JP2019135210A - Dithiazolonaphthodithiophene compound, production method thereof, and transistor element - Google Patents

Abstract

To provide: a novel organic semiconductor having solvent solubility; a film-forming composition comprising the organic semiconductor; an organic thin film formed using the film-forming composition; and an organic transistor element having the organic thin film as an active layer.SOLUTION: The invention provides a dithiazolonaphthodithiophene compound represented by general formula (1). (In the formula, Rand Reach independently represent one of: a hydrogen atom; a C1-20 alkyl group; a C1-20 haloalkyl group; and a C6-14 aromatic hydrocarbon group optionally substituted with a C1-12 alkyl group. R, R, Rand Reach independently represent one of: a hydrogen atom; a halogen atom; a C1-20 alkyl group; and a C1-20 alkyloxy group.)SELECTED DRAWING: None

Description

  The present invention relates to a novel dithiazolonaphthodithiophene compound having solvent solubility and a method 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 dithiazolonaphthodithiophene compound having excellent solubility in a solvent.

  The organic transistor element is a rectifying element including an active layer made of an organic semiconductor, a substrate, an insulating layer, an electrode, and the like. In an organic transistor element, an active layer can be produced by applying a solution in which an organic semiconductor is dissolved in an appropriate solvent. In this respect, an inorganic layer that requires high temperature and high vacuum conditions for the production of the active layer. Compared with a transistor element, the manufacturing cost for device fabrication can be greatly reduced, which is economically advantageous.

  The organic semiconductor used for the production of the organic transistor element by such coating is preferably one having solubility in various organic solvents from the viewpoint of the element production process.

  As a low molecular weight organic semiconductor that can be used for an organic transistor element, for example, dinaphtho [2,3-b: 2 ′, 3′-f] thieno [3,2-b] thiophene (Non-patent Document 1), Dinaphtho [2,1-b: 2 ′, 1′-f] thieno [3,2-b] thiophene (Patent Document 1) similar to the compound has been proposed, but these have solubility in organic solvents. There is a problem in the low point.

  The dithiazolonaphthodithiophene compound of the present invention is a novel substance, and not only its physical properties such as solvent solubility, but also no production method has been reported.

JP 2010-161323 A

Journal of the American Chemical Society, 2007, 129, 2224

  An object of the present invention is to provide a novel organic semiconductor having solvent solubility, a film-forming composition containing the organic semiconductor, an organic thin film formed using the film-forming composition, and the organic thin film as an active layer An organic transistor element is provided.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a dithiazolonaphthodithiophene compound, which is a novel hetero-condensed ring compound, exhibits high solvent solubility. In addition, the present invention has also been found out that an organic thin film can be easily formed using a film-forming composition containing the compound, and that an organic transistor element using the organic thin film as an active layer exhibits good rectification characteristics. It came to be completed.

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. R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom; a halogen atom; an alkyl group having 1 to 20 carbon atoms; or carbon. A dithiazolonaphthodithiophene compound represented by the formula 1-20:
[2]
The dithiazolone naphthodithiophene compound according to [1], wherein R ¹ and R ² each independently represents an alkyl group having 1 to 20 carbon atoms;
[3]
The dithiazolone naphthodithiophene compound according to the above [1] or [2], wherein R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a halogen atom.

The present invention also provides
[4]
General formula (2a)

(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. R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom; a halogen atom; an alkyl group having 1 to 20 carbon atoms; or carbon. And a dithiazolyl naphthalene compound represented by the following formula: X ^1a represents a halogen atom, and two X ^2's are the same or different and represent a halogen atom. And a method for producing a dithiazolonaphthodithiophene compound represented by the general formula (1);
[5]
The production method according to the above [4], wherein X ^1a is a bromine atom and X ² is a chlorine atom;
[6]
The production method according to the above [4] or [5], wherein the sulfurizing agent is an alkali metal sulfide salt;
[7]
The production method according to the above [6], wherein the alkali metal sulfide salt is lithium sulfide, sodium sulfide or a hydrate thereof;
About.

Furthermore, the present invention provides
[8]
A film-forming composition comprising the dithiazolonaphthodithiophene compound according to any one of [1] to [3];
[9]
The film-forming composition as described in [8] above, comprising 0.01 to 10% by weight of a dithiazolonaphthodithiophene compound;
[10]
An organic thin film formed by using the film-forming composition according to [8] or [9];
[11]
The present invention relates to an organic transistor element comprising the organic thin film according to [10] in an active layer.

  The present invention is described in detail below.

R ¹ , R ² , R in the dithiazolylnaphthalene compound represented by the above general formula (2a), useful as a production intermediate of the dithiazolone naphthodithiophene compound of the present invention and the dithiazolone naphthodithiophene compound of the present invention ³ , definitions of R ⁴ , R ⁵ , R ⁶ , X ^1a and X ² will be described.

The alkyl group having 1 to 20 carbon atoms represented by R ¹ and R ² may be any of a linear, branched or cyclic alkyl group. Specifically, a methyl group, a cyclohexylmethyl group, an 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, cycl Pentyl group, 2,5-dimethylcyclopentyl group, 3-ethylcyclopentyl group, hexyl group, 2-methylhexyl group, 3,3-dimethylhexyl group, 4-ethylhexyl group, 2-hexyl group, 2-methylhexane-2 -Yl group, 5,5-dimethylhexane-2-yl group, 3-hexyl group, 2,4-dimethylhexane-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- Examples include a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an icosyl group. Among these, an alkyl group having 2 to 12 carbon atoms is preferable from the viewpoint of good crystallinity of the dithiazolonaphthodithiophene compound of the present invention.

The haloalkyl group having 1 to 20 carbon atoms represented by R ¹ and R ² may be any of a linear, branched or cyclic haloalkyl group, and specifically includes a trifluoromethyl group, a difluoromethyl group, and perfluoroethyl. Group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl 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-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-heptafluoro Pentyl 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-undecafluorohexyl group 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, 4,4,5,5,6,6,6-heptafluorohexyl group, 5,5,6,6 , 6-pentafluorohexyl group, 6,6,6-trifluorohexyl group, perfluorocyclohexyl group, chloromethyl group, bromomethyl group, iodomethyl group, 2-chloroethyl group, 3-bromopropyl group, etc. it can.

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 and R ² is substituted with an alkyl group having 1 to 12 carbon atoms. An optionally substituted phenyl group, a naphthyl group optionally substituted with an alkyl group having 1 to 12 carbon atoms, a biphenylyl group optionally substituted with an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms An anthryl group which may be substituted with may be exemplified.

  Specific examples of the phenyl group which may be substituted with an alkyl group having 1 to 12 carbon atoms include a phenyl group, a p-tolyl group, an m-tolyl group, an o-tolyl group, a 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-dibutyl Phenyl 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, Tilphenyl 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-decyl Examples thereof include a ruphenyl group, a 4-undecylphenyl group, and a 4-dodecylphenyl group.

  Specific examples of the naphthyl group which may be substituted with an alkyl group having 1 to 12 carbon atoms include 1-naphthyl group, 4-methylnaphthalen-1-yl group, 5-methylnaphthalen-1-yl group, 4- Ethylnaphthalen-1-yl group, 5-ethylnaphthalen-1-yl group, 4-propylnaphthalen-1-yl group, 5-propylnaphthalen-1-yl group, 4-butylnaphthalen-1-yl group, 4- tert-butylnaphthalen-1-yl group, 5-butylnaphthalen-1-yl group, 5-tert-butylnaphthalen-1-yl group, 4-pentylnaphthalen-1-yl group, 5-hexylnaphthalen-1-yl Group, 8-heptylnaphthalen-1-yl group, 5-octylnaphthalen-1-yl group, 7-nonylnaphthalen-1-yl group, 4-decylnaphthalen-1-yl group 5-dodecylnaphthalen-1-yl group, 2-naphthyl group, 4-methylnaphthalen-2-yl group, 5-methylnaphthalen-2-yl group, 4-ethylnaphthalen-2-yl group, 5-ethylnaphthalene- 2-yl group, 4-propylnaphthalen-2-yl group, 5-propylnaphthalen-2-yl group, 4-butylnaphthalen-2-yl group, 4-tert-butylnaphthalen-2-yl group, 5-butyl Naphthalen-2-yl group, 5-tert-butylnaphthalen-2-yl group, 4-pentylnaphthalen-2-yl group, 5-hexylnaphthalen-2-yl group, 8-heptylnaphthalen-2-yl group, 5 -Octylnaphthalen-2-yl group, 7-nonylnaphthalen-2-yl group, 4-decylnaphthalen-2-yl group, 5-dodecylnaphthalen-2-yl group, etc. It can be exemplified.

