JP5716821B2 - Heteroacene derivatives, precursor compounds thereof, and methods for producing the same - Google Patents

Description

  The present invention relates to a heteroacene derivative that can be developed into an electronic material such as an organic semiconductor, its use, and a production method thereof. The present invention further relates to di (alkylchalcogeno) diarylethyne derivatives and di (alkylchalcogeno) diarylethylene derivatives, which are precursor compounds of the heteroacene derivative, and methods for producing them.

  Organic semiconductor devices typified by organic thin film transistors have recently attracted attention because they have features not found in inorganic semiconductor devices such as energy saving, low cost, and flexibility. This organic semiconductor device is composed of several kinds of materials such as an organic semiconductor active phase, a substrate, an insulating phase, and an electrode. Among them, the organic semiconductor active phase responsible for charge carrier movement has a central role of the device. . The organic semiconductor device performance is affected by the carrier mobility of the organic material constituting the organic semiconductor active phase.

  As a method for producing an organic semiconductor active phase, there are generally known a vacuum deposition method in which an organic material is vaporized under a high temperature vacuum and a coating method in which the organic material is dissolved in an appropriate solvent and applied. Yes. In the coating method, the coating can be carried out using a printing technique without using high temperature and high vacuum conditions. Therefore, the coating method is an economically preferable process because it can greatly reduce the manufacturing cost of device fabrication by printing. However, conventionally, there has been a problem that a material having higher performance as an organic semiconductor device has a difficulty in forming an organic semiconductor active phase by a coating method.

  For example, it has been reported that a crystalline material such as pentacene has a carrier mobility as high as that of amorphous silicon and exhibits excellent organic semiconductor device characteristics (for example, see Non-Patent Document 1). An attempt to manufacture an organic semiconductor device by a coating method by dissolving polyacene such as pentacene has also been reported (see, for example, Patent Document 1). However, pentacene has low cohesion due to its strong cohesiveness, and conditions such as high-temperature heating are required to apply the coating method, and the solution of pentacene is very easily oxidized by air. The application of was difficult in terms of process and economy. Self-assembled materials such as poly- (3-hexylthiophene) are soluble in a solvent, and although organic semiconductor device fabrication by a coating method has been reported, the carrier mobility is 1 lower than that of a crystalline low molecular compound. Since it is a little lower (for example, refer nonpatent literature 2), there was a problem that the characteristic of the obtained organic semiconductor device was low.

  Further, heteroacene in which a dinaphtho ring and a thienothiophene ring are condensed has been reported, but there are problems that the molecular long axis is short and the solubility is low (for example, see Non-Patent Document 3).

WO2003 / 016599

“Journal of Applied Physics” (USA), 2002, 92, 5259-5263. “Science”, (USA), 1998, 280, 1741-1744. “Journal of American Chemical Society” (USA), 2007, 129, 2224-2225.

  Therefore, in view of the problems of the above-described conventional technology, the present invention has a heteroacene derivative having excellent oxidation resistance and capable of forming an organic semiconductor active phase by a coating method, and an oxidation resistant organic semiconductor material using the same. An object of the present invention is to provide an organic thin film. Another object of the present invention is to provide di (alkylchalcogeno) diarylethyne derivatives and di (alkylchalcogeno) diarylethylene derivatives useful as precursors of the heteroacene derivatives, and methods for producing them.

  As a result of intensive studies to solve the above problems, the present inventors have found a novel heteroacene derivative of the present invention. In addition, since the heteroacene derivative has a long molecular long axis, it has excellent performance and at the same time excellent oxidation resistance, can be applied by a coating method, and can easily produce a crystalline thin film stably. Therefore, the present inventors have found an oxidation-resistant organic semiconductor material containing the heteroacene derivative and an organic thin film thereof and completed the present invention.

  Furthermore, the present inventors have found a novel precursor compound capable of efficiently producing the heteroacene derivative, namely a specific di (alkylchalcogeno) diarylethyne derivative and di (alkylchalcogeno) diarylethylene derivative, and The inventors have found a method for efficiently producing such di (alkylchalcogeno) diarylethyne derivatives and di (alkylchalcogeno) diarylethylene derivatives, and have completed the present invention.

  The present invention is described in detail below. The description includes a heteroacene derivative and a process for producing the same, a di (alkylchalcogeno) diarylethyne derivative and a di (alkylchalcogeno) diarylethylene derivative which are precursors of the heteroacene derivative and a process for producing them, and oxidation resistance including the heteroacene derivative The conductive organic semiconductor material and the organic thin film thereof will be described.

(Heteroacene derivative)
The heteroacene derivative of the present invention is represented by the following general formula (1).

[Wherein T ¹ and T ² are the same or different and each represents a sulfur atom, a selenium atom or a tellurium atom, and rings A and B are the same or different, and the following general formulas (A-1) and (A-2 Or a structure represented by (A-3), and the present invention is characterized by a structure represented by formula (A-2).)

(Wherein the substituents R ^{1 to} R ⁸ are the same or different, a hydrogen atom, a fluorine atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 4 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, It indicates an alkynyl group having 2 to 30 carbon atoms, n is an integer of 0 or 1. However, when n is 0, the substituents ^R 1 to R ⁴ except in the case of simultaneously hydrogen.)
The substituent of the heteroacene derivative represented by the general formula (1) of the present invention will be described.

The alkyl group having 1 to 30 carbon atoms in the substituents R ^{1 to} R ⁸ is not particularly limited, and examples thereof include a methyl group, a propyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, a hexyl group, a heptyl group, Chain alkyl groups such as octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, 2-ethylhexyl group; cyclic such as cyclooctyl group Alkyl group; perfluoroalkyl group such as trifluoromethyl group, pentafluoroethyl group, perfluorooctyl group, perfluorododecyl group, perfluorooctadecyl group, perfluorocyclohexyl group, perfluorocyclooctyl group; pentadecafluorooctyl group , Octadeca Fluoro A halogenated alkyl group in which a part of hydrogen such as a decyl group and a 2-ethylperfluorohexyl group is substituted with fluorine can be mentioned, preferably an alkyl group having 6 to 30 carbon atoms, more preferably a dodecyl group. , Octadecyl group, perfluorododecyl group and perfluorooctadecyl group, particularly preferably dodecyl group and perfluorododecyl group.

The aryl group having 4 to 30 carbon atoms in the substituents R ^{1 to} R ⁸ is not particularly limited, and examples thereof include a phenyl group, p-tolyl group, p- (octyl) phenyl group, p- (dodecyl) phenyl group, p- (Cyclohexyl) phenyl group, m- (octyl) phenyl group, m- (dodecyl) phenyl group, p-fluorophenyl group, pentafluorophenyl group, p- (trifluoromethyl) phenyl group, p- (perfluorooctyl) Phenyl group, p- (perfluorododecyl) phenyl group, m- (perfluorododecyl) phenyl group, 2-thienyl group, 5- (dodecyl) -2-thienyl group, 2,2′-bithienyl-5-group, List biphenyl group, perfluorobiphenyl group, 1-naphthyl group, 2-naphthyl group, 1-perfluoronaphthyl group, anthracenyl group, etc. Preferably a phenyl group, a p- (octyl) phenyl group, a p- (perfluorooctyl) phenyl group, a 5- (dodecyl) -2-thienyl group, and more preferably a phenyl group.

The alkenyl group having 2 to 30 carbon atoms in the substituents R ^{1 to} R ⁸ is not particularly limited. For example, ethenyl group, methyl ethenyl group, isopropyl ethenyl group, tert-butylethenyl group, (octyl) ethenyl group, (decyl) Ethenyl, (dodecyl) ethenyl, (trifluoromethyl) ethenyl, (perfluorooctyl) ethenyl, (perfluorodecyl) ethenyl, (perfluorododecyl) ethenyl, phenylethenyl, {p- ( (Hexyl) phenyl} ethenyl group, {p- (octyl) phenyl} ethenyl group, {p- (dodecyl) phenyl} ethenyl group, {m- (dodecyl) phenyl} ethenyl group, 2-phenyl-1,2-difluoroe Tenenyl group, 2-phenyl-1,2-dimethylethenyl group, diphenylethenyl group, triphenyl group Enylethenyl, naphthylethenyl, anthracenylethenyl, benzylethenyl, phenyl (methyl) ethenyl, (perfluorophenyl) ethenyl, {p- (trifluoromethyl) phenyl} ethenyl, {5- (hexyl) ) Thienyl-2-} ethenyl group, {5- (perfluorohexyl) thienyl-2-} ethenyl group, etc., preferably (octyl) ethenyl group, (decyl) ethenyl group, (perfluorooctyl) An ethenyl group, a (perfluorodecyl) ethenyl group, and the like. The alkenyl group having 2 to 30 carbon atoms may be either a trans isomer or a cis isomer, or may be a mixture of any ratio thereof.

The alkynyl group having 2 to 30 carbon atoms in the substituents R ^{1 to} R ⁸ is not particularly limited. For example, ethynyl group, methylethynyl group, isopropylethynyl group, tert-butylethynyl group, (octyl) ethynyl group, (decyl) ) Ethynyl group, (trifluoromethyl) ethynyl group, (perfluorooctyl) ethynyl group, (perfluorodecyl) ethynyl group, phenylethynyl group, {p- (octyl) phenyl} ethynyl group, {p- (dodecyl) phenyl } Ethynyl group, {m- (dodecyl) phenyl} ethynyl group, naphthylethynyl group, anthracenylethynyl group, benzylethynyl group, perfluorophenylethynyl group, {p- (trifluoromethyl) phenyl} ethynyl group, {p -(Perfluorooctyl) phenyl} ethynyl group, {p- (per (Luorododecyl) phenyl} ethynyl group, {m- (perfluorododecyl) phenyl} ethynyl group, 5- (hexyl) thienyl-2-} ethynyl group, {5- (perfluorohexyl) thienyl-2-} ethynyl group, etc. Preferred examples include (octyl) ethynyl group, (decyl) ethynyl group, (perfluorooctyl) ethynyl group, (perfluorodecyl) ethynyl group, and the like.

Among these substituents R ^{1 to} R ^8, a hydrogen atom, a fluorine atom, an alkyl group having 7 to 30 carbon atoms, and an alkynyl group having 2 to 30 carbon atoms are particularly preferable, and a hydrogen atom, a fluorine atom, a dodecyl group, and octadecyl are preferred. Group, perfluorododecyl group, perfluorooctadecyl group, (decyl) ethynyl group, (perfluorodecyl) ethynyl group and the like are preferable.

The substituents T ¹ and T ² are a sulfur atom, a selenium atom, and a tellurium atom, and among them, a sulfur atom is preferable.

  N in (A-1) in the general formula (1) is an integer of 0 or 1, and preferably 1 among them.

As the substitution pattern of the substituents R ^{1 to} R ⁸ of the heteroacene derivative represented by the general formula (1) of the present invention, R ¹ and R ² are the same or different, and a fluorine atom, an alkyl group having 1 to 30 carbon atoms, It is at least one group selected from the group consisting of an aryl group having 4 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and an alkynyl group having 2 to 30 carbon atoms, and R ³ and R ⁴ are the same Or, it is preferably at least one group selected from the group consisting of a hydrogen atom and a fluorine atom. The substituent R ⁵ is a group selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, an aryl group having 4 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and an alkynyl group having 2 to 30 carbon atoms. And R ⁶ is preferably at least one group selected from the group consisting of a hydrogen atom and an alkyl group having 7 to 30 carbon atoms. Further, the substituents R ⁷ and R ⁸ are the same or different and are each composed of a hydrogen atom, a fluorine atom, an alkyl group having 7 to 30 carbon atoms, an aryl group having 4 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms. It is preferably at least one group selected from the group.

  The rings A and B of the heteroacene derivative represented by the general formula (1) of the present invention will be described. Rings A and B are the same or different and have a structure represented by general formula (A-1), (A-2), or (A-3), among which general formulas (A-1), (A -2) is preferred. In particular, it is preferable that the rings A and B have the structure represented by the general formula (A-1) or (A-2) at the same time. Rings A and B particularly preferably have a structure in which n is 1 in formula (A-1). Moreover, when one of the rings A and B has a structure represented by the general formula (A-3), the other is preferably a ring represented by (A-1). The present invention is characterized in that the rings A and B of the heteroacene derivative represented by the general formula (1) have a structure represented by the general formula (A-2). When rings A and B have the structure of general formula (A-2), the structure of the heteroacene derivative represented by general formula (1) is preferably that represented by the following general formula (12).

(Here, the substituents T ¹ , T ² , R ⁵ , and R ⁶ have the same meaning as the substituent represented by the general formula (1).)
Among these, the heteroacene derivative represented by the general formula (1) of the present invention is such that the heteroacene derivative, the oxidation-resistant organic semiconductor material containing the heteroacene derivative, and the organic thin film thereof exhibit high oxidation resistance and carrier mobility. Therefore, the following compounds, wherein the rings A and B are the same or different and have the structure represented by the general formula (A-2), are preferred,

Particularly preferred are the following compounds, wherein the rings A and B are the same or different and have a structure represented by the general formula (A-2).

(Di (alkylchalcogeno) diarylethyne derivatives)
Next, a di (alkylchalcogeno) diarylethyne derivative that is a precursor compound of the heteroacene derivative represented by the general formula (1) of the present invention will be described.

  The di (alkylchalcogeno) diarylethyne derivative which is a precursor compound of the heteroacene derivative represented by the general formula (1) of the present invention is represented by the following general formula (2).

(Here, the substituents R ⁹ and R ¹⁰ represent an alkyl group having 1 to 8 carbon atoms, and the substituents T ¹ and T ² and rings A and B are the same as the substituent and ring represented by the general formula (1) Shows significance.)
The alkyl group having 1 to 8 carbon atoms in the substituents R ⁹ and R ¹⁰ is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a benzyl group, preferably a methyl group and a benzyl group. Group, more preferably a methyl group.

  The rings A and B of the di (alkylchalcogeno) diarylethyne derivative represented by the general formula (2) will be described. Rings A and B have a structure represented by general formula (A-1), (A-2), or (A-3), and among them, represented by general formula (A-1) or (A-3) The structure is preferred. Rings A and B particularly preferably have a structure in which n is 1 in formula (A-1). In the present invention, the rings A and B are most preferably a structure represented by the general formula (A-2).

  The di (alkylchalcogeno) diarylethyne derivative represented by the general formula (2) of the present invention is the following compound, wherein the rings A and B are the same or different and represented by the general formula (A-2) Compounds having a structure are preferred,

Particularly preferred are the following compounds, wherein the rings A and B are the same or different and have a structure represented by the general formula (A-2).

(Dihalodiaryl ethyne derivatives)
Next, the dihalodiaryl ethyne derivative which is a raw material compound of the di (alkylchalcogeno) diaryl ethyne derivative represented by the general formula (2) of the present invention will be described.

  The dihalodiaryl ethyne derivative which is a raw material compound of the di (alkylchalcogeno) diaryl ethyne derivative represented by the general formula (2) of the present invention is represented by the following general formula (3).

(Here, the substituents X ¹ and X ² represent a bromine atom, an iodine atom, and a chlorine atom, and the rings A and B have the same meaning as the ring represented by the general formula (2).)
The substituents X ¹ and X ² represent a bromine atom, an iodine atom or a chlorine atom, preferably a bromine atom or an iodine atom, and particularly preferably a bromine atom.

  The rings A and B of the dihalodiarylethyne derivative represented by the general formula (3) will be described. Rings A and B have a structure represented by general formula (A-1), (A-2), or (A-3), and among them, represented by general formula (A-1) or (A-3) The structure is preferred. In the present invention, the rings A and B are most preferably a structure represented by the general formula (A-2).

  The dihalodiarylethyne derivative represented by the general formula (3) of the present invention is the following compound, wherein the rings A and B are the same or different and have the structure represented by the general formula (A-2) Is preferred,

Particularly preferred are the following compounds, wherein the rings A and B are the same or different and have a structure represented by the general formula (A-2).

(Di (alkylchalcogeno) diarylethylene derivatives)
Next, a di (alkylchalcogeno) diarylethylene derivative that is a precursor compound of the heteroacene derivative represented by the general formula (1) of the present invention will be described.

The di (alkylchalcogeno) diarylethylene derivative which is a precursor compound of the heteroacene derivative represented by the general formula (1) of the present invention is represented by the following general formula (4).

(Here, the substituents R ¹¹ and R ¹² represent an alkyl group having 1 to 8 carbon atoms, and the substituents T ¹ and T ² and rings A and B are the same as the substituent and ring represented by the general formula (1) Shows significance.)
The alkyl group having 1 to 8 carbon atoms in the substituents R ¹¹ and R ¹² is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a benzyl group, preferably a methyl group and a benzyl group. Group, more preferably a methyl group.

  The rings A and B of the di (alkylchalcogeno) diarylethylene derivative represented by the general formula (4) will be described. Rings A and B have a structure represented by general formula (A-1), (A-2), or (A-3), and among them, a structure represented by general formula (A-1) is preferable. Rings A and B particularly preferably have a structure in which n is 1 in formula (A-1). In the present invention, the rings A and B are most preferably a structure represented by the general formula (A-2).

  The di (alkylchalcogeno) diarylethylene derivative represented by the general formula (4) is preferably a trans isomer, but may be either a trans isomer or a cis isomer, and a mixture of any ratio thereof. There may be.

  The di (alkylchalcogeno) diarylethylene derivative represented by the general formula (4) of the present invention is the following compound, wherein the rings A and B are the same or different and represented by the general formula (A-2) Compounds having a structure are preferred,

Particularly preferred are the following compounds, wherein the rings A and B are the same or different and have a structure represented by the general formula (A-2).

(Formyl (alkyl chalcogeno) arene derivative)
Next, the formyl (alkyl chalcogeno) arene derivative, which is a raw material compound of the di (alkylchalcogeno) diarylethylene derivative represented by the general formula (4) of the present invention, will be described.

  The formyl (alkylchalcogeno) arene derivative, which is a raw material compound of the di (alkylchalcogeno) diarylethylene derivative represented by the general formula (4) of the present invention, is represented by the following general formula (5).

(Here, the substituents R ¹¹ and T ¹ and ring A have the same meaning as the substituent and ring represented by formula (4).)
The ring A of the formyl (alkylchalcogeno) arene derivative represented by the general formula (5) will be described. Ring A has a structure represented by general formula (A-1), (A-2), or (A-3), and among them, a structure represented by general formula (A-1) is preferable. Further, ring A particularly preferably has a structure in which n is 1 in formula (A-1). In the present invention, the ring A is most preferably a structure represented by the general formula (A-2).

  The formyl (alkyl chalcogeno) arene derivative represented by the general formula (5) of the present invention is preferably the following compound, wherein the ring A has a structure represented by the general formula (A-2).

(Halo (alkylchalcogeno) arene derivatives)
Next, a halo (alkylchalcogeno) arene derivative that is a raw material compound of the formyl (alkylchalcogeno) arene derivative represented by the general formula (5) of the present invention will be described.

  The halo (alkylchalcogeno) arene derivative, which is a raw material compound of the formyl (alkylchalcogeno) arene derivative represented by the general formula (5) of the present invention, is represented by the following general formula (6).

