JP7109208B2 - Diimidazolobenzodithiophene compound, method for producing the same, and transistor element - Google Patents

Description

The present invention relates to novel solvent-soluble diimidazolobenzodithiophene compounds and methods for producing the same. The present invention also relates to a film-forming composition, an organic thin film and an organic transistor element using the diimidazolobenzodithiophene compound having excellent solubility in a solvent.

An organic transistor element is a rectifying element composed of an active layer, a substrate, an insulating layer, an electrode, and the like, which are made of an organic semiconductor. In organic transistor elements, the active layer can be produced by applying a solution in which an organic semiconductor is dissolved in an appropriate solvent. Compared to transistor elements, it is economically superior because it can significantly reduce the manufacturing cost of device fabrication.

From the viewpoint of the process of fabricating the device, it is preferable that the organic semiconductor used for fabricating the organic transistor device by such coating has solubility in various organic solvents. In addition, from the viewpoint of high carrier mobility and the device fabrication process, it is preferable to have heat resistance of 150° C. or higher, and accordingly, an organic semiconductor having a melting point of at least 150° C. or higher is required.

Examples of low-molecular-weight organic semiconductors that can be used for organic transistor elements by coating include bis[(triisopropylsilyl)ethynyl]pentacene (see, for example, Non-Patent Document 1) and dialkyl-substituted benzothienobenzothiophenes (see, for example, Patent Document 1), dialkyl-substituted dinaphthothienothiophenes (see, for example, Patent Document 2), and the like. However, an organic transistor element having an active layer of bis[(triisopropylsilyl)ethynyl]pentacene exhibits a hole carrier mobility of 0.3 to 1.0 cm ² /Vs immediately after fabrication. It has been reported that the carrier mobility decreases to 0.2 cm ² /Vs after the element is heat-treated at 120° C. and the heat resistance is not sufficient (see, for example, Non-Patent Document 1). Further, it has been reported that the organic transistor element using dioctylbenzothienobenzothiophene described in Patent Document 1 loses transistor operation by heat treatment at 130° C. (see Patent Document 1, for example). Furthermore, dioctyldinaphthothienothiophene described in Patent Document 2 exhibits a mobility of 0.17 cm ² /Vs by the drop casting method, but has a problem of solubility in solvents at room temperature.

The diimidazolobenzodithiophene compound of the present invention is a novel substance, and its various physical properties such as solvent solubility, as well as its production method, have not been reported at all.

WO2008/047896 pamphlet Japanese Patent No. 5477978

Journal of Polymer Science Part B: Polymer Physics, 2006, 44, 3631

The present invention has been made in view of the above problems, and an object of the present invention is to provide a novel organic semiconductor having high heat resistance and high solvent solubility, a film-forming composition containing the organic semiconductor, and a film-forming composition containing the organic semiconductor. An object of the present invention is to provide an organic thin film formed using the composition, and an organic transistor element having the organic thin film as an active layer.

As a result of intensive studies aimed at solving the above problems, the present inventors have found that diimidazolobenzodithiophene compounds, which are novel heterocyclic condensed compounds, have high heat resistance and high solvent solubility. . In addition, the inventors also found that an organic thin film can be easily formed by using a film-forming composition containing the compound, and completed the present invention.

That is, the present invention
[1]
General formula (1)

(wherein R ¹ and R ² are each independently substituted with a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; a haloalkyl group having 1 to 20 carbon atoms; or an alkyl group having 1 to 12 carbon atoms; represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, wherein R ³ and R ⁴ each independently represent an alkyl group having 1 to 20 carbon atoms; represents an aromatic hydrocarbon group having 6 to 14 carbon atoms which may be substituted with an alkyl group of 12. Further, R ¹ and R ³ , and R ² and R ⁴ each combine together to form a represents an oligomethylene group having 3 to 6 carbon atoms which may be substituted with an alkyl group of up to 12);
[2]
It relates to the diimidazolobenzodithiophene compound according to [1] above, wherein R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group having 1 to 20 carbon atoms.

Further, the present invention
[3]
general formula (2a)

(R ¹ and R ² are each independently a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; a haloalkyl group having 1 to 20 carbon atoms; or a carbon atom optionally substituted by an alkyl group having 1 to 12 carbon atoms represents an aromatic hydrocarbon group having a number of 6 to 14. R ³ and R ⁴ are each independently an alkyl group having 1 to 20 carbon atoms; a haloalkyl group having 1 to 20 carbon atoms; represents an aromatic hydrocarbon group having 6 to 14 carbon atoms which may be substituted with a group, and R ¹ and R ³ , and R ² and R ⁴ each combine together to form a represents an oligomethylene group having 3 to 6 carbon atoms which may be substituted with an alkyl group, X ^1a represents a halogen atom, and two X ² are the same or different and represent a halogen atom. A method for producing a diimidazolobenzodithiophene compound represented by the general formula (1), characterized by reacting an imidazole compound represented by the above general formula (1) with a sulfurizing agent;
[4]
The production method according to the above [3], wherein X ^1a is a bromine atom and X ² is a fluorine atom;
[5]
The production method according to the above [3] or [4], wherein the sulfiding agent is an alkali metal sulfide salt;
[6]
It relates to the production method according to the above [5], wherein the alkali metal sulfide salt is sodium sulfide or its hydrate.

Further, the present invention
[7]
general formula (2b)

(R ¹ and R ² are each independently a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; a haloalkyl group having 1 to 20 carbon atoms; or a carbon atom optionally substituted by an alkyl group having 1 to 12 carbon atoms represents an aromatic hydrocarbon group having a number of 6 to 14. R ³ and R ⁴ are each independently an alkyl group having 1 to 20 carbon atoms; a haloalkyl group having 1 to 20 carbon atoms; represents an aromatic hydrocarbon group having 6 to 14 carbon atoms which may be substituted with a group, and R ¹ and R ³ , and R ² and R ⁴ each combine together to form a represents an oligomethylene group having 3 to 6 carbon atoms which may be substituted with an alkyl group, and two X ² are the same or different and represent a halogen atom. The production of the diimidazolobenzodithiophene compound represented by the general formula (1), characterized by reacting to obtain the imidazole compound represented by the general formula (2a), and then reacting it with a sulfurizing agent. Method;
[8]
The production method according to the above [7], wherein X ^1a is a bromine atom and X ² is a fluorine atom.
[9]
The production method according to the above [7] or [8], wherein the sulfiding agent is an alkali metal sulfide salt;
[10]
It relates to the production method according to the above [9], wherein the alkali metal sulfide salt is sodium sulfide or its hydrate.

Further, the present invention
[11]
general formula (2)

(wherein R ¹ and R ² are each independently substituted with a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; a haloalkyl group having 1 to 20 carbon atoms; or an alkyl group having 1 to 12 carbon atoms; represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, wherein R ³ and R ⁴ each independently represent an alkyl group having 1 to 20 carbon atoms; represents an aromatic hydrocarbon group having 6 to 14 carbon atoms which may be substituted with an alkyl group of 12. Further, R ¹ and R ³ , and R ² and R ⁴ each combine together to form a represents an oligomethylene group having 3 to 6 carbon atoms which may be substituted with an alkyl group of up to 12. X ¹ represents a hydrogen atom or a halogen atom, two X ² are the same or different and a halogen atom represents an imidazole compound represented by;
[12]
The imidazole compound according to [11] above, wherein R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group having 1 to 20 carbon atoms;
[13]
The imidazole compound according to the above [11] or [12], wherein X ¹ is a hydrogen atom or a bromine atom, and X ² is a fluorine atom.

Further, the present invention
[14]
general formula (3a)

(wherein R ¹ is a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; a haloalkyl group having 1 to 20 carbon atoms; or an alkyl group having 1 to 12 carbon atoms and optionally substituted with an alkyl group having 6 to 14 carbon atoms represents an aromatic hydrocarbon group of R ³ is an alkyl group having 1 to 20 carbon atoms; a haloalkyl group having 1 to 20 carbon atoms; represents an aromatic hydrocarbon group having 1 to 14. Further, R ¹ and R ³ together represent an oligomethylene group having 3 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 12 carbon atoms. ) and a 1,2-disubstituted imidazole represented by the general formula (4)

(Wherein, two X ² are the same or different and represent a halogen atom. X ³ represents an iodine atom or a bromine atom.) with a benzene compound represented by in the presence of a palladium catalyst and a base. reacted to give the general formula (5)

(Wherein, R ¹ , R ³ , X ² and X ³ have the same meanings as above) to obtain 5-phenylimidazole represented by general formula (3b)

(wherein R ² is a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; a haloalkyl group having 1 to 20 carbon atoms; or an alkyl group having 1 to 12 carbon atoms and optionally substituted with an alkyl group having 6 to 14 carbon atoms represents an aromatic hydrocarbon group of R ⁴ is an alkyl group having 1 to 20 carbon atoms; a haloalkyl group having 1 to 20 carbon atoms; represents an aromatic hydrocarbon group of 1 to 14. Further, R ² and R ⁴ together represent an oligomethylene group having 3 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 12 carbon atoms. A method for producing an imidazole compound represented by the general formula (2b), characterized by reacting a 1,2-disubstituted imidazole represented by ) in the presence of a palladium catalyst and a base;
[15]
The production method according to the above [14], wherein the palladium catalyst is a divalent palladium salt.

Furthermore, the present invention
[16]
A film-forming composition comprising the diimidazolobenzodithiophene compound according to [1] or [2];
[17]
The film-forming composition according to [16] above, comprising 0.01 to 10% by weight of a diimidazolobenzodithiophene compound;
[18]
An organic thin film comprising the diimidazolobenzodithiophene compound according to [1] or [2];
[19]
The present invention relates to an organic transistor element comprising the organic thin film according to [18] in an active layer.

The present invention will be described in detail below.

The diimidazolobenzodithiophene compound of the present invention and the imidazole compound represented by the above general formula (2), which is useful as an intermediate for the production of the diimidazolobenzodithiophene compound of the present invention (hereinafter referred to as "intermediate of the present invention ), the definitions of R ¹ , R ² , R ³ , R ⁴ , X ¹ and X ² will be explained.

The alkyl group having 1 to 20 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ may be a linear, branched or cyclic alkyl group, specifically methyl group, cyclohexylmethyl group, ethyl group, 2-cyclopentylethyl group, propyl group, 2-methylpropyl group, 2,2-dimethylpropyl group, 3-cyclopropylpropyl group, isopropyl group, cyclopropyl group, butyl group, 2-methylbutyl group, 3-methylbutyl group, 2-butyl group, 3-methylbutan-2-yl group, tert-butyl group, cyclobutyl group, pentyl group, 2-methylpentyl group, 3-ethylpentyl group, 2,4-dimethylpentyl group, 2-pentyl group, 2-methylpentan-2-yl group, 4,4-dimethylpentan-2-yl group, 3-pentyl group, 3-ethylpentan-3-yl group, cyclopentyl group, 2,5-dimethyl cyclopentyl group, 3-ethylcyclopentyl group, hexyl group, 2-methylhexyl group, 3,3-dimethylhexyl group, 4-ethylhexyl group, 2-hexyl group, 2-methylhexan-2-yl group, 5,5- dimethylhexan-2-yl group, 3-hexyl group, 2,4-dimethylhexan-3-yl group, cyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, 4,4-dimethylcyclohexyl group, heptyl group , 2-heptyl group, 3-heptyl group, 4-heptyl group, bicyclo[2.2.1]heptyl group, octyl group, 2-octyl group, 3-octyl group, 4-octyl group, cyclooctyl group, bicyclo [2.2.2] octyl group, nonyl group, 5-nonyl group, decyl group, 2-decyl group, 5-decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and the like. Among these, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 2 to 8 carbon atoms is more preferable, because the diimidazolobenzodithiophene compound of the present invention has good crystallinity.