  Specific examples of the biphenylyl group which may be 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- -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'-pro Rubiphenyl-3-yl group, 5-propylbiphenyl-2-yl group, 4′-propylbiphenyl-2-yl group, 2 ′, 4 ′, 6′-tripropylbiphenyl-2-yl group, 3-isopropyl Biphenyl-4-yl group, 4′-isopropylbiphenyl-4-yl group, 2 ′, 4 ′, 6′-triisopropylbiphenyl-4-yl group, 6-isopropylbiphenyl-3-yl group, 4′-isopropyl Biphenyl-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-yl 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 ' Octyl biphenyl-4-yl group, 4'-decyl-4-yl group, can be exemplified 4'-dodecyl-4-yl group.

  Specific examples of the anthryl group which may be 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.

The alkyl group having 1 to 20 carbon atoms represented by R ³ , R ⁴ , R ⁵ and R ⁶ may be any of a linear, branched or cyclic alkyl group, specifically, a methyl group or an ethyl group. Propyl group, 1-methylethyl group, cyclopropyl group, butyl group, 2-butyl group, tert-butyl group, cyclobutyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group And a dodecyl group and the like, and an alkyl group having 1 to 4 carbon atoms is preferable.

The alkyloxy group having 1 to 20 carbon atoms represented by R ³ , R ⁴ , R ⁵ and R ⁶ may be any of a linear, branched or cyclic alkyloxy group, specifically, a methoxy group, Ethoxy group, 1-methylethyloxy group, 1,1-dimethylethyloxy group, propyloxy group, 1-methylpropyloxy group, cyclopropyloxy group, butyloxy group, cyclobutyloxy group, pentyloxy group, hexyloxy group , Heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, and the like, and an alkyloxy group having 1 to 4 carbon atoms is preferable.

Examples of the halogen atom represented by R ³ , R ⁴ , R ⁵ and R ⁶ include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Of these, a bromine atom is preferred because it is easily synthesized.

Examples of the halogen atom represented by X ^1a include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Among these, a bromine atom is preferable in terms of good reactivity.

Examples of the halogen atom represented by X ² include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Of these, a chlorine atom is preferred because it is easy to synthesize.

  Although it does not specifically limit as the dithiazolo naphthodithiophene compound (1) of this invention, For example, the compound of the structure shown to the following 1-1-1-50 can be illustrated concretely.

  Among the compounds represented by 1-1 to 1-50, the compounds represented by 1-1, 1-2, and 1-3 are used as the dithiazolonaphthodithiophene compound of the present invention in terms of good performance as an organic semiconductor. Is preferred.

  Next, the manufacturing method of the dithiazolone naphthodithiophene compound (1) of this invention is demonstrated.

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

^{(Wherein, R 1, R 2, R} 3, R 4, R 5, R 6, X 1a and ^{X 2} are the same meanings as .R ⁷ and ^{R 8} are hydrogen atoms, 1 to 4 carbon atoms Each of R ⁷ and R ⁸ in B (OR ⁷ ) ₂ or B (OR ⁸ ) ₂ may be the same or different, and the two R ⁷ and R ⁸ are respectively (It can also be combined to form a ring containing an oxygen atom and a boron atom. X ³ represents a halogen atom or a sulfonyloxy group having 1 to 10 carbon atoms.)
Step 1 is a step of producing 5-naphthylthiazole (5) used in Step 2 by reacting a boronated thiazole (3a) with a naphthalene compound (4) in the presence of a palladium catalyst and a base. By applying the reaction conditions of the nazuki Suzuki-Miyaura reaction, the desired product can be obtained in good yield.

  The borated thiazole (3a) used in Step 1 can be produced, for example, using the method shown in Reference Examples-1 to 6 described later.

Examples of B (OR ⁷ ) ₂ in the boronated thiazole (3a) include B (OH) ₂ , B (OMe) ₂ , B (O ⁱ Pr) ₂ , B (OBu) ₂ , B (OPh) _{2 and the} like. can do. Me represents a methyl group, ⁱ Pr represents an isopropyl group, Bu represents a butyl group, and Ph represents a phenyl group. Examples of B (OR ⁷ ) ₂ in the case where two R ⁷ are combined to form a ring containing an oxygen atom and a boron atom include groups represented by the following (I) to (VI): The group represented by (II) is preferable because it can be exemplified and the yield is good.

  The naphthalene compound (4) used in Step 1 can be produced, for example, using the method disclosed in WO2014 / 123215. Moreover, you may use a commercial item. Although there is no restriction | limiting in particular in the molar ratio of a naphthalene compound (4) and a boronation thiazole (3a), 1: 10-1: 1 are preferable and 1: 5-1: 2 are more preferable at the point with a sufficient yield.

Examples of the halogen atom represented by X ³ in the naphthalene compound (4) include a chlorine atom, a fluorine atom, a bromine atom, or an iodine atom.

Examples of the sulfonyloxy group having 1 to 10 carbon atoms represented by X ³ in the naphthalene compound (4) include arylsulfonyloxy groups such as a benzenesulfonyloxy group, a p-fluorobenzenesulfonyloxy group, and a p-toluenesulfonyloxy group, Examples thereof include alkylsulfonyloxy groups such as methanesulfonyloxy group, trifluoromethanesulfonyloxy group, and nonafluorobutanesulfonyloxy group. An alkylsulfonyloxy group is preferable in terms of good reactivity, and a trifluoromethanesulfonyloxy group is more preferable in terms of low cost.

  The palladium catalyst used in step 1 is not particularly limited, and specific examples thereof include palladium salts such as palladium chloride, palladium acetate, palladium trifluoroacetate and palladium nitrate. Further, palladium complex compounds such as π-allyl palladium chloride dimer, palladium acetylacetonate, tris (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, dichloro (1, A tertiary phosphine such as 1′-bis (diphenylphosphino) ferrocene) palladium, bis (tri-tert-butylphosphine) palladium, bis (tricyclohexylphosphine) palladium, dichlorobis (tricyclohexylphosphine) palladium and the like as a ligand. The palladium complex which has can be illustrated. Among them, a palladium complex or palladium salt having a tertiary phosphine as a ligand is preferable in that the reaction yield of 5-naphthylthiazole (5) is good, and dichloro (1,1′-bis (diphenylphosphino) ferrocene is preferable. Palladium is more preferred. Although there is no restriction | limiting in the quantity of the palladium catalyst used at the process 1, In the point with a sufficient reaction yield, the molar ratio of a palladium catalyst and a naphthalene compound (4) has the preferable range of 1: 200-1: 5.

  In addition, the palladium complex which has the said tertiary phosphine as a ligand can also add a tertiary phosphine to a palladium salt or a complex compound, and can also prepare it in a reaction system. Although it does not specifically limit as a tertiary phosphine, Specifically, a triphenyl phosphine, a trimethyl phosphine, a tributyl phosphine, a tri (tert- butyl) phosphine, a tricyclohexyl phosphine, a tert- butyl diphenyl phosphine, 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 (Dife Ruphosphino) 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 can be exemplified. Of these, 1,1'-bis (diphenylphosphino) ferrocene is preferred because it is readily available and yields are good. The molar ratio of tertiary phosphine to palladium salt or complex compound is preferably in the range of 1:10 to 20: 1 for tertiary phosphine: palladium salt or complex compound.

  Although it does not specifically limit as a base used for the process 1, For example, metal hydroxide salts, such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, etc. 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 And metal alkoxides such as potassium methoxide, sodium ethoxide, potassium isopropyl oxide and potassium tert-butoxide. Among these, a metal phosphate is preferable in terms of a good yield, and potassium phosphate is more preferable. The molar ratio of the base to be used and the boronated thiazole (3a) is preferably such that base: borated thiazole (3a) is in the range of 10: 1 to 1: 3, and 5: 1 to 1 in terms of good yield. More preferably, it is in the range of 1: 1.

  Step 1 can be carried out in a solvent. There is no restriction | limiting in particular in the solvent which can be used, What is necessary is just a solvent which does not inhibit reaction. Specific examples of such solvents include diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, dimethoxyethane, and other ethers, benzene, toluene. , Aromatic hydrocarbons such as xylene, mesitylene, tetralin, carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 4-fluoroethylene carbonate, ethyl acetate, butyl acetate, methyl propionate, propion Esters such as ethyl acetate, methyl butyrate, γ-lactone, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methylpyrrole Examples include amides such as Don (NMP), ureas such as N, N, N ′, N′-tetramethylurea (TMU), N, N′-dimethylpropyleneurea (DMPU) or dimethylsulfoxide (DMSO), and water. These may be mixed and used at an arbitrary ratio. There is no restriction | limiting in particular in the usage-amount of a solvent. Of these, aromatic hydrocarbon, water, or a mixed solvent thereof is preferable in view of a good reaction yield, and toluene, water, or a mixed solvent thereof is more preferable.