(Here, the substituent X ³ represents a bromine atom, an iodine atom, or a chlorine atom, and the substituents R ¹¹ and T ¹ and ring A have the same meaning as the substituent and ring represented by the general formula (5).)
The substituent X ³ represents a bromine atom, an iodine atom, or a chlorine atom, preferably bromine or iodine, and the halo (alkylchalcogeno) arene derivative represented by the general formula (6) has an X ³ of bromine and iodine. It may be a mixture of any ratio.

  The ring A of the halo (alkylchalcogeno) arene derivative represented by the general formula (6) will be described. Ring A has a structure represented by general formula (A-1), (A-2), or (A-3), and among them, a structure represented by general formula (A-1) is preferable. Further, ring A particularly preferably has a structure in which n is 1 in formula (A-1). In the present invention, the ring A is most preferably a structure represented by the general formula (A-2).

  The halo (alkylchalcogeno) arene derivative represented by the general formula (6) of the present invention is preferably the following compound, wherein the ring A has a structure represented by the general formula (A-2).

(Dihalochalcogenophenylaryl derivatives)
Next, a dihalochalcogenophenylaryl derivative that is a precursor compound of the heteroacene derivative represented by the general formula (1) of the present invention will be described.

  The dihalochalcogenophenylaryl derivative which is a precursor compound of the heteroacene derivative represented by the general formula (1) of the present invention is represented by the following general formula (7).

(Here, the substituents X ² and X ⁴ represent a bromine atom, an iodine atom, and a chlorine atom, and the substituent T ¹ and the rings A and B have the same meaning as the substituent and the ring represented by the general formula (1). .)
Substituents X ² is a bromine atom, an iodine atom, shows a chlorine atom, preferably a bromine atom, an iodine atom, particularly preferably a bromine atom. Substituent X ⁴ is a bromine atom, an iodine atom, shows a chlorine atom, preferably a bromine atom, an iodine atom, particularly preferably a iodine atom.

  The rings A and B of the dihalochalcogenophenylaryl derivative represented by the general formula (7) will be described. Rings A and B have a structure represented by general formula (A-1), (A-2), or (A-3), and among them, a structure represented by general formula (A-2) is preferable. In the present invention, the rings A and B are most preferably a structure represented by the general formula (A-2).

  The dihalochalcogenophenylaryl derivative represented by the general formula (7) of the present invention is the following compound, wherein the rings A and B are the same or different and have the structure represented by the general formula (A-2). Certain compounds are preferred,

Particularly preferred are the following compounds, wherein the rings A and B are the same or different and have a structure represented by the general formula (A-2).

(Method for producing heteroacene derivative)
A method for producing the heteroacene derivative represented by the general formula (1) of the present invention will be described.

  The heteroacene derivative represented by the general formula (1) of the present invention can be produced by reacting the di (alkylchalcogeno) diarylethyne derivative represented by the general formula (2) with a halogen derivative.

  The halogen derivative is not particularly limited as long as it can halogenate an unsaturated bond. For example, iodine, bromine, chlorine, N-iodosuccinimide (hereinafter abbreviated as NIS), N-bromosuccinimide (hereinafter abbreviated as NBS). N-chlorosuccinimide (hereinafter abbreviated as NCS) and the like, preferably iodine and bromine, particularly preferably iodine. The amount of the halogen derivative used is preferably from 0.9 to 30 equivalents, more preferably from 1.5 to 20 equivalents, particularly preferably from 1 equivalent of the di (alkylchalcogeno) diarylethyne derivative represented by the general formula (2). Is 2 to 15 equivalents.

  The reaction with the halogen derivative is preferably carried out in a solvent. The solvent to be used is not particularly limited. For example, dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, dichlorobenzene, tetrahydrofuran (hereinafter abbreviated as THF), diethyl ether (hereinafter ether) Abbreviation), methyl-tert-butyl ether, ethyl-tert-butyl ether, ethylene glycol dimethyl ether, dioxane, toluene, hexane, cyclohexane and the like, particularly preferably dichloromethane and chloroform. These solvents may be used alone or as a mixture of two or more. The reaction temperature is preferably 20 to 150 ° C, particularly preferably 30 to 70 ° C. The reaction time is preferably 1 to 24 hours, particularly preferably 2 to 12 hours. The progress of the reaction can be monitored by analyzing with thin layer chromatography or gas chromatography.

  Another method for producing the heteroacene derivative represented by the general formula (1) of the present invention will be described.

  The heteroacene derivative represented by the general formula (1) of the present invention can be produced by reacting the di (alkylchalcogeno) diarylethylene derivative represented by the general formula (4) with a halogen derivative.

  The halogen derivative is not particularly limited as long as the unsaturated bond can be halogenated, and examples thereof include iodine, bromine, chlorine, NIS, NBS, NCS, etc., preferably iodine and bromine, particularly preferably. It is iodine. The amount of the halogen derivative used is preferably from 0.9 to 30 equivalents, more preferably from 1.5 to 20 equivalents, particularly preferably from 1 equivalent of the di (alkylchalcogeno) diarylethylene derivative represented by the general formula (4). Is 2 to 15 equivalents.

  The reaction with the halogen derivative is preferably carried out in a solvent. The solvent to be used is not particularly limited. For example, dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, dichlorobenzene, THF, ether, methyl-tert-butyl ether, ethyl-tert-butyl ether. , Ethylene glycol dimethyl ether, dioxane, toluene, hexane, cyclohexane and the like, particularly preferably dichloromethane and chloroform. These solvents may be used alone or as a mixture of two or more. The reaction temperature is preferably 20 to 150 ° C, particularly preferably 30 to 70 ° C. The reaction time is preferably 1 to 24 hours, particularly preferably 2 to 12 hours. The progress of the reaction can be monitored by analyzing with thin layer chromatography or gas chromatography.

  Another method for producing the heteroacene derivative represented by the general formula (1) of the present invention will be described.

  The heteroacene derivative represented by the general formula (1) of the present invention is obtained by metallizing a dihalochalcogenophenylaryl derivative represented by the general formula (7) using a metallizing agent to produce bis (phenylsulfonyl) sulfide, sulfur dichloride. , Sulfur, or selenium.

Here, metalation means that both or one of X ² and X ⁴ in the general formula (7) is replaced with metal.

When the dihalochalcogenophenylaryl derivative represented by the general formula (7) is metalated, the metalating agent used is one that can replace X ² and / or X ⁴ in the general formula (7) with a metal. As long as there is no limitation, for example, n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, alkyllithium such as hexyllithium; phenyllithium, p-tert-butylphenyllithium, p-methoxyphenyllithium, Aryl lithium such as p-fluorophenyl lithium; lithium amide such as lithium diisopropylamide and lithium hexamethyldisilazide; lithium metal such as lithium powder; methylmagnesium bromide, ethylmagnesium bromide, isopropylmagnesium bromide Alkyl Grignard reagents such as isopropylmagnesium chloride, tert-butylmagnesium chloride, cyclohexylmagnesium bromide; magnesium metal; zinc metal and the like, preferably alkyllithium and alkylgrignard reagents, particularly preferably n-butyllithium , Sec-butyllithium, tert-butyllithium, isopropylmagnesium bromide, cyclohexylmagnesium bromide. When both X ² and X ⁴ in the general formula (7) are substituted with metal, it can be preferably carried out using alkyllithium, and only one of X ² and X ⁴ in the general formula (7) can be used. In the case of substituting with metal, it can be preferably carried out using an alkyl Grignard reagent.

The amount of the metallizing agent used is preferably 0.9 to 4.0 equivalents, more preferably 1.1 to 3.0 equivalents, relative to 1 equivalent of the dihalochalcogenophenylaryl derivative represented by the general formula (7). Particularly preferred is 1.1 to 2.5 equivalents. Further, the amount of the metalating agent used when substituting both X ² and X ⁴ in the general formula (7) with a metal is 1 equivalent of the dihalochalcogenophenylaryl derivative represented by the general formula (7). 1.9 to 4.0 equivalents by weight, more preferably 2.0 to 3.0 equivalents, metalation when replacing one of ^{X 2} and ^{X 4} only to the metal in the general formula (7) The amount of the agent used is preferably 0.9 to 2.0 equivalents, more preferably 1.0 to 1.6 equivalents per equivalent of the dihalochalcogenophenylaryl derivative represented by the general formula (7). .

  The metallization is preferably carried out in a solvent. The solvent to be used is not particularly limited, and examples thereof include THF, ether, methyl-tert-butyl ether, ethyl-tert-butyl ether, ethylene glycol dimethyl ether, dioxane, toluene, hexane, cyclohexane, and the like, and particularly preferably THF and ether. These solvents may be used alone or as a mixture of two or more. The metallization temperature is preferably −90 to 60 ° C., particularly preferably −80 to 30 ° C. The reaction time is preferably 1 to 240 minutes, particularly preferably 10 to 120 minutes. The progress of metalation can be monitored by taking out a part of the reaction solution, stopping the reaction with water, and then analyzing by thin layer chromatography or gas chromatography.

  In the metalation, a metallating agent may be added to the dihalochalcogenophenylaryl derivative represented by the general formula (7), or the dihalochalcogenophenyl represented by the general formula (7) is used as the metallating agent. Any method of adding an aryl derivative may be used.

  The metal salt formed by the metalation is then reacted with bis (phenylsulfonyl) sulfide, which is a chalcogen reagent, sulfur dichloride, sulfur, selenium or tellurium, so that the heteroacene derivative represented by the general formula (1) is obtained. It is obtained. The reaction with the chalcogen reactant may be any one of a method of adding the chalcogen reactant to the reaction mixture containing the metal salt generated by the metalation; and a method of adding the reaction mixture containing the generated metal salt to the chalcogen reactant. May be used.

In addition, when both X ² and X ⁴ in the dihalochalcogenophenylaryl derivative represented by the general formula (7) are substituted with metal, the chalcogen reactant used is preferably bis (phenylsulfonyl) sulfide or sulfur dichloride. Yes, when any one of X ² and X ⁴ in the general formula (7) is substituted with metal, the chalcogen reactant used is preferably sulfur or selenium.

  When reacting the metal salt produced by metalation with the chalcogen reactant, it is preferably carried out in a solvent. The solvent to be used is not particularly limited, and examples thereof include THF, ether, methyl-tert-butyl ether, ethyl-tert-butyl ether, ethylene glycol dimethyl ether, diglyme, dioxane, toluene, hexane, and cyclohexane, and preferably THF and ether. The amount of the chalcogen reactant used is preferably 0.8 to 1.4 equivalents, particularly preferably 0.9 to 1.2 equivalents, relative to 1 equivalent of the dihalochalcogenophenylaryl derivative represented by the general formula (7). It is. The reaction temperature with the reactant is preferably -90 to 50 ° C, particularly preferably -80 to 30 ° C, and the reaction time is preferably 0.5 to 30 hours, particularly preferably 1 to 18 hours.

In the case where only one of X ² and X ⁴ in the dihalochalcogenophenylaryl derivative represented by the general formula (7) is substituted with a metal, it is represented by the general formula (1) after the reaction with the chalcogen reagent. In order to convert to a heteroacene derivative, further heating is preferable.

  The heating is preferably carried out in a solvent. The solvent to be used is not particularly limited. For example, N-methylpyrrolidone (hereinafter abbreviated as NMP), N, N-dimethylformamide (hereinafter abbreviated as DMF), dimethyl sulfoxide, water, ethanol, THF, ethylene glycol dimethyl ether, diglyme, Dioxane, toluene and the like, preferably THF and ether. These solvents may be used alone or as a mixture of two or more. The heating reaction temperature is preferably 60 to 200 ° C., particularly preferably 80 to 180 ° C., and the reaction time is preferably 1 to 20 hours, particularly preferably 2 to 15 hours.

  In the heating, a base can be present in the reaction system. The type of base in this case is not particularly limited, and examples thereof include sodium carbonate, sodium hydrogen carbonate, potassium carbonate, cesium carbonate, potassium phosphate, sodium phosphate, sodium tert-butoxide, potassium tert-butoxide, and potassium fluoride. 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, triethylamine, triethylamine, tripropylamine, tributylamine, ethylenediamine, Preferable examples include organic bases such as N, N, N ′, N′-tetramethylethylenediamine, diisopropylamine and pyridine. The amount of these bases used is preferably 1.0-10.0 equivalents, particularly preferably 1.5-4.0 equivalents, relative to 1 equivalent of the dihalochalcogenophenylaryl derivative represented by the general formula (7). is there.

  The production of the heteroacene derivative represented by the general formula (1) of the present invention is preferably carried out under an inert atmosphere such as nitrogen or argon.

  The method for producing the heteroacene derivative represented by the general formula (1) is, for example, 2,2′-dibromodiphenylacetylene described in “Journal of Heterocyclic Chemistry”, 1998, Vol. 35, pages 725-726. It can also be carried out by a method of lithiation with tert-butyllithium (corresponding to a dihalodiarylethine derivative represented by the general formula (3) of the present invention) and reacting with sulfur or selenium.

  The heteroacene derivative represented by the general formula (1) of the present invention thus obtained can be further purified. The method for purification is not particularly limited, and examples thereof include column chromatography, recrystallization, or sublimation.

(Method for producing di (alkylchalcogeno) diarylethyne derivative)
Next, a method for producing a di (alkylchalcogeno) diarylethyne derivative represented by the general formula (2) which is a precursor compound of the heteroacene derivative represented by the general formula (1) of the present invention will be described.

  The di (alkylchalcogeno) diarylethyne derivative represented by the general formula (2) of the present invention is metallized using a metallizing agent to the dihalodiarylethine derivative represented by the general formula (3) to obtain a dialkyldisulfide and / or dialkyl. It can be produced by reacting with diselenide.

Here, metallization means that X ¹ and X ² in the general formula (3) are each replaced with metal.

When the dihalodiarylethyne derivative represented by the general formula (3) is metalated, the metallizing agent used is particularly limited as long as X ¹ and X ² in the general formula (3) can be substituted with metal. For example, alkyllithium such as n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, hexyllithium; phenyllithium, p-tert-butylphenyllithium, p-methoxyphenyllithium, p-fluorophenyl Aryl lithium such as lithium; lithium amide such as lithium diisopropylamide and lithium hexamethyldisilazide; lithium metal such as lithium powder; methylmagnesium bromide, ethylmagnesium bromide, isopropylmagnesium bromide, isopropyl Alkyl Grignard reagents such as gnesium chloride, tert-butylmagnesium chloride, cyclohexylmagnesium bromide; magnesium metal; zinc metal and the like can be mentioned, preferably alkyllithium and alkylgrignard reagents, particularly preferably n-butyllithium, sec -Butyllithium, tert-butyllithium.

  The amount of the metallizing agent used is preferably 1.5 to 5.0 equivalents, more preferably 2.0 to 4.5 equivalents, particularly preferably 1 equivalent of the dihalodiarylethyne derivative represented by the general formula (3). Preferably it is 2.2-4.2 equivalent.

  The metallization is preferably carried out in a solvent. The solvent to be used is not particularly limited, and examples thereof include THF, ether, methyl-tert-butyl ether, ethyl-tert-butyl ether, ethylene glycol dimethyl ether, dioxane, toluene, hexane, cyclohexane, and the like, and particularly preferably THF and ether. These solvents may be used alone or as a mixture of two or more. The metallization temperature is preferably −90 to 30 ° C., particularly preferably −80 to 20 ° C. The reaction time is preferably 1 to 240 minutes, particularly preferably 10 to 120 minutes. The progress of metalation can be monitored by taking out a part of the reaction solution, stopping the reaction with water, and then analyzing by thin layer chromatography or gas chromatography.

  In the metalation, a metallizing agent may be added to the dihalodiarylethine derivative represented by the general formula (3), or a dihalodiarylethine derivative represented by the general formula (3) may be added to the metallizing agent. Any method can be used.

  The metal salt produced by the metalation is then reacted with dialkyl disulfide and / or dialkyl diselenide to obtain a di (alkylchalcogeno) diarylethyne derivative represented by the general formula (2). The reaction includes a method of adding the dialkyl disulfide and / or dialkyl diselenide to the reaction mixture containing the metal salt produced by the metalation; the reaction mixture containing the produced metal salt is added to the dialkyl disulfide and / or dialkyl diselede. Any method of adding to the nido may be used.

  The reaction between the metal salt formed by metalation and dialkyl disulfide and / or dialkyl diselenide is preferably carried out in a solvent. The solvent to be used is not particularly limited, and examples thereof include THF, ether, methyl-tert-butyl ether, ethyl-tert-butyl ether, ethylene glycol dimethyl ether, diglyme, dioxane, toluene, hexane, and cyclohexane, and preferably THF and ether. The amount of the dialkyl disulfide and / or dialkyl diselenide to be used is preferably 1.5 to 5.0 equivalents, more preferably 2.0 to 1 equivalent to 1 equivalent of the dihalodiarylethine derivative represented by the general formula (3). 4.0 equivalents. The reaction temperature with the reactant is preferably -90 to 30 ° C, particularly preferably -80 to 20 ° C, and the reaction time is preferably 0.5 to 10 hours, particularly preferably 1 to 5 hours.

  The di (alkylchalcogeno) diarylethyne derivative represented by the general formula (2) of the present invention thus obtained can be further purified. The method for purification is not particularly limited, and examples thereof include column chromatography, recrystallization, or sublimation.

(Method for producing dihalodiarylethine derivative)
Next, a method for producing the dihalodiarylethyne derivative represented by the general formula (3) used as a raw material for the di (alkylchalcogeno) diarylethyne derivative represented by the general formula (2) of the present invention will be described.

  In the dihalodiarylethine derivative represented by the general formula (3) of the present invention, a 2,3-dihaloarene derivative represented by the following general formula (8) and a trialkylsilylacetylene were reacted in the presence of palladium and / or nickel catalyst. Thereafter, detrialkylsilyl treatment was performed, and the resulting 2-ethynyl-3-haloarene derivative represented by the following general formula (9) and the 2,3-dihaloarene derivative represented by the following general formula (10) were converted into palladium and / or It can manufacture by making it react in nickel catalyst presence. The 2,3-dihaloarene derivative represented by the general formula (8) and the general formula (10) may be the same compound.

(Here, the substituent X ³ represents a bromine atom, an iodine atom, or a chlorine atom. The substituent X ^{1 and the} ring A have the same meaning as the substituent and the ring represented by the general formula (3).)

(Here, the substituent X ^{1 and} ring A have the same meaning as the substituent and ring represented by formula (3).)

(Here, the substituent X ⁵ represents a bromine atom, an iodine atom, or a chlorine atom. The substituent X ^{2 and the} ring B have the same meanings as the substituent and the ring represented by the general formula (3).)
As another method for producing the dihalodiarylethyne derivative represented by the general formula (3), the 2,3-dihaloarene derivative represented by the general formula (8) and acetylene or trimethylsilylacetylene are present in the presence of a palladium and / or nickel catalyst. Dihalodiaryl ethyne derivatives can also be produced by reaction under the following conditions.

  The substituents of the 2,3-dihaloarene derivatives represented by the general formulas (8) and (10) of the present invention will be described.

Substituent X ³ in the general formula (8), a bromine atom, an iodine atom, shows a chlorine atom, preferably a bromine atom and an iodine atom, more preferably an iodine atom.

The substituent X ^{5 in} the general formula (10) represents a bromine atom, an iodine atom or a chlorine atom, preferably a bromine atom or an iodine atom, and more preferably an iodine atom.