The haloalkyl group having 1 to 20 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ may be a linear, branched or cyclic haloalkyl group, specifically a trifluoromethyl group, difluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, perfluoropropyl group, 2,2,3,3,3-penta fluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 1,1-difluoropropyl group, perfluoroisopropyl group, 2,2,2-trifluoro-1 -(trifluoromethyl)ethyl group, perfluorocyclopropyl group, 2,2,3,3-tetrafluorocyclopropyl group, perfluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group , 3,3,4,4,4-pentafluorobutyl group, 4,4,4-trifluorobutyl group, 1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl group, 1-(trifluoromethyl)propyl group, 1-methyl-3,3,3-trifluoropropyl group, perfluorocyclobutyl group, 2,2,3,3,4,4-hexafluorocyclobutyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 3,3,4,4,5,5,5-heptafluoropentyl group, 4,4, 5,5,5-pentafluoropentyl group, 5,5,5-trifluoropentyl group, 1,2,2,3,3,3-hexafluoro-1-(perfluoroethyl)propyl group, 2,2, 3,3,3-pentafluoro-1-(perfluoroethyl)propyl group, perfluorocyclopentyl group, perfluorohexyl group, 2,2,3,3,4,4,5,5,6,6,6-undeca fluorohexyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, 4,4,5,5,6,6,6-heptafluorohexyl group, 5,5, Examples include 6,6,6-pentafluorohexyl group, 6,6,6-trifluorohexyl group, perfluorocyclohexyl group, chloromethyl group, bromomethyl group, iodomethyl group, 2-chloroethyl group, 3-bromopropyl group and the like. can do.

The aromatic hydrocarbon group having 6 to 14 carbon atoms which may be substituted with an alkyl group having 1 to 12 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ includes a phenyl group optionally substituted by an alkyl group, a naphthyl group optionally substituted by an alkyl group having 1 to 12 carbon atoms, a biphenylyl group optionally substituted by an alkyl group having 1 to 12 carbon atoms, and a number of carbon atoms Examples include an anthryl group optionally substituted with 1 to 12 alkyl groups.

Specific examples of the phenyl group optionally substituted with an alkyl group having 1 to 12 carbon atoms include a phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, 2,4-dimethylphenyl group, 3 , 5-dimethylphenyl group, mesityl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,4-diethylphenyl group, 3,5-diethylphenyl group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 2,4-dipropylphenyl group, 3,5-dipropylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2, 4-diisopropylphenyl group, 3,5-diisopropylphenyl group, 4-(1-methylpropyl)phenyl group, 4-(2-methylpropyl)phenyl group, 4-(1-ethylpropyl)phenyl group, cyclopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 2,4-dibutylphenyl group, 3,5-dibutylphenyl group, 2-tert-butylphenyl group, 3-tert-butylphenyl group, 4-tert-butylphenyl group, 2,4-di-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, 4-(1-methylbutyl)phenyl group, 4-(2-methylbutyl ) phenyl group, 4-(3-methylbutyl)phenyl group, 4-(1,1,3,3-tetramethylbutyl)phenyl group, 4-(2-ethylbutyl)phenyl group, 4-(1-propylbutyl) phenyl group, 2-pentylphenyl group, 3-pentylphenyl group, 4-pentylphenyl group, 3,4-dipentylphenyl group, 4-(4-methylpentyl)phenyl group, 4-(3-ethylpentyl)phenyl group , 4-cyclopentylphenyl group, 4-(3-ethylcyclopentyl)phenyl group, 2-hexylphenyl group, 3-hexylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, 4-(4-ethylcyclohexyl) phenyl group, 4-(4-propylcyclohexyl)phenyl group, 4-(4-butylcyclohexyl)phenyl group, 2-heptylphenyl group, 3-heptylphenyl group, 4-heptylphenyl group, 2-octylphenyl group, 3 -octylphenyl group, 4-octylphenyl group, 3,5-dioctylphenyl group, 4-cyclooctylphenyl group, 4-nonylphenyl group, 4-decylphenyl group phenyl group, 4-undecylphenyl group, 4-dodecylphenyl group and the like. Among these, a phenyl group optionally substituted with an alkyl group having 1 to 10 carbon atoms is preferable, and a straight chain having 2 to 8 carbon atoms, in terms of good solubility of the diimidazolobenzodithiophene compound of the present invention. A phenyl group optionally substituted with a branched or branched alkyl group is more preferred.

The naphthyl group optionally substituted with an alkyl group having 1 to 12 carbon atoms, specifically, 1-naphthyl group, 4-methylnaphthalene-1-yl group, 5-methylnaphthalene-1-yl group, 4- ethylnaphthalene-1-yl group, 5-ethylnaphthalene-1-yl group, 4-propylnaphthalene-1-yl group, 5-propylnaphthalene-1-yl group, 4-butylnaphthalene-1-yl group, 4- tert-butylnaphthalene-1-yl group, 5-butylnaphthalene-1-yl group, 5-tert-butylnaphthalene-1-yl group, 4-pentylnaphthalene-1-yl group, 5-hexylnaphthalene-1-yl group, 8-heptylnaphthalene-1-yl group, 5-octylnaphthalene-1-yl group, 7-nonylnaphthalene-1-yl group, 4-decylnaphthalene-1-yl group, 5-dodecylnaphthalene-1-yl group, 2-naphthyl group, 4-methylnaphthalen-2-yl group, 5-methylnaphthalen-2-yl group, 4-ethylnaphthalen-2-yl group, 5-ethylnaphthalen-2-yl group, 4-propyl naphthalene-2-yl group, 5-propylnaphthalene-2-yl group, 4-butylnaphthalene-2-yl group, 4-tert-butylnaphthalene-2-yl group, 5-butylnaphthalene-2-yl group, 5 -tert-butylnaphthalene-2-yl group, 4-pentylnaphthalene-2-yl group, 5-hexylnaphthalene-2-yl group, 8-heptylnaphthalene-2-yl group, 5-octylnaphthalene-2-yl group , 7-nonylnaphthalene-2-yl group, 4-decylnaphthalene-2-yl group, 5-dodecylnaphthalene-2-yl group and the like.

Specific examples of the biphenylyl group optionally substituted with an alkyl group having 1 to 12 carbon atoms include 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, 2-methylbiphenyl-4-yl group, 3 -methylbiphenyl-4-yl group, 2'-methylbiphenyl-4-yl group, 4'-methylbiphenyl-4-yl group, 2,2'-dimethylbiphenyl-4-yl group, 2',4', 6'-trimethylbiphenyl-4-yl group, 6-methylbiphenyl-3-yl group, 5-methylbiphenyl-3-yl group, 2'-methylbiphenyl-3-yl group, 4'-methylbiphenyl-3- yl group, 6,2'-dimethylbiphenyl-3-yl group, 2',4',6'-trimethylbiphenyl-3-yl group, 5-methylbiphenyl-2-yl group, 6-methylbiphenyl-2- yl group, 2'-methylbiphenyl-2-yl group, 4'-methylbiphenyl-2-yl group, 6,2'-dimethylbiphenyl-2-yl group, 2',4',6'-trimethylbiphenyl- 2-yl group, 3-ethylbiphenyl-4-yl group, 4'-ethylbiphenyl-4-yl group, 2',4',6'-triethylbiphenyl-4-yl group, 6-ethylbiphenyl-3- yl group, 4'-ethylbiphenyl-3-yl group, 5-ethylbiphenyl-2-yl group, 4'-ethylbiphenyl-2-yl group, 2',4',6'-triethylbiphenyl-2-yl group, 3-propylbiphenyl-4-yl group, 4'-propylbiphenyl-4-yl group, 2',4',6'-tripropylbiphenyl-4-yl group, 6-propylbiphenyl-3-yl group , 4'-propylbiphenyl-3-yl group, 5-propylbiphenyl-2-yl group, 4'-propylbiphenyl-2-yl group, 2',4',6'-tripropylbiphenyl-2-yl group , 3-isopropylbiphenyl-4-yl group, 4′-isopropylbiphenyl-4-yl group, 2′,4′,6′-triisopropylbiphenyl-4-yl group, 6-isopropylbiphenyl-3-yl group, 4'-isopropylbiphenyl-3-yl group, 5-isopropylbiphenyl-2-yl group, 4'-isopropylbiphenyl-2-yl group, 2',4',6'-triisopropylbiphenyl-2-yl group, 3-butylbiphenyl-4-yl group, 4'-butylbiphenyl-4-yl group, 2',4',6'-tributylbiphenyl-4-yl group, 6-butylbiphenyl-3-y group, 4'-butylbiphenyl-3-yl group, 5-butylbiphenyl-2-yl group, 4'-butylbiphenyl-2-yl group, 2',4',6'-tributylbiphenyl-2-yl group, 3-tert-butylbiphenyl-4-yl group, 4'-tert-butylbiphenyl-4-yl group, 2',4',6'-tri-tert-butylbiphenyl-4-yl group, 6- tert-butylbiphenyl-3-yl group, 4'-tert-butylbiphenyl-3-yl group, 5-tert-butylbiphenyl-2-yl group, 4'-tert-butylbiphenyl-2-yl group, 4' -Pentylbiphenyl-4-yl group, 4'-cyclopentylbiphenyl-4-yl group, 4'-hexylbiphenyl-4-yl group, 4'-cyclohexylbiphenyl-4-yl group, 4'-octylbiphenyl-4- Examples include an yl group, a 4'-decylbiphenyl-4-yl group, a 4'-dodecylbiphenyl-4-yl group and the like.

Examples of the anthryl group optionally substituted with an alkyl group having 1 to 12 carbon atoms include 1-anthryl group, 4-butylanthryl-1-yl group, 5-hexylanthryl-1-yl group, 6-octylanthryl-1-yl group, 2-anthryl group, 7-hexylanthryl-2-yl group, 8-decylanthryl-2-yl group, 1,3-dimethylanthryl-2-yl group , 5-anthryl group, 10-butylanthryl-5-yl group, 10-dodecylanthryl-5-yl group and the like.

R ¹ and R ³ , and R ² and R ⁴ are combined to form an oligomethylene group having 3 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 12 carbon atoms. such as trimethylene group (-(CH ₂ ) ₃ -), tetramethylene group (-(CH ₂ ) ₄ -), pentamethylene group (-(CH ₂ ) ₅ -), hexamethylene group (-(CH ₂ ) _6- ) can be formed. The oligomethylene group having 3 to 6 carbon atoms may be substituted with an alkyl group having 1 to 12 carbon atoms. Any cyclic alkyl group may be used, for example, methyl group, cyclohexylmethyl group, ethyl group, 2-cyclopentylethyl group, propyl group, 2-methylpropyl group, 2,2-dimethylpropyl group, 3-cyclopropylpropyl group, isopropyl group, cyclopropyl group, butyl group, 2-methylbutyl group, 3-methylbutyl group, 2-butyl group, 3-methylbutan-2-yl group, tert-butyl group, cyclobutyl group, pentyl group, 2-methylpentyl group , 3-ethylpentyl group, 2,4-dimethylpentyl group, 2-pentyl group, 2-methylpentan-2-yl group, 4,4-dimethylpentan-2-yl group, 3-pentyl group, 3-ethyl Pentan-3-yl group, cyclopentyl group, 2,5-dimethylcyclopentyl group, 3-ethylcyclopentyl group, hexyl group, 2-methylhexyl group, 3,3-dimethylhexyl group, 4-ethylhexyl group, 2-hexyl group , 2-methylhexan-2-yl group, 5,5-dimethylhexan-2-yl group, 3-hexyl group, 2,4-dimethylhexan-3-yl group, cyclohexyl group, 4-ethylcyclohexyl group, 4 -propylcyclohexyl group, 4,4-dimethylcyclohexyl group, heptyl group, 2-heptyl group, 3-heptyl group, 4-heptyl group, bicyclo[2.2.1]heptyl group, octyl group, 2-octyl group, 3-octyl group, 4-octyl group, cyclooctyl group, bicyclo[2.2.2]octyl group, nonyl group, 5-nonyl group, decyl group, 2-decyl group, 5-decyl group, undecyl group, dodecyl and the like.