  Although there is no restriction | limiting in particular in the reaction temperature at the time of implementing Process 1, It is preferable to implement at the temperature suitably selected from 30-200 degreeC, and it was suitably selected from 60-150 degreeC in the point with a sufficient yield. More preferably, it is carried out at temperature.

  5-Naphthylthiazole (5) can be obtained by performing a normal treatment after completion of the reaction in Step 1. 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 2 is a step of producing a dithiazolyl naphthalene compound (2b) used in Step 3 by reacting boronated thiazole (3b) with 5-naphthylthiazole (5) in the presence of a palladium catalyst and a base. By applying the same reaction conditions as in step 1, the target product can be obtained with good yield.

  The borated thiazole (3b) used in Step 2 can be obtained in the same manner as the borated thiazole (3a).

  Examples of the palladium catalyst used in step 2 include the same palladium catalyst as exemplified in step 1. Among them, a palladium complex or a palladium salt having a tertiary phosphine as a ligand is preferable in that the reaction yield of the dithiazolyl naphthalene compound (2b) is good, and dichloro (1,1′-bis (diphenylphosphino)) Ferrocene) palladium is more preferred. Although there is no restriction | limiting in the quantity of the palladium catalyst used at the process 1, The molar ratio of a palladium catalyst and 5-naphthyl thiazole (5) has the preferable range of 1: 200-1: 5 by the point with a sufficient reaction yield.

  Examples of the base used in step 2 include the same bases as exemplified in step 1. Among these, a metal phosphate is preferable in terms of a good yield, and potassium phosphate is more preferable. The molar ratio of the base to be used and the boronated thiazole (3b) is preferably such that base: borated thiazole (3b) is in the range of 10: 1 to 1: 3, and 5: 1 to 1 in terms of good yield. More preferably, it is in the range of 1: 1.

  Step 2 can be carried out in a solvent. Examples of the solvent that can be used include the same solvents as those exemplified in Step 1. Among these, aromatic hydrocarbons, water, or a mixed solvent thereof is preferable from the viewpoint of good reaction yield, and toluene, water, or a mixed solvent thereof is more preferable.

  Although there is no restriction | limiting in particular in the reaction temperature at the time of implementing step 2, It is preferable to implement at the temperature suitably selected from 30-200 degreeC, and it was suitably selected from 60-150 degreeC in the point with a sufficient yield. More preferably, it is carried out at temperature.

  The dithiazolyl naphthalene compound (2b) can be obtained by carrying out 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 3 without purification.

  Step 3 is a step of producing the dithiazolyl naphthalene compound (2a) used in Step 4 by reacting the dithiazolyl naphthalene compound (2b) with a halogenating agent.

As the halogenating agent used in Step 3, when X ^1a in the dithiazolyl naphthalene (2a) compound is a chlorine atom, chlorine, N-chlorosuccinimide, N-chlorophthalimide, benzyltrimethylammonium tetrachloroiodide, tert-butyl hypochloride, chloramine B, chloramine T, cyanuric chloride, dichloramine, oxalyl chloride, trichloroisocyanuric acid, thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, etc., 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-dimethyla Toamide, bromodimethylsulfonium bromide, N-bromophthalimide, N-bromosaccharin, carbon tribromide, 1-butyl-3-methylimidazolium bromide, 1,8-diazabicyclo [5,4,0] -7 -Undecene = hydrogen tribromide complex, 5,5-dibromomerdramic acid, 1,2-dibromo-1,1,2,2-tetrachloroethane, 4-dimethylaminopyridine = hydrogen tribromide complex, pyridine = three Hydrogen bromide complex, phosphorus tribromide, phosphorus oxytribromide, 2,4,4,6-tetrabromo-2,5-cyclohexadienone, tetrabutylammonium tribromide, trimethylphenylammonium tribromide, triphenylphosphine = dibromide and the like, if X ^1a is iodine atom, iodine, hydrogen iodide, Benjirutorime Ruammonium = 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 and the like, and when X ^1a is a fluorine atom, 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 Oro-1-methylpyridinium = p-toluenesulfonate can be exemplified 1-fluoro-pyridinium = tetrafluoroborate complex, 1-fluoro-2,4,6-trimethyl pyridinium = tetrafluoroborate complexes. Bromine or N-bromosuccinimide is preferable in that the reaction yield of the dithiazolyl naphthalene compound (2a) is good. The molar ratio of the halogenating agent to be used and the dithiazolyl naphthalene compound (2b) is not particularly limited, but the halogenating agent: dithiazolyl naphthalene compound (2b) may be in the range of 1: 2 to 30: 1. The range of 2: 1 to 20: 1 is more preferable in terms of good reaction yield.

  Step 3 can be carried out in a solvent. There is no restriction | limiting in particular in the solvent which can be used, What is necessary is just a solvent which does not inhibit reaction. Specific examples of such solvents include diisopropyl ether, dibutyl ether, CPME, THF, 2-methyltetrahydrofuran, 1,4-dioxane, dimethoxyethane, and other ethers, methanol, ethanol, 2-propanol, butanol, octanol. , Alcohols such as benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 2,2,2-trifluoroethanol, dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, Halogenated hydrocarbons such as dichlorobenzene, chlorobenzene, trichlorobenzene, 1-chloronaphthalene, acetonitrile, propionitrile, valeronitrile, glutaronitrile, adiponi Illustrative examples include nitriles such as ril, methoxyacetonitrile, and 3-methoxypropionitrile, amides such as DMF, DMAc, and NMP, ureas such as TMU and DMPU, and DMSO. Also good. There is no restriction | limiting in particular in the usage-amount of a solvent. Of these, amide or nitrile is preferable from the viewpoint of good reaction yield, and DMF or acetonitrile is more preferable.

  Although there is no restriction | limiting in particular in the reaction temperature at the time of implementing step 3, It can implement at the temperature suitably selected from 0-150 degreeC, and was suitably selected from 10-60 degreeC in the point with a sufficient yield. It is preferable to carry out at temperature.

  The dithiazolyl naphthalene compound (2a) can be obtained by performing ordinary 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 4 without purification.

  Step 4 is the production method of the present invention in which the dithiazolylnaphthalene compound (2a) is reacted with a sulfurizing agent to obtain the dithiazolone naphthodithiophene compound (1) of the present invention.

  Examples of the sulfiding agent used in Step 4 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 sulfides such as sulfide and bis (tributylstannyl) sulfide can be exemplified. In view of the good reaction yield of the dithiazolone naphthodithiophene compound (1) of the present invention, alkali metal sulfide salts and hydrates thereof are preferred, and lithium sulfide, sodium sulfide or hydrates thereof are more preferred. The molar ratio of the sulfurizing agent to be used and the dithiazolyl naphthalene compound (2a) is not particularly limited, but the sulfurizing agent: dithiazolyl naphthalene compound (2a) is preferably in the range of 1: 2 to 10: 1. The reaction yield is more preferably in the range of 1: 1 to 5: 1.

  Step 4 can be performed in a solvent. There is no restriction | limiting in particular in the solvent which can be used, What is necessary is just a solvent which does not inhibit reaction. Specific examples of such solvents include diisopropyl ether, dibutyl ether, CPME, THF, 2-methyltetrahydrofuran, 1,4-dioxane, dimethoxyethane, and other ethers, benzene, toluene, xylene, mesitylene, nitrobenzene, and anisole. , Aromatic hydrocarbons such as tetralin, halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene and benzotrifluoride, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, Esters such as carbonates such as 4-fluoroethylene carbonate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, and γ-lactone Nitriles such as acetonitrile, propionitrile, valeronitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile, amides such as DMF, DMAc, NMP, ureas such as TMU, DMPU, DMSO, hexamethylphosphorus An acid triamide (HMPA) etc. can be illustrated and these may be mixed and used by arbitrary ratios. There is no restriction | limiting in particular in the usage-amount of a solvent. Of these, amide, urea, DMSO, HMPA, and a mixed solvent thereof are preferably used, and NMP or HMPA is more preferable in that the reaction yield of the dithiazolonaphthodithiophene compound (1) of the present invention is good.

  Although there is no restriction | limiting in particular in the reaction temperature at the time of implementing step 4, It can implement at the temperature suitably selected from 40-280 degreeC, and the reaction yield of the dithiazolone naphthodithiophene compound (1) of this invention can be implemented. It is preferable to carry out at a temperature appropriately selected from 120 to 220 ° C. in terms of a good rate.

  The dithiazolonaphthodithiophene compound (1) of the present invention can be obtained by performing a usual treatment after completion of the reaction in Step 4. If necessary, it may be purified by recrystallization, column chromatography, sublimation or preparative HPLC.