  Specific examples of the compound represented by the general formula (8) and the general formula (10) include 2-bromo-3-iodo-6,7-dioctylanthracene, 2-bromo-3-iodo-6,7-di. Decylanthracene, 2-bromo-3-iodo-6,7-didodecylanthracene, 2-bromo-3-iodo-6,7-dipentadecylanthracene, 2-bromo-3-iodo-6-dodecyl-7- Fluoroanthracene, 2-bromo-3-iodo-7-dodecyl-6-fluoroanthracene, 2-bromo-3-iodo-6,7-di (perfluorododecyl) anthracene, 2-bromo-3-iodo-6 7-di (decylethynyl) anthracene, 2-bromo-3-iodo-6,7-di (perfluorodecylethynyl) anthracene, 2-bromo-3-iodo-6 7-diphenylanthracene, 2,3-dibromo-6-octylbenzothiophene, 2,3-dibromo-6-decylbenzothiophene, 2,3-dibromo-6-dodecylbenzothiophene, 2,3-dibromo-6-penta Decylbenzothiophene, 2,3-dibromo-6-octadecylbenzothiophene, 2,3-dibromo-6- (perfluorododecyl) benzothiophene, 2,3-dibromo-6- (perfluorooctadecyl) benzothiophene, 2, 3-dibromo-4,6-didecylbenzothiophene, 2,3-dibromo-4,6-didodecylbenzothiophene, etc., among which 2-bromo-3-iodo-6,7-didodecylanthracene, 2-bromo-3-iodo-6,7-di (perfluorododecyl) anthracene, 2 Among the compounds selected from the group consisting of 3-dibromo-6-dodecylbenzothiophene and 2,3-dibromo-6-octadecylbenzothiophene, ring A or B is a structure represented by the general formula (A-2) Compounds are preferred.

  The 2-ethynyl-3-haloarene derivative represented by the general formula (9) was obtained by reacting the 2,3-dihaloarene derivative represented by the general formula (8) with a trialkylsilylacetylene in the presence of palladium and / or a nickel catalyst. Thereafter, it can be obtained by detrialkylsilyl treatment.

  The catalyst used for the reaction of the 2,3-dihaloarene derivative represented by the general formula (8) and the trialkylsilylacetylene is not particularly limited as long as it is a palladium and / or nickel catalyst. For example, tetrakis (triphenylphosphine) palladium, tris ( Dibenzylideneacetone) dipalladium / triphenylphosphine mixture, dichlorobis (triphenylphosphine) palladium, dichlorobis (acetonitrile) palladium, bis (tri-tert-butylphosphine) palladium, diacetatobis (triphenylphosphine) palladium, dichloro (1,2 -Bis (diphenylphosphino) ethane) palladium, dichloro (1,3-bis (diphenylphosphino) propane) palladium, palladium acetate / triphenylphosphine mixture, acetic acid Radium / tri (o-tolyl) phosphine mixture, palladium acetate / tri-tert-butylphosphine mixture, palladium acetate / 2- (dicyclohexylphosphino) -1,1′-biphenyl mixture, dichloro (ethylenediamine) palladium, dichloro (N , N, N ′, N′-tetramethylethylenediamine) palladium, dichloro (N, N, N ′, N′-tetramethylethylenediamine) palladium / triphenylphosphine mixture and other palladium catalysts; dichlorobis (triphenylphosphine) nickel, Dichloro (1,2-bis (diphenylphosphino) ethane) nickel, dichloro (1,3-bis (diphenylphosphino) propane) nickel, dichloro (ethylenediamine) nickel, dichloro (N, N, N ', N'- Tet Methylethylenediamine) nickel, dichloro (N, N, N ′, N′-tetramethylpropanediamine) nickel, dichloro (N, N, N ′, N′-tetramethylethylenediamine) nickel / triphenylphosphine mixture, bis (1 , 5-cyclooctadiene) nickel catalyst such as nickel / triphenylphosphine mixture; Among these, a preferable catalyst is a palladium compound, and particularly preferable catalysts are tetrakis (triphenylphosphine) palladium and dichlorobis (triphenylphosphine) palladium. These catalysts may be used alone or as a mixture of two or more.

  When the 2,3-dihaloarene derivative represented by the general formula (8) is reacted with the trialkylsilylacetylene in the presence of palladium and / or nickel catalyst, it is preferably carried out in a solvent. The solvent to be used is not particularly limited. For example, THF, ether, methyl-tert-butyl ether, ethyl-tert-butyl ether, dioxane, ethylene glycol dimethyl ether, benzene, toluene, xylene, hexane, cyclohexane, ethanol, water, DMF, NMP, triethylamine , Tributylamine, piperidine, pyrrolidine, diethylamine, diisopropylamine and the like, and these solvents may be used alone or as a mixture of two or more thereof. For example, THF / diisopropylamine, THF / triethylamine, toluene / Two to three component systems such as piperidine, toluene / water, diisopropylamine / toluene / water, toluene / ethanol / water can also be used.

  The amount of the palladium catalyst and nickel catalyst used is preferably 0.05 to 10 mol%, particularly preferably 0.1 to 5 mol%, relative to 1 mol of the 2,3-dihaloarene derivative represented by the general formula (8). .

  The amount of trialkylsilylacetylene used is preferably 0.4 to 1.8 equivalents, more preferably 0.4 to 1.6 equivalents, relative to 1 equivalent of the 2,3-dihaloarene derivative represented by the general formula (8). Particularly preferred is 0.5 to 1.2 equivalents. Examples of the trialkylsilylacetylene include trimethylsilylacetylene, triethylsilylacetylene, triisopropylsilylacetylene, tributylsilylacetylene and the like, and trimethylsilylacetylene is preferable.

  In addition, it is preferable to make a copper compound exist in a reaction system. The copper compound is not particularly limited. For example, monovalent copper such as copper (I) chloride, copper (I) bromide, copper (I) iodide, copper (I) acetate; copper (II) chloride, odor Examples thereof include divalent copper such as copper (II) iodide, copper (II) iodide, copper (II) acetate, and copper (II) acetylacetonate. Among them, monovalent copper is preferable, and copper (I) iodide is particularly preferable. The amount of these copper compounds used is preferably 0.5 to 4.0 equivalents, particularly preferably 0.6 to 2.0 equivalents, per equivalent of the palladium and / or nickel catalyst.

  The temperature during the reaction is preferably 10 to 120 ° C, more preferably 20 to 80 ° C, particularly preferably 20 to 60 ° C, and the reaction time is preferably 1 to 96 hours, particularly preferably 2 to 72 hours. .

  A base can also be present in the reaction system. There are no particular limitations on the type of base in this case. For example, sodium carbonate, sodium bicarbonate, potassium carbonate, cesium carbonate, potassium phosphate, sodium phosphate, sodium tert-butoxide, potassium tert-butoxide, potassium fluoride, fluoride. Inorganic bases such as sodium chloride and cesium fluoride; 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, triethylamine, trimethylamine, tri Preferable examples include organic bases such as propylamine, tributylamine, ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, diisopropylamine, pyridine, and tetrabutylammonium fluoride. The amount of these bases used is preferably 0.4 to 10.0 equivalents, particularly preferably 0.5 to 4.0 equivalents, relative to 1 equivalent of 2,3-dihaloarene represented by the general formula (8). Furthermore, a phase transfer catalyst can be used in combination with these bases. The type of the phase transfer catalyst is not particularly limited, and examples thereof include trioctylmethylammonium chloride, tetrabutylammonium chloride, cetylpyridinium chloride, benzyltrimethylammonium chloride and the like. The amount of these phase transfer catalysts used is preferably 0.1 to 1.5 equivalents, particularly preferably 0.2 to 0.8 equivalents, relative to 1 equivalent of 2,3-dihaloarene represented by the general formula (8). is there.

  Furthermore, phosphines such as triphenylphosphine and tri (o-tolyl) phosphine can be present in the reaction system. The amount of these phosphines used is preferably 0.9 to 5.0 equivalents, particularly preferably 1.0 to 3.0 equivalents, relative to 1 equivalent of the palladium and / or nickel catalyst.

  A method of reacting the 2,3-dihaloarene derivative represented by the general formula (8) with a trialkylsilylacetylene in the presence of a palladium and / or nickel catalyst is described in, for example, “Sinlet”, 2004, pages 165-168. It can also be carried out in the manner described.

  The 2-trialkylsilylethynyl-3-haloarene derivative thus obtained is a 2-ethynyl-3-haloarene derivative represented by the general formula (9) by eliminating the trialkylsilyl group (detrialkylsilyl treatment). Can be converted to The method for removing the trialkylsilyl group can be carried out using an inorganic base or a fluoride. Examples of the inorganic base include potassium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, sodium hydroxide and the like, and potassium carbonate is preferable. On the other hand, examples of the fluoride include tetrabutylammonium fluoride, sodium fluoride, potassium fluoride and the like, and tetrabutylammonium fluoride is preferable. The amount of the inorganic base or fluorinated compound used is preferably 0.8 to 7 equivalents, particularly preferably 1.0 to 4.0 equivalents, relative to 1 equivalent of the 2-trialkylsilylethynyl-3-haloarene derivative. The detrialkylsilylation reaction is preferably carried out in a solvent. There are no particular limitations on the solvent used, for example, THF, ether, methyl-tert-butyl ether, dioxane, ethylene glycol dimethyl ether, toluene, xylene, hexane, cyclohexane, ethanol, methanol, water, DMF, NMP, triethylamine, piperidine, pyrrolidine, diethylamine. In addition, one or a mixture of two or more of these solvents may be used, for example, 2 to 3 components such as ether / methanol, toluene / water, toluene / ethanol / water. It can also be used in systems. The temperature during the reaction is preferably −10 to 90 ° C., more preferably 0 to 60 ° C., particularly preferably 20 to 50 ° C., and the reaction time is preferably 1 to 10 hours, particularly preferably 2 to 4 hours. is there. The detrialkylsilylation reaction can also be carried out by a method of treating with potassium carbonate in methanol / ether described in “Sinlet”, 2004, pages 165-168.

  The 2-ethynyl-3-haloarene derivative represented by the general formula (9) thus obtained can be purified. The method for purification is not particularly limited, and examples thereof include column chromatography, recrystallization, or sublimation. Moreover, it can also be used as a raw material for the next reaction without isolation and purification.

  Next, the 2-ethynyl-3-haloarene derivative represented by the general formula (9) and the 2,3-dihaloarene derivative represented by the general formula (10) are reacted in the presence of a palladium and / or nickel catalyst. The catalyst used in the reaction is not particularly limited as long as it is a palladium and / or nickel catalyst, and the palladium and nickel catalyst used in the reaction of the 2,3-dihaloarene derivative represented by the general formula (8) and the trialkylsilylacetylene. The same catalyst can be mentioned. The amount of these catalysts used, solvent, reaction conditions, and additives such as copper compounds, bases, and phosphines are the same as in the reaction of the 2,3-dihaloarene derivative represented by the general formula (8) with trialkylsilylacetylene. Use amount, substance and conditions can be applied. The amount of the 2,3-dihaloarene derivative represented by the general formula (10) is 0.8 to 2.0 equivalents relative to 1 equivalent of the 2-ethynyl-3-haloarene derivative represented by the general formula (9). Preferably, it is 1.0-1.6 equivalent, More preferably, it is 1.0-1.3 equivalent.

  The method for producing the dihalodiarylethyne derivative represented by the general formula (3) described above is a method for producing the dihalodiarylethyne derivative represented by the general formula (3) when the rings A and B are the same or different. However, the production method of the dihalodiarylethyne derivative represented by the general formula (3) only when the rings A and B are the same will be described below.

  That is, the 2,3-dihaloarene derivative represented by the general formula (8), which is another production method of the dihalodiarylethyne derivative represented by the general formula (3), and acetylene or trimethylsilylacetylene are present in a palladium and / or nickel catalyst. Dihalodiaryl ethyne derivatives can be produced by reaction under the following conditions.

  The catalyst used in the reaction is not particularly limited as long as it is a palladium and / or nickel catalyst, and the palladium and nickel catalyst used in the reaction of the 2,3-dihaloarene derivative represented by the general formula (8) and the trialkylsilylacetylene. And the same catalyst. The amount of these catalysts used, solvent, reaction conditions, and additives such as copper compounds, bases, and phosphines are the same as in the reaction of the 2,3-dihaloarene derivative represented by the general formula (8) with trialkylsilylacetylene. Use amount, substance and conditions can be applied. The amount of the 2,3-dihaloarene derivative represented by the general formula (8) is preferably 1.6 to 3.2 equivalents, more preferably 1.8 to 2.8 with respect to 1 equivalent of acetylene or trimethylsilylacetylene. The equivalent amount, particularly preferably 1.9 to 2.4 equivalents.

  In addition, a method of reacting the 2,3-dihaloarene derivative represented by the general formula (8) and acetylene in the presence of a palladium and / or nickel catalyst is, for example, “Journal of Heterocyclic Chemistry”, 1998, Vol. 35. , Pages 725 to 726, and a method of coupling o-bromoiodobenzene and acetylene, and a 2,3-dihaloarene derivative and trimethylsilylacetylene in the presence of a palladium and / or nickel catalyst. For example, the reaction may be performed by a method of coupling 4-bromobiphenyl and trimethylsilylacetylene described in “Journal of American Chemical Society” (USA), 2006, Vol. 128, pages 3044-3050. so That.

  The dihalodiarylethine derivative represented by the general formula (3) uses bis (tri-n-butylstannyl) acetylene instead of acetylene, and the 2,3-dihaloarene derivative represented by the general formula (8) Can also be produced by reacting in the presence of a palladium and / or nickel catalyst.

  The dihalodiarylethyne derivative represented by the general formula (3) of the present invention thus obtained can be further purified. The method for purification is not particularly limited, and examples thereof include column chromatography, recrystallization, or sublimation.

(Method for producing di (alkylchalcogeno) diarylethylene derivative)
Next, a method for producing a di (alkylchalcogeno) diarylethylene derivative represented by the general formula (4), which is a precursor compound of the heteroacene derivative represented by the general formula (1) of the present invention, will be described.

  The di (alkylchalcogeno) diarylethylene derivative represented by the general formula (4) of the present invention is obtained by reacting a formyl (alkylchalcogeno) arene derivative represented by the general formula (5) with a reagent comprising titanium chloride and a reducing agent. Can be manufactured.

  The titanium chloride in the reaction is not particularly limited and is preferably titanium tetrachloride or titanium trichloride.

  The reducing agent in the reaction is not particularly limited as long as it can reduce titanium chloride to trivalent to zerovalent titanium. For example, zinc, copper, iron, lithium, sodium, potassium, lithium aluminum hydride, etc. Zinc, copper and iron are preferable, and zinc is particularly preferable.

  The amount of the reducing agent used is preferably 0.5 to 15 equivalents, more preferably 1.0 to 12 equivalents, and particularly preferably 3.0 to 10 equivalents with respect to 1 equivalent of titanium chloride.

  The amount of titanium chloride used is preferably 0.8 to 5.0 equivalents, more preferably 1.1 to 4.0 equivalents, based on 1 equivalent of the formyl (alkyl chalcogeno) arene derivative represented by the general formula (5). Particularly preferred is 1.1 to 3.0 equivalents.

  The reaction is preferably carried out in a solvent. The solvent to be used is not particularly limited, and examples thereof include THF, ether, methyl-tert-butyl ether, ethyl-tert-butyl ether, ethylene glycol dimethyl ether, dioxane, toluene, hexane, cyclohexane, and the like, and particularly preferably THF and ether. These solvents may be used alone or as a mixture of two or more. The metalation temperature is preferably 0 to 120 ° C, particularly preferably 20 to 80 ° C. The reaction time is preferably 1 to 24 hours, particularly preferably 2 to 15 hours. The progress of the reaction can be monitored by taking out a part of the reaction solution, stopping the reaction with water, and then analyzing by thin layer chromatography or gas chromatography.

  In this reaction, after mixing and heating titanium chloride and a reducing agent in advance, a formyl (alkylchalcogeno) arene derivative represented by general formula (5) may be added, or formyl represented by general formula (5) Any method of adding a reducing agent to a mixture of an (alkylchalcogeno) arene derivative and titanium chloride can be used.

  The di (alkylchalcogeno) diarylethylene derivative represented by the general formula (4) of the present invention thus obtained can be further purified. The method for purification is not particularly limited, and examples thereof include column chromatography, recrystallization, or sublimation.

(Method for producing formyl (alkylchalcogeno) arene derivative)
Next, a method for producing a formyl (alkylchalcogeno) arene derivative which is a raw material compound of a di (alkylchalcogeno) diarylethylene derivative represented by the general formula (4) will be described.

  The formyl (alkylchalcogeno) arene derivative represented by the general formula (5) is produced by metallizing the halo (alkylchalcogeno) arene derivative represented by the general formula (6) using a metallizing agent and reacting with DMF. can do.

Here, metalation means that X ³ in the general formula (6) is replaced with metal.

When the halo (alkylchalcogeno) arene derivative represented by the general formula (6) is metalated, the metalating agent used is particularly limited as long as X ³ in the general formula (6) can be substituted with metal. For example, alkyllithium such as n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium and hexyllithium; lithiumamide such as lithium diisopropylamide and lithium hexamethyldisilazide; lithium metal such as lithium powder An alkyl Grignard reagent such as methylmagnesium bromide, ethylmagnesium bromimide, isopropylmagnesium bromide, isopropylmagnesium chloride, tert-butylmagnesium chloride, cyclohexylmagnesium bromide; Cium metal; zinc metal and the like can be mentioned, and alkyl lithium and alkyl Grignard reagents are preferable, and n-butyl lithium, sec-butyl lithium and tert-butyl lithium are particularly preferable.

  The amount of the metallizing agent used is preferably 1.0 to 3.0 equivalents, more preferably 1.5 to 2.2 relative to 1 equivalent of the halo (alkylchalcogeno) arene derivative represented by the general formula (6). Equivalents, particularly preferably 1.7 to 2.1 equivalents.

  The metallization is preferably carried out in a solvent. The solvent to be used is not particularly limited, and examples thereof include THF, ether, methyl-tert-butyl ether, ethyl-tert-butyl ether, ethylene glycol dimethyl ether, hexane, and the like, and particularly preferably THF and ether. These solvents may be used alone or as a mixture of two or more. The metallization temperature is preferably −90 to 30 ° C., particularly preferably −80 to 20 ° C. The reaction time is preferably 1 to 60 minutes, particularly preferably 10 to 30 minutes. The progress of metalation can be monitored by taking out a part of the reaction solution, stopping the reaction with water, and then analyzing by thin layer chromatography or gas chromatography.

  The metal salt produced by the metalation is then reacted with DMF to obtain a formyl (alkylchalcogeno) arene derivative represented by the general formula (5). When reacting the metal salt formed by metalation with DMF, it is preferably carried out in a solvent. The solvent to be used is not particularly limited, and examples thereof include THF, ether, methyl-tert-butyl ether, ethyl-tert-butyl ether, ethylene glycol dimethyl ether, hexane and the like, preferably THF and ether. The amount of DMF used is preferably 1.0 to 3.0 equivalents, more preferably 1.5 to 2.2 equivalents per equivalent of the halo (alkylchalcogeno) arene derivative represented by the general formula (6). is there. The reaction temperature with DMF is preferably −90 to 30 ° C., particularly preferably −80 to 20 ° C., and the reaction time is preferably 0.5 to 8 hours, particularly preferably 1 to 4 hours.