The halogen atom represented by X ¹ can be exemplified by a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, a bromine atom is preferable in terms of good reactivity.

^A fluorine atom, a chlorine atom, a bromine atom or an iodine atom can be exemplified as the halogen atom represented by X2. Among these, a fluorine atom is preferable because of its good reactivity.

The diimidazolobenzodithiophene compound of the present invention is not particularly limited, but specific examples thereof include compounds having structures shown in 1-1 to 1-281 below.

Among the compounds represented by 1-1 to 1-281, 1-5, 1-110, 1-111 and 1- are diimidazolobenzodithiophene compounds of the present invention in terms of good performance as an organic semiconductor. Compounds represented by 280 are preferred.

Next, the manufacturing method of the present invention will be described.

The diimidazolobenzodithiophene compound (1) of the present invention can be produced by steps 1 to 4 shown in the following reaction scheme.

(wherein R ¹ and R ² are each independently substituted with a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; a haloalkyl group having 1 to 20 carbon atoms; or an alkyl group having 1 to 12 carbon atoms; represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, wherein R ³ and R ⁴ each independently represent an alkyl group having 1 to 20 carbon atoms; represents an aromatic hydrocarbon group having 6 to 14 carbon atoms which may be substituted with an alkyl group of 12. X ^1a represents a halogen atom, and two X ² 's are the same or different and represent a halogen atom. ^.X3 represents an iodine atom or a bromine atom.)
In step 1, the imidazole compound (2a) contained in the intermediate of the present invention (hereinafter referred to as "intermediate (2a) of the present invention") is reacted with a sulfurizing agent to obtain the diimidazolobenzodithiophene of the present invention. This is the step of producing compound (1).

Examples of the sulfiding agent used in step 1 include alkali metal sulfide salts such as lithium sulfide, sodium sulfide, potassium sulfide, sodium hydrogen sulfide and potassium hydrogen sulfide, or hydrates thereof, bis(trimethylsilyl) sulfide, and bis(trimethylstannyl). Group 14 sulfiding agents such as sulfide and bis(tributylstannyl)sulfide can be exemplified. Alkali metal sulfide salts or hydrates thereof are preferable, and sodium sulfide or sodium sulfide nonahydrate is more preferable, because the reaction yield of the diimidazolobenzodithiophene compound (1) of the present invention is good. The molar ratio of the sulfurizing agent to be used and the intermediate (2a) of the present invention is not particularly limited, but the ratio of the sulfurizing agent to the intermediate (2a) of the present invention is preferably in the range of 1:2 to 10:1. The range of 1:1 to 5:1 is more preferable because the ratio is good.

Step 1 can be carried out in a solvent. Solvents that can be used are not particularly limited as long as they do not inhibit the reaction. Specific examples of such solvents include ethers such as diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, and dimethoxyethane, benzene, and toluene. , xylene, mesitylene, nitrobenzene, anisole, tetralin and other aromatic hydrocarbons, chlorobenzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, benzotrifluoride and other halogenated aromatic hydrocarbons, ethylene carbonate, propylene carbonate, dimethyl carbonate , Diethyl carbonate, ethyl methyl carbonate, carbonate esters such as 4-fluoroethylene carbonate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, esters such as γ-lactone, acetonitrile, propionitrile, valeronitrile , glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile and other nitriles, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and other amides , N,N,N',N'-Tetramethylurea (TMU), N,N'-Dimethylpropyleneurea (DMPU) and other ureas, dimethylsulfoxide (DMSO), etc. can be exemplified. You may mix and use by a ratio. There are no particular restrictions on the amount of solvent used. Among these, amide, urea, DMSO and a mixed solvent thereof are preferably used, and NMP is more preferable, because the reaction yield of the diimidazolobenzodithiophene compound (1) of the present invention is good.

The reaction temperature for carrying out step 1 is not particularly limited; It is preferable to carry out the reaction at a temperature appropriately selected from 160 to 220° C. in terms of good yield.

The diimidazolobenzodithiophene compound (1) of the present invention can be obtained by performing a normal treatment after the reaction in step 1 is completed. If necessary, it may be purified by recrystallization, column chromatography, sublimation or preparative HPLC.

In step 2, the imidazole compound (2b) contained in the intermediate of the present invention (hereinafter referred to as "intermediate (2b) of the present invention") is reacted with a halogenating agent to obtain the intermediate of the present invention used in step 1. This is the step of manufacturing the body (2a).

Halogenating agents used in step 2 include chlorine, N-chlorosuccinimide, N-chlorophthalimide, benzyltrimethylammonium=tetrachloroiodide, when X ^1a in the intermediate (2a) of the present invention is a chlorine atom. tert-butyl hypochloride, chloramine B, chloramine T, cyanuric chloride, dichloramine, oxalyl chloride, trichloroisocyanuric acid, thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, etc., and when X ^1a is a bromine atom, bromine, N -bromosuccinimide, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-dibromoisocyanuric acid, benzyltrimethylammonium tribromide, boron tribromide, N-bromoacetamide, 2-bromo-2-cyano-N , N-dimethylacetamide, bromodimethylsulfonium bromide, N-bromophthalimide, N-bromosaccharin, carbon trichloride bromide, 1-butyl-3-methylimidazolium bromide, 1,8-diazabicyclo[5,4, 0]-7-undecene = hydrogen tribromide complex, 5,5-dibromomeldrum acid, 1,2-dibromo-1,1,2,2-tetrachloroethane, 4-dimethylaminopyridine = hydrogen tribromide complex , pyridine hydrogen tribromide complex, phosphorus tribromide, phosphorus oxytribromide, 2,4,4,6-tetrabromo-2,5-cyclohexadienone, tetrabutylammonium tribromide, trimethylphenylammonium tribromide, triphenylphosphine = dibromide, etc., when X ^1a is an iodine atom, iodine, hydrogen iodide, benzyltrimethylammonium = dichloroiodide, bis(pyridine)iodonium = boron tetrafluoride complex, bis(2,4, 6-trimethylpyridine)iodonium = phosphorus hexafluoride complex, trimethyliodosilane, iodine chloride, 1,3-diiodo-5,5-dimethylhydantoin, N-iodosuccinimide, N-iodosaccharin, etc., and X ^1a is fluorine if atomic, 2,6-dichloro-1-fluoropyridinium = trifluoromethanesulfonate, 2,6-dichloro-1-fluoropyridinium = boron tetrafluoride complex, 1,1'-difluoro-2,2'- Bipyridinium = bis (boron tetrafluoride) complex, N-fluorobenzenesulfonimide, N-fluoro-N'-chloromethyltriethylenediamine = bis (boron tetrafluoride) complex, 2-fluoro -1-methylpyridinium=p-toluenesulfonate, 1-fluoropyridinium=boron tetrafluoride complex, 1-fluoro-2,4,6-trimethylpyridinium=boron tetrafluoride complex and the like can be exemplified. N-bromosuccinimide is preferred in that the reaction yield of the intermediate (2a) of the present invention is good. The molar ratio of the halogenating agent to be used and the intermediate (2b) of the present invention is not particularly limited, but the halogenating agent:intermediate (2b) of the present invention is preferably in the range of 1:2 to 10:1. The ratio is preferably in the range of 1:1 to 5:1 from the viewpoint of good reaction yield.

The reaction temperature in carrying out step 2 is not particularly limited, but it can be carried out at a temperature appropriately selected from 0 to 150 ° C., and it was appropriately selected from 10 to 60 ° C. in terms of good yield. It is preferred to work at temperature.

Intermediate (2a) of the present invention can be obtained by performing a normal treatment after completion of the reaction in step 2. If necessary, it may be purified by recrystallization, column chromatography, sublimation, preparative HPLC, or the like, but may be subjected to step 1 without purification.

In step 3, 1,2-disubstituted imidazole (3b) and 5-phenylimidazole (5) are reacted in the presence of a palladium catalyst and a base to produce intermediate (2b) of the present invention used in step 2. By applying reaction conditions for a cross-coupling reaction involving activation of a general carbon-hydrogen bond, the desired product can be obtained in good yield.

X ³ represents a bromine atom or an iodine atom, and a bromine atom is preferable in that it is easily available.

The 1,2-disubstituted imidazole (3b) used in step 3 can be produced, for example, using the methods shown in Reference Examples-1 to 3 below. Moreover, you may use a commercial item.

5-phenylimidazole (5) used in step 3 is, for example, Organometallics, 2016, 35, 2655-2663, or Advanced Synthesis & Catalysis, 2016, 358, 597-609, Organometallics, 2011, 30, 5160-5169, Tetrahedron, 2009, 65, 9722-9781, Bulletin of the Chemical Society of Japan, 1998, 71, 467-478, etc. can do. Moreover, you may use a commercial item. The molar ratio of 5-phenylimidazole (5) and 1,2-disubstituted imidazole (3b) is not particularly limited, but is preferably from 1:10 to 1:1, and from 1:5 to 1:5 in terms of good reaction yield. 1:1 is more preferred.

The palladium catalyst used in step 3 is not particularly limited, but specific examples include salts such as palladium chloride, palladium acetate, palladium trifluoroacetate, and palladium nitrate. Furthermore, complex compounds such as π-allylpalladium chloride dimer, palladium acetylacetonate, tris(dibenzylideneacetone)dipalladium, and dichlorobis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)palladium, dichloro(1,1) Tertiary phosphines such as '-bis(diphenylphosphino)ferrocene)palladium, bis(tri-tert-butylphosphine)palladium, bis(tricyclohexylphosphine)palladium, bis(tricyclohexylphosphine)chloride palladium, etc. can be exemplified by palladium complexes having Among them, a palladium complex or a palladium salt having a tertiary phosphine as a ligand is preferable, and palladium acetate is more preferable, because the reaction yield of the intermediate (2b) of the present invention is good. Although the amount of the palladium catalyst used in step 3 is not limited, the molar ratio of the palladium catalyst and 5-phenylimidazole (5) is preferably in the range of 1:200 to 1:5 from the viewpoint of good reaction yield.

The palladium complex having a tertiary phosphine as a ligand can also be prepared in a reaction system by adding a tertiary phosphine to a palladium salt or complex compound. The tertiary phosphine is not particularly limited, but specific examples include triphenylphosphine, trimethylphosphine, tributylphosphine, tri(tert-butyl)phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine, 9, 9-dimethyl-4,5-bis(diphenylphosphino)xanthene, 2-(diphenylphosphino)-2'-(N,N-dimethylamino)biphenyl, 2-(di-tert-butylphosphino)biphenyl, 2-(dicyclohexylphosphino)biphenyl, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino) ) butane, 1,1′-bis(diphenylphosphino)ferrocene, tri(2-furyl)phosphine, tri(o-tolyl)phosphine, tris(2,5-xylyl)phosphine, (±)-2,2′ -bis(diphenylphosphino)-1,1'-binaphthyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl and the like. Among these, tricyclohexylphosphine is preferable because of its easy availability and good yield. The molar ratio of the tertiary phosphine and the palladium salt or complex compound is preferably in the range of 1:10 to 20:1 for the tertiary phosphine: palladium salt or complex compound, and from 1:2 to 1:2 for good yield. A 10:1 range is more preferred.

