (2 mmol) was used instead of the compound represented by the formula (2-1). Except that, Exemplified Compound No. 71 was obtained according to the procedure described in Example 1. Yield 76%

Example 10 Production of Compound of Illustrative Compound No. 76 In Example 8, the compound (2 mmol) represented by the formula (2-76) was used instead of the compound represented by the formula (2-69). Except that, Exemplified Compound No. 76 was obtained according to the procedure described in Example 8. Yield 85%

Example 11 Production of Compound with Exemplified Compound No. 85 In Example 8, the compound (2 mmol) represented by the formula (2-85) was used instead of the compound represented by the formula (2-69). Except that, Exemplified Compound No. 85 was obtained according to the procedure described in Example 8. Yield 88%

Example 12 Production of Compound of Illustrative Compound No. 88 In Example 8, the compound (2 mmol) represented by the formula (2-88) was used instead of the compound represented by the formula (2-69). Except that, Exemplified Compound No. 88 was obtained according to the procedures described in Example 8. Yield 85%

Example 13 Production of Compound of Example Compound No. 90 In Example 8, the compound represented by the formula (2-90) (2 mmol) was used instead of the compound represented by the formula (2-69). Except for the above, the compound of Example Compound No. 90 was obtained according to the procedures described in Example 8. Yield 81%

(Comparative Example) Production of Compound of Example Compound No. 90 In a nitrogen atmosphere, the compound represented by formula (D) (744 mg) and iodine (16.1 g) were added to chloroform (60 ml), and the mixture was refluxed for 11 hours. Stir.

After cooling the reaction mixture to room temperature, a saturated aqueous solution of sodium hydrogen sulfite (90 ml) was added, and the precipitated solid was filtered off. This solid was further washed with water (50 ml) and methanol (30 ml).
The washed solid was dried and purified by sublimation at 250 ° C. under vacuum (5 × 10 ⁻⁴ Pa) to obtain 205 mg of Compound No. 69. Yield 30%
This production method was found to have a lower yield than the method described in Example 13 of the present invention.

According to the method of the present invention, it has become possible to provide a novel method capable of producing a compound useful as various functional materials (for example, materials for organic transistors) in high yield.
Further, an organic transistor using a compound produced by the method of the present invention for an organic semiconductor layer has high charge mobility, a large current on / off ratio, and excellent storage stability. It can be used for organic electroluminescence devices, electronic paper, various sensors, RFIDs (radio frequency identification cards) and the like.

Claims (1)

In the method for producing the compound represented by the general formula (1), the compound represented by the general formula (2) or the general formula (3) is allowed to act with an acid, and then the resulting compound is allowed to act with a base. The method to manufacture the compound represented by General formula (1).

[Wherein, X _{1 to} X ₈ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, or a linear chain. Represents a branched or cyclic alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxy group, or a substituted or unsubstituted aryl group, and further selected from a combination of X _{1 to} X ₄ and / or X _{5 to} X ₈ Two adjacent substituents may be bonded to each other to form a substituted or unsubstituted benzene ring or a substituted or unsubstituted naphthalene ring together with the substituted carbon atom, and R ₁ and R ₂ Each independently represents an alkyl group.