  The formyl (alkylchalcogeno) arene derivative represented by the general formula (5) thus obtained can be further purified. The method for purification is not particularly limited, and examples thereof include column chromatography, recrystallization, or sublimation.

(Method for producing halo (alkylchalcogeno) arene derivative)
Next, a method for producing a halo (alkylchalcogeno) arene derivative, which is a raw material compound of the formyl (alkylchalcogeno) arene derivative represented by the general formula (5) of the present invention, will be described.

  The halo (alkylchalcogeno) arene derivative represented by the general formula (6) of the present invention reacts with a 2,3-dihaloarene derivative represented by the general formula (8) and a metal chalcogenoalkoxide represented by the following general formula (11). Can be manufactured.

R ¹¹ T ¹ M ¹ (11)
(Here, M ¹ represents an alkali metal, and the substituents R ¹¹ and T ¹ have the same meaning as the substituent represented by the general formula (6).)
M ¹ in the metal chalcogenoalkoxide represented by the general formula (11) is an alkali metal, specifically, sodium, lithium, potassium, or cesium, and preferably sodium or lithium. Specific examples of the compound represented by the general formula (11) include sodium thiomethoxide, lithium thiomethoxide, potassium thiomethoxide, cesium thiomethoxide, sodium thioethoxide, sodium thiobenzyl oxide, sodium selenomethoxy. , Lithium selenomethoxide and sodium selenobenzyl oxide, preferably sodium thiomethoxide, sodium thiobenzyl oxide and sodium selenomethoxide, particularly preferably sodium thiomethoxide.

  The amount of the metal chalcogenoalkoxylating agent used is preferably 0.9 to 2.1 equivalents, more preferably 1.4 to 1.1, with respect to 1 equivalent of the 2,3-dihaloarene derivative represented by the general formula (8). 7 equivalents, particularly preferably 1.2 to 1.5 equivalents.

  The reaction with the metal chalcogeno alkoxide is preferably carried out in a solvent. The solvent used is not particularly limited, and examples thereof include NMP, DMF, THF, ether, ethyl tert-butyl ether, ethylene glycol dimethyl ether, dioxane, dimethylthiol sulfoxide, toluene, hexane, and the like, and particularly preferably NMP, DMF, dioxane. . These solvents may be used alone or as a mixture of two or more. The reaction temperature is preferably 10 to 100 ° C, particularly preferably 20 to 80 ° C. The reaction time is preferably 0.5 to 6 hours, particularly preferably 1 to 4 hours. The progress of the reaction can be monitored by analyzing with thin layer chromatography or gas chromatography.

  The halo (alkylchalcogeno) arene derivative represented by the general formula (6) thus obtained can be further purified. The method for purification is not particularly limited, and examples thereof include column chromatography, recrystallization, or sublimation.

  The 2,3-dihaloarene derivative represented by the general formula (8) is produced by, for example, using a reduction reaction of a 2,3-dihaloquinone derivative with diisobutylaluminum hydride described in JP2008 / 81494A. can do.

(Method for producing dihalochalcogenophenylaryl derivative)
Next, a method for producing a dihalochalcogenophenylaryl derivative that is a raw material compound of the heteroacene derivative represented by the general formula (1) will be described.

  The dihalochalcogenophenylaryl derivative represented by the general formula (7) includes, for example, a dihalochalcogenophene derivative represented by the following general formula (13) and a 3-haloaryl metal reagent represented by the following general formula (14) as palladium. And / or by reacting in the presence of a nickel catalyst.

(Here, the substituent X ⁶ represents a bromine atom, an iodine atom, or a chlorine atom. The substituents X ⁴ and T ¹ , and ring A have the same meaning as the substituent and ring represented by the general formula (7). )

(Wherein M ² represents a halide of magnesium, boron, zinc, tin, and silicon; a hydroxide; an alkoxide; an alkylated product, and the substituent X ^{2 and the} B ring represent a substituent represented by the general formula (7) and It shows the same meaning as a ring.)
General formulas (13) and (14) will be further described.

The substituent X ^{6 in} the general formula (13) represents a bromine atom, an iodine atom or a chlorine atom, preferably a bromine atom or an iodine atom, and more preferably an iodine atom.

  As examples of the dihalochalcogenophene derivative represented by the general formula (13), the following compounds are preferable.

The substituent M ^{2 in} the general formula (14) is a halide of magnesium, boron, zinc, tin, or silicon; a hydroxide; an alkoxide; an alkylated product, and is eliminated by the palladium and / or nickel catalyst described above. or it is not particularly limited as long as it is a group which can be substituted with nickel, for example _{MgCl, MgBr, B (OH)} 2, B (OMe) 2, tetramethyl dioxaborolanyl group, ZnCl, ZnBr, ZnI, Sn (Bu- n) ₃ , Si (OMe) _{3 and the} like can be mentioned, and ZnCl, B (OH) ₂ and Si (OMe) ₃ are preferable.

  Specific examples of the compound represented by the general formula (14) include 3-bromo-6-dodecylbenzothienyl-2-zinc chloride, 3-bromo-6-octadecylbenzothienyl-2-trimethoxysilane, 3 -Bromo-6,7-didodecylanthracenylboronic acid, 3-bromo-6,7-dipentadecylanthracenyl-2-boronic acid and the like.

The 3-haloaryl metal reagent represented by the general formula (14) is, for example, a 2,3-dihaloarene derivative represented by the general formula (10) used as a raw material thereof or a Grignard reagent such as isopropylmagnesium bromide or n-butyl. After halogen / metal exchange reaction with an organic lithium reagent such as lithium, zinc chloride, trimethoxyborane, tri (isopropoxy) borane, 2-isopropoxy-4,4,5,5-tetramethyl-1,3 , 2-dioxaborolane, tetramethoxysilane and the like. In addition, when the substituents M ¹ and M ² in the general formulas (6) and (7) are Si (OMe) ₃ or Si (OEt) ₃ , aryl dihalogen substituents and Pd or Rh catalysts as raw materials thereof are used. It can also be prepared by reaction with a trialkoxysilane. For the halogen / metal exchange reaction using the Grignard reagent, for example, the method described in “Journal of Organic Chemistry”, 2000, 65, 4618-4634 can also be used.

  The catalyst used for the catalytic reaction is not particularly limited as long as it is a palladium and / or nickel catalyst. In the production of the dihalodiarylethyne derivative represented by the general formula (3), 2, Mention may be made of the same catalysts as the palladium and nickel catalysts used in the reaction of the 3-dihaloarene derivative and the trialkylsilylacetylene. The amount of these catalysts used, solvent, reaction conditions, and additives such as copper compounds, bases, and phosphines are the same as in the reaction of the 2,3-dihaloarene derivative represented by the general formula (8) with trialkylsilylacetylene. Use amount, substance and conditions can be applied. The amount of the 3-haloaryl metal reagent represented by the general formula (14) is preferably 0.9 to 2.0 equivalents relative to 1 equivalent of the dihalochalcogenophene derivative represented by the general formula (13), and Preferably it is 1.1-1.5 equivalent, Most preferably, it is 1.1-1.3 equivalent.

The carbon-carbon bond in the reaction of the dihalochalcogenophene derivative represented by the general formula (13) and the 3-haloaryl metal reagent represented by the general formula (14) is the dihalochalcone represented by the general formula (13). It is formed at the 2-position of the genophene derivative (position where the substituent X ⁷ is bonded). This is based on the extremely high reactivity at the 2-position of the dihalochalcogenophene derivative represented by the general formula (13).

Further, the dihalochalcogenophenylaryl derivative represented by the general formula (7) can be used for halogen / metal exchange with a dihalochalcogenophene derivative represented by the general formula (13) and an organic lithium reagent such as Grignard reagent or n-butyllithium. It can also be produced by metallizing the substituent X ⁷ by a reaction and then reacting it with a 2,3-dihaloarene derivative represented by the general formula (10) in the presence of a palladium and / or nickel catalyst.

  The dihalochalcogenophenylaryl derivative represented by the general formula (7) thus obtained can be further purified. The method for purification is not particularly limited, and examples thereof include column chromatography, recrystallization, or sublimation.

(Method for producing dihalochalcogenophene derivative)
Next, a method for producing a dihalochalcogenophene derivative which is a raw material compound of the dihalochalcogenophenylaryl derivative represented by the general formula (7) will be described.

  The dihalochalcogenophene derivative represented by the general formula (13) can be produced, for example, by reacting a halo (trimethylsilyl) chalcogenophene derivative represented by the following general formula (15) with a halogen derivative.

(Here, the substituents X ⁴ and T ¹ and ring A have the same meanings as the substituent and ring represented by formula (13).)
The halogen derivative is not particularly limited as long as the trimethylsilyl group of the general formula (15) can be substituted with a halogen atom. For example, iodine monochloride, iodine bromide, iodine, bromine, chlorine, NIS, NBS NCS, etc., preferably iodine monochloride and iodine bromide, particularly preferably iodine monochloride.

  The amount of the halogen derivative used is preferably 0.9 to 1.5, more preferably 1.0 to 1.2 equivalents per 1 equivalent of the halo (trimethylsilyl) chalcogenophene derivative represented by the general formula (15). .

  The reaction with the halogen derivative is preferably carried out in a solvent. The solvent to be used is not particularly limited, and examples thereof include dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, THF, ether, ethyl-tert-butyl ether, toluene, hexane, and the like. Preferred are dichloromethane and chloroform. These solvents may be used alone or as a mixture of two or more. The temperature of the reaction is preferably -20 to 50 ° C, particularly preferably -10 to 30 ° C. The reaction time is preferably 0.5 to 6 hours, particularly preferably 1 to 4 hours. The progress of the reaction can be monitored by analyzing with thin layer chromatography or gas chromatography.

  The dihalochalcogenophene derivative represented by the general formula (13) thus obtained can be further purified. The method for purification is not particularly limited, and examples thereof include column chromatography, recrystallization, or sublimation.

  On the other hand, a halo (trimethylsilyl) chalcogenophene derivative represented by the general formula (15), which is a raw material of the dihalochalcogenophene derivative represented by the general formula (13), is represented by the following general formula (16) (alkylchalcogenyl). ) (Trimethylsilylethynyl) arene derivative and halogen derivative can be reacted.

(Here, the substituent R ¹³ represents an alkyl group having 1 to 8 carbon atoms, and the substituent T ¹ and ring A have the same meaning as the substituent and ring represented by the general formula (15).)
The alkyl group having 1 to 8 carbon atoms in the substituent R ¹³ is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a benzyl group, preferably a methyl group and a benzyl group. More preferably, it is a methyl group.

  The halogen derivative is not particularly limited as long as the unsaturated bond can be halogenated, and examples thereof include iodine, bromine, chlorine, NIS, NBS, NCS, etc., preferably iodine and bromine, particularly preferably. It is iodine. The amount of the halogen derivative used is preferably 0.9 to 1.6 equivalents, more preferably 1.0 to 1 equivalent to 1 equivalent of the (alkylchalcogenyl) (trimethylsilylethynyl) arene derivative represented by the general formula (16). 1.3 equivalents.

  The halogenation is preferably carried out in a solvent. The solvent to be used is not particularly limited. For example, dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, dichlorobenzene, THF, ether, methyl-tert-butyl ether, ethyl-tert-butyl ether. , Ethylene glycol dimethyl ether, dioxane, toluene, hexane, cyclohexane and the like, particularly preferably dichloromethane and chloroform. These solvents may be used alone or as a mixture of two or more. The halogenation temperature is preferably 0 to 80 ° C., particularly preferably 20 to 60 ° C. The reaction time is preferably 1 to 24 hours, particularly preferably 2 to 12 hours. The progress of halogenation can be monitored by analysis by thin layer chromatography or gas chromatography.

  In addition, the (alkylchalcogenyl) (trimethylsilylethynyl) arene derivative represented by the general formula (16) is obtained by metallizing a 2-trimethylsilylethynyl-3-haloarene derivative using a metallizing agent, for example, and dialkyldisulfide and / or dialkyl. It can be produced by reacting with diselenide. As the reaction conditions for this reaction, the same reaction conditions as those for producing the di (alkylchalcogeno) diarylethyne derivative represented by the general formula (2) can be applied. Further, the 2-trimethylsilylethynyl-3-haloarene derivative can be prepared by a palladium-catalyzed reaction (Sonogashira coupling) of a 2,3-dihaloarene derivative represented by the general formula (8) and trimethylsilylacetylene. As the catalyst and conditions for this reaction, the same catalyst and conditions as in the production of the dihalodiarylethyne derivative represented by the general formula (3) can be applied.

(Oxidation-resistant organic semiconductor materials)
Next, an oxidation resistant organic semiconductor material containing the heteroacene derivative represented by the general formula (1) of the present invention will be described. The oxidation-resistant organic semiconductor material is excellent in solubility in a solvent and oxidation resistance, and has suitable coating properties. The oxidation-resistant organic semiconductor material can be produced by dissolving the heteroacene derivative represented by the general formula (1) of the present invention in a solvent.

The solvent used for dissolving the heteroacene derivative represented by the general formula (1) of the present invention is not particularly limited. For example, o-dichlorobenzene, chlorobenzene, trichlorobenzene, 1,2-dichloroethane, 1,1,2,2- Halogen solvents such as tetrachloroethane, chloroform and dichloromethane; ether solvents such as THF and dioxane; aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, biphenyl, ethylbenzene and octylbenzene; ethyl acetate, γ-butyrolactone, etc. Ester solvents; amide solvents such as DMF and NMP; and the like. These solvents may be used alone or as a mixture of two or more. Of these, chlorobenzene, toluene and the like are preferable.

  By mixing and stirring the above-mentioned solvent and the heteroacene derivative represented by the general formula (1), an oxidation-resistant organic semiconductor material containing the heteroacene derivative represented by the general formula (1) is obtained. The temperature at the time of mixing and stirring is preferably 10 to 150 ° C, particularly preferably 20 to 100 ° C. The density | concentration of the heteroacene derivative shown by General formula (1) at the time of mixing and stirring can be changed with a solvent and temperature, and it is preferable that it is 0.01-10.0 weight%. The solution can be prepared in air, but is preferably prepared in an inert atmosphere such as nitrogen or argon.

  Evaluation of the oxidation resistance of the oxidation-resistant organic semiconductor material containing the heteroacene derivative represented by the general formula (1) can be performed by a method in which the solution is brought into contact with air for a predetermined time. First, the solvent to be used is degassed in advance to remove dissolved oxygen. The contact time with air can be appropriately selected depending on the temperature, and is preferably 0.5 minutes to 3 hours. Oxidation can proceed by changing the color of the solution and detecting oxides by thin layer chromatography, gas chromatography, and gas chromatography (GC) -mass spectrum (GCMS) analysis.

  The oxidation-resistant organic semiconductor material containing the heteroacene derivative represented by the general formula (1) of the present invention has a relatively low temperature because the heteroacene derivative itself represented by the general formula (1) used has appropriate cohesiveness. Since it can be dissolved in a solvent and has oxidation resistance, it can be suitably applied to the production of an organic thin film by a coating method. That is, since it is not necessary to strictly remove air from the atmosphere, the coating process can be simplified. The coating can be carried out in the air, but is preferably performed under a nitrogen stream in consideration of drying of the solvent. In order to obtain suitable coating properties, the viscosity of the oxidation-resistant organic semiconductor material containing the heteroacene derivative represented by the general formula (1) of the present invention is preferably in the range of 0.005 to 20 poise.

(Organic thin film)
Next, an organic thin film using an oxidation-resistant organic semiconductor material containing a heteroacene derivative represented by the general formula (1) of the present invention will be described. Such an organic thin film can be produced by recrystallization of the above-mentioned oxidation-resistant organic semiconductor material (solution) or application to a substrate, and it is particularly preferred to produce it by application to a substrate. And it becomes an organic thin film formed on a board | substrate by manufacturing by application | coating to a board | substrate.

  The thin film by recrystallization can be formed by cooling the oxidation-resistant organic semiconductor material. The atmosphere for cooling the organic thin film is preferably carried out under an inert gas such as nitrogen or argon or under air, particularly preferably under an inert gas such as nitrogen or argon. The concentration of the heteroacene derivative represented by the general formula (1) in the solution is not particularly limited and is, for example, 0.01 to 10.0% by weight. Cooling is preferably performed at a temperature of 60 to 150 ° C. to −20 to 60 ° C., particularly preferably by cooling between −10 ° C. and 40 ° C. In addition, the crystalline organic thin film thus produced can be laminated on an appropriate substrate, that is, produced on the substrate by lamination or the like. The thickness of the organic thin film obtained by recrystallization is not particularly limited, and is preferably 50 nm to 2 mm, particularly preferably 1 to 500 μm.

  The production of the organic thin film by application to the substrate can be performed by applying the oxidation-resistant organic semiconductor material on the substrate and then evaporating the solvent by a method such as heating, air flow, and natural drying. The concentration of the heteroacene derivative represented by the general formula (1) in the solution is not particularly limited, and is preferably 0.01 to 10.0% by weight, for example. There is no particular limitation on the coating temperature, and for example, it can be suitably carried out between 20 and 150 ° C. The specific method of application is not particularly limited, and known methods such as spin coating, cast coating, and dip coating can be used. Further, it can be produced by using a printing technique such as screen printing, ink jet printing, or gravure printing. The material of the substrate to be used is not particularly limited, and various crystalline and non-crystalline materials can be used. Specific examples of the substrate include, for example, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polyethylene, polypropylene, polystyrene, cyclic polyolefin, polyimide, polycarbonate, polyvinylphenol, polyvinyl alcohol, poly (diisopropyl fumaric acid), poly (diethyl fumaric acid). ), Plastic substrates such as poly (diisopropylmaleic acid); inorganic material substrates such as glass, quartz, aluminum oxide, silicon, silicon oxide, tantalum dioxide, tantalum pentoxide, indium tin oxide; gold, copper, chromium, titanium, A metal substrate such as aluminum can be suitably used. Also, the surface of these substrates is used even if it is modified with silanes such as octadecyltrichlorosilane, octyltrichlorosilane, octadecyltrimethoxysilane, and β-phenethyltrichlorosilane; and silylamines such as hexamethyldisilazane. can do. Further, the substrate may be made of an insulating or dielectric material. Drying of the solvent after coating can be removed under normal pressure or reduced pressure, or it may be dried by heating or a nitrogen stream. Furthermore, crystal growth of the heteroacene derivative represented by the general formula (1) of the present invention can be controlled by adjusting the evaporation rate of the solvent. The film thickness of the organic thin film obtained by application | coating to a board | substrate does not have limitation in particular, Preferably it is 1 nm-100 micrometers, Especially preferably, it is 10 nm-20 micrometers.

  The organic thin film can be annealed at 40 to 120 ° C. after coating and drying.