The base used in step 3 is not particularly limited, but examples include metal hydroxide salts such as sodium hydroxide, potassium hydroxide and calcium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate and the like. Metal carbonates, metal acetates such as potassium acetate and sodium acetate, metal phosphates such as potassium phosphate and sodium phosphate, metal fluoride salts such as sodium fluoride, potassium fluoride and cesium fluoride, sodium methoxide , potassium methoxide, sodium ethoxide, potassium isopropyl oxide, potassium tert-butoxide and the like metal alkoxides. Among these, metal carbonates or metal acetates are preferred because of good yield, and potassium carbonate or potassium acetate is more preferred. The molar ratio of the base and 5-phenylimidazole (5) is preferably in the range of 10:1 to 1:2 (base:5-phenylimidazole (5)), and 5:1 to 1:1 in terms of good yield. A range of 1 is more preferred.

Step 3 may be carried out in the presence of a carboxylic acid. Examples of the carboxylic acid include, but are not limited to, formic acid, acetic acid, chloroacetic acid, trichloroacetic acid, trifluoroacetic acid, propionic acid, 2-methylpropionic acid, pivalic acid, butyric acid, valeric acid, and cyclohexanecarboxylic acid. , 1-adamantanecarboxylic acid, oxalic acid, malonic acid, aliphatic carboxylic acids such as adipic acid, benzoic acid, 4-methoxybenzoic acid, 4-nitrobenzoic acid, 2,4-dinitrobenzoic acid, 4-trifluoromethyl Aromatic carboxylic acids such as benzoic acid, 2,4,6-trimethylbenzoic acid, 3-chlorobenzoic acid, salicylic acid and phthalic acid can be exemplified. Among these, pivalic acid is preferable in that the reaction yield is good. The molar ratio of carboxylic acid and 5-phenylimidazole (5) is preferably 1:1 to 1:100 for carboxylic acid:5-phenylimidazole (5), and 1:2 to 1:2 for good yield. A range of 1:10 is more preferred.

Step 3 can be carried out in a solvent. Solvents that can be used are not particularly limited as long as they do not inhibit the reaction. Specific examples of such solvents include ethers such as diisopropyl ether, dibutyl ether, CPME, THF, 2-methyltetrahydrofuran, 1,4-dioxane and dimethoxyethane; Aromatic hydrocarbons, carbonate esters such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 4-fluoroethylene carbonate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, γ- Examples include esters such as lactones, amides such as DMF, DMAc and NMP, urea such as TMU and DMPU, DMSO, water, and the like, and these may be used by mixing at any ratio. There are no particular restrictions on the amount of solvent used. Among these, aromatic hydrocarbons or amides are preferable, and toluene or DMAc is more preferable, because of good reaction yield.

The reaction temperature in carrying out step 3 is not particularly limited, but it is preferable to carry out at a temperature appropriately selected from 50 to 250 ° C., and it was appropriately selected from 80 to 180 ° C. in terms of good yield. It is even more preferred to work at temperature.

Intermediate (2b) of the present invention can be obtained by performing a normal treatment after the reaction in step 3 is completed. If necessary, it may be purified by recrystallization, column chromatography, sublimation, preparative HPLC, or the like, but may be subjected to step 2 without purification.

Step 4 is a step of reacting 1,2-disubstituted imidazole (3a) and benzene compound (4) in the presence of a palladium catalyst and a base to produce 5-phenylimidazole (5) used in step 3. Yes, and by applying the same reaction conditions as in step 3, the desired product can be obtained in good yield.

The 1,2-disubstituted imidazole (3a) used in Step 4 can be produced, for example, using the methods shown in Reference Examples-1 to 3 below. Moreover, you may use a commercial item.

The benzene compound (4) used in step 4 can be produced, for example, by the method disclosed in European Journal of Organic Chemistry, 2002, pp. 3351-3358. Moreover, you may use a commercial item. The molar ratio between the benzene compound (4) and the 1,2-disubstituted imidazole (3a) is not particularly limited, but is preferably 1:10 to 1:1, and 1:5 to 1:1 for good yield. is more preferred.

As the palladium catalyst used in step 4, the same palladium catalysts as exemplified in step 3 can be exemplified. Among them, a palladium complex or a palladium salt having a tertiary phosphine as a ligand is preferable, and palladium acetate is more preferable, because the reaction yield of 5-phenylimidazole (5) is good. Although the amount of the palladium catalyst used in step 4 is not limited, the molar ratio of the palladium catalyst to the benzene compound (4) is preferably in the range of 1:200 to 1:5 in terms of yield.

A palladium complex having a tertiary phosphine as a ligand can also be prepared in a reaction system by adding a tertiary phosphine to a palladium salt or complex compound. As the tertiary phosphine, the same tertiary phosphine as exemplified in Step 3 can be exemplified. Among these, tricyclohexylphosphine is preferable because it is easily available and the reaction yield is good. The molar ratio of the tertiary phosphine and the palladium salt or complex compound is preferably in the range of 1:10 to 20:1 for the tertiary phosphine: palladium salt or complex compound, and from 1:2 to 1:2 for good yield. A 10:1 range is more preferred.

As the base used in step 4, the same bases as exemplified in step 3 can be mentioned. Of these, metal carbonates or metal acetates are preferred, and potassium carbonate or potassium acetate is more preferred, because of good yield. The molar ratio between the base and the benzene compound (4) is preferably in the range of 10:1 to 1:2 (base:benzene compound (4)), and in terms of good yield, it is preferably in the range of 5:1 to 1:1. More preferred.

Step 4 may be carried out in the presence of a carboxylic acid. As the carboxylic acid, the same carboxylic acid as exemplified in step 3 can be exemplified. Among these, pivalic acid is preferable in that the reaction yield is good. The molar ratio of carboxylic acid to benzene compound (4) is preferably in the range of 1:1 to 1:100 for carboxylic acid:benzene compound (4), and 1:2 to 1:10 for good yield. Ranges are more preferred.

Step 4 can be carried out in a solvent. Solvents that can be used are not particularly limited as long as they do not inhibit the reaction. As such a solvent, the same solvents as those exemplified in Step 3 can be exemplified. There are no particular restrictions on the amount of solvent used. Among these, aromatic hydrocarbons or amides are preferable, and toluene or DMAc is more preferable, because of good reaction yield.

The reaction temperature in carrying out step 4 is not particularly limited, but it is preferable to carry out at a temperature appropriately selected from 50 to 250° C., and from the viewpoint of good reaction yield, it is appropriately selected from 80 to 180° C. It is more preferable to carry out at a temperature

5-Phenylimidazole (5) can be obtained by normal treatment after completion of the reaction in step 4. If necessary, it may be purified by recrystallization, column chromatography, sublimation, preparative HPLC, or the like, but may be subjected to step 3 without purification.

Further, the imidazole compound represented by the general formula (2c) contained in the intermediate (2) of the present invention (hereinafter referred to as "the intermediate (2c) of the present invention") can be prepared by the steps shown in the following reaction scheme. 5.

(In the formula, R ¹ , R ³ , X ² and X ³ have the same meanings as above.)
Whereas intermediate (2b) of the present invention is obtained by stepwise reaction (step 3, step 4) of benzene compound (4) with different 1,2-disubstituted imidazoles (3a) and (3b) , the intermediate (2c) of the present invention is obtained by introducing the same kind of 1,2-disubstituted imidazole (3a) into the benzene compound (4), so that it can be carried out in a one-step reaction (step 5). It is possible.

Step 5 is a step of reacting 1,2-disubstituted imidazole (3a) and benzene compound (4) in the presence of a palladium catalyst and a base to produce intermediate (2c) of the present invention used in step 2. By applying the same reaction conditions as in step 4 or 3, the desired product can be obtained in good yield.

The molar ratio between the benzene compound (4) and the 1,2-disubstituted imidazole (3a) used in step 5 is not particularly limited, but is preferably 1:1 to 10:1, and 1:1 in terms of good yield. ~3:1 is more preferred.

As the palladium catalyst used in step 5, the same palladium catalysts as exemplified in step 4 or 3 can be exemplified. Among them, a palladium complex or a palladium salt having a tertiary phosphine as a ligand is preferable, and palladium acetate is more preferable, because the reaction yield of the intermediate (2c) of the present invention is good. Although the amount of the palladium catalyst used in step 5 is not limited, the molar ratio of the palladium catalyst to the benzene compound (4) is preferably in the range of 1:200 to 1:5 in terms of yield.

The palladium complex having a tertiary phosphine as a ligand can also be prepared in a reaction system by adding a tertiary phosphine to a palladium salt or complex compound. As the tertiary phosphine, the same tertiary phosphines as exemplified in step 4 or 3 can be exemplified. Among these, tricyclohexylphosphine is preferable because of its easy availability and good yield. The molar ratio of the tertiary phosphine and the palladium salt or complex compound is preferably in the range of 1:10 to 20:1 for the tertiary phosphine: palladium salt or complex compound, and from 1:2 to 1:2 for good yield. A 10:1 range is more preferred.

As the base used in step 5, the same bases as exemplified in step 4 or 3 can be mentioned. Of these, metal carbonates or metal acetates are preferred, and potassium carbonate or potassium acetate is more preferred, because of good yield. The molar ratio between the base and the 1,2-disubstituted imidazole (3a) is preferably in the range of 10:1 to 1:2 (base: 1,2-disubstituted imidazole (3a)) in terms of good yield. A range of 5:1 to 1:1 is more preferred.

Step 5 may be carried out in the presence of a carboxylic acid. As the carboxylic acid, the same carboxylic acid as exemplified in step 4 or 3 can be exemplified. Among these, pivalic acid is preferable in that the reaction yield is good. The molar ratio of carboxylic acid to benzene compound (4) is preferably in the range of 1:1 to 1:100 for carboxylic acid:benzene compound (4), and 1:2 to 1:10 for good yield. Ranges are more preferred.

Step 5 can be carried out in a solvent. Solvents that can be used are not particularly limited as long as they do not inhibit the reaction. Examples of such a solvent include the same solvents as those exemplified in step 4 or 3. There are no particular restrictions on the amount of solvent used. Among these, aromatic hydrocarbons or amides are preferable, and toluene or DMAc is particularly preferable, because of good reaction yield.

The reaction temperature in carrying out step 5 is not particularly limited, but it can be carried out at a temperature appropriately selected from 50 to 250 ° C., and it was appropriately selected from 80 to 180 ° C. in terms of good yield. It is preferred to work at temperature.

Intermediate (2c) of the present invention can be obtained by normal treatment after completion of the reaction in step 5. If necessary, it may be purified by recrystallization, column chromatography, sublimation, preparative HPLC, or the like, but may be subjected to step 2 without purification.

Next, a method for producing a film-forming composition containing the diimidazolobenzodithiophene compound of the present invention (hereinafter referred to as "the film-forming composition of the present invention") will be described.

The film-forming composition of the present invention can be prepared by dissolving or dispersing the diimidazolobenzodithiophene compound of the present invention in a solvent.