  Moreover, the dithiazolyl naphthalene compound (2c) which can be used for the process 3 can be manufactured by the process 5 shown by following Reaction Formula.

(In the formula, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X ² and X ³ represent the same meaning as described above.)
Step 5 is a step of reacting the boronated thiazole (3a) with the naphthalene compound (4) in the presence of a palladium catalyst and a base to produce the dithiazolyl naphthalene compound (2c) used in Step 4. By applying the same reaction conditions as in 1 or 2, the target product can be obtained in good yield.

  The molar ratio of the boronated thiazole (3a) and naphthalene compound (4) used in Step 5 is not particularly limited, but is preferably 10: 1 to 1: 1, and 5: 1 to 2: 1 in terms of good yield. Is more preferable.

  Examples of the palladium catalyst used in step 5 include the same palladium catalysts as exemplified in step 1 or 2. Among them, a palladium complex or a palladium salt having a tertiary phosphine as a ligand is preferable in that the reaction yield of the dithiazolyl naphthalene compound (2c) is good, and dichloro [1,1′-bis (diphenylphosphino) is preferable. Ferrocene] palladium is more preferred. Although there is no restriction | limiting in the quantity of the palladium catalyst used at the process 5, In the point with a sufficient reaction yield, the molar ratio of a palladium catalyst and a naphthalene compound (4) has the preferable range of 1: 200-1: 5.

  Step 5 can be carried out in a solvent. Examples of the solvent that can be used include the same solvents as those exemplified in Step 1. Among these, aromatic hydrocarbons, water, or a mixed solvent thereof is preferable from the viewpoint of good reaction yield, and toluene, water, or a mixed solvent thereof is more preferable.

  Although there is no restriction | limiting in particular in the reaction temperature at the time of implementing step 5, It is preferable to implement at the temperature suitably selected from 30-200 degreeC, and it was suitably selected from 60-150 degreeC in the point with a sufficient yield. More preferably, it is carried out at temperature.

  Dithiazolyl naphthalene (2c) can be obtained by performing a 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 3 without purification.

  Next, the manufacturing method of the film forming composition (henceforth "the film forming composition of this invention") containing the dithiazolone naphthodithiophene compound (1) of this invention is demonstrated.

  The film-forming composition of the present invention can be prepared by dissolving or dispersing the dithiazolone naphthodithiophene compound (1) of the present invention in a solvent.

  The solvent is not particularly limited as long as it dissolves or disperses the dithiazolonaphthodithiophene compound (1) of the present invention. For example, toluene, xylene, mesitylene, ethylbenzene, pentylbenzene, hexylbenzene, octylbenzene , Aromatic compounds such as cyclohexylbenzene, indane, tetralin, anisole, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, 1,2-dimethylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole, nitrobenzene Hydrocarbon, hexane, heptane, octane, decane, dodecane, tetradecane, decalin and other aliphatic hydrocarbons, dichlorobenzene, chlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1,2-dichloroethane, 1,1,2,2- Tetra Halogenated hydrocarbons such as chloroethane, chloroform and dichloromethane, ethers such as diisopropyl ether, dibutyl ether, CPME, THF, 2-methyltetrahydrofuran and 1,4-dioxane, acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, cyclohexanone, acetophenone, etc. Ketones, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, γ-butyrolactone, cyclohexanol acetate, 3-methoxybutyl acetate, esters, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl Carbonates such as methyl carbonate and 4-fluoroethylene carbonate, acetonitrile, propionitrile, Nitriles such as valeronitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile, amides such as DMF, DMAc, NMP, dipropylene 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 Seteto, can be exemplified glycol and diethylene glycol monobutyl ether acetate. Of these, aromatic hydrocarbons are preferable in that they have a high boiling point and volatilize gently, and toluene, mesitylene, cyclohexylbenzene, tetralin or 3,4-dimethylanisole is more preferable. There is no restriction | limiting in particular in the usage-amount of a solvent, The density | concentration of the dithiazolo naphthodithiophene compound (1) of this invention becomes like this. Preferably it is 0.001-95 weight%, More preferably, it selects from 0.01-10 weight% suitably. The solvent can be added to achieve a high concentration.

  As the solvent used in the present invention, one kind of solvent can be used alone, or two or more kinds of solvents having different properties such as boiling point, polarity and solubility parameter can be mixed and used.

  The temperature for mixing and dissolving the dithiazolonaphthodithiophene compound (1) in a solvent is preferably 0 to 80 ° C. for the purpose of promoting dissolution, and is preferably 10 to 60 ° C. More preferably, it is performed.

  The time for dissolving and mixing the dithiazolonaphthodithiophene compound (1) in the organic solvent is preferably 1 minute to 1 hour in order to obtain a uniform solution.

  As a method of dissolution or dispersion, for example, methods well known to those skilled in the art such as stirring, shaking, and ball milling can be used.

  You may add the binder for improving film forming property to the film forming composition of this invention. Examples of such a binder include polystyrene, poly-α-methylstyrene, polyvinyl naphthalene, poly (ethylene-co-norbornene), polymethyl methacrylate, polytriarylamine, poly (9,9-dioctylfluorene-co— Examples thereof include polymers such as dimethyltriphenylamine). Although there is no restriction | limiting in particular in the density | concentration of this binder, It is preferable that it is 0.1 to 10.0 weight% at a point with applicability | paintability.

  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 coatability.

  Next, a method for forming an organic thin film (hereinafter referred to as “the organic thin film of the present invention”) formed using the film forming composition of the present invention will be described.

  The method for forming the organic thin film of the present invention using the film-forming composition of the present invention is not particularly limited. For example, a simple coating method such as spin coating, drop casting, dip coating, cast coating; Examples of the printing method include ink jet, slit coat, blade coat, flexographic printing, screen printing, gravure printing, and offset printing. Among these, drop cast or ink jet is preferable in terms of easy and efficient film formation. Although there is no restriction | limiting in particular in the film thickness of the organic thin film of this invention, 1 nm-1 micrometer are preferable at a point with a high carrier mobility, and 10 nm-300 nm are further more preferable.

  The organic thin film of the present invention can be obtained by drying the solvent after film formation. If necessary, annealing may be performed at a temperature appropriately selected from the range of 40 ° C to 200 ° C.

  Further, a method for producing an organic transistor element including the organic thin film of the present invention in an active layer (hereinafter referred to as “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.

  In FIG. 1, the structure of the element contained in the organic transistor element of this invention is shown. 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 the substrate include polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polymethyl acrylate, polyethylene, polypropylene, polystyrene, cyclic polyolefin, polyimide, polycarbonate, polyvinyl phenol, polyvinyl alcohol, poly (diisopropyl fumarate), and poly (diethyl). Fumarate), poly (diisopropyl maleate), polyethersulfone, polyphenylene sulfide, cellulose triacetate and other plastic substrates, glass, quartz, aluminum oxide, silicon, highly doped silicon, silicon oxide, tantalum dioxide, tantalum pentoxide, indium tin Examples include inorganic substrates such as oxides, metal substrates such as gold, copper, chromium, titanium, and aluminum.Among these, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, and glass are preferable because they are inexpensive.

  As the gate electrode, for example, aluminum, gold, silver, copper, highly doped silicon, tin oxide, indium oxide, indium tin oxide, inorganic electrode such as chromium, titanium, tantalum, chromium, graphene, carbon nanotube, or doped An organic electrode such as a conductive polymer (for example, PEDOT-PSS). Among these, an inorganic electrode is preferable in terms of good conductivity, and gold and silver are more preferable.

  Examples of the insulating layer 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, polyvinyl phenol, polyvinyl alcohol, poly (diisopropyl fumarate), poly (diethyl fumarate), polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, polycyclopentane, Polycyclohexane, polycyclohexane-ethylene copolymer, polyfluorinated cyclopentane, polyfluorinated cyclohexane, polyfluorinated cyclohexane-ethylene copolymer Body, BCB resin (trade name: CYCLOTENE, manufactured by Dow Chemical Company), Cytop (TM), Teflon (TM), and organic insulating layer such as parylene (TM) s such as Parylene C. Among these, a polymer insulating material (polymer gate insulating layer) is preferable because the manufacturing method is simple. The surfaces of these insulating layers are, for example, octadecyltrichlorosilane, decyltrichlorosilane, decyltrimethoxysilane, octyltrichlorosilane, octadecyltrimethoxysilane, β-phenethyltrichlorosilane, β-phenethyltrimethoxysilane, phenyltrichlorosilane. Modification may be made with a silane such as phenyltrimethoxysilane, a phosphonic acid such as octadecylphosphonic acid, decylphosphonic acid or octylphosphonic acid, or an amine such as hexamethyldisilazane. Among these, octadecyltrichlorosilane, octyltrichlorosilane, β-phenethyltrichlorosilane, octadecylphosphonic acid are used in that the carrier mobility and current on / off ratio of the organic transistor element of the present invention are improved and the threshold voltage is lowered. Octylphosphonic acid and hexamethyldisilazane are preferred.