  Since the heteroacene derivative represented by the general formula (1) of the present invention has a molecular structure with high planar rigidity, it can be expected to give excellent semiconductor characteristics. Further, the heteroacene derivative is dissolved in a solvent such as toluene or chlorobenzene, and is not easily oxidized by air even in a solution state. Therefore, a semiconductor thin film can be easily formed by a coating method. Therefore, the heteroacene derivative represented by the general formula (1) of the present invention is used in an organic semiconductor active phase of a transistor such as an electronic paper, an organic EL display, a liquid crystal display, and an IC tag; an organic EL display material; an organic semiconductor laser material; Organic thin-film solar cell materials; can be used for electronic materials such as photonic crystal materials.

  Provided are a heteroacene derivative having high performance and excellent oxidation resistance due to a long molecular long axis, and capable of forming an organic semiconductor active phase by a coating method, and uses thereof. Furthermore, the present invention also provides di (alkylchalcogeno) diarylethyne derivatives and di (alkylchalcogeno) diarylethylene derivative derivatives, which are precursor compounds of the heteroacene derivative, and methods for producing them.

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

For the identification of the product, ¹ H-NMR spectrum and mass spectrum were used. For the ¹ H-NMR spectrum, JEOL GSX-270WB (270 MHz) manufactured by JEOL Ltd. was used. The mass spectrum (MS) is obtained by directly introducing a sample using JEOL JMS-700 manufactured by JEOL, and by electron impact (EI) method (70 electron volts) or FAB method (6 kiloelectron volts, xenon gas, matrix (2- Nitrophenyl octyl ether).

  For confirmation of the progress of the reaction, etc., thin layer chromatography, gas chromatography (GC), or gas chromatography-mass spectrum (GCMS) analysis was used.

Gas chromatography analyzer Shimadzu GC14B
Column J & W Scientific, DB-1, 30m
Gas chromatography-mass spectrum analyzer Perkin Elmer Auto System XL (MS part; Turbomass Gold)
Column J & W Scientific, DB-1, 30m
Commercially available reagents and solvents for reaction were used unless otherwise specified. When a Grignard reagent or an organometallic reagent such as butyl lithium was used, a commercially available dehydrated solvent was used as it was.

Synthesis Example 1 (Synthesis of 4-bromo-5-iodophthalic anhydride)
4-Bromo-5-iodophthalic anhydride was synthesized as follows with reference to “Journal of Organic Chemistry” (USA), 1951, Vol. 16, pp. 1577-1581.

4-Bromophthalimide (Tokyo Chemical Industry Co., Ltd.) 9.95 g (44.0 mmol) was placed in a 50 ml two-necked eggplant flask substituted with nitrogen gas. Subsequently, 5.87 g (23.1 mmol) of iodine and 12 ml of 10% fuming sulfuric acid (manufactured by Yotsuhata Chemical Industry) were added, and the reaction was performed at 90 ° C. for 23 hours. The reaction mixture was cooled to room temperature and poured into ice, and then filtered through a glass filter to obtain 12.8 g of a yellow solid. The obtained solid was dissolved in 35 ml of concentrated sulfuric acid and reacted at 130 ° C. for 5 hours. The reaction mixture was ice-cooled, ice water was added and the precipitated solid was filtered to obtain 13.8 g of a phthalic acid derivative solid. Next, the obtained solid was dissolved in an aqueous solution obtained by dissolving 3.6 g of sodium hydroxide in 18 ml of water at room temperature. Acetic acid was added to this basic aqueous solution to adjust the pH to 3 to 4, and the white precipitate of the monosodium salt of the phthalic acid derivative was filtered. The obtained white solid was suspended in water, the pH was adjusted to 1 or less with concentrated hydrochloric acid, and 6.45 g of a white solid was obtained again as a phthalic acid derivative. This solid was dissolved in 48 ml of toluene, 8.7 g (85.7 mmol) of acetic anhydride was added, and the reaction was performed at 105 ° C. for 4 hours. The reaction solution was concentrated under reduced pressure to obtain 5.87 g of a white solid. This solid was recrystallized and purified with toluene to obtain 5.13 g (14.5 mmol) of the desired 4-bromo-5-iodophthalic anhydride (yield 33%).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 8.51 (s, 1H), 8.23 (s, 1H).
_{^{MS m / z: 353 (M}} +, 100%), 309 (M + -CO 2, 18%), 282 (M + -C 2 O 3, 10%), 155 (M + -C 2 O 3 - _{^{I, 16%), 74 (}} M + -C 2 O 3 -I-Br, 32%).

Synthesis Example 2 (Synthesis of 1,2-didodecylbenzene)
1,2-didodecylbenzene was synthesized as follows according to “The Chemical Society of Japan”, 1989, pages 983-987.

Dodecyl was added to a mixture of 2.22 g (15.1 mmol) of 1,2-dichlorobenzene, 131 mg (0.24 mmol) of dichloro [1,3-bis (diphenylphosphino) propane] nickel (Tokyo Chemical Industry) and 12 ml of ether. 45 ml (45.0 mmol) of magnesium bromide (manufactured by Sigma-Aldrich, 1.0 mol / l ether solution) was added dropwise at 0 ° C. in a nitrogen atmosphere. The reaction was performed at 35 ° C. for 20 hours, the reaction mixture was cooled to 0 ° C., diluted hydrochloric acid was added, and the mixture was extracted with ether. The ether solution was washed with water, a saturated aqueous sodium hydrogen carbonate solution and water in this order, and dried over calcium chloride. The resulting liquid was purified by silica gel column chromatography (eluent: hexane) and vacuum distillation to obtain 5.56 g (13.4 mmol) of the desired 1,2-didodecylbenzene (yield 88%).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 7.11 (m, 4H), 2.59 (t, J = 7.8 Hz, 4H), 1.55 (m, 4H), 1.26 ( m, 36H), 0.88 (t, J = 6.8 Hz, 6H).
_{^{MS m / z: 414 (M}} +, 100%), 260 (M + -C 11 H 23, 71%), 106 (M + -C 22 H 46, 98%).

Synthesis Example 3 (Synthesis of 2-bromo-3-iodo-6,7-didodecylanthraquinone)
2-Bromo-3-iodo-6,7-didodecylanthraquinone was synthesized as follows with reference to “Berichte” (Germany), 1933, 66B, pages 1876-1891.

4-Bromo-5-iodophthalic anhydride 2.82 g (8.00 mmol) obtained in Synthesis Example 1, 3.32 g (8.00 mmol) of 1,2-didodecylbenzene obtained in Synthesis Example 2, tetra To a mixed solution of 5.0 ml of chloroethane, 2.41 g (18.1 mmol) of aluminum chloride was added and reacted at room temperature for 3 hours. The reaction was quenched by adding water, and further washed with water. After heating and vacuum drying, 6.2 g of a white solid was obtained. 44 ml of concentrated sulfuric acid was added to the obtained solid and reacted at 80 ° C. for 1 hour. The reaction mixture was poured into ice, and the precipitated solid was filtered and washed with water. After drying, the product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate, 10: 1) and recrystallization from heptane, and a solid of 2.20 g of 2-bromo-3-iodo-6,7-didodecylanthraquinone. (5.60 mmol) was obtained (yield 70%).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 8.73 (s, 1H), 8.45 (s, 1H), 8.05 (s, 2H), 2.75 (m, 4H), 1 .62 (m, 4H), 1.26 (m, 36H), 0.88 (m, 6H).
_{^{MS m / z: 750 (M}} +, 100%), 440 (M + -C 22 H 46, 8%), 313 (M + -C 22 H 46 I, 2%), 233 (M + -C 22 H ₄₆ IBr, 1%).

Synthesis Example 4 (Synthesis of 2-bromo-3-iodo-6,7-didodecylanthracene) (Synthesis of compounds of general formulas (8) and (10))
Under a nitrogen atmosphere, 1.10 g (1.47 mmol) of 2-bromo-3-iodo-6,7-didodecylanthraquinone synthesized in Synthesis Example 3 was placed in a 100 ml Schlenk reaction vessel. Next, 17 ml of THF was added, 4.0 ml (4.0 mmol) of diisobutylaluminum hydride (manufactured by Kanto Chemical Co., 0.99 mol / l, toluene solution) was added, and the reaction was performed at room temperature for 1.5 hours. Subsequently, 10 ml of 6M hydrochloric acid aqueous solution was added to the reaction mixture, and the reaction was performed at 65 ° C. for 3 hours. The reaction mixture was cooled to room temperature and extracted with ether. The ether solution was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. To the obtained residue was again added 17 ml of THF, 4.0 ml (4.0 mmol) of diisobutylaluminum hydride was added, and 1.5 ml at room temperature. Time reaction was performed. Subsequently, 10 ml of 6M hydrochloric acid aqueous solution was added to the reaction mixture, and reaction was performed for 3 hours. The reaction mixture was cooled to room temperature and extracted with ether. The ether solution was washed with saturated brine, dried over anhydrous sodium sulfate, and dried under reduced pressure. Purification by silica gel column chromatography (eluent: hexane) gave 629 mg (0.87 mmol) of a yellow solid of 2-bromo-3-iodo-6,7-didodecylanthracene (yield 59%).
_{^{1 H NMR (CDCl 3, 22}} ℃): δ = 8.55 (s, 1H), 8.27 (s, 1H), 8.16 (s, 1H), 8.15 (s, 1H), 7 .72 (s, 2H), 2.78 (m, 4H), 1.71 (m, 4H), 1.27 (m, 36H), 0.88 (m, 6H).
_{^{MS m / z: 720 (M}} +, 100%), 410 (M + -C 22 H 46, 16%), 283 (M + -C 22 H 46 -I, 4%), 203 (M + -C _{22 H 46 -I-Br, 5} ).

Example 1 (Synthesis of dibromo (tetradodecyl) dianthrylethine) (Synthesis of dihalodiarylethyne derivative of general formula (3))
Under a nitrogen atmosphere, 625 mg (0.868 mmol) of 2-bromo-3-iodo-6,7-didodecylanthracene (a compound of the general formula (8)) synthesized in Synthesis Example 4 in a 100 ml Schlenk reaction vessel, 4 ml of THF, and diisopropyl 12 ml of amine was added. Further, 30.5 mg (0.043 mmol) of dichlorobis (triphenylphosphine) palladium (manufactured by Wako Pure Chemical Industries), 19.8 mg (0.10 mmol) of copper (I) iodide (manufactured by Wako Pure Chemical Industries), and trimethylsilylacetylene ( 0.15 ml (1.05 mmol) of Wako Pure Chemical Industries) was added. The mixture was reacted at 26 ° C. for 16 hours. The reaction mixture was concentrated under reduced pressure, the solvent was distilled off, and further dried under vacuum. Toluene was added to the obtained residue, 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) (0.06 ml) was added, and the mixture was stirred at room temperature for 1 hour. This solution was washed with water, and the organic phase was passed through silica gel (solvent: toluene). The eluate was concentrated under reduced pressure, and 8 ml of methanol and 360 mg (2.60 mmol) of potassium carbonate were added to 608 mg of the resulting residue (based on 2-trimethylsilylethynyl-3-bromo-6,7-didodecylanthracene). And allowed to react at room temperature for 10 hours (detrialkylylsilyl treatment). The reaction mixture was concentrated under reduced pressure, the solvent was distilled off, and further dried under vacuum. Ether was added to the resulting residue and washed with water. The organic phase was concentrated under reduced pressure, and 550 mg of a viscous product containing 2-ethynyl-3-bromo-6,7-didodecylanthracene (2-ethynyl-3-haloarene derivative represented by the general formula (9)) as a main component Got.

4 ml of THF and 12 ml of diisopropylamine were added to 550 mg of a viscous product mainly composed of 2-ethynyl-3-bromo-6,7-didodecylanthracene. In dichlorobis (triphenylphosphine) palladium (manufactured by Wako Pure Chemical Industries) 29.0 mg (0.041 mmol), copper (I) iodide (manufactured by Wako Pure Chemical Industries) 19.4 mg (0.10 mmol), and Synthesis Example 4 630 mg (0.875 mmol) of synthesized 2-bromo-3-iodo-6,7-didodecylanthracene (compound of general formula (10)) was added. The mixture was reacted at 26 ° C. for 16 hours. The reaction mixture was concentrated under reduced pressure, the solvent was distilled off, and further dried under vacuum. Toluene was added to the obtained residue, 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) (0.06 ml) was added, and the mixture was stirred at room temperature for 1 hour. This solution was washed with water, and the organic phase was concentrated under reduced pressure and purified by silica gel column chromatography (solvent; hexane: methylene chloride = 10: 1) to obtain 724 mg of dibromo (tetradodecyl) dianthrylethine as a yellow solid ( Yield 69%).
FABMS m / z: 1210 (M ⁺ , 100%), 1130 (M ⁺ -Br, 8).

  From MS measurement, it was confirmed that dibromo (tetradodecyl) dianthrylethine was obtained. The structural formula is shown below.

Example 2 (Synthesis of dibromo (tetradodecyl) dianthracenylethine) (dihalodiarylethyne derivative of general formula (3))
Under a nitrogen atmosphere, 879 mg (1.22 mmol) of 2-bromo-3-iodo-6,7-didodecylanthracene (compound of general formula (8)) synthesized in Synthesis Example 4 in a 100 ml Schlenk reaction vessel, 6 ml of toluene, and 5 ml piperidine was added. Further, 16.8 mg (0.024 mmol) of dichlorobis (triphenylphosphine) palladium (manufactured by Wako Pure Chemical Industries) and 10.0 mg (0.053 mmol) of copper (I) iodide (manufactured by Wako Pure Chemical Industries) were added. The mixture was heated to 60 ° C., and the reaction was carried out for 1.5 hours while slowly introducing an acetylene gas through a dip tube immersed in the solution. After stopping the introduction of the acetylene gas, the reaction was continued for another 3 hours. After cooling to room temperature, toluene was added and washed with water. The organic phase was washed with 5% sulfuric acid aqueous solution, saturated aqueous sodium hydrogen carbonate and saturated brine in this order. A 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) (0.06 ml) was added to the obtained organic phase, and the mixture was stirred at room temperature for 1 hour. This solution was washed with water, and the organic phase was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; hexane: methylene chloride = 10: 1) to obtain 530 mg of dibromo (tetradodecyl) dianthrylethine as a yellow solid (yield 72%).

Example 3 (Synthesis of dibromo (tetradodecyl) dianthrylethine) (dihalodiarylethyne derivative of general formula (3))
Under a nitrogen atmosphere, 454 mg (0.631 mmol) of 2-bromo-3-iodo-6,7-didodecylanthracene (compound of general formula (8)) synthesized in Synthesis Example 4 in a 100 ml Schlenk reaction vessel, trimethylsilylacetylene 31. 0 mg (0.315 mmol), diisopropylamine 5 ml, toluene 2 ml, water 4.4 mg (0.246 mmol), and 1,8-diazabicyclo [5.4.0] -7-undecene 57.7 mg (0.379 mmol) ( Tokyo Chemical Industry) was added. Further, 22.1 mg (0.032 mmol) of dichlorobis (triphenylphosphine) palladium (manufactured by Wako Pure Chemical Industries) and 16.8 mg (0.088 mmol) of copper (I) iodide (manufactured by Wako Pure Chemical Industries) were added. The mixture was heated to 60 ° C. and the reaction was continued for 20 hours. After cooling to room temperature, toluene was added and washed with water. The organic phase was washed with 5% sulfuric acid aqueous solution, saturated aqueous sodium hydrogen carbonate and saturated brine in this order. A 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) (0.06 ml) was added to the obtained organic phase, and the mixture was stirred at room temperature for 1 hour. This solution was washed with water, and the organic phase was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; hexane: methylene chloride = 10: 1) to obtain 126 mg of dibromo (tetradodecyl) dianthrylethine as a yellow solid (yield 33%).

Synthesis Example 5 (Synthesis of 2-bromo-3-iodo-6,7- (dodecyl) fluoroanthracene) (Synthesis of compounds of general formulas (8) and (10))
The same operation as in Synthesis Example 2 was repeated except that 1-chloro-2-fluorobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 1,2-dichlorobenzene in Synthesis Example 2, and 1-dodecyl-2-fluorobenzene was repeated. Was synthesized. Using this 1-dodecyl-2-fluorobenzene and 4-bromo-5-iodophthalic anhydride obtained in Synthesis Example 1, the same operation as in Synthesis Example 3 was repeated and 2-bromo-3-iodo-6,7- (Dodecyl) fluoroanthraquinone was obtained, and further the same operation as in Synthesis Example 4 was repeated to convert to 2-bromo-3-iodo-6,7- (dodecyl) fluoroanthracene.

Example 4 (Synthesis of dibromodifluoro (didodecyl) dianthrylethine) (dihalodiarylethyne derivative of general formula (3))
Under a nitrogen atmosphere, 464 mg (0.815 mmol) of 2-bromo-3-iodo-6-dodecyl-7-fluoroanthracene (compound of general formula (8)) synthesized in Synthesis Example 5 in a 100 ml Schlenk reaction vessel, 4 ml of toluene, And 3 ml of piperidine was added. Further, 14.5 mg (0.021 mmol) of dichlorobis (triphenylphosphine) palladium (manufactured by Wako Pure Chemical Industries) and 8.4 mg (0.044 mmol) of copper (I) iodide (manufactured by Wako Pure Chemical Industries) were added. The mixture was heated to 60 ° C., and the reaction was carried out for 1.5 hours while slowly introducing an acetylene gas through a dip tube immersed in the solution. After stopping the introduction of the acetylene gas, the reaction was continued for another 3 hours. After cooling to room temperature, toluene was added and washed with water. The organic phase was washed with 5% sulfuric acid aqueous solution, saturated aqueous sodium hydrogen carbonate and saturated brine in this order. A 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) (0.06 ml) was added to the obtained organic phase, and the mixture was stirred at room temperature for 1 hour. This solution was washed with water, and the organic phase was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; hexane: methylene chloride = 10: 1) to obtain 237 mg of a yellow solid composed of a mixture of isomers of dibromodifluoro (didodecyl) dianthrylethine (yield: 64). %).
FABMS m / z: 909 (M ⁺ , 100%), 829 (M ⁺ -Br, 7).
From the MS measurement, it was confirmed that dibromodifluoro (didodecyl) dianthrylethine was obtained. The structural formula is shown below.

Synthesis Example 6 (Synthesis of 4-bromo-1,2-diiodobenzene)
To a 100 ml Schlenk reaction vessel, 5.56 g (16.8 mmol) of 1,2-diiodobenzene (manufactured by Tokyo Chemical Industry) and 30 ml of dichloromethane were added and cooled to 0 ° C. After adding 67 mg of iron powder (manufactured by Sigma-Aldrich) and 10 mg (0.04 mmol) of iodine, 0.87 ml (17 mmol) of bromine was added dropwise. After stirring at 0 ° C. for 8 hours, an aqueous sodium hydrogen sulfite solution was added to stop the reaction. The organic phase was washed with water and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the resulting residue was recrystallized twice from THF / methanol to obtain 4.94 g of white crystals of 4-bromo-1,2-diiodobenzene (yield 72%).

Synthesis Example 7 (Synthesis of 4-bromo-1,2- (perfluorododecyl) benzene)
4-Bromo-1,2- (perfluorododecyl) benzene was synthesized as follows with reference to “Journal of Fluorine Chemistry”, 1989, 43, 207-228.