The solvent is not particularly limited as long as it dissolves or disperses the diimidazolobenzodithiophene compound of the present invention. Examples include toluene, xylene, mesitylene, ethylbenzene, pentylbenzene, hexylbenzene, octylbenzene, and cyclohexyl. Aromatic hydrocarbons such as benzene, indane, tetralin, anisole, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, 1,2-dimethylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole, nitrobenzene , hexane, heptane, octane, decane, dodecane, tetradecane, decalin and other aliphatic hydrocarbons, dichlorobenzene, chlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane , chloroform, halogenated hydrocarbons such as dichloromethane, ethers such as diisopropyl ether, dibutyl ether, CPME, THF, 2-methyltetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, cyclohexanone, acetophenone, etc. Esters such as ketones, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, γ-butyrolactone, cyclohexanol acetate, 3-methoxybutyl acetate, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl Carbonates, carbonate esters such as 4-fluoroethylene carbonate, acetonitrile, propionitrile, valeronitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, nitriles such as 3-methoxypropionitrile, amides such as DMF, DMAc, NMP, etc. Propylene glycol dimethyl ether, dipropylene glycol diacetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,3-butylene Glycol diacetate, 1,6-hexanediol diacetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate Glycols such as tate and diethylene glycol monobutyl ether acetate can be exemplified. Among these, aromatic hydrocarbons are preferred, and toluene, mesitylene, cyclohexylbenzene, tetralin, or 3,4-dimethylanisole are more preferred, since they have a high boiling point and volatilize moderately. The amount of the solvent used is not particularly limited, and the concentration of the diimidazolobenzodithiophene compound of the present invention is preferably 0.001 to 95% by weight, more preferably 0.01 to 10% by weight. Solvent can be added so that

As the dissolving or dispersing method, methods known to those skilled in the art such as stirring, shaking, ball milling, ultrasonic irradiation, etc. can be used. At this time, heating may be performed.

A binder may be added to the film-forming composition of the present invention to improve film-forming properties. Examples of such binders include polystyrene, poly-α-methylstyrene, polyvinylnaphthalene, poly(ethylene-co-norbornene), polymethylmethacrylate, polytriarylamine, poly(9,9-dioctylfluorene-co- dimethyltriphenylamine) can be exemplified. Although the concentration of the binder is not particularly limited, it is preferably 0.1 to 10.0% by weight from the viewpoint of good coatability.

The viscosity of the film-forming composition of the present invention is preferably in the range of 0.5 to 50 mPa·s from the viewpoint of good applicability.

Next, a method for forming an organic thin film containing the diimidazolobenzodithiophene compound of the present invention (hereinafter referred to as "organic thin film of the present invention") will be described.

The method for forming the organic thin film of the present invention is not particularly limited, and examples thereof include a resistance heating vapor deposition method and a coating method.

Among them, simple coating methods such as spin coating, drop casting, dip coating, and cast coating; printing methods such as dispenser, inkjet, slit coating, blade coating, flexographic printing, screen printing, gravure printing, and offset printing. Among them, drop casting or inkjet is preferable in terms of being able to form a film easily and efficiently. The organic thin film of the present invention can be obtained by drying the solvent after forming the film.

Further, the organic thin film of the present invention may be annealed at a temperature appropriately selected from the range of 40° C. to 200° C., if necessary.

Although the thickness of the organic thin film of the present invention is not particularly limited, it is preferably 1 nm to 1 μm, more preferably 10 nm to 300 nm, in view of high carrier mobility.

Further, a method for producing an organic transistor element containing the diimidazolobenzodithiophene compound of the present invention in the active layer (hereinafter referred to as "the organic transistor element of the present invention") will be described.

The organic transistor element of the present invention is obtained by forming the organic thin film of the present invention as an insulating layer and an active layer on a substrate, and attaching a source electrode, a drain electrode and a gate electrode thereto.

FIG. 1 shows the structure of an element included in the organic transistor element of the present invention. Here, (A) is a bottom gate-top contact type, (B) is a bottom gate-bottom contact type, (C) is a top gate-top contact type, and (D) is a top gate-bottom contact type. 1 is an active layer, 2 is a substrate, 3 is a gate electrode, 4 is a gate insulating layer, 5 is a source electrode, and 6 is a drain electrode.

Examples of substrates include polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polymethyl acrylate, polyethylene, polypropylene, polystyrene, cyclic polyolefin, polyimide, polycarbonate, polyvinylphenol, polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate), poly(diisopropyl maleate), polyethersulfone, polyphenylene sulfide, cellulose triacetate plastic substrates, glass, quartz, aluminum oxide, silicon, highly doped silicon, silicon oxide, tantalum dioxide, tantalum pentoxide, indium tin Inorganic substrates such as oxides, metal substrates such as gold, copper, chromium, titanium, and aluminum can be used. Among these, silicon or highly doped silicon is preferable in terms of good transistor performance.

As the gate electrode, for example, inorganic electrodes such as aluminum, gold, silver, copper, highly doped silicon, tin oxide, indium oxide, indium tin oxide, chromium, titanium, tantalum, chromium, graphene, carbon nanotubes, etc., or doped organic electrodes such as conductive polymers (for example, PEDOT-PSS) and the like. Among these, inorganic electrodes are preferred because of their good conductivity, and gold is particularly preferred.

Examples of insulating layers include inorganic materials such as silicon oxide, silicon nitride, aluminum oxide, aluminum nitride, titanium oxide, tantalum dioxide, tantalum pentoxide, indium tin oxide, tin oxide, vanadium oxide, barium titanate, and bismuth titanate. Insulating layer, polymethyl methacrylate, polymethyl acrylate, polyimide, polycarbonate, polyvinylphenol, polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate), polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polycyclopentane, Examples include organic insulating layers such as polycyclohexane, polycyclohexane-ethylene copolymer, polyfluorinated cyclopentane, polyfluorinated cyclohexane, and polyfluorinated cyclohexane-ethylene copolymer. Among these, an inorganic insulating layer is preferable because of its good insulating properties, and silicon oxide is more preferable. Further, the surfaces of these insulating layers are, for example, octadecyltrichlorosilane, decyltrichlorosilane, decyltrimethoxysilane, octyltrichlorosilane, octadecyltrimethoxysilane, β-phenethyltrichlorosilane, β-phenethyltrimethoxysilane, phenyltrichlorosilane. , silanes such as phenyltrimethoxysilane, phosphonic acids such as octadecylphosphonic acid, decylphosphonic acid and octylphosphonic acid, and amines such as hexamethyldisilazane. Among these, octadecyltrichlorosilane, octyltrichlorosilane, β-phenethyltrichlorosilane, and octadecylphosphonic acid are preferred in terms of improving the carrier mobility and current on/off ratio of the organic transistor device of the present invention and lowering the threshold voltage. , octylphosphonic acid and hexamethyldisilazane are preferred.

As the source electrode and the drain electrode, electrodes similar to those exemplified for the gate electrode can be exemplified. Among these, an inorganic electrode is preferred because of its good conductivity, and gold is more preferred. Moreover, in order to increase the efficiency of carrier injection, these electrodes can be surface-treated using a surface-treating agent. Examples of such surface treatment agents include benzenethiol and pentafluorobenzenethiol.

The diimidazolobenzodithiophene compound of the present invention can be used for electronic materials such as organic EL display materials, organic semiconductor laser materials, organic thin film solar cell materials, and photonic crystal materials. Moreover, the organic transistor element of the present invention can be used for electronic paper, organic EL displays, liquid crystal displays, IC tags (RFID tags), pressure sensors, and the like.

The diimidazolobenzodithiophene compound of the present invention is an organic semiconductor having both high solvent solubility and heat resistance, and can efficiently drive an organic transistor element using this as an active layer.

; It is a figure which shows the structure by the cross-sectional shape of an organic transistor element.

EXAMPLES The present invention will be described in more detail below with reference to examples, reference examples, test examples and comparative examples, but the present invention should not be construed as being limited thereto.

The following analytical methods were used to identify the diimidazolobenzodithiophene compounds of the present invention and the intermediates of the present invention. Bruker ULTRASHIELD AVANCE III (400 MHz and 376 MHz) was used for ¹ H-NMR and ¹⁹ F-NMR measurements. ¹ H-NMR was measured using deuterated chloroform (CDCl ₃ ) as a measurement solvent and tetramethylsilane (TMS) as an internal standard substance. Commercially available reagents were used.
Example-1
(Synthesis of 1,4-bis(1,2-dimethylimidazol-5-yl)-2,5-difluorobenzene)

1,2-dimethylimidazole (385 mg, 4.0 mmol), 1,4-dibromo-2,5-difluorobenzene (272 mg, 1.0 mmol), potassium acetate (393 mg, 4.0 mmol) and palladium acetate under an argon stream. (11 mg, 0.05 mmol) was suspended in dimethylacetamide (DMAc, 5.0 mL) and stirred at 150° C. for 48 hours. After allowing to cool, water is added to the reaction mixture, the precipitated solid is collected by filtration, and washed with water to give the desired 1,4-bis(1,2-dimethylimidazol-5-yl)-2 as a milky white solid. ,5-difluorobenzene (198 mg, 66%).

¹ H-NMR (CDCl ₃ ): δ 7.13 (t, J = 7.9 Hz, 2H), 7.03 (s, 2H), 3.51 (s, 6H), 2.47 (s, 6H) .
¹⁹ F-NMR (CDCl ₃ ): δ-118.3 (s, 2F).
Example-2
(Synthesis of 1,4-bis(4-bromo-1,2-dimethylimidazol-5-yl)-2,5-difluorobenzene)

Under an argon stream, 1,4-bis(1,2-dimethylimidazol-5-yl)-2,5-difluorobenzene (76 mg, 0.25 mmol) and N-bromosuccinimide (NBS, 98 mg, 0.55 mmol) Suspended in methanol (1.2 mL). The suspension was stirred at room temperature for 16 hours. After the reaction, ethyl acetate and an aqueous sodium thiosulfate solution were added to the reaction mixture, the organic layer was extracted, and the organic layer was washed with water and then with brine. After adding sodium sulfate to the organic layer and stirring, the desiccant is filtered off, the solvent is distilled off, and the target 1,4-bis(4-bromo-1,2-dimethylimidazol-5-yl)-2, 5-difluorobenzene was obtained as an off-white solid (94 mg, 82%).

¹ H-NMR (DMSO-d ₆ ): δ 7.55 (t, J=7.9 Hz, 2H), 3.45 (s, 6H), 2.37 (s, 6H).
¹⁹ F-NMR (CDCl ₃ ): δ-116.9 (s, 2F).
Example-3
(Synthesis of 1,2,6,7-tetramethyldiimidazolo[4,5-d;4',5'-d']benzo[1,2-b;3,4-b']dithiophene)

Under an argon stream, 1,4-bis(4-bromo-1,2-dimethylimidazol-5-yl)-2,5-difluorobenzene (276 mg, 0.6 mmol) and sodium sulfide (140 mg, 1.8 mmol) Suspended in NMP (12 mL). This suspension was stirred at 200° C. for 10 hours. After cooling to room temperature, water was added to the reaction mixture, the suspension was centrifuged (2500 rpm, 10 minutes) and the supernatant was removed. This centrifugation operation was repeated twice. Chloroform was added to the resulting solid and centrifuged again (2500 rpm, 10 minutes). After removing the supernatant, the residue is evaporated to dryness under reduced pressure to obtain the desired 1,2,6,7-tetramethyldiimidazolo[4,5-d;4′,5′-d′]benzo[1,2-b]. an off-white solid of 3,4-b']dithiophene was obtained (34 mg, 18%).