  Examples of the source electrode and the drain electrode include the same electrodes as those exemplified for the gate electrode. Among these, an inorganic electrode is preferable in terms of good conductivity, and gold is more preferable. Moreover, in order to raise the injection | pouring efficiency of a carrier, surface treatment can also be implemented using a surface treating agent for these electrodes. Examples of such a surface treatment agent include benzenethiol and pentafluorobenzenethiol.

  The dithiazolone naphthodithiophene 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. 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 dithiazolonaphthodithiophene compound of the present invention is an organic semiconductor having high solvent solubility, and an organic transistor element using this as an active layer can be driven efficiently.

FIG. 2 is a view showing a structure of a cross-sectional shape of an organic transistor element.

(A): Bottom gate-top contact type organic thin film transistor (B): Bottom gate-bottom contact type organic thin film transistor (C): Top gate-top contact type organic thin film transistor (D): Top gate-bottom contact type organic thin film transistor 1: Organic semiconductor layer 2: Substrate 3: Gate electrode 4: Gate insulating layer 5: Source electrode 6: Drain electrode

  EXAMPLES Hereinafter, although an Example, a reference example, and a comparative example demonstrate this invention further in detail, this invention is limited to these and is not interpreted.

The following analysis method was used for identification of the dithiazolonaphthodithiophene compound of the present invention. ^For measurement of ¹ H-NMR, Bruker ASCEND ^™ AVANCE III HD (400 MHz) was used. ¹ H-NMR was measured using deuterated chloroform (CDCl ₃ ) as a measurement solvent and tetramethylsilane (TMS) as an internal standard substance. In addition, commercially available reagents were used.
Reference Example-1

Under argon atmosphere, a mixture of 2- (2-methylpropyl) thiazole (1.41 g, 10 mmol) and N-bromosuccinimide (1.95 g, 11 mmol) was dissolved in N, N-dimethylformamide (5.0 mL). And stirred at room temperature. After 18 hours, water and ethyl acetate were added to the reaction mixture. The organic layer was separated and a desiccant was added here. The desiccant was filtered off and the filtrate was concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 10/1) to obtain the desired 5-bromo-2- (2-methylpropyl) thiazole as a brown liquid (2.18 g). 9.9 mmol, 99%).
¹ H-NMR (CDCl ₃ ) δ 0.99 (d, J = 6.6 Hz, 6H), 2.02-2.12 (m, 1H), 2.83 (d, J = 7.2 Hz, 2H) 7.55 (s, 1H).
Reference example-2

Under an argon atmosphere, a mixture of 2-hexylthiazole (1.35 g, 8.0 mmol) and N-bromosuccinimide (1.56 g, 8.8 mmol) was dissolved in N, N-dimethylformamide (5.0 mL), Stir at room temperature. After 18 hours, water and ethyl acetate were added to the reaction mixture. The organic layer was separated and a desiccant was added here. The desiccant was filtered off and the filtrate was concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 10/1) to obtain the desired 5-bromo-2-hexylthiazole as a brown liquid (1.68 g, 6.8 mmol, 85%).
¹ H-NMR (CDCl ₃ ) δ 0.88 (t, J = 7.2 Hz, 3H), 1.27-1.34 (m, 4H), 1.35-1.42 (m, 2H), 1 72-1.79 (m, 2H), 2.95 (t, J = 7.8 Hz, 2H), 7.53 (s, 1H).
Reference example-3

Under an argon atmosphere, a mixture of 2-undecylthiazole (4.88 g, 20 mmol) and N-bromosuccinimide (3.99 g, 22 mmol) was dissolved in N, N-dimethylformamide (15 mL) and stirred at room temperature. After 18 hours, water and ethyl acetate were added to the reaction mixture. The organic layer was separated and a desiccant was added here. The desiccant was filtered off and the filtrate was concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 10/1) to obtain the desired 5-bromo-2-undecylthiazole as a brown liquid (6.23 g, 19 mmol, 96 %).
¹ H-NMR (CDCl ₃ ) δ 0.88 (t, J = 6.6 Hz, 3H), 1.25-1.31 (m, 14H), 1.34-1.40 (m, 2H), 1 72-1.79 (m, 2H), 2.94 (t, J = 7.8 Hz, 2H), 7.53 (s, 1H).
Reference example-4

  Under argon atmosphere, THF (20 mL) was added to 5-bromo-2- (2-methylpropyl) thiazole (2.18 g, 9.9 mmol), and the solution was cooled to -78 ° C. Butyl lithium (1.6M-hexane solution, 7.2 mL, 11.5 mmol) was added dropwise thereto over 30 minutes. The reaction mixture was stirred at −78 ° C. for 30 minutes, and 2-isopropyloxy 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.0 mL, 14 mmol) was added. The reaction mixture was stirred for 20 hours while gradually raising the reaction temperature to room temperature, and then a saturated aqueous ammonium chloride solution and ethyl acetate were added. The organic layer was separated and a desiccant was added here. After the desiccant was filtered off, the filtrate was concentrated under reduced pressure to give 2- (2-methylpropyl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl). A crude product of thiazole (1.95 g) was obtained. This was used in the next reaction without purification.

2- (2-methylpropyl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiazole crude product (800 mg) under argon atmosphere, 2, 6-dichloro-3,7-bis (trifluoromethanesulfonyloxy) naphthalene (490 mg, 1.0 mmol), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium / dichloromethane adduct (81 mg, 0.10 mmol) ) Was dissolved in toluene (6.0 mL). To the reaction mixture was added 2.0M potassium phosphate aqueous solution (4.5 mL), and the mixture was stirred at 90 ° C. for 15 hours. After cooling to room temperature, water and chloroform were added to the reaction mixture. The organic layer was separated and a desiccant was added here. The desiccant was filtered off and the filtrate was dried under reduced pressure. The obtained crude product was purified by silica gel column chromatography (chloroform / ethyl acetate = 15/1) to obtain the desired 2,6-dichloro-3,7-bis [2- (2-methylpropyl) thiazole-5. -Il] naphthalene was obtained as a pale yellow solid (260 mg, 0.56 mmol, 56%).
¹ H-NMR (CDCl ₃ ) δ 1.06 (d, J = 6.6 Hz, 12H), 2.14-2.24 (m, 2H), 2.94 (d, J = 7.2 Hz, 4H) , 7.90 (s, 2H), 7.93 (s, 2H), 7.96 (s, 2H).
Reference Example-5

  Under argon atmosphere, THF (15 mL) was added to 5-bromo-2-hexylthiazole (1.68 g, 6.8 mmol) and the solution was cooled to -78 ° C. Butyl lithium (1.6 M hexane solution, 5.0 mL, 8.0 mmol) was added dropwise thereto over 30 minutes. The reaction mixture was stirred at −78 ° C. for 30 minutes before 2- (2-methylpropyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.0 mL, 10 mmol) was added. . The reaction mixture was stirred for 18 hours while gradually raising the reaction temperature to room temperature, and then a saturated aqueous ammonium chloride solution and ethyl acetate were added. The organic layer was separated and a desiccant was added here. The desiccant was filtered off and the filtrate was concentrated under reduced pressure to give a crude product of 2-hexyl-5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiazole ( 2.08 g) was obtained. This was used in the next reaction without purification.

Under argon atmosphere, 2-hexyl-5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiazole crude product (1.77 g), 2,6-dichloro A mixture of -3,7-bis (trifluoromethanesulfonyloxy) naphthalene (840 mg, 1.7 mmol), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium / dichloromethane adduct (130 mg, 0.17 mmol) Was dissolved in toluene (15 mL). To the reaction mixture was added 2.0M aqueous potassium phosphate solution (10 mL), and the mixture was stirred at 90 ° C. for 16 hours. After cooling to room temperature, water and chloroform were added to the reaction mixture. The organic layer was separated and a desiccant was added here. The desiccant was filtered off and the filtrate was dried under reduced pressure. The resulting crude product was purified by silica gel column chromatography (chloroform / ethyl acetate = 15/1) to obtain the desired 2,6-dichloro-3,7-bis (2-hexylthiazol-5-yl) naphthalene. Obtained as a pale yellow solid (440 mg, 0.83 mmol, 48%).
¹ H-NMR (CDCl ₃ ) δ 0.91 (t, J = 7.2 Hz, 6H), 1.32-1.38 (m, 8H), 1.43-1.50 (m, 4H), 1 .83-1.91 (m, 4H), 3.07 (t, J = 7.8 Hz, 4H), 7.89 (s, 2H), 7.91 (s, 2H), 7.96 (s , 2H).
Reference Example-6

  Under an argon atmosphere, THF (45 mL) was added to 5-bromo-2-undecylthiazole (6.23 g, 19 mmol), and the solution was cooled to -78 ° C. Butyl lithium (1.6 M hexane solution, 14 mL, 22 mmol) was added dropwise thereto over 30 minutes. The reaction mixture was stirred at −78 ° C. for 30 minutes before 2- (2-methylpropyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6.0 mL, 29 mmol) was added. . The reaction mixture was stirred for 18 hours while gradually raising the reaction temperature to room temperature, and then a saturated aqueous ammonium chloride solution and ethyl acetate were added. The organic layer was separated and a desiccant was added here. The desiccant was filtered off, and the filtrate was concentrated under reduced pressure to give a crude product of 2-undecyl-5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiazole ( 7.11 g) was obtained. This was used in the next reaction without purification.