  In a 100 ml Schlenk reaction vessel under a nitrogen atmosphere, 2.85 g (44.8 mmol) of copper powder (copper bronze) (manufactured by Sigma-Aldrich), 18.4 g (24.6 mmol) of perfluorododecyl iodide (manufactured by Synquest), 4.58 g (11.2 mmol) of 4-bromo-1,2-diiodobenzene synthesized in Synthesis Example 6 and 18 ml of dimethyl sulfoxide were added, heated to 125 ° C., and reacted for 8 hours. After cooling to room temperature, water was added to stop the reaction. More ether was added and the mixture was filtered through celite. The filtrate was extracted with ether, and the combined organic phases were washed with water and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the resulting residue was purified by silica gel column chromatography (solvent: hexane) to obtain 6.24 g of 4-bromo-1,2- (perfluorododecyl) benzene as a colorless liquid (yield 40). %).

Synthesis Example 8 (Synthesis of 2-bromo-3-iodo-6,7-di (perfluorododecyl) anthraquinone)
Under a nitrogen atmosphere, 6.11 g (4.39 mmol) of 4-bromo-1,2- (perfluorododecyl) benzene obtained in Synthesis Example 7 and 80 ml of THF were added to a 300 ml Schlenk reaction vessel. The solution was cooled to −50 ° C., and 6.8 ml (4.4 mmol) of a THF solution of isopropyl magnesium bromide (manufactured by Kanto Chemical Co., Ltd., 0.65 M) was added dropwise. After aging at −50 ° C. for 30 minutes, a solution consisting of 1.48 g (4.20 mmol) of 4-bromo-5-iodophthalic anhydride synthesized in Synthesis Example 1 and 20 ml of THF was added dropwise thereto. The reaction mixture was allowed to warm to room temperature overnight, then cooled on ice and 3M aqueous hydrochloric acid was added. The mixture was extracted with ether, and the combined organic phases were washed with saturated brine and dried over anhydrous magnesium sulfate. Concentration under reduced pressure gave 7.00 g of a white solid. Concentrated sulfuric acid (40 ml) was added to the obtained solid and reacted at 80 ° C. for 12 hours. The reaction mixture was poured into ice, and the precipitated solid was filtered and washed with water. After drying, it was purified by silica gel column chromatography (eluent; hexane: methylene chloride = 15: 1) and recrystallization from heptane, and 2-bromo-3-iodo-6,7-di (perfluorododecyl) anthraquinone was purified. 1.86 g (1.13 mmol) of solid was obtained (27% yield).

Synthesis Example 9 (Synthesis of 2-bromo-3-iodo-6,7-di (perfluorododecyl) anthracene) (Synthesis of compounds of general formulas (8) and (10))
Under a nitrogen atmosphere, 1.81 g (1.10 mmol) of 2-bromo-3-iodo-6,7-di (perfluorododecyl) anthraquinone synthesized in Synthesis Example 8 was placed in a 100 ml Schlenk reaction vessel. Next, 15 ml of THF was added, 3.5 ml (3.5 mmol) of diisobutylaluminum hydride (manufactured by Kanto Chemical Co., 0.99 mol / l, toluene solution) was added, and the reaction was performed at room temperature for 1.5 hours. Subsequently, 10 ml of 6M hydrochloric acid aqueous solution was added to the reaction mixture, and the reaction was performed at 65 ° C. for 3 hours. The reaction mixture was cooled to room temperature and extracted with ether. The ether solution was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. To the obtained residue, 15 ml of THF was added again, 3.5 ml (3.5 mmol) of diisobutylaluminum hydride was added, and the reaction was performed at room temperature for 1.5 hours. Subsequently, 10 ml of 6M hydrochloric acid aqueous solution was added to the reaction mixture, and reaction was performed for 3 hours. The reaction mixture was cooled to room temperature and extracted with ether. The ether solution was washed with saturated brine, dried over anhydrous sodium sulfate, and dried under reduced pressure. Purification by silica gel column chromatography (eluent: hexane) gave 1.12 g of a yellow solid of 2-bromo-3-iodo-6,7-di (perfluorododecyl) anthracene (yield 63%).

Example 5 (Synthesis of dibromotetra (perfluorododecyl) dianthracenylethine) (dihalodiarylethyne derivative of general formula (3))
Under a nitrogen atmosphere, 1.07 g (0.661 mmol) of 2-bromo-3-iodo-6,7-di (perfluorododecyl) anthracene (compound of general formula (8)) synthesized in Synthesis Example 9 in a 100 ml Schlenk reaction vessel ), 7 ml of toluene, and 6 ml of piperidine. Further, 23.2 mg (0.033 mmol) of dichlorobis (triphenylphosphine) palladium (manufactured by Wako Pure Chemical Industries) and 13.2 mg (0.069 mmol) of copper (I) iodide (manufactured by Wako Pure Chemical Industries) were added. The mixture was heated to 60 ° C., and the reaction was carried out for 1.5 hours while slowly introducing an acetylene gas through a dip tube immersed in the solution. After stopping the introduction of the acetylene gas, the reaction was continued for another 3 hours. After cooling to room temperature, toluene was added and washed with water. The organic phase was washed with 5% sulfuric acid aqueous solution, saturated aqueous sodium hydrogen carbonate and saturated brine in this order. A 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) (0.08 ml) was added to the obtained organic phase, and the mixture was stirred at room temperature for 1 hour. This solution was washed with water, and the organic phase was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; hexane: methylene chloride = 20: 1) to obtain 407 mg of dibromotetra (perfluorododecyl) dianthrylethine as a yellow solid (yield 41%).
FABMS m / z: 3009 (M ⁺ , 100%).

  From MS measurement, it was confirmed that dibromotetra (perfluorododecyl) dianthrylethine was obtained. The structural formula is shown below.

Synthesis Example 10 (Synthesis of 4-bromo-1,2-diphenylbenzene)
Under a nitrogen atmosphere, in a 200 ml Schlenk reaction vessel, 2.47 g (5.25 mmol) of 4-bromo-1,2-diiodobenzene obtained in Synthesis Example 6 and 1.47 g of dihydroxyphenylborane (manufactured by Wako Pure Chemical Industries, Ltd.) (12.1 mmol), tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) 458 mg (0.40 mmol), sodium carbonate 3.34 g (31.5 mmol), toluene 42 ml, ethanol 10.5 ml, water 13.3 ml. In addition, the mixture was reacted at 80 ° C. for 29 hours. The reaction was quenched with 1M aqueous hydrochloric acid and extracted with toluene. The organic layer was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and purified by silica gel column chromatography (eluent: hexane) to obtain 1.46 g (4.72 mmol) of the desired 4-bromo-1,2-diphenylbenzene (yield 90%). .

Synthesis Example 11 (Synthesis of 2-bromo-3-iodo-6,7-diphenylanthraquinone)
Under a nitrogen atmosphere, 1.46 g (4.72 mmol) of 4-bromo-1,2-diphenylbenzene obtained in Synthesis Example 10 was placed in a 300 ml Schlenk reaction vessel. Next, 28 ml of THF was added and cooled to −78 ° C., and 3.0 ml (4.77 mmol) of n-butyllithium (manufactured by Kanto Chemical Co., Ltd., 1.59 mol / l, hexane solution) was added and reacted for 30 minutes. Next, 1.66 g (4.72 mmol) of 4-bromo-5-iodophthalic anhydride synthesized in Synthesis Example 1 was added, and the temperature was raised to room temperature. The solid obtained by quenching by adding water was filtered, washed with water, and dried under heating in vacuum to obtain 3.2 g of a white solid. 26 ml of concentrated sulfuric acid was added to the obtained solid and reacted at 80 ° C. for 1 hour. The reaction mixture was poured into ice, and the precipitated solid was filtered and washed with water. After drying, the residue was purified by silica gel column chromatography (eluent: hexane / methylene chloride, 10: 1) and recrystallization from heptane to give 298 mg (0 mg of a yellow solid of 2-bromo-3-iodo-6,7-diphenylanthraquinone. .53 mmol) (yield 11%).

Synthesis Example 12 (Synthesis of 2-bromo-3-iodo-6,7-diphenylanthracene) (Synthesis of compounds of general formulas (8) and (10))
Under a nitrogen atmosphere, 243 mg (0.43 mmol) of 2-bromo-3-iodo-6,7-diphenylanthraquinone synthesized in Synthesis Example 11 and 5 ml of THF were added to a 50 ml Schlenk reaction vessel. 1.20 ml (1.20 mmol) of diisobutylaluminum hydride (manufactured by Kanto Chemical Co., 0.99 mol / l, toluene solution) was added dropwise, and a reduction reaction was performed at room temperature for 1.5 hours. To this reaction mixture, 3 ml of 6M aqueous hydrochloric acid was added, and dehydration reaction was performed at 65 ° C. for 3 hours. The reaction mixture was cooled to room temperature and extracted with ether. The ether solution was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. To the obtained residue was added 5 ml of THF again, and diisobutylaluminum hydride (manufactured by Kanto Chemical Co., 0.99 mol / l, toluene solution) 1 20 ml (1.20 mmol) was added, and a reduction reaction was performed at room temperature for 1.5 hours. Subsequently, 3 ml of 6M hydrochloric acid aqueous solution was added to the reaction mixture, and dehydration reaction was performed for 3 hours. The reaction mixture was cooled to room temperature and extracted with ether. The ether solution was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Purification by silica gel column chromatography (eluent: hexane) gave 128 mg (0.239 mmol) of 2-bromo-3-iodo-6,7-diphenylanthracene as a yellow solid (yield 56%).

Example 6 (Synthesis of dibromotetraphenyl dianthryl ethyne) (dihalodiaryl ethyne derivative of general formula (3))
Under a nitrogen atmosphere, in a 100 ml Schlenk reaction vessel, 128 mg (0.239 mmol) of 2-bromo-3-iodo-6,7-diphenylanthracene synthesized in Synthesis Example 12 (0.239 mmol), 4 ml of toluene, and piperidine 3 ml was added. Further, 8.4 mg (0.012 mmol) of dichlorobis (triphenylphosphine) palladium (manufactured by Wako Pure Chemical Industries) and 4.8 mg (0.025 mmol) of copper (I) iodide (manufactured by Wako Pure Chemical Industries) were added. The mixture was heated to 60 ° C., and the reaction was carried out for 1.5 hours while slowly introducing an acetylene gas through a dip tube immersed in the solution. After stopping the introduction of the acetylene gas, the reaction was continued for another 3 hours. After cooling to room temperature, toluene was added and washed with water. The organic phase was washed with 5% sulfuric acid aqueous solution, saturated aqueous sodium hydrogen carbonate and saturated brine in this order. A 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) (0.06 ml) was added to the obtained organic phase, and the mixture was stirred at room temperature for 1 hour. This solution was washed with water, and the organic phase was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; hexane: methylene chloride = 10: 1) to obtain 66 mg of dibromotetraphenyldianthrylethine as a yellow solid (yield 66%).
FABMS m / z: 841 (M ⁺ , 100%), 761 (M ⁺ -Br, 7).

  From the MS measurement, it was confirmed that dibromotetraphenyl dianthrylethine was obtained. The structural formula is shown below.

Synthesis Example 13 (Synthesis of 2-bromo-3-iodo-6,7-di (pentadecyl) anthracene) (Synthesis of compounds of general formulas (8) and (10))
The same procedure as in Synthesis Example 2 was repeated except that pentadecylmagnesium bromide (prepared from 1-bromopentadecane and magnesium in ether) was used instead of dodecylmagnesium bromide in Synthesis Example 2, and 1,2-di (pentadecyl) was repeated. Benzene was synthesized. Using this 1,2-di (pentadecyl) benzene and 4-bromo-5-iodophthalic anhydride obtained in Synthesis Example 1, the same operation as in Synthesis Example 3 was repeated and 2-bromo-3-iodo-6,7 -Di (pentadecyl) fluoroanthraquinone was obtained, and further the same operation as in Synthesis Example 4 was repeated to convert to 2-bromo-3-iodo-6,7-di (pentadecyl) anthracene.
_{^{1 H NMR (CDCl 3, 22}} ℃): δ = 8.55 (s, 1H), 8.27 (s, 1H), 8.16 (s, 1H), 8.15 (s, 1H), 7 .72 (s, 2H), 2.78 (m, 4H), 1.71 (m, 4H), 1.27 (m, 36H), 0.88 (m, 6H).
_{^{MS m / z: 720 (M}} +, 100%), 410 (M + -C 22 H 46, 16%), 283 (M + -C 22 H 46 -I, 4%), 203 (M + -C _{22 H 46 -I-Br, 5} %).

Example 7 (Synthesis of dibromotetra (pentadecyl) dianthrylethine) (Synthesis of dihalodiarylethyne derivative of general formula (3))
Under a nitrogen atmosphere, 201 mg (0.250 mmol) of 2-bromo-3-iodo-6,7-di (pentadecyl) anthracene (compound of general formula (8)) synthesized in Synthesis Example 13 in a 100 ml Schlenk reaction vessel, 5 ml of THF, And 12 ml of diisopropylamine was added. Furthermore, 8.5 mg (0.0074 mmol) of dichlorobis (triphenylphosphine) palladium (manufactured by Wako Pure Chemical Industries), 3.4 mg (0.018 mmol) of copper (I) iodide (manufactured by Wako Pure Chemical Industries), and trimethylsilylacetylene ( 0.035 ml (0.25 mmol) of Wako Pure Chemical Industries, Ltd.) was added. The mixture was reacted at 26 ° C. for 1.5 hours, 50 ° C. for 3 hours, and 60 ° C. for 1 hour. The reaction mixture was filtered through silica gel (solvent; toluene), the solvent was distilled off, and the residue was further dried in vacuum. The obtained residue was purified by silica gel column chromatography (solvent: hexane) to obtain 143 mg of 2-trimethylsilylethynyl-3-bromo-6,7-di (pentadecyl) anthracene (yield 74%). Methanol 2.5 ml, THF 5 ml, and potassium carbonate 53 mg (0.383 mmol) were added here, and it was made to react at room temperature for 1.5 hours (detrialkylylsilyl treatment). Toluene was added to the reaction mixture and washed with water. The organic phase was concentrated under reduced pressure, and 130 mg of orange having 2-ethynyl-3-bromo-6,7-di (pentadecyl) anthracene (2-ethynyl-3-haloarene derivative represented by the general formula (9)) as a main component A solid was obtained.

To 130 mg of a solid containing 2-ethynyl-3-bromo-6,7-di (pentadecyl) anthracene as a main component, 5 ml of toluene and 1 ml of triethylamine were added. Tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) 6.7 mg (0.0058 mmol), copper (I) iodide (Wako Pure Chemical Industries, Ltd.) 2.8 mg (0.015 mmol), and synthesis example 13 149 mg (0.185 mmol) of 2-bromo-3-iodo-6,7-di (pentadecyl) anthracene (compound of general formula (10)) was added. The mixture was reacted at 26 ° C. for 24 hours. The reaction mixture was filtered through silica gel (solvent; toluene), and the solvent was distilled off, followed by vacuum drying. The obtained residue was purified by silica gel column chromatography (solvent: hot heptane) to obtain 201 mg of dibromotetra (pentadecyl) dianthrylethine as a yellow solid (yield 82%).
¹ H NMR (deuterium toluene, 80 ° C.): δ = 8.28 (s, 2H), 8.11 (s, 2H), 7.98 (s, 2H), 7.87 (s, 2H), 7 .66 (s, 4H), 2.81 (t, J = 7.5 Hz, 8H), 1.81-1.70 (m, 8H), 1.55-1.11 (m, 96H), 0 .86 (t, J = 5.8 Hz, 12H).
FABMS m / z: 1375 (M ⁺ ).

  From the MS measurement, it was confirmed that dibromotetra (pentadecyl) dianthrylethine was obtained. The structural formula is shown below.

Synthesis Example 14 (Synthesis of 4-bromo-5-iodo-1,2-didodecylbenzene) (Synthesis of compounds of general formulas (8) and (10))
Under a nitrogen atmosphere, 1.95 g (12.0 mmol) of 1,2-didodecylbenzene synthesized in Synthesis Example 2 in a 100 ml Schlenk reaction vessel, 684 mg (3.00 mmol) of periodic acid dihydrate, 1.62 g of iodine (6.36 mmol), 6.9 ml acetic acid, 1.4 ml water, and 0.21 ml sulfuric acid were added. After stirring at 65 ° C. for 6 hours and cooling to room temperature, an aqueous sodium hydrogen sulfite solution was added to stop the reaction. Extraction was performed with dichloromethane, and the organic phase was washed with water and then dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (solvent: hexane) to obtain 3.73 g of a liquid. To 3.47 g of this liquid, 20 ml of dichloromethane was added and cooled to 0 ° C. After adding 67 mg of iron powder (manufactured by Sigma-Aldrich) and 10 mg (0.04 mmol) of iodine, 0.48 ml (9.37 mmol) of bromine was added dropwise. After stirring at 0 ° C. for 2 hours, an aqueous sodium hydrogen sulfite solution was added to stop the reaction. The organic phase was washed with water and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the resulting residue was filtered using silica gel, and the filtrate was concentrated and then recrystallized and purified with hexane at −78 ° C. to obtain 4-bromo-5-iodo-1,2-didodecylbenzene. (3.14 g, 75% yield).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 7.59 (s, 1H), 7.37 (s, 1H), 2.58-2.40 (m, 4H), 1.57-1. 45 (m, 4H), 1.42-1.23 (m, 36H), 0.90 (t, J = 6.6 Hz, 6H).

Example 8 (Synthesis of dibromotetra (dodecyl) diphenylethyne) (Synthesis of dihalodiarylethyne derivative of general formula (3))
Under a nitrogen atmosphere, 353 mg (0.570 mmol) of 4-bromo-5-iodo-1,2-didodecylbenzene (compound of general formula (8)) synthesized in Synthesis Example 14 in a 100 ml Schlenk reaction vessel, 12 ml of toluene, and 2 ml of triethylamine was added. Furthermore, tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) 20.0 mg (0.017 mmol), copper iodide (I) (manufactured by Wako Pure Chemical Industries, Ltd.) 6.5 mg (0.034 mmol), and trimethylsilylacetylene (Japanese 0.080 ml (55.6 mg, 0.566 mmol) from Kojun Pharmaceutical Co., Ltd. was added. The mixture was reacted at 50 ° C. for 7 hours. The reaction mixture was cooled to room temperature, 1.0 ml (1.0 mmol) of tetrabutylammonium fluoride (manufactured by Sigma-Aldrich, 1.0 mol / l, THF solution) was added, and the mixture was stirred at room temperature for 1 hour for detrialization. It was treated with xylyl to prepare 3-ethynyl-4-bromo-1,2-didodecylbenzene (2-ethynyl-3-haloarene derivative represented by the general formula (9)). To this was added 353 mg (0.570 mmol) of 4-bromo-5-iodo-1,2-didodecylbenzene (compound of general formula (10)) synthesized in Synthesis Example 14. This mixture was reacted at 26 ° C. for 16 hours and further at 40 ° C. for 2 hours. Toluene and saturated brine were added, and after phase separation, the organic phase was concentrated under reduced pressure and purified by silica gel column chromatography (solvent; heptane) to obtain 396 mg of dibromotetra (dodecyl) diphenylethyne as a white solid (yield) 69%).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 7.365 (s, 2H), 7.355 (s, 2H), 2.56-2.42 (m, 8H), 1.61-1. 42 (m, 8H), 1.26 (m, 72H), 0.88 (t, J = 6.9 Hz, 12H).
MS m / z: 1009 (M ⁺ , 100%), 929 (M ⁺ -Br, 15), 849 (M ⁺ -2Br, 1).