¹ H-NMR (CDCl ₃ ): δ 8.19 (s, 2H), 4.02 (s, 6H), 2.61 (s, 6H).
Melting point: >300°C
Example-4
(Synthesis of 2,5-difluoro-1,4-bis(2-hexyl-1-methylimidazol-5-yl)benzene)

2-hexyl-1-methylimidazole (249 mg, 1.5 mmol), 1,4-dibromo-2,5-difluorobenzene (136 mg, 0.5 mmol), potassium acetate (147 mg, 1.5 mmol) and Palladium acetate (11 mg, 0.1 mmol) was suspended in DMAc (2.5 mL) and stirred at 150° C. for 72 hours. After allowing to cool, the solvent was distilled off, water was added to the residue, and the solid was collected by filtration. The resulting solid was purified by silica gel column chromatography (chloroform/ethyl acetate) to remove the desired 2,5-difluoro-1,4-bis(2-hexyl-1-methylimidazol-5-yl)benzene as a milky white solid. (141 mg, 64%) as

¹ H-NMR (CDCl ₃ ): δ 7.13 (t, J = 7.9 Hz, 2H), 7.06 (s, 2H), 3.51 (s, 6H), 2.73 (t, J = 7.7Hz, 4H), 1.82 (tt, J = 7.8, 7.7Hz, 4H), 1.41-1.46 (m, 4H), 1.33-1.37 (m, 8H) ), 0.90 (t, J=7.0 Hz, 6H).
¹⁹ F-NMR (CDCl ₃ ): δ-118.3 (s, 2F).
Example-5
(Synthesis of 1,4-bis(4-bromo-2-hexyl-1-methylimidazol-5-yl)-2,5-difluorobenzene)

Under an argon stream, 2,5-difluoro-1,4-bis(2-hexyl-1-methylimidazol-5-yl)benzene (89 mg, 0.20 mmol) and NBS (78 mg, 0.44 mmol) were dissolved in methanol (0.0 .9 mL). The suspension was stirred at room temperature for 16 hours. After the reaction, ethyl acetate and an aqueous sodium thiosulfate solution were added to the reaction mixture, the organic layer was extracted, and the organic layer was washed with water and then with brine. After adding sodium sulfate to the organic layer and stirring, the desiccant was filtered off and the solvent was distilled off. The resulting solid was purified by silica gel column chromatography (ethyl acetate:hexane=1:2) to give the desired 1,4-bis(4-bromo-2-hexyl-1-methylimidazol-5-yl)-2 ,5-difluorobenzene was obtained as an off-white solid (85 mg, 71%).

¹ H-NMR (CDCl ₃ ): δ 7.26 (t, J = 7.7 Hz, 2H), 3.49 (s, 6H), 2.72 (t, J = 7.9 Hz, 4H), 1. 80 (tt, J = 7.9, 7.7 Hz, 4H), 1.39-1.45 (m, 4H), 1.32-1.38 (m, 8H), 0.90 (t, J = 7.0Hz, 6H).
¹⁹ F-NMR (CDCl ₃ ): δ-116.8 (s, 2F).
Example-6
(Synthesis of 2,7-dihexyl-1,6-dimethyldiimidazolo[4,5-d;4',5'-d']benzo[1,2-b;3,4-b']dithiophene)

1,4-bis(4-bromo-2-hexyl-1-methylimidazol-5-yl)-2,5-difluorobenzene (60 mg, 0.10 mmol) and sodium sulfide (39 mg, 0.50 mmol) under an argon stream ) was suspended in NMP (2.0 mL) and stirred at 200° C. for 12 hours. After allowing to cool, 1N hydrochloric acid was added to the reaction mixture, the suspension was centrifuged (3000 rpm, 10 minutes), and the supernatant was removed. Water was added again and the supernatant was removed by centrifugation twice. The resulting solid was purified by silica gel column chromatography (chloroform/ethyl acetate) and then by recycle HPLC to obtain the target 2,7-dihexyl-1,6-dimethyldiimidazolo[4,5-d;4', A milky white solid of 5′-d′]benzo[1,2-b;3,4-b′]dithiophene was obtained (18 mg, 39%).

¹ H-NMR (CDCl ₃ ): δ 8.17 (s, 2H), 4.02 (s, 6H), 2.87 (t, J = 7.8 Hz, 4H), 1.86 (tt, J = 7.8, 7.5Hz, 4H), 1.45-1.48 (m, 4H), 1.34-1.38 (m, 8H), 0.90 (t, J = 7.0Hz, 6H ).
Melting point: >300°C
Example-7
(Synthesis of 1,4-bis(1-ethyl-2-hexylimidazol-5-yl)-2,5-difluorobenzene)

Under an argon stream, 1-ethyl-2-hexylimidazole (2.23 g, 12.4 mmol), 1,4-dibromo-2,5-difluorobenzene (1.12 g, 4.1 mmol), potassium acetate (1.22 g) , 12.4 mmol) and palladium acetate (92 mg, 0.4 mmol) were suspended in DMAc (20 mL) and stirred at 150° C. for 48 hours. After allowing to cool, diethyl ether and water were added to the reaction mixture, the organic layer was extracted, and the organic layer was washed with brine. After adding sodium sulfate to the organic layer and stirring, the desiccant was filtered off and the solvent was distilled off. The resulting solid is purified by silica gel column chromatography (ethyl acetate) and then passed through alumina (chloroform) to give the desired 1,4-bis(1-ethyl-2-hexylimidazol-5-yl)-2 ,5-difluorobenzene was obtained as a brown solid (1.44 g, 74%).

¹ H-NMR (CDCl ₃ ): δ 7.12 (t, J = 7.8 Hz, 2H), 7.04 (s, 2H), 3.92 (q, J = 7.2 Hz, 4H), 2. 73 (t, J = 7.7Hz, 4H), 1.85 (tt, J = 7.8, 7.7Hz, 4H), 1.42-1.47 (m, 4H), 1.34-1 .38 (m, 8H), 1.20 (t, J=7.2Hz, 6H), 0.91 (t, J=7.0Hz, 6H).
¹⁹ F-NMR (CDCl ₃ ): δ-118.0 (s, 2F).
Example-8
(Synthesis of 1,4-bis(4-bromo-1-ethyl-2-hexylimidazol-5-yl)-2,5-difluorobenzene)

1,4-bis(1-ethyl-2-hexylimidazol-5-yl)-2,5-difluorobenzene (1.19 g, 2.5 mmol) and NBS (1.13 g, 6.3 mmol) under an argon stream was suspended in methanol (12 mL). The suspension was stirred at room temperature for 21 hours. After the reaction, ethyl acetate and water were added to the reaction mixture, the organic layer was extracted, and the organic layer was washed with brine. After adding sodium sulfate to the organic layer and stirring, the desiccant was filtered off and the solvent was distilled off. The resulting solid was purified by silica gel column chromatography (ethyl acetate:hexane=1:2) and washed with hexane to obtain the desired 1,4-bis(4-bromo-1-ethyl-2-hexylimidazole). -5-yl)-2,5-difluorobenzene was obtained as an off-white solid (660 mg, 41%).

¹ H-NMR (CDCl ₃ ): δ 7.21 (t, J = 7.5 Hz, 2H), 3.88 (q, J = 7.2 Hz, 4H), 2.71 (t, J = 7.8 Hz , 4H), 1.83 (tt, J = 7.9, 7.8Hz, 4H), 1.40-1.46 (m, 4H), 1.32-1.37 (m, 8H), 1 .18 (t, J=7.2 Hz, 6 H), 0.91 (t, J=7.1 Hz, 6 H).
¹⁹ F-NMR (CDCl ₃ ): δ-116.4 (s, 2F).
Example-9
(Synthesis of 1,6-diethyl-2,7-dihexyldiimidazolo[4,5-d;4',5'-d']benzo[1,2-b;3,4-b']dithiophene)

1,4-bis(4-bromo-1-ethyl-2-hexylimidazol-5-yl)-2,5-difluorobenzene (63 mg, 0.10 mmol) and sodium sulfide (39 mg, 0.50 mmol) under an argon stream ) was suspended in NMP (2.0 mL) and stirred at 200° C. for 12 hours. After allowing to cool, water was added to the reaction mixture, and the precipitated solid was collected by filtration. The resulting solid was purified by silica gel column chromatography (chloroform:methanol=9:1) and then by recycle HPLC to give the desired 1,6-diethyl-2,7-dihexyldiimidazolo[4,5-d;4 An off-white solid of ',5'-d']benzo[1,2-b;3,4-b']dithiophene was obtained (14 mg, 28%).

¹ H-NMR (CDCl ₃ ): δ 8.11 (s, 2H), 4.38 (q, J = 7.2 Hz, 4H), 2.86 (t, J = 7.8 Hz, 4H), 1. 88 (tt, J = 7.8, 7.6Hz, 4H), 1.58 (t, J = 7.2Hz, 6H), 1.44-1.49 (m, 4H), 1.35-1 .38 (m, 8H), 0.91 (t, J=7.0Hz, 6H).
Liquid crystal transition point: 76°C
Melting point: 211°C
Example-10
(Synthesis of 1,4-bis(2-ethyl-1-hexylimidazol-5-yl)-2,5-difluorobenzene)

1-hexyl-2-ethylimidazole (589 mg, 3.3 mmol), 1,4-dibromo-2,5-difluorobenzene (296 mg, 1.1 mmol), potassium acetate (321 mg, 3.3 mmol) and Palladium acetate (24 mg, 0.1 mmol) was suspended in DMAc (5.4 mL) and stirred at 150° C. for 89 hours. After the reaction, ethyl acetate and water were added to the reaction mixture, the organic layer was extracted, and the organic layer was washed with brine. After adding sodium sulfate to the organic layer and stirring, the desiccant was filtered off and the solvent was distilled off. The resulting solid was washed with hexane and passed through alumina (chloroform). After concentrating the filtrate, the obtained solid was washed with hexane to obtain the target 1,4-bis(2-ethyl-1-hexylimidazol-5-yl)-2,5-difluorobenzene as a yellow solid. (176 mg, 34%).

¹ H-NMR (CDCl ₃ ): δ 7.11 (t, J = 7.8 Hz, 2H), 7.05 (s, 2H), 3.85 (t, J = 7.6 Hz, 4H), 2. 76 (q, J = 7.5Hz, 4H), 1.50-1.53 (m, 4H), 1.43 (t, J = 7.5Hz, 6H), 1.13-1.21 (m , 12H), 0.82 (t, J=7.1 Hz, 6H).
¹⁹ F-NMR (CDCl ₃ ): δ-118.2 (s, 2F).
Example-11
(Synthesis of 1,4-bis(4-bromo-2-ethyl-1-hexylimidazol-5-yl)-2,5-difluorobenzene)

Under an argon stream, 1,4-bis(2-ethyl-1-hexylimidazol-5-yl)-2,5-difluorobenzene (510 mg, 1.1 mmol) and NBS (424 mg, 2.4 mmol) were added to methanol (5 .1 mL). The suspension was stirred at room temperature for 21 hours. After the reaction, ethyl acetate and an aqueous sodium thiosulfate solution were added to the reaction mixture, the organic layer was extracted, and the organic layer was washed with brine. After adding sodium sulfate to the organic layer and stirring, the solid was filtered off and the solvent was distilled off. After the obtained solid was passed through alumina (chloroform), the filtrate was concentrated, and the obtained solid was washed with hexane to give the target 1,4-bis(4-bromo-2-ethyl-1-hexyl). Imidazol-5-yl)-2,5-difluorobenzene was obtained as an off-white solid (429 mg, 63%).

¹ H-NMR (CDCl ₃ ): δ 7.20 (t, J = 7.5 Hz, 2H), 3.81 (t, J = 7.5 Hz, 4H), 2.74 (q, J = 7.5 Hz , 4H), 1.46-1.51 (m, 4H), 1.41 (t, J = 7.5Hz, 6H), 1.14-1.23 (m, 12H), 0.82 (t , J=7.2 Hz, 6H).
¹⁹ F-NMR (CDCl ₃ ): δ-116.5 (s, 2F).
Example-12
(Synthesis of 2,7-diethyl-1,6-dihexyldiimidazolo[4,5-d;4′,5′-d′]benzo[1,2-b;3,4-b′]dithiophene)

1,4-bis(4-bromo-2-ethyl-1-hexylimidazol-5-yl)-2,5-difluorobenzene (126 mg, 0.20 mmol) and sodium sulfide (78 mg, 1.0 mmol) under an argon stream ) was suspended in NMP (4.0 mL) and stirred at 200° C. for 13 hours. After the reaction, chloroform and 4N potassium hydroxide aqueous solution were added to the reaction mixture, the organic layer was extracted, and the organic layer was washed with brine. After adding sodium sulfate to the organic layer and stirring, the desiccant was filtered off and the solvent was distilled off. The resulting oil was suspended in hexane and the solid filtered and washed with a very small amount of ethanol. The resulting solid was dissolved in chloroform, water was added to extract the organic layer, and the organic layer was washed with brine. After the organic layer was dried by adding sodium sulfate, the desiccant was filtered off and the solvent was distilled off. The resulting solid is passed through alumina (chloroform) to give the desired 2,7-diethyl-1,6-dihexyldiimidazolo[4,5-d;4',5'-d']benzo[1,2 -b;3,4-b']dithiophene was obtained as an off-white solid (18 mg, 18%).