Under argon atmosphere, crude product of 2-undecyl-5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiazole (2.68 g), 2,6-dichloro -3,7-bis (trifluoromethanesulfonyloxy) naphthalene (1.03 g, 2.1 mmol), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium / dichloromethane adduct (170 mg, 0.21 mmol) Was dissolved in toluene (20 mL). To the reaction mixture was added 2.0M potassium phosphate aqueous solution (11 mL), and the mixture was stirred at 90 ° C. for 16 hours. After cooling to room temperature, water and chloroform were added to the reaction mixture. The organic layer was separated and a desiccant was added here. The desiccant was filtered off and the filtrate was dried under reduced pressure. The obtained crude product was purified by silica gel column chromatography (chloroform / ethyl acetate = 15/1) to obtain the desired 2,6-dichloro-3,7-bis (2-undecylthiazol-5-yl) naphthalene. Was obtained as a pale yellow solid (730 mg, 1.0 mmol, 52%).
¹ H-NMR (CDCl ₃ ) δ 0.88 (t, J = 6.6 Hz, 6H), 1.27-1.36 (m, 28H), 1.42-1.54 (m, 4H), 1 .83-1.90 (m, 4H), 3.06 (t, J = 7.8 Hz, 4H), 7.89 (s, 2H), 7.91 (s, 2H), 7.96 (s) , 2H).
Reference Example-7

Under an argon atmosphere, 2,6-dichloro-3,7-bis [2- (2-methylpropyl) thiazol-5-yl] naphthalene (47 mg, 0.10 mmol) and N-bromosuccinimide (71 mg, 0.40 mmol) Was suspended in acetonitrile (1 mL) and heated at 80 ° C. for 12 hours. After cooling to room temperature, water and chloroform were added to the reaction mixture. The organic layer was separated and a desiccant was added here. The desiccant was filtered off and the filtrate was dried under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 15/1) to obtain the desired 3,7-bis [4-bromo-2- (2-methylpropyl) thiazol-5-yl. ] -2,6-dichloronaphthalene was obtained as a white solid (39 mg, 0.063 mmol, 63%).
¹ H-NMR (CDCl ₃ ) δ 1.06 (d, J = 6.6 Hz, 12H), 2.13-2.23 (m, 2H), 2.92 (d, J = 7.2 Hz, 4H) , 7.93 (s, 2H), 8.00 (s, 2H).
Reference Example-8

Under an argon atmosphere, N, N-dimethylformamide (20 mL) was added to 2,6-dichloro-3,7-bis (2-hexylthiazol-5-yl) naphthalene (1.00 g, 1.8 mmol), and Bromine (1.41 mL, 28 mmol) was added dropwise at room temperature and stirred for 12 hours. Water, saturated aqueous sodium thiosulfate and ethyl acetate were added to the reaction mixture. The organic layer was separated and a desiccant was added here. The desiccant was filtered off and the filtrate was dried under reduced pressure. The obtained crude product was purified by silica gel column chromatography (chloroform / ethyl acetate = 15/1) to obtain the desired 3,7-bis (4-bromo-2-hexylthiazol-5-yl) -2,6. -Dichloronaphthalene was obtained as a white solid (1.10 g, 1.6 mmol, 89%).
¹ H-NMR (CDCl ₃ ) δ 0.91 (t, J = 7.2 Hz, 6H), 1.33-1.37 (m, 8H), 1.42-1.50 (m, 4H), 1 81-1.89 (m, 4H), 3.05 (t, J = 7.9 Hz, 4H), 7.92 (s, 2H), 7.99 (s, 2H).
Reference Example-9

Under an argon atmosphere, N, N-dimethylformamide (10 mL) was added to 2,6-dichloro-3,7-bis (2-undecylthiazol-5-yl) naphthalene (300 mg, 0.45 mmol) and bromine. (330 μL, 6.7 mmol) was added dropwise at room temperature and stirred for 12 hours. Water, saturated aqueous sodium thiosulfate and ethyl acetate were added to the reaction mixture. The organic layer was separated and a desiccant was added here. The desiccant was filtered off and the filtrate was dried under reduced pressure. The resulting crude product was purified by silica gel column chromatography (hexane / chloroform = 1/1) to obtain the desired 3,7-bis (4-bromo-2-undecylthiazol-5-yl) -2,6. -Dichloronaphthalene was obtained as a white solid (150 mg, 0.18 mmol, 41%).
¹ H-NMR (CDCl ₃ ) δ 0.88 (t, J = 6.8 Hz, 6H), 1.27-1.37 (m, 28H), 1.41-1.49 (m, 4H), 1 .81-1.87 (m, 4H), 3.05 (t, J = 7.7 Hz, 4H), 7.92 (s, 2H), 7.99 (s, 2H).
Reference Example-10

Under an argon atmosphere, 2,6-dichloro-3,7-bis (trifluoromethylsulfonyloxy) naphthalene (4.04 g, 8.2 mmol), 2-undecyl-5- (4,4,5,5-tetramethyl) -1,3,2-Dioxaborolan-2-yl) thiazole crude product (7.49 g) and dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium / dichloromethane adduct (660 mg, 0.82 mmol) ) Was dissolved in toluene (60 mL). To the reaction mixture was added 2.0M potassium phosphate aqueous solution (30 mL), and the mixture was stirred at 90 ° C. for 16 hours. After cooling to room temperature, water and chloroform were added to the reaction mixture. The organic layer was separated and a desiccant was added here. The desiccant was filtered off and the filtrate was dried under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane / chloroform = 1/1) to obtain the desired 2,6-dichloro-3-trifluoromethylsulfonyloxy-7- (2-undecylthiazole-5). -Yl) Naphthalene was obtained as a pale yellow solid (2.51 g, 4.3 mmol, 53%).
¹ HNMR (CDCl ₃ ) δ 0.88 (t, J = 7.0 Hz, 3H), 1.27-1.38 (m, 14H), 1.42-1.49 (m, 2H), 1.82 -1.90 (m, 2H), 3.06 (t, J = 7.8 Hz, 2H), 7.74 (s, 1H), 7.89 (s, 1H), 7.90 (s, 1H) ), 7.97 (s, 2H).
¹⁹ FNMR (CDCl ₃ ) δ-73.1.
Reference Example-11

Under an argon atmosphere, 2,6-dichloro-3-trifluoromethylsulfonyloxy-7- (2-undecylthiazol-5-yl) naphthalene (180 mg, 0.31 mmol), 2- (2-methylpropyl) -5 -(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiazole crude product (160 mg) and dichloro [1,1'-bis (diphenylphosphino) ferrocene] palladium A mixture of dichloromethane adduct (26 mg, 0.31 mmol) was dissolved in toluene (2.0 mL). To the reaction mixture was added 2.0M potassium phosphate aqueous solution (0.95 mL), and the mixture was stirred at 90 ° C. for 16 hours. After cooling to room temperature, water and chloroform were added to the reaction mixture. The organic layer was separated and a desiccant was added here. The desiccant was filtered off and the filtrate was dried under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane / chloroform = 1/2), and the desired 2,6-dichloro-3- [2- (2-methylpropyl) thiazol-5-yl]- 7- (2-Undecylthiazol-5-yl) naphthalene was obtained as a pale yellow solid (110 mg, 0.20 mmol, 64%).
¹ HNMR (CDCl ₃ ) δ 0.88 (t, J = 7.0 Hz, 3H), 1.06 (d, J = 6.6 Hz, 6H), 1.27-1.38 (m, 14H), 1 .42-1.49 (m, 2H), 1.83-1.90 (m, 2H), 2.14-2.24 (m, 1H), 2.94 (d, J = 7.2 Hz, 2H), 3.06 (t, J = 7.8 Hz, 2H), 7.87 (s, 1H), 7.88 (s, 1H), 7.91 (s, 1H), 7.93 (s) , 1H), 7.94 (s, 2H).
Reference Example-12