  From NMR and MS measurements, it was confirmed that dibromotetra (dodecyl) diphenylethyne was obtained. The structural formula is shown below.

Example 9 (Synthesis of dibromotetra (dodecyl) anthrylphenylethyne) (Synthesis of dihalodiarylethyne derivative of general formula (3))
Under a nitrogen atmosphere, 309 mg (0.500 mmol) of 4-bromo-5-iodo-1,2-didodecylbenzene (compound of general formula (8)) synthesized in Synthesis Example 14 in a 100 ml Schlenk reaction vessel, 11 ml of toluene, and 2 ml of triethylamine was added. Furthermore, tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) 17.0 mg (0.015 mmol), copper (I) iodide (manufactured by Wako Pure Chemical Industries, Ltd.) 5.7 mg (0.030 mmol), and trimethylsilylacetylene (Japanese 0.070 ml (48.7 mg, 0.496 mmol) manufactured by Kojun Pharmaceutical Co., Ltd. was added. The mixture was reacted at 50 ° C. for 7 hours. The reaction mixture was cooled to room temperature, 1.0 ml (1.0 mmol) of tetrabutylammonium fluoride (manufactured by Sigma-Aldrich, 1.0 mol / l, THF solution) was added, and the mixture was stirred at room temperature for 1 hour for detrialization. It was treated with xylyl to prepare 3-ethynyl-4-bromo-1,2-didodecylbenzene (2-ethynyl-3-haloarene derivative represented by the general formula (9)). 309 mg (0.500 mmol) of 2-bromo-3-iodo-6,7-didodecylanthracene (compound of general formula (10)) synthesized in Synthesis Example 4 was added thereto. This mixture was reacted at 26 ° C. for 16 hours and further at 40 ° C. for 2 hours. Toluene and saturated brine were added, and after phase separation, the organic phase was concentrated under reduced pressure and purified by silica gel column chromatography (solvent; heptane) to obtain 351 mg of dibromotetra (dodecyl) anthrylphenylethyne as a white solid ( Yield 63%).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 8.26 (s, 1H), 8.25 (s, 1H), 8.23 (s, 1H), 8.17 (s, 1H), 7 .73 (s, 2H), 7.43 (s, 1H), 7.40 (s, 1H), 2.84-2.72 (m, 4H), 2.65-2.49 (m, 4H) ), 1.80-1.63 (m, 4H), 1.63-1.48 (m, 4H), 1.48-1.08 (m, 72H), 0.88 (t, J = 6) .5Hz, 12H).

  From NMR, it was confirmed that dibromotetra (dodecyl) anthrylphenylethyne was obtained. The structural formula is shown below.

Example 10 (Synthesis of dibromodi (benzothienyl) ethyne) (Synthesis of dihalodiarylethyne derivative of general formula (3))
In a 100 ml Schlenk reaction vessel under a nitrogen atmosphere, 2,3-dibromobenzothiophene (manufactured by Sigma-Aldrich) (compound of general formula (8)) 500 mg (1.71 mmol), dichlorobis (triphenylphosphine) palladium (Wako Pure Chemical Industries, Ltd.) 24.9 mg (0.035 mmol), copper (I) iodide (Wako Pure Chemical Industries) 13.5 mg (0.071 mmol), THF 6 ml, and triethylamine 3 ml were added. Further, 198 mg (2.01 mmol) of trimethylsilylacetylene (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The mixture was reacted at room temperature (27 ° C.) for 17 hours. To the reaction mixture, 2.0 ml (2.0 mmol) of tetrabutylammonium fluoride (manufactured by Sigma-Aldrich, 1.0 mol / l THF solution) was added, and the mixture was stirred at room temperature for 1 hour for detrialkylylsilyl treatment. -Ethynyl-3-bromobenzothiophene (2-ethynyl-3-haloarene derivative represented by the general formula (9)) was prepared. 2,3-dibromobenzothiophene (manufactured by Sigma-Aldrich) (compound of general formula (10)) 500 mg (1.71 mmol), dichlorobis (triphenylphosphine) palladium (manufactured by Wako Pure Chemical Industries) 20.4 mg (0 0.029 mmol) and 13.0 mg (0.068 mmol) of copper (I) iodide (Wako Pure Chemical Industries, Ltd.) were added. The mixture was stirred at room temperature for 5 days. Toluene and 3M aqueous hydrochloric acid were added, and after phase separation, the organic phase was washed with water and dried over anhydrous sodium sulfate. The organic phase is concentrated under reduced pressure, and the resulting residue is purified by silica gel column chromatography (solvent; hexane: toluene = 30: 1 to 5: 1), and further purified by recrystallization from a solvent of heptane: toluene = 5: 2. And 289 mg of dibromodi (benzothienyl) ethyne yellow solid was obtained (yield 38%).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 7.87-7.76 (m, 4H), 7.54-7.44 (m, 4H).

  From NMR measurement, it was confirmed that dibromodi (benzothienyl) ethyne was obtained. The structural formula is shown below.

Example 11 (Synthesis of di (methylthio) tetra (dodecyl) diphenylethyne) (Synthesis of di (alkylchalcogeno) diarylethyne derivative of general formula (2))
Under a nitrogen atmosphere, 85 mg (0.085 mmol) of dibromotetra (dodecyl) diphenylethyne (the compound of the general formula (3)) synthesized in Example 8 and 4 ml of ether were added to a 100 ml Schlenk reaction vessel. At 0 ° C., 0.21 ml (0.34 mmol) of n-butyllithium (manufactured by Kanto Chemical Co., Ltd., 1.61 mol / l, hexane solution) was added dropwise and stirred at 0 ° C. for 30 minutes. At 0 ° C., 32.4 mg (0.344 mmol) of dimethyl disulfide (manufactured by Wako Pure Chemical Industries, Ltd.) was added. After stirring at 0 ° C. for 1 hour, water and chloroform were added and the phases were separated. The organic phase was washed with water, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; hexane: chloroform = 10: 1) to obtain 60 mg of white solid of di (methylthio) tetra (dodecyl) diphenylethyne (yield 75%).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 7.31 (s, 2H), 6.97 (s, 2H), 2.62-2.51 (m, 8H), 2.51 (s, 6H), 1.62-1.45 (m, 8H), 1.44-1.12 (m, 72H), 0.88 (t, J = 6.9 Hz, 12H).
_{^{MS m / z: 944 (M}} + +1,17%), 928 (M + -CH 3, 100), 913 (M + -2CH 3, 14).

  From NMR measurement and MS measurement, it was confirmed that di (methylthio) tetra (dodecyl) diphenylethyne was obtained. The structural formula is shown below.

Example 12 (Synthesis of tetra (dodecyl) benzothienobenzothiophene) (Synthesis of heteroacene derivative of general formula (1))
Under a nitrogen atmosphere, in a 100 ml Schlenk reaction vessel, 57 mg (0.060 mmol) of di (methylthio) tetra (dodecyl) diphenylethyne (compound of general formula (2)) synthesized in Example 11, 6 ml of tetrachloroethane, and 307 mg of iodine (1 .21 mmol) was added. The resulting mixture was stirred at 100 ° C. for 3 days. After cooling to room temperature, a saturated aqueous sodium thiosulfate solution and dichloromethane were added, and the phases were separated. The organic phase was washed with water, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; hexane) to obtain 19 mg of tetra (dodecyl) benzothienobenzothiophene as a white solid (yield 35%).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 7.65 (s, 2H), 7.59 (s, 2H), 2.71 (m, 8H), 1.65 (m, 8H), 1 .26 (m, 72H), 0.88 (t, J-7.0 Hz, 12H).

  From NMR measurement, it was confirmed that tetra (dodecyl) benzothienobenzothiophene was obtained. The structural formula is shown below.

Example 13 (Synthesis of di (methylthio) tetra (dodecyl) anthrylphenylethyne) (Synthesis of di (alkylchalcogeno) diarylethyne derivative of general formula (2))
The same operation as in Example 11 except that dibromotetra (dodecyl) anthrylphenylethine (compound of general formula (3)) synthesized in Example 9 was used instead of dibromotetra (dodecyl) diphenylethine in Example 11. To obtain a yellow solid of di (methylthio) tetra (dodecyl) anthrylphenylethyne (yield 57%).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 8.18 (s, 2H), 8.13 (s, 1H), 7.70 (s, 1H), 7.68 (s, 1H), 7 .55 (s, 1H), 7.39 (s, 1H), 7.00 (s, 1H), 2.77 (t, J = 7.6 Hz, 4H), 2.63 (s, 3H), 2.58 (t, J = 7.6 Hz, 4H), 2.55 (s, 3H), 1.79-1.45 (m, 8H), 1.44-1.12 (m, 72H), 0.88 (t, J = 6.1 Hz, 12H).

  From NMR measurement, it was confirmed that di (methylthio) tetra (dodecyl) anthrylphenylethyne was obtained. The structural formula is shown below.

Example 14 (Synthesis of tetra (dodecyl) anthrachienobenzothiophene) (Synthesis of heteroacene derivative of general formula (1))
Under a nitrogen atmosphere, the di (methylthio) tetra (dodecyl) anthrylphenylethyne (compound of general formula (2)) 105 mg (0.101 mmol), tetrachloroethane 8 ml, and iodine 840 mg synthesized in Example 13 in a 100 ml Schlenk reaction vessel. (3.31 mmol) was added. The resulting mixture was stirred at 100 ° C. for 17 hours. After cooling to room temperature, a saturated aqueous sodium bisulfite solution and chloroform were added, and the phases were separated. The organic phase was washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent: hexane) to obtain 24 mg of an orange solid of tetra (dodecyl) anthrachienobenzothiophene (yield 24%).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 8.47 (s, 1H), 8.46 (s, 1H), 8.41 (s, 1H), 8.38 (s, 1H), 7 .77 (s, 2H), 7.70 (s, 1H), 7.62 (s, 1H), 2.81 (t, J = 6.5 Hz, 4H), 2.76 (t, J = 6) .5 Hz, 4H), 1.80-1.57 (m, 8H), 1.53-1.08 (m, 72H), 0.88 (t, J = 6.5 Hz, 12H).
^{The 1} H NMR spectrum is shown in FIG.

  From NMR measurement, it was confirmed that tetra (dodecyl) anthrachienobenzothiophene was obtained. The structural formula is shown below.

Example 15 (Synthesis of di (methylthio) di (benzothienyl) ethyne) (Synthesis of di (alkylchalcogeno) diarylethyne derivative of general formula (2))
The same operation as in Example 11 was repeated except that dibromodi (benzothienyl) ethine (compound of general formula (3)) synthesized in Example 10 was used instead of dibromotetra (dodecyl) diphenylethine in Example 11. A yellow solid of di (methylthio) di (benzothienyl) ethyne was obtained (83% yield).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 7.92-7.86 (m, 2H), 7.72-7.67 (m, 2H), 7.38-7.33 (m, 4H) ), 2.58 (s, 6H).

  From NMR measurement, it was confirmed that di (methylthio) di (benzothienyl) ethyne was obtained. The structural formula is shown below.

Example 16 (Synthesis of 2-bromo (iodo) -3-methylthio-6,7-di (pentadecyl) anthracene) (Synthesis of halo (alkylchalcogenyl) arene derivative of general formula (6))
Under a nitrogen atmosphere, 502 mg (0.625 mmol) of 2-bromo-3-iodo-6,7-di (pentadecyl) anthracene synthesized in Synthesis Example 13 (0.625 mmol), sodium thiol in a 100 ml Schlenk reaction vessel 48.3 mg (0.687 mmol) of methoxide (manufactured by Sigma-Aldrich) (compound of general formula (11)) and 5 ml of NMP were added. After making this mixture react at 40 degreeC for 8 hours, water and toluene were added and phase-separated. The organic phase was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent: hexane), and further recrystallized from hexane to give yellow 2-bromo (iodo) -3-methylthio-6,7-di (pentadecyl) anthracene. 326 mg of solid was obtained (70% yield).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 8.48 (s, 0.5H), 8.17 (s, 0.5H), 8.16 (s, 0.5H), 8.14 ( s, 1H), 8.11 (s, 0.5H), 7.70 (s, 1H), 7.69 (s, 1H), 7.55 (s, 0.5H), 7.52 (s 0.5H), 2.78 (t, J = 7.8 Hz, 4H), 2.60 (s, 1.5H), 2.58 (s, 1.5H), 1.73-1.62. (M, 4H), 1.53-1.10 (m, 48H), 0.88 (t, J = 6.6 Hz, 6H).

  From NMR measurement, it was confirmed that this was a 1: 1 mixture of 2-bromo-3-methylthio-6,7-di (pentadecyl) anthracene and 2-iodo-3-methylthio-6,7-di (pentadecyl) anthracene. did. The structural formula is shown below.

Example 17 (Synthesis of 2-formyl-3-methylthio-6,7-di (pentadecyl) anthracene) (Synthesis of formyl (alkylchalcogenyl) arene derivative of general formula (5))
150 mg (0.200 mmol) of 2-bromo (iodo) -3-methylthio-6,7-di (pentadecyl) anthracene (compound of general formula (6)) synthesized in Example 16 in a 100 ml Schlenk reaction vessel under nitrogen atmosphere And 10 ml of THF were added. The mixture was cooled to −58 ° C., 0.25 ml (0.40 mmol) of n-butyllithium (manufactured by Kanto Chemical Co., 1.61 mol / l, hexane solution) was added dropwise, and the mixture was stirred at −58 ° C. for 8 minutes. DMF47.2mg (0.646mmol) was added there, and it was made to react at -58 degreeC for 20 minutes, Then, 1M hydrochloric acid aqueous solution was added and reaction was quenched. Water and toluene were added, and after phase separation, the organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent; hexane: chloroform = 1: 1 to chloroform) to obtain 118 mg of 2-formyl-3-methylthio-6,7-di (pentadecyl) anthracene as a yellow solid. (Yield 87%).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 10.34 (s, 1H), 8.46 (s, 1H), 8.41 (s, 1H), 8.19 (s, 1H), 7 .76 (s, 1H), 7.73 (s, 1H), 7.66 (s, 1H), 2.80 (t, J = 7.0 Hz, 4H), 2.61 (s, 3H), 1.79-1.65 (m, 4H), 1.55-1.10 (m, 48H), 0.88 (t, J = 6.6 Hz, 6H).

  From the NMR measurement, it was confirmed that 2-formyl-3-methylthio-6,7-di (pentadecyl) anthracene was obtained. The structural formula is shown below.

Example 18 (Synthesis of tetra (pentadecyl) di (methylthio) dianthrylethylene) (Synthesis of di (alkylchalcogenyl) diarylethylene derivative of general formula (4))
Under a nitrogen atmosphere, 39.5 mg (0.604 mmol) of zinc powder, 1 ml of THF, and 56.9 mg (0.30 mmol) of titanium tetrachloride were sequentially added to a 100 ml Schlenk reaction vessel. The resulting mixture was heated to reflux for 1.5 hours, cooled to room temperature, and 2-formyl-3-methylthio-6,7-di (pentadecyl) anthracene synthesized in Example 17 (compound of general formula (5)). ) A solution consisting of 135 mg (0.200 mmol) and 5 ml of THF was added. The resulting mixture was heated to reflux for 4 hours, then cooled to room temperature, a saturated aqueous potassium carbonate solution was added, and the mixture was stirred for 1 hour. The resulting reaction solution was filtered through Celite, the filtrate was phase-separated, and the aqueous phase was extracted with toluene. The combined organic phases were dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; hexane: chloroform = 4: 1), and further recrystallized and purified from heptane to obtain 26.4 mg of tetra (pentadecyl) di (methylthio) dianthrylethylene as a yellow solid. Obtained (yield 20%).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 8.31 (s, 2H), 8.23 (s, 2H), 8.18 (s, 2H), 7.73 (s, 4H), 7 .72 (s, 4H), 2.80 (t, J = 7.7 Hz, 8H), 2.64 (s, 6H), 1.81-1.62 (m, 8H), 1.53-1 .12 (m, 96H), 0.88 (t, J = 6.1 Hz, 12H).

  From NMR measurement, it was confirmed that tetra (pentadecyl) di (methylthio) dianthrylethylene was obtained. The structural formula is shown below.

Example 19 (Synthesis of tetra (pentadecyl) anthrachienoanthrathiophene) (Synthesis of heteroacene derivative of general formula (1))
Under a nitrogen atmosphere, 36.3 mg (0.0276 mmol) of tetra (pentadecyl) di (methylthio) dianthrylethylene synthesized in Example 18 in a 100 ml Schlenk reaction vessel (compound of general formula (4)), 225 mg (0.886 mmol) of iodine ), And 2.5 ml of chloroform were added. The resulting mixture was reacted for 20 hours under heating to reflux. After cooling to room temperature, it was washed with a saturated aqueous sodium hydrogen sulfite solution, and the whole was filtered. The solid remaining on the filter was washed with water and chloroform, and further recrystallized and purified from toluene to obtain 6.0 mg of tetra (pentadecyl) anthracenoenoanthrathiophene red solid (yield 17%).
¹ H NMR (CDCl ₃ , 50 ° C.): δ = 8.47 (s, 4H), 8.41 (s, 2H), 8.37 (s, 2H), 7.76 (s, 4H), 2 .81 (t, J = 7.8 Hz, 8H), 1.82-1.66 (m, 8H), 1.58-1.10 (m, 96H), 0.88 (t, J = 6. 6Hz, 12H).
^{The 1} H NMR spectrum is shown in FIG.

  From NMR measurement, it was confirmed that tetra (pentadecyl) anthrhienoanthrathiophene was obtained. The structural formula is shown below.

Synthesis Example 15 (Synthesis of 2,3-dibromo-6-octadecylbenzothiophene)
1) Synthesis of 2,3-dibromo-6-octadecanoylbenzothiophene Under nitrogen atmosphere, 200 ml two-necked eggplant with octadecanoyl chloride (manufactured by Sigma-Aldrich) 7.50 ml (6.75 g, 22.3 mmol) and dichloromethane 50 ml was added. After cooling to −15 ° C., 2.76 g (20.7 mmol) of aluminum chloride (Wako Pure Chemical Industries) was added. After stirring at −15 ° C. for 30 minutes, the mixture was cooled to −25 ° C., 5.02 g (17.1 mmol) of 2,3-dibromobenzothiophene (manufactured by Sigma-Aldrich) was added, and the mixture was reacted at −25 ° C. for 3 days. Thereafter, water was added to stop the reaction. After adding dichloromethane, the phases were separated and the organic phase was washed with water. Saturated aqueous sodium carbonate solution was added to the organic phase, and the mixture was stirred overnight to convert octadecanoic acid into a sodium salt. The phases were separated and the organic phase was concentrated under reduced pressure. The obtained residue was purified by short silica gel column chromatography (solvent; heptane to heptane: toluene = 3: 1), and further recrystallized from heptane to obtain 2,3-dibromo-6-octadecanoylbenzothiophene. 3.91 g of white solid was obtained (yield 41%).
¹ H NMR (CDCl ₃ , 23 ° C.): δ = 8.33 (s, 1H), 8.00 (dd, J = 8.5 Hz, 1.4 Hz, 1H), 7.80 (d, J = 8 .4 Hz, 1H), 3.02 (t, J = 7.6 Hz, 2H), 1.77 (m, 2H), 1.26 (m, 28H), 0.88 (t, J = 8.1 Hz) , 3H).
^{MS m / z: 558 (M} +, 18%), 479 (M + -Br + 1,8%), 334 (M + -C 16 H 33 + 1,100%).