¹ H-NMR (CDCl ₃ ): δ 8.07 (s, 2H), 4.30 (t, J = 7.5 Hz, 4H), 2.90 (q, J = 7.5 Hz, 4H), 1. 94 (tt, J = 7.7, 7.5Hz, 4H), 1.48 (t, J = 7.5Hz, 6H), 1.33-1.37 (m, 12H), 0.90 (t , J=7.1 Hz, 6H).
Melting point: 179°C
Example-13
(Synthesis of 1,4-bis(1-ethyl-2-undecylimidazol-5-yl)-2,5-difluorobenzene)

Under an argon atmosphere, 1-ethyl-2-undecylimidazole (18.0 g, 72 mmol), 1,4-dibromo-2,5-difluorobenzene (6.53 g, 24 mmol), potassium acetate (14.1 g, 144 mmol). and palladium acetate (539 mg, 2.4 mmol) were suspended in DMAc (120 mL) and stirred at 155° C. for 48 hours. After allowing to cool, ethyl acetate and water were added to the reaction mixture, the organic layer was extracted, and the organic layer was washed with brine. After adding sodium sulfate to the organic layer and stirring, the desiccant was filtered off and the solvent was distilled off. The resulting solid was dissolved in chloroform and passed through alumina, and the solvent was distilled off. The resulting solid was washed repeatedly with acetone and hexane to obtain the target 1,4-bis(1-ethyl-2-undecylimidazol-5-yl)-2,5-difluorobenzene as a white solid. (7.03 g, 48%).
¹ H-NMR (CDCl ₃ ): δ 7.12 (t, J = 7.8 Hz, 2H), 7.04 (s, 2H), 3.92 (q, J = 7.2 Hz, 4H), 2. 72 (t, J = 7.8Hz, 4H), 1.85 (tt, J = 7.8, 7.4Hz, 4H), 1.40-1.48 (m, 4H), 1.27-1 .38 (m, 28H), 1.20 (t, J=7.2Hz, 6H), 0.88 (t, J=7.0Hz, 6H).
¹⁹ F-NMR (CDCl ₃ ): −118.0 (s, 2F).
Example-14
(Synthesis of 1,4-bis(4-bromo-1-ethyl-2-undecylimidazol-5-yl)-2,5-difluorobenzene)

Under an argon atmosphere, 1,4-bis(1-ethyl-2-undecylimidazol-5-yl)-2,5-difluorobenzene (4.89 g, 8.0 mmol) and NBS (3.42 g, 19 mmol) Suspended in methanol (38 mL). The suspension was stirred at 40° C. for 25 hours. After the reaction, chloroform and water were added to the reaction mixture, the organic layer was extracted, and the organic layer was washed with brine. After adding sodium sulfate to the organic layer and stirring, the desiccant was filtered off and the solvent was distilled off. The obtained solid was dissolved in chloroform and passed through alumina to give the desired 1,4-bis(4-bromo-1-ethyl-2-undecylimidazol-5-yl)-2,5-difluorobenzene as a milky white solid. (5.63 g, 92%).
¹ H-NMR (CDCl ₃ ): δ 7.21 (t, J = 7.5 Hz, 2H), 3.88 (q, J = 7.2 Hz, 4H), 2.70 (t, J = 7.8 Hz , 4H), 1.83 (tt, J=7.8, 7.2Hz, 4H), 1.39-1.45 (m, 4H), 1.27-1.37 (m, 28H), 1 .18 (t, J=7.2 Hz, 6H), 0.88 (t, J=7.0 Hz, 6H).
¹⁹ F-NMR (CDCl ₃ ): −116.4 (s, 2F).
Example-15
Synthesis of (1,6-diethyl-2,7-diundecyldiimidazolo[4,5-d;4′,5′-d′]benzo[1,2-b;3,4-b′]dithiophene )

1,4-bis(4-bromo-1-ethyl-2-undecylimidazol-5-yl)-2,5-difluorobenzene (154 mg, 0.20 mmol) and sodium sulfide (78.0 mg, 1.0 mmol) was suspended in HMPA (4.0 mL) and stirred at 200° C. for 6 hours. After allowing to cool, water was added to the reaction mixture, the suspension was centrifuged (3000 rpm, 10 minutes), and the supernatant was removed. This operation was repeated twice using water and then 1.0 M-hydrochloric acid. The resulting solid was dried under reduced pressure and subjected to silica gel column chromatography (chloroform:methanol=9:1). The obtained solid was washed with acetone to give the desired 1,6-diethyl-2,7- An off-white solid of diundecyldiimidazolo[4,5-d;4′,5′-d′]benzo[1,2-b;3,4-b′]dithiophene was obtained (63 mg, 49%).
¹ H-NMR (CDCl ₃ ): δ 8.11 (s, 2H), 4.38 (q, J = 7.3 Hz, 4H), 2.86 (t, J = 7.7 Hz, 4H), 1. 88 (tt, J = 7.8, 7.3Hz, 4H), 1.58 (t, J = 7.3Hz, 6H), 1.43-1.50 (m, 4H), 1.26-1 .39 (m, 28H), 0.88 (t, J=7.0Hz, 6H).
Reference example-1
(Synthesis of 1-methyl-2-hexylimidazole)

Heptanal (20.5 g, 180 mmol) was suspended in chloroform (300 mL) under an argon stream. The suspension was cooled to 0° C., ethylenediamine (11.3 g, 189 mmol) was added, stirred at the same temperature for 15 minutes, stirred at room temperature for 30 minutes, and further stirred at 40° C. for 12 hours. The reaction mixture was cooled to 0° C. again, NBS (33.6 g, 189 mmol) was added thereto, stirred for 15 minutes, then allowed to room temperature and stirred for 24 hours. After the reaction, diethyl ether and 1N hydrochloric acid were added to the reaction mixture, and the aqueous layer was separated. After adding sodium hydrogencarbonate to the aqueous layer to adjust the pH to 8, the aqueous layer was washed with diethyl ether. Chloroform was added to the collected aqueous layer, the organic layer was extracted, and the organic layer was washed with brine. After adding sodium sulfate to the organic layer and stirring, the desiccant was filtered off and the solvent was distilled off. The obtained solid was washed with hexane to obtain 2-hexylimidazoline as a milky white solid (16.5 g, 60%).

¹ H-NMR (CDCl ₃ ): δ 3.88 (s, 4H), 2.68 (t, J = 7.7 Hz, 2H), 1.77 (tt, J = 7.7, 7.4 Hz, 2H ), 1.33-1.38 (m, 2H), 1.27-1.31 (m, 4H), 0.87 (t, J=7.1Hz, 3H).
The synthesized 2-hexylimidazoline (16.5 g, 107 mmol), potassium permanganate (22.0 g, 139 mmol) and alumina (74.9 g) were suspended in acetonitrile (1.5 L) and stirred at room temperature for 6 hours. After the reaction, methanol was added to the reaction mixture and filtered through celite. The filtrate was concentrated, the resulting oil was dissolved in 1N hydrochloric acid, and the aqueous layer was washed with chloroform. After adjusting the aqueous layer to pH=11 using 1N-sodium hydroxide aqueous solution, chloroform was added to extract the organic layer, which was then washed with brine. After adding sodium sulfate to the organic layer and stirring, the desiccant was filtered off and dried under reduced pressure to obtain 2-hexylimidazole as a milky white solid (4.65 g, 29%).

¹ H-NMR (CDCl ₃ ): δ 6.95 (s, 2H), 2.73 (t, J = 7.7 Hz, 2H), 1.73 (tt, J = 7.7, 7.5 Hz, 2H ), 1.27-1.37 (m, 6H), 0.87 (t, J=7.0Hz, 3H).
Under an argon stream, the synthesized 2-hexylimidazole (1.83 g, 12.0 mmol) and sodium hydride (504 mg, 12.6 mmol) were suspended in tetrahydrofuran (18 mL) and cooled to 0°C. Iodomethane (1.87 g, 13.2 mmol) was added to this suspension, and the mixture was allowed to warm to room temperature and stirred for 20 hours. After the reaction, chloroform and water were added to the reaction mixture, the organic layer was extracted, and the organic layer was washed with brine. After adding sodium sulfate to the organic layer and stirring, the solid was filtered off and the solvent was distilled off. The resulting oil was purified by silica gel column chromatography (chloroform/methanol=10:1) to give 1-methyl-2-hexylimidazole as a yellow oil (1.20 g, 60%).

¹ H-NMR (CDCl ₃ ): δ 6.91 (d, J = 1.2 Hz, 1 H), 6.77 (d, J = 1.2 Hz, 1 H), 3.56 (s, 3 H), 2. 64 (t, J = 7.7Hz, 2H), 1.73 (tt, J = 7.8, 7.7Hz, 2H), 1.28-1.40 (m, 6H), 0.88 (t , J=7.0 Hz, 3H).
Reference example-2
(Synthesis of 1-ethyl-2-hexylimidazole)

Under an argon stream, 2-hexylimidazole (609 mg, 4.0 mmol) and sodium hydride (168 mg, 4.2 mmol) were suspended in tetrahydrofuran (6.0 mL) and cooled to 0°C. Iodoethane (686 mg, 4.4 mmol) was added to this suspension, and the mixture was stirred at room temperature for 4 hours and then at 75° C. for 15 hours. After allowing to cool, diethyl ether and water were added to the reaction mixture, the organic layer was extracted, and the organic layer was washed with brine. After adding sodium sulfate to the organic layer and stirring, the solid was filtered off and the solvent was distilled off. The resulting oil was purified by silica gel column chromatography (ethyl acetate, chloroform/methanol=10:1) to give 1-ethyl-2-hexylimidazole (589 mg, 81%) as a yellow oil.

¹ H-NMR (CDCl ₃ ): δ 6.93 (d, J = 1.3 Hz, 1 H), 6.82 (d, J = 1.3 Hz, 1 H), 3.88 (q, J = 7.3 Hz , 2H), 2.64 (t, J = 7.7Hz, 2H), 1.74 (tt, J = 7.8, 7.7Hz, 2H), 1.38 (t, J = 7.3Hz, 3H), 1.29-1.40 (m, 6H), 0.88 (t, J=7.0Hz, 3H).
Reference example - 3
(Synthesis of 1-hexyl-2-ethylimidazole)

Under an argon stream, 2-ethylimidazole (1.92 g, 20 mmol) and sodium hydride (0.84 g, 21 mmol) were suspended in tetrahydrofuran (30 mL) and cooled to 0°C. 1-Iodohexane (4.67 g, 22 mmol) was added to this suspension, and the mixture was stirred at room temperature for 30 minutes and then stirred at 75° C. for 24 hours. After allowing to cool, diethyl ether and water were added to the reaction mixture, the organic layer was extracted, and the organic layer was washed with brine. After adding sodium sulfate to the organic layer and stirring, the solid was filtered off and the solvent was distilled off. The resulting oil was purified by silica gel column chromatography (chloroform/methanol=10:1) to give 1-hexyl-2-ethylimidazole as a yellow oil (2.93 g, 81%).