Under an argon atmosphere, 2,6-dichloro-3- [2- (2-methylpropyl) thiazol-5-yl] -7- (2-undecylthiazol-5-yl) naphthalene (170 mg, 0.30 mmol) A mixture of N-bromosuccinimide (420 mg, 2.3 mmol) was suspended in acetonitrile (3.0 mL) and heated at 80 ° C. for 15 hours. After cooling to room temperature, water and chloroform were added to the reaction mixture. The organic layer was separated and a desiccant was added here. The desiccant was filtered off and the filtrate was dried under reduced pressure. The obtained crude product was purified by silica gel column chromatography (chloroform / ethyl acetate = 20/1) to obtain the desired 3- [4-bromo-2- (2-methylpropyl) thiazol-5-yl] -7. -(4-Bromo-2-undecylthiazol-5-yl) -2,6-dichloronaphthalene was obtained as a white solid (110 mg, 0.15 mmol, 52%).
¹ HNMR (CDCl ₃ ) δ 0.88 (t, J = 7.0 Hz, 3H), 1.06 (d, J = 6.6 Hz, 6H), 1.27-1.37 (m, 14H), 1 .41-1.49 (m, 2H), 1.81-1.88 (m, 2H), 2.13-2.23 (m, 1H), 2.92 (d, J = 7.2 Hz, 2H), 3.05 (t, J = 8.0 Hz, 2H), 7.92 (s, 1H), 7.93 (s, 1H), 7.99 (s, 2H).
Example-1

Under an argon atmosphere, 3,7-bis [4-bromo-2- (2-methylpropyl) thiazol-5-yl] -2,6-dichloronaphthalene (95 mg, 0.15 mmol), sodium sulfide (58 mg,. 75 mmol) and water (40 μL, 2.2 mmol) were suspended in N-methylpyrrolidone (4.5 mL) and heated at 200 ° C. for 3 hours. After cooling to room temperature, 1.0 M hydrochloric acid and ethyl acetate were added to the reaction mixture. The organic layer was separated and a desiccant was added here. The desiccant was filtered off and the filtrate was dried under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 10/1), and the desired 2,8-bis (2-methylpropyl) dithiazolo [4,5-d; 4 ′, 5 '-D'] naphtho [2,3-b; 6,7-b '] dithiophene was obtained as a pale yellow solid (6 mg, 0.013 mmol, 9%).
¹ H-NMR (CDCl ₃ ) δ 1.08 (d, J = 6.6 Hz, 12H), 2.21-2.31 (m, 2H), 3.05 (d, J = 7.2 Hz, 4H) , 8.26 (s, 2H), 8.43 (s, 2H).
Example-2

Under an argon atmosphere, a mixture of 3,7-bis (4-bromo-2-hexylthiazol-5-yl) -2,6-dichloronaphthalene (100 mg, 0.15 mmol) and sodium sulfide (23 mg, 0.30 mmol) was added. And suspended in hexamethylphosphoric triamide (4.5 mL) and heated at 150 ° C. for 3 hours. After cooling to room temperature, 1.0 M hydrochloric acid and ethyl acetate were added to the reaction mixture. The organic layer was separated and a desiccant was added here. The desiccant was filtered off and the filtrate was dried under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 10/1) to obtain the desired 2,8-dihexyl dithiazolo [4,5-d; 4 ′, 5′-d ′]. Naphtho [2,3-b; 6,7-b ′] dithiophene was obtained as a pale yellow solid (12 mg, 0.022 mmol, 15%).
¹ H-NMR (CDCl ₃ ) δ 0.91 (t, J = 7.1 Hz, 6H), 1.35 to 1.39 (m, 8H), 1.45 to 1.52 (m, 4H), 1 88-1.96 (m, 4H), 3.18 (t, J = 7.8 Hz, 4H), 8.26 (s, 2H), 8.43 (s, 2H).
Example-3
The same operation as in Example 2 was carried out except that lithium sulfide (14 mg, 0.30 mmol) was used in place of sodium sulfide, and the desired 2,8-dihexyldithiazolo [4,5-d; 4 ′, 5 '-D'] naphtho [2,3-b; 6,7-b '] dithiophene was obtained (8 mg, 0.016 mmol, 11%).
Example-4

A mixture of 3,7-bis (4-bromo-2-undecylthiazol-5-yl) -2,6-dichloronaphthalene (120 mg, 0.15 mmol) and sodium sulfide (23 mg, 0.30 mmol) under an argon atmosphere Was suspended in hexamethylphosphoric triamide (4.5 mL) and heated at 150 ° C. for 3 hours. After cooling to room temperature, 1.0 M hydrochloric acid and ethyl acetate were added to the reaction mixture. The organic layer was separated and a desiccant was added here. The desiccant was filtered off and the filtrate was dried under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 12/1) to obtain the desired 2,8-diundecyldithiazolo [4,5-d; 4 ′, 5′-d ′. ] Naphtho [2,3-b; 6,7-b ′] dithiophene was obtained as a pale yellow solid (10 mg, 0.015 mmol, 10%).
¹ H-NMR (CDCl ₃ ) δ 0.88 (t, J = 6.8 Hz, 6H), 1.25-1.37 (m, 28H), 1.45-1.52 (m, 4H), 1 .85-1.95 (m, 4H), 3.18 (t, J = 7.7 Hz, 4H), 8.27 (s, 2H), 8.43 (s, 2H).
Example-5

3- [4-Bromo-2- (2-methylpropyl) thiazol-5-yl] -7- (4-bromo-2-undecylthiazol-5-yl) -2,6-dichloronaphthalene under argon atmosphere A mixture of (110 mg, 0.15 mmol) and sodium sulfide (24 mg, 0.30 mmol) was suspended in hexamethylphosphoric triamide (4.5 mL) and heated at 150 ° C. for 3 hours. After cooling to room temperature, 1.0 M hydrochloric acid and ethyl acetate were added to the reaction mixture. The organic layer was separated and a desiccant was added here. The desiccant was filtered off and the filtrate was dried under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 12/1) to obtain the desired 2- (2-methylpropyl) -8-undecyldithiazolo [4,5-d; 4 ', 5'-d'] naphtho [2,3-b; 6,7-b '] dithiophene was obtained as a pale yellow solid (5 mg, 0.0095 mmol, 6%).
¹ HNMR (CDCl ₃ ) δ 0.88 (t, J = 7.0 Hz, 3H), 1.08 (d, J = 6.6 Hz, 6H), 1.27-1.38 (m, 14H), 1 .42-1.49 (m, 2H), 1.88-1.95 (m, 2H), 2.22-2.32 (m, 1H), 3.06 (d, J = 7.2 Hz, 2H), 3.19 (t, J = 7.7 Hz, 2H), 8.28 (s, 2H), 8.45 (s, 2H).
Example-6