2) Synthesis of 2,3-dibromo-6-octadecylbenzothiophene 2.18 g of 2,3-dibromo-6-octadecanoylbenzothiophene synthesized in 1) of Synthesis Example 15 in a 100 ml Schlenk reaction vessel under a nitrogen atmosphere ( 3.90 mmol) and 5 ml of trifluoroacetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) were added. 1.5 ml of triethylsilane (manufactured by Shin-Etsu Chemical) was added dropwise at room temperature. The resulting mixture was reacted at 60 ° C. for 4 hours and then concentrated under reduced pressure. The residue was heated under vacuum at 120 Pascal and 100 ° C. to remove the low boiling point. 2.11 g of a white solid of 2,3-dibromo-6-octadecylbenzothiophene was obtained in the residue (99% yield).
¹ H NMR (CDCl ₃ , 23 ° C.): δ = 7.63 (d, J = 8.1 Hz, 1H), 7.50 (d, J = 1.1 Hz, 1H), 7.24 (dd, J = 8.1 Hz, 1.4 Hz, 1 H), 2.71 (t, J = 8.1 Hz, 2 H), 1.65 (m, 2 H), 1.25 (m, 30 H), 0.88 (t J = 8.1 Hz, 3H).

Synthesis Example 16 (Synthesis of 3-bromo-2-trimethylsilylethynyl-6-octadecylbenzothiophene)
Under a nitrogen atmosphere, 351 mg (0.644 mmol) of 2,3-dibromo-6-octadecylbenzothiophene synthesized in Synthesis Example 15 in a 100 ml Schlenk reaction vessel, 4.2 mg of dichlorobis (triphenylphosphine) palladium (manufactured by Wako Pure Chemical Industries, Ltd.) (0.0060 mmol), copper (I) iodide (manufactured by Wako Pure Chemical Industries) 0.8 mg (0.0042 mmol), THF 4 ml, and triethylamine 3 ml were added. Further, 72.3 mg (0.736 mmol) of trimethylsilylacetylene (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The mixture was reacted at room temperature for 15 hours. The obtained mixture was ice-cooled, 3M aqueous hydrochloric acid and toluene were added, and the phases were separated. The obtained organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (solvent; hexane) to obtain 345 mg of white solid of 3-bromo-2-trimethylsilylethynyl-6-octadecylbenzothiophene (yield 95%).
¹ H NMR (CDCl ₃ , 23 ° C.): δ = 7.66 (d, J = 8.1 Hz, 1H), 7.52 (d, J = 1.1 Hz, 1H), 7.27 (dd, J = 8.1 Hz, 1.4 Hz, 1 H), 2.72 (t, J = 8.1 Hz, 2 H), 1.65 (m, 2 H), 1.25 (m, 30 H), 0.88 (t , J = 8.1 Hz, 3H), 0.30 (s, 9H).

Synthesis Example 17 (Synthesis of 3-methylthio-2-trimethylsilylethynyl-6-octadecylbenzothiophene) (Synthesis of compound of general formula (16))
Under a nitrogen atmosphere, 345 mg (0.614 mmol) of 3-bromo-2-trimethylsilylethynyl-6-octadecylbenzothiophene synthesized in Synthesis Example 16 and 7 ml of THF were added to a 100 ml Schlenk reaction vessel. The obtained mixture was cooled to −74 ° C., and 0.84 ml (1.22 mmol) of tert-butyllithium (manufactured by Kanto Chemical Co., Ltd., 1.46 mol / l, pentane solution) was added dropwise. After stirring at −74 ° C. for 20 minutes, 115 mg (1.22 mmol) of dimethyl disulfide (manufactured by Sigma-Aldrich) was added dropwise. After stirring at -74 ° C for 1.5 hours, 3M aqueous hydrochloric acid was added to quench the reaction. Water and toluene were added, and after phase separation, the organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent: hexane) to obtain 278 mg of 3-methylthio-2-trimethylsilylethynyl-6-octadecylbenzothiophene as a white solid (yield 86%).
¹ H NMR (CDCl ₃ , 23 ° C.): δ = 7.80 (d, J = 8.1 Hz, 1H), 7.52 (d, J = 1.1 Hz, 1H), 7.23 (dd, J = 8.1 Hz, 1.4 Hz, 1 H), 2.71 (t, J = 8.1 Hz, 2 H), 2.55 (s, 3 H), 1.65 (m, 2 H), 1.25 (m , 30H), 0.88 (t, J = 8.1 Hz, 3H), 0.30 (s, 9H).

Synthesis Example 18 (Synthesis of 3-iodo-2-trimethylsilyl (octadecyl) benzothienothiophene) (Synthesis of compound of general formula (15))
Under a nitrogen atmosphere, 277 mg (0.525 mmol) of 3-methylthio-2-trimethylsilylethynyl-6-octadecylbenzothiophene synthesized in Synthesis Example 17 and 14 ml of dichloromethane were added to a 100 ml Schlenk reaction vessel. To the obtained mixture, 146 mg (0.577 mmol) of iodine was added and stirred at 40 ° C. for 10 hours. The reaction mixture was cooled to room temperature, an aqueous sodium thiosulfate solution was added, phase separation was performed, and the organic phase was washed with water and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the resulting residue was purified by silica gel column chromatography (solvent: hexane) to obtain 283 mg of colorless oil of 3-iodo-2-trimethylsilyl (octadecyl) benzothienothiophene (yield 84%).
¹ H NMR (CDCl ₃ , 23 ° C.): δ = 7.68 (d, J = 8.1 Hz, 1H), 7.63 (d, J = 1.1 Hz, 1H), 7.23 (dd, J = 8.1 Hz, 1.4 Hz, 1 H), 2.72 (t, J = 8.1 Hz, 2 H), 1.67 (m, 2 H), 1.25 (m, 30 H), 0.88 (t , J = 8.1 Hz, 3H), 0.49 (s, 9H).

Synthesis Example 19 (Synthesis of 2,3-diiodo (octadecyl) benzothienothiophene) (Synthesis of compound of general formula (13))
Under a nitrogen atmosphere, 283 mg (0.441 mmol) of 3-iodo-2-trimethylsilyl (octadecyl) benzothienothiophene synthesized in Synthesis Example 18 and 12 ml of dichloromethane were added to a 100 ml Schlenk reaction vessel. The obtained mixture was ice-cooled, 0.49 ml (0.49 mmol) of iodine monochloride (manufactured by Sigma-Aldrich, 1.0 mol / l, dichloromethane solution) was added, and the mixture was stirred at room temperature for 5 hours. The obtained reaction mixture was concentrated under reduced pressure, and the residue was recrystallized and purified from heptane to obtain 288 mg (0.415 mmol) of a light yellow solid of 2,3-diiodo (octadecyl) benzothienothiophene (yield 94%).
¹ H NMR (CDCl ₃ , 23 ° C.): δ = 7.63 (brs, 1H), 7.62 (d, J = 8.1 Hz, 1H), 7.23 (d, J = 8.1 Hz, 1H) ), 2.73 (t, J = 8.1 Hz, 2H), 1.67 (m, 2H), 1.25 (m, 30H), 0.88 (t, J = 8.1 Hz, 3H).

Example 20 (Synthesis of bromoiododi (octadecyl) benzothienothienylbenzothienyl) (Synthesis of dihalochalcogenophenylaryl derivative of general formula (7))
Under a nitrogen atmosphere, 237 mg (0.434 mmol) of 2,3-dibromo-6-octadecylbenzothiophene (the compound of general formula (10)) synthesized in Synthesis Example 15 and 15 ml of THF were added to a 100 ml Schlenk reaction vessel. The obtained mixture was cooled to −72 ° C., and 1.1 ml (0.86 mmol) of isopropylmagnesium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., 0.78 mmol / l, THF solution) was added, and −28 over 3.5 hours. The temperature was raised to ° C. The mixture was cooled again to −72 ° C., and 0.9 ml (0.9 mmol) of zinc chloride (manufactured by Sigma-Aldrich, 1.0 mmol / l, ether solution) was added. After slowly warming to room temperature, the mixture was concentrated under reduced pressure. To the obtained residue (compound of general formula (14)), 200 mg (0.288 mmol) of 2,3-diiodo (octadecyl) benzothienothiophene (compound of general formula (13)) synthesized in Synthesis Example 19 and tetrakis ( 16.5 mg (0.014 mmol) of triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry) and 8 ml of THF were added. The mixture was reacted at 65 ° C. for 5 hours. After cooling the obtained reaction mixture to room temperature, 3M aqueous hydrochloric acid was added to quench the reaction. Toluene was added thereto, and after phase separation, the organic phase was washed with water and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; hexane) to obtain 151 mg of a light yellow solid of bromoiododi (octadecyl) benzothienothienylbenzothienyl (yield 51%).
¹ H NMR (CDCl ₃ , 23 ° C.): δ = 7.81 (d, J = 8.1 Hz, 1H), 7.69 (d, J = 8.1 Hz, 1H), 7.59 (s, 1H ), 7.46 (s, 1H), 7.29 (dd, J = 8.1 Hz, 1.4 Hz, 1H), 7.24 (dd, J = 8.1 Hz, 1.4 Hz, 1H), 2 .74 (m, 4H), 1.65 (m, 4H), 1.25 (m, 60H), 0.88 (m, 6H).

  From the NMR measurement, it was confirmed that bromoiododi (octadecyl) benzothienothienylbenzothienyl was obtained. The structural formula is shown below.

Example 21 (Synthesis of di (octadecyl) di (benzothieno) thienothiophene) (Synthesis of heteroacene derivative of general formula (1))
Under a nitrogen atmosphere, 1111 mg (0.107 mmol) of bromoiododi (octadecyl) benzothienothienylbenzothienyl (compound of general formula (7)) synthesized in Example 20 and 6 ml of ether were added to a 100 ml Schlenk reaction vessel. The obtained mixture was cooled to 0 ° C., and 0.28 ml (0.45 mmol) of n-butyllithium (manufactured by Kanto Chemical Co., 1.61 mol / l, pentane solution) was added dropwise. After stirring at 0 ° C. for 30 minutes, the mixture was cooled to −72 ° C., and 42.8 mg (0.136 mmol) of bis (phenylsulfonyl) sulfide (manufactured by Acros) was added. After raising the temperature to room temperature overnight, water and toluene were added and the phases were separated. The obtained organic phase was washed with water and concentrated under reduced pressure. The obtained residue was washed with hexane, and the residue was purified by silica gel column chromatography (solvent: hexane) to obtain 45 mg of a yellow solid containing di (octadecyl) di (benzothieno) thienothiophene.

  The structural formula of di (octadecyl) di (benzothieno) thienothiophene is shown below.

Example 22 (Synthesis of oxidation-resistant organic semiconductor material and evaluation of oxidation resistance)
Under a nitrogen atmosphere, 5.4 g of toluene was added to a 100 ml Schlenk container, and dissolved oxygen was removed by repeating the cycle consisting of freezing (liquid nitrogen) -depressurization-nitrogen replacement-thawing three times. Thereto, 7.1 mg of the red solid of tetra (pentadecyl) dianthrylthienothiophene obtained in Example 19 was added, heated to 60 ° C. to dissolve, and the oxidation-resistant organic semiconductor containing tetra (pentadecyl) dianthrylthienothiophene The material was synthesized (red solution). Next, the upper stopper of the Schlenk container was opened and air was introduced (oxidation resistance evaluation) by bringing it into contact with the outside air for 10 minutes, followed by stirring at 60 ° C., but no color change was observed. Therefore, since no color change was observed, the oxidation resistance was excellent. Further, even when this solution was brought into contact with air at 70 ° C. for 1 hour under stirring, no change in the color of the solution was observed, and the oxidation resistance was excellent.

Example 23 (Preparation of organic thin film)
Under a nitrogen atmosphere, 6.5 mg of the red solid of tetra (pentadecyl) dianthrylthienothiophene obtained in Example 19 was mixed with 15 g of toluene in a 100 ml Schlenk container, stirred at 70 ° C. for 1 hour, and tetra (pentadecyl) dianthryl. A red solution of thienothiophene was prepared (synthesis of oxidation-resistant organic semiconductor material containing heteroacene).

  Under a nitrogen atmosphere, a concave glass substrate was heated to 70 ° C., and the above solution was applied onto the substrate using a dropper and dried under normal pressure to produce an organic thin film having a thickness of 230 nm.

Comparative Example 1 (Oxidation resistance evaluation)
The oxidation resistance was evaluated using pentacene.

  Under a nitrogen atmosphere, 2.9 g of o-dichlorobenzene was added to a 20 ml Schlenk container, and dissolved oxygen was removed by repeating the cycle consisting of freezing (liquid nitrogen), reduced pressure, nitrogen substitution, and thawing three times. Thereto was added 2.5 mg of pentacene (manufactured by Tokyo Chemical Industry Co., Ltd.), and when heated to 120 ° C. and dissolved, a reddish purple solution was obtained. Next, the stopper at the top of the Schlenk container was opened, air was introduced by contact with outside air for 1 minute, and the mixture was further stirred at 120 ° C. From gas chromatography and gas chromatography-mass spectrum (GCMS) analysis, it was found that 6,13-pentacenequinone was produced.

  Further, when this solution was brought into contact with air at 120 ° C. for 1 hour under stirring, the color of the solution changed to yellow. Gas chromatographic analysis showed increased production of 6,13-pentacenequinone.

  Therefore, since the change in the color of the solution and 6,13-pentacenequinone were produced, the oxidation proceeded and the oxidation resistance was poor.

Comparative Example 2 (Preparation of organic thin film)
Dinaphtho [2,3-b: 2 ′, 3′-f] thieno [3,2-b] thiophene described in “Journal of American Chemical Society” (USA), 2007, 129, 2224-2225. The production of the organic thin film was evaluated using (DNTT).

  Under a nitrogen atmosphere, 15 g of toluene was added to a 100 ml Schlenk container, and dissolved oxygen was removed by repeating the cycle consisting of freezing (liquid nitrogen) -depressurization-nitrogen replacement-thawing three times. DNTT 6.0mg was added there, and it stirred at 110 degreeC for 1 hour, However, It melt | dissolved only slightly and most remained as solid and it was inferior to solubility.

  In addition, a glass substrate having a concave surface was heated to 70 ° C. in a nitrogen atmosphere, and the above solution portion was applied onto the substrate using a dropper and dried under normal pressure. However, there are portions where the material is present and portions where the material is not present, and a uniform film cannot be obtained, making it difficult to produce a thin film by coating.

¹ H NMR spectrum of tetra (dodecyl) anthrachienobenzothiophene synthesized in Example 14 ¹ H NMR spectrum of tetra (pentadecyl) anthrhienoanthrathiophene synthesized in Example 19

Claims (16)

A heteroacene derivative represented by the following general formula (1):

[Wherein T ¹ and T ² are the same or different and each represents a sulfur atom, a selenium atom or a tellurium atom, and the rings A and B are the same or different, each having a structure represented by the following general formula (A-2). Have)

(Wherein the substituents R ⁵ or R ⁶ are the same or different and are a hydrogen atom, a fluorine atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 4 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, Represents an alkynyl group having 2 to 30 carbon atoms.)] The heteroacene derivative according to claim 1, wherein T ¹ and T ² are sulfur atoms. A di (alkylchalcogeno) diarylethyne derivative represented by the following general formula (2):

(Here, the substituents R ⁹ and R ¹⁰ represent an alkyl group having 1 to 8 carbon atoms, and the substituents T ¹ and T ² and rings A and B are represented by the general formula (1) according to claim 1. (It has the same meaning as the substituent and ring.) A dihalodiarylethyne derivative represented by the following general formula (3):

(Here, the substituents X ¹ and X ² represent a bromine atom, an iodine atom, and a chlorine atom, and the rings A and B have the same meaning as the ring represented by the general formula (2) according to claim 3). A dihalochalcogenophenylaryl derivative represented by the following general formula (7):

(Wherein X ² and X ⁴ represent a bromine atom, an iodine atom, and a chlorine atom, the substituent T ¹ and the rings A and B represent the substituent and the ring represented by the general formula (1) according to claim 1; It shows the same significance.) The method for producing a heteroacene derivative according to claim 1 or 2, wherein the di (alkylchalcogeno) diarylethyne derivative represented by the general formula (2) according to claim 3 is reacted with a halogen derivative. Method for producing a heteroacene derivative according to claim 1 or claim 2 di (alkyl chalcogenopyryloarylidene) diaryl ethylene derivative comprising reacting a halogen derivative represented by the following general formula (4).

(Wherein the substituents R ¹¹ and R ¹² represent an alkyl group having 1 to 8 carbon atoms, and T ¹ and T ² and rings A and B are substituents represented by the general formula (1) according to claim 1. And the same meaning as the ring.) The dihalochalcogenophenylaryl derivative represented by the general formula (7) according to claim 5 is metallated using a metallizing agent and reacted with bis (phenylsulfonyl) sulfide, sulfur dichloride, sulfur or selenium. The method for producing a heteroacene derivative according to claim 1 or 2, wherein: The method for producing a heteroacene derivative according to claim 8 , wherein alkyllithium is used as the metallizing agent. The method for producing a heteroacene derivative according to claim 8 , wherein a Grignard reagent is used as the metallizing agent. The dihalodiarylethine derivative represented by the general formula (3) according to claim 4 is metallated using a metallizing agent and reacted with a dialkyl disulfide and / or a dialkyl diselenide. A process for producing the di (alkylchalcogeno) diarylethyne derivative. A 2,3-dihaloarene derivative represented by the following general formula (8) and a trialkylsilylacetylene are reacted in the presence of palladium and / or nickel catalyst, followed by detrialkylsilyl treatment, and the resulting general formula (9 5) and a 2,3-dihaloarene derivative represented by the following general formula (10) are reacted in the presence of a palladium and / or nickel catalyst. Of producing a dihalodiarylethyne derivative.

(Here, the substituent X ³ represents a bromine atom, an iodine atom, or a chlorine atom. The substituent X ^{1 and the} ring A have the same meaning as the substituent and the ring represented by the general formula (3) of claim 4. Show.)

(Here, the substituent X ^{1 and the} ring A have the same meaning as the substituent and the ring represented by the general formula (3) described in claim 4).

(Here, the substituent X ⁵ represents a bromine atom, an iodine atom, or a chlorine atom. The substituent X ^{2 and the} ring B have the same meaning as the substituent and the ring represented by the general formula (3) described in claim 4. Show.) The dihalo of claim 4, wherein the 2,3-dihaloarene derivative represented by the general formula (8) according to claim 12 is reacted with acetylene or trimethylsilylacetylene in the presence of palladium and / or nickel catalyst. A method for producing a diarylethine derivative. An oxidation-resistant organic semiconductor material comprising the heteroacene derivative according to claim 1. An organic thin film using the oxidation-resistant organic semiconductor material according to claim 14 . The organic thin film according to claim 15 , wherein the organic thin film is formed on a substrate.

Images