¹ H-NMR (CDCl ₃ ): δ 6.93 (d, J = 1.3 Hz, 1 H), 6.80 (d, J = 1.3 Hz, 1 H), 3.81 (t, J = 7.3 Hz , 2H), 2.67 (q, J = 7.5Hz, 2H), 1.71 (tt, J = 7.3, 7.0Hz, 2H), 1.34 (t, J = 7.5Hz, 3H), 1.29-1.36 (m, 6H), 0.88 (t, J=6.8Hz, 3H).
Reference example-4

Under an argon atmosphere, 2-undecylimidazole (25.2 g, 113 mmol) and sodium hydride (2.86 g, 119 mmol) were suspended in tetrahydrofuran (165 mL) and cooled to 0°C. Iodoethane (19.5 g, 125 mmol) was added to this suspension, and the mixture was stirred at 0° C. for 30 minutes, then at room temperature for 30 minutes, and then stirred at 80° C. for 24 hours. After allowing to cool, ethyl acetate and water were added to the reaction mixture, the organic layer was extracted, and the organic layer was washed with brine. After adding sodium sulfate to the organic layer and stirring, the solid was filtered off and the solvent was distilled off. The resulting oil was purified by silica gel column chromatography (chloroform/ethyl acetate) to give 1-ethyl-2-undecylimidazole as a yellow oil (17.7 g, 62%).

¹ H-NMR (CDCl ₃ ): δ 6.94 (d, J = 1.3 Hz, 1 H), 6.82 (d, J = 1.3 Hz, 1 H), 3.88 (q, J = 7.3 Hz , 2H), 2.63 (t, J = 7.7Hz, 2H), 1.75 (tt, J = 7.8, 7.7Hz, 2H), 1.38 (t, J = 7.3Hz, 3H), 1.25-1.35 (m, 16H), 0.88 (t, J=7.0Hz, 3H).
Example-16
(Preparation of organic thin film forming solution (film forming composition))
1,6-diethyl-2,7-dihexyldiimidazolo[4,5-d;4′,5′-d′]benzo[1,2 -b; 0.87 mg of 3,4-b']dithiophene and 0.43 g of toluene (Wako Pure Chemical Industries, Ltd., pure grade) were added, dissolved by heating to 50°C, and allowed to stand at room temperature (25°C) for 12 hours. . Since no precipitation of crystals was observed and the solution state of 0.20% by weight was maintained, it was confirmed that the material was suitable for the coating process.
Example-17
(Preparation of organic thin film)
Under air, 0.1 μL of the solution obtained in Example-13 was applied to a silicon substrate (Miyoshi, resistance value: 0.004Ω, with a silicon oxide film of 200 nm on the surface) highly doped n-type with a diameter of 2 inches. Drop casting was performed using a syringe. After air drying at room temperature (25° C.), 1,6-diethyl-2,7-dihexyldiimidazolo[4,5-d;4′,5′-d′]benzo[1,2-b;3 ,4-b′]dithiophene formation was confirmed.
Example-18
(Preparation of organic transistor element)
A 2-inch diameter n-type high-doped silicon substrate (Miyoshi, resistance value: 0.004Ω, with a 200 nm silicon oxide film on the surface) treated with octyltrichlorosilane was placed in a vacuum deposition apparatus, and the vacuum inside the apparatus was reduced. The gas was evacuated until the temperature became 8.0×10 ⁻⁴ Pa or less. The 1,6-diethyl-2,7-dihexyldiimidazolo[4,5-d;4′,5′-d′]benzo[1,6-diethyl-2,7-dihexyldiimidazolo[4,5-d;4′,5′-d′]benzo[1, 2-b;3,4-b']dithiophene was deposited to a thickness of 46 nm to form an organic thin film. Next, a shadow mask for electrode production was attached to this substrate, placed in a vacuum deposition apparatus, the vacuum inside the apparatus was evacuated to 8.0×10 ⁻⁴ Pa or less, and a gold electrode was formed by a resistance heating deposition method. That is, a source electrode and a drain electrode were deposited to a thickness of 50 nm to fabricate a bottom-gate-top-contact p-type organic thin film transistor.

Using a semiconductor parameter analyzer (Keithley 4200SCS), the electrical properties of the fabricated organic thin film transistor were scanned at the drain voltage (Vd = -80 V) and the gate voltage (Vg) from +10 to -80 V in increments of 1 V to evaluate the transfer characteristics. did The carrier mobility of holes was 1.42×10 ⁻⁵ cm ² /V·s.

Comparative example 1
(Preparation of organic thin film forming solution (film forming composition))
Under air, 0.87 mg of 2,9-dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (DNTT, Sigma-Aldrich) and toluene (sum When 0.43 g of Kojunyaku Kogyo Co., Ltd., pure grade) was added and heated to 50° C., undissolved solids were observed, confirming poor solubility.

The diimidazolobenzodithiophene compound of the present invention can be expected to be applied as a semiconductor device material represented by an organic transistor element because of its excellent solubility in solvents.

Claims (19)

General formula (1)

(wherein R ¹ and R ² are each independently substituted with a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; a haloalkyl group having 1 to 20 carbon atoms; or an alkyl group having 1 to 12 carbon atoms; represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, wherein R ³ and R ⁴ each independently represent an alkyl group having 1 to 20 carbon atoms; represents an aromatic hydrocarbon group having 6 to 14 carbon atoms which may be substituted with an alkyl group of 12. Further, R ¹ and R ³ , and R ² and R ⁴ each combine together to form a represents an oligomethylene group having 3 to 6 carbon atoms which may be substituted with up to 12 alkyl groups.). 2. The diimidazolobenzodithiophene compound according to claim 1, wherein R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group having 1 to 20 carbon atoms. general formula (2a)

(R ¹ and R ² are each independently a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; a haloalkyl group having 1 to 20 carbon atoms; or a carbon atom optionally substituted by an alkyl group having 1 to 12 carbon atoms represents an aromatic hydrocarbon group having a number of 6 to 14. R ³ and R ⁴ are each independently an alkyl group having 1 to 20 carbon atoms; a haloalkyl group having 1 to 20 carbon atoms; represents an aromatic hydrocarbon group having 6 to 14 carbon atoms which may be substituted with a group, and R ¹ and R ³ , and R ² and R ⁴ each combine together to form a represents an oligomethylene group having 3 to 6 carbon atoms which may be substituted with an alkyl group, X ^1a represents a halogen atom, and two X ² are the same or different and represent a halogen atom. General formula (1), characterized by reacting an imidazole compound obtained by reacting with a sulfurizing agent

(Wherein, R ¹ , R ² , R ³ and R ⁴ have the same meanings as above.) A method for producing a diimidazolobenzodithiophene compound. 4. The production method according to claim ³ , wherein ^X1a is a bromine atom and X2 is a fluorine atom. 5. The production method according to claim 3 or 4, wherein the sulfiding agent is an alkali metal sulfide salt. 6. The production method according to claim 5, wherein the alkali metal sulfide salt is sodium sulfide or its hydrate. general formula (2b)

(R ¹ and R ² are each independently a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; a haloalkyl group having 1 to 20 carbon atoms; or a carbon atom optionally substituted by an alkyl group having 1 to 12 carbon atoms represents an aromatic hydrocarbon group having a number of 6 to 14. R ³ and R ⁴ are each independently an alkyl group having 1 to 20 carbon atoms; a haloalkyl group having 1 to 20 carbon atoms; represents an aromatic hydrocarbon group having 6 to 14 carbon atoms which may be substituted with a group, and R ¹ and R ³ , and R ² and R ⁴ each combine together to form a represents an oligomethylene group having 3 to 6 carbon atoms which may be substituted with an alkyl group, and two X ² are the same or different and represent a halogen atom. reacted to give the general formula (2a)

(Wherein, R ¹ , R ² , R ³ , R ⁴ and X ² have the same meanings as above, and X ^1a represents a halogen atom. ) to obtain an imidazole compound represented by General formula (1), characterized by reacting

(Wherein, R ¹ , R ² , R ³ and R ⁴ have the same meanings as above.) A method for producing a diimidazolobenzodithiophene compound. The production method according to claim ⁷ , wherein ^X1a is a bromine atom and X2 is a fluorine atom. 9. The production method according to claim 7 or 8, wherein the sulfiding agent is an alkali metal sulfide salt. 10. The production method according to claim 9, wherein the alkali metal sulfide salt is sodium sulfide or its hydrate. general formula (2)

(wherein R ¹ and R ² are each independently substituted with a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; a haloalkyl group having 1 to 20 carbon atoms; or an alkyl group having 1 to 12 carbon atoms; represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, wherein R ³ and R ⁴ each independently represent an alkyl group having 1 to 20 carbon atoms; represents an aromatic hydrocarbon group having 6 to 14 carbon atoms which may be substituted with an alkyl group of 12. Further, R ¹ and R ³ , and R ² and R ⁴ each combine together to form a represents an oligomethylene group having 3 to 6 carbon atoms which may be substituted with an alkyl group of up to 12. X ¹ represents a hydrogen atom or a halogen atom, two X ² are the same or different and a halogen atom represents an imidazole compound represented by ). 12. The imidazole compound according to claim 11, wherein R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group having 1 to 20 carbon atoms. 13. The imidazole compound according to claim 11 or ¹² , wherein X1 is ^a hydrogen atom or a bromine atom, and X2 is a fluorine atom. general formula (3a)

(wherein R ¹ is a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; a haloalkyl group having 1 to 20 carbon atoms; or an alkyl group having 1 to 12 carbon atoms and optionally substituted with an alkyl group having 6 to 14 carbon atoms represents an aromatic hydrocarbon group of R ³ is an alkyl group having 1 to 20 carbon atoms; a haloalkyl group having 1 to 20 carbon atoms; represents an aromatic hydrocarbon group having 1 to 14. Further, R ¹ and R ³ together represent an oligomethylene group having 3 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 12 carbon atoms. ) and a 1,2-disubstituted imidazole represented by the general formula (4)

(Wherein, two X ² are the same or different and represent a halogen atom. X ³ represents an iodine atom or a bromine atom.) in the presence of a palladium catalyst and a base. reacted to give the general formula (5)

(Wherein, R ¹ , R ³ , X ² and X ³ have the same meanings as above) to obtain 5-phenylimidazole represented by general formula (3b)

(wherein R ² is a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; a haloalkyl group having 1 to 20 carbon atoms; or an alkyl group having 1 to 12 carbon atoms and optionally substituted with an alkyl group having 6 to 14 carbon atoms represents an aromatic hydrocarbon group of R ⁴ is an alkyl group having 1 to 20 carbon atoms; a haloalkyl group having 1 to 20 carbon atoms; represents an aromatic hydrocarbon group of 1 to 14. Further, R ² and R ⁴ together represent an oligomethylene group having 3 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 12 carbon atoms. Represented by the general formula (2b), characterized by reacting a 1,2-disubstituted imidazole represented by ) in the presence of a palladium catalyst and a base

(Wherein, R ¹ , R ² , R ³ , R ⁴ and X ² have the same meanings as defined above.). 15. The production method according to claim 14, wherein the palladium catalyst is a divalent palladium salt. A film-forming composition comprising the diimidazolobenzodithiophene compound according to claim 1 or 2. 17. The film-forming composition according to claim 16, comprising 0.01 to 10% by weight of the diimidazolobenzodithiophene compound. An organic thin film comprising the diimidazolobenzodithiophene compound according to claim 1 or 2. 19. An organic transistor element comprising the organic thin film according to claim 18 in an active layer.

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