2,8-dihexyldithiazolo [4,5-d; 4 ′, 5′-d ′] naphtho [2,3-b; 6,7-b ′] dithiophene (30 mg, 0.05 mmol) under argon atmosphere And a mixture of bromine (0.14 mL, 2.7 mmol) was stirred at room temperature for 24 hours. Water, saturated aqueous sodium thiosulfate solution and chloroform were added to the reaction mixture. The organic layer was separated and a desiccant was added here. The desiccant was filtered off and the filtrate was dried under reduced pressure. The obtained crude product was purified by recycle preparative HPLC (chloroform), and the desired 6-bromo-2,8-dihexyldithiazolo [4,5-d; 4 ′, 5′-d ′] naphtho [2 , 3-b; 6,7-b ′] dithiophene (1.9 mg, 0.003 mmol, 6%), 5,6-dibromo-2,8-dihexyldithiazolo [4,5-d; 4 ′, 5 '-D'] naphtho [2,3-b; 6,7-b '] dithiophene (1.2 mg, 0.002 mmol, 4%), 5,12-dibromo-2,8-dihexyldithiazolo [4 5-d; 4 ′, 5′-d ′] naphtho [2,3-b; 6,7-b ′] dithiophene (0.5 mg, 0.0007 mmol, 1%), 6,12-dibromo-2, 8-dihexyldithiazolo [4,5-d; 4 ′, 5′-d ′] naphtho [2,3-b; 6,7-b ′] dithio Fen (2.2 mg, 0.003 mmol, 6%), 5,6,12-tribromo-2,8-dihexyldithiazolo [4,5-d; 4 ′, 5′-d ′] naphtho [2,3 -B; 6,7-b '] dithiophene (7.0 mg, 0.009 mmol, 18%) and 5,6,11,12-tetrabromo-2,8-dihexyldithiazolo [4,5-d; 4 ', 5'-d'] naphtho [2,3-b; 6,7-b '] dithiophene (6.3 mg, 0.007 mmol, 15%) was obtained.
6-Bromo-2,8-dihexyldithiazolo [4,5-d; 4 ′, 5′-d ′] naphtho [2,3-b; 6,7-b ′] dithiophene
¹ H-NMR (CDCl ₃ ) δ 0.91 (t, J = 7.0 Hz, 3H), 0.92 (t, J = 7.2 Hz, 3H), 1.35 to 1.39 (m, 8H) , 1.45-1.52 (m, 4H), 1.83-1.96 (m, 4H), 3.07 (t, J = 8.0 Hz, 2H), 3.14 (t, J = 7.4 Hz, 2H), 8.45 (s, 1H), 8.52 (s, 1H), 8.92 (s, 1H).
5,6-dibromo-2,8-dihexyldithiazolo [4,5-d; 4 ′, 5′-d ′] naphtho [2,3-b; 6,7-b ′] dithiophene
¹ H-NMR (CDCl ₃ ) δ 0.91 (t, J = 7.2 Hz, 3H), 0.92 (t, J = 7.0 Hz, 3H), 1.34-1.38 (m, 8H) , 1.45-1.50 (m, 4H), 1.84-1.96 (m, 4H), 3.06 (t, J = 8.0 Hz, 2H), 3.18 (t, J = 7.8 Hz, 2H), 8.50 (s, 1H), 8.61 (s, 1H).
5,12-dibromo-2,8-dihexyldithiazolo [4,5-d; 4 ′, 5′-d ′] naphtho [2,3-b; 6,7-b ′] dithiophene
¹ H-NMR (CDCl ₃ ) δ 0.91 (t, J = 7.0 Hz, 3H), 0.92 (t, J = 7.2 Hz, 3H), 1.35 to 1.39 (m, 8H) , 1.45-1.52 (m, 4H), 1.83-1.96 (m, 4H), 3.07 (t, J = 8.0 Hz, 2H), 3.14 (t, J = 7.4 Hz, 2H), 8.65 (s, 1H), 8.92 (s, 1H).
6,12-dibromo-2,8-dihexyldithiazolo [4,5-d; 4 ′, 5′-d ′] naphtho [2,3-b; 6,7-b ′] dithiophene
¹ H-NMR (CDCl ₃ ) δ 0.91 (t, J = 7.1 Hz, 6H), 1.34-1.37 (m, 8H), 1.45-1.52 (m, 4H), 1 .82-1.90 (m, 4H), 3.06 (t, J = 7.8 Hz, 4H), 8.83 (s, 2H).
5,6,12-tribromo-2,8-dihexyldithiazolo [4,5-d; 4 ′, 5′-d ′] naphtho [2,3-b; 6,7-b ′] dithiophene
¹ H-NMR (CDCl ₃ ) δ 0.88 (t, J = 7.0 Hz, 3H), 0.92 (t, J = 6.9 Hz, 3H), 1.35 to 1.39 (m, 8H) , 1.44-1.52 (m, 4H), 1.87-1.95 (m, 4H), 3.09 (t, J = 9.0 Hz, 2H), 3.11 (t, J = 9.2 Hz, 2H), 8.82 (s, 1H).
5,6,11,12-tetrabromo-2,8-dihexyldithiazolo [4,5-d; 4 ′, 5′-d ′] naphtho [2,3-b; 6,7-b ′] dithiophene
¹ H-NMR (CDCl ₃ ) δ 0.92 (t, J = 7.2 Hz, 6H), 1.35 to 1.39 (m, 8H), 1.45 to 1.52 (m, 4H), 1 .83-1.96 (m, 4H), 3.15 (t, J = 7.9 Hz, 4H).
Example-7
(Preparation of organic thin film forming solution (film forming composition))
In a sample tube under air, 2,8-dihexyldithiazolo [4,5-d; 4 ′, 5′-d ′] naphtho [2,3-b; 6,7- b ′] Dithiophene (0.87 mg) and toluene (430 mg) were taken, heated and dissolved at 50 ° C., and allowed to stand for 12 hours. Since no crystal precipitation was observed and the solution state was 0.20% by weight, it was confirmed that the material was suitable for the coating process.
Example-8
(Preparation of organic thin film)
Drop 0.5 mL of the solution obtained in Example-7 onto an n-type highly doped silicon substrate (Miyoshi, resistance value: 0.004Ω, with a 200 nm silicon oxide film on the surface) of 2 inches in diameter under air. Cast. Formation of a thin film of 2,8-dihexyldithiazolo [4,5-d; 4 ′, 5′-d ′] naphtho [2,3-b; 6,7-b ′] dithiophene by air drying at room temperature It was confirmed.
Example-9
(Production of organic transistor elements)
Eagle XG (manufactured by Corning) as a glass substrate is placed in a vacuum vapor deposition apparatus, exhausted until the degree of vacuum in the apparatus becomes 3.0 × 10 ⁻⁴ Pa or less, and an aluminum electrode is formed by resistance heating vapor deposition. That is, the gate electrode was deposited to a thickness of 50 nm. On top of this, dichloro-di-p-xylylene (trade name: DPX-C, Specialty Coating Systems, 900 mg) was vacuum-deposited to a film thickness of 500 nm using a lab coater (manufactured by Japan Parylene LLC, PDS2010). A gate insulating film of poly (chloro-p-paraxylylene) (parylene C) was formed. On top of this, the 2,8-dihexyl dithiazolo [4,5-d; 4 ′, 5′-d ′] naphtho [2,3-b; 6,7-b ′] dithiophene solution prepared in Example-7 (0.3 mL) was drop-cast, then air dried, and 2,8-dihexyldithiazolo [4,5-d; 4 ′, 5′-d ′] naphtho [2,3-b; 6,7- b ′] A thin film of dithiophene was formed. Next, a shadow mask for electrode preparation is attached on this, and it is placed in a vacuum vapor deposition apparatus, exhausted until the degree of vacuum in the apparatus becomes 3.0 × 10 ⁻⁴ Pa or less, and gold electrode is formed by resistance heating vapor deposition. That is, a source electrode and a drain electrode were vapor-deposited (film thickness = 50 nm, channel length = 100 nm) to produce a bottom gate-top contact type p-type organic thin film transistor.

Using the semiconductor parameter analyzer (Keutley 4200SCS), the electrical properties of the fabricated organic thin film transistor are scanned with a drain voltage (Vd = −70V) and a gate voltage (Vg) from +10 to −70V in increments of 1V to evaluate transfer characteristics. Went. The carrier mobility of holes was 0.10 cm ² / V · s.
Comparative Example-1
(Preparation of organic thin film forming solution (film forming composition))
In a 9 mL sample tube, 2,9-dinaphtho [2,3-b: 2 ′, 3′-f] thieno [3,2-b] thiophene (DNTT, Sigma-Aldrich, 0.87 mg) and toluene (430 mg) ) And heated to 50 ° C., undissolved solid was observed and it was confirmed that the solubility was poor.

  The dithiazolone naphthodithiophene compound of the present invention is expected to be applied as a semiconductor device material typified by an organic transistor element because of its excellent solubility in a solvent.

Claims (11)

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. R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom; a halogen atom; an alkyl group having 1 to 20 carbon atoms; or carbon. A dithiazolonaphthodithiophene compound represented by the formula 1-20. The dithiazolone naphthodithiophene compound according to claim ^1, wherein R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms. The dithiazolone naphthodithiophene compound according to claim 1 or 2, wherein R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a halogen atom. General formula (2a)

(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. R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom; a halogen atom; an alkyl group having 1 to 20 carbon atoms; or carbon. And a dithiazolyl naphthalene compound represented by the following formula: X ^1a represents a halogen atom, and two X ^2's are the same or different and represent a halogen atom. And the general formula (1)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent the same meaning as described above), a method for producing a dithiazolone naphthodithiophene compound. The production method according to claim 4, wherein X ^1a is a bromine atom and X ² is a chlorine atom.   The production method according to claim 4 or 5, wherein the sulfurizing agent is an alkali metal sulfide salt.   The production method according to claim 6, wherein the alkali metal sulfide salt is lithium sulfide, sodium sulfide or a hydrate thereof.   A film-forming composition comprising the dithiazolone naphthodithiophene compound according to any one of claims 1 to 3.   The film-forming composition according to claim 8, comprising 0.01 to 10% by weight of a dithiazolonaphthodithiophene compound.   An organic thin film formed by using the film-forming composition according to claim 8 or 9.   The organic thin film element characterized by including the organic thin film of Claim 10 in an active layer.

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