Fused ring chalcogenadiazole compound, its production method and organic transistor device

Abstract

To provide a condensed chalcogenadiazole compound that can be used in an organic transistor element producible by an application process, excels in solubility to organic solvent and heat resistance, and shows n-type semiconductor properties, and a method for production thereof.SOLUTION: The present disclosure includes, for example, compounds illustrated below.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a fused ring chalcogenadiazole compound, a method for producing the same, and an organic transistor device containing the compound. [Background technology]

[0002] Organic semiconductors are used in organic thin-film solar cells, organic transistor elements, organic electroluminescence (EL), etc., and have characteristics not found in inorganic semiconductors, such as energy saving, low cost, solubility in organic solvents, light weight, and flexibility. They can also be used as coating materials applied to printed electronics (see, for example, Patent Document 1).

[0003] Many n-type organic semiconductors that use electrons as charge carriers have a π-conjugated structure with a deep lowest unoccupied molecular orbital (LUMO) level to which an electron-withdrawing group has been introduced. For example, it has been reported that π-conjugated compounds such as BQQDI derivatives (e.g., Non-Patent Document 1) and benzobis(thiazole) derivatives (e.g., Patent Document 2) exhibit n-type semiconductor properties and can be used in organic transistor elements.

[0004] However, there are very few reports of n-type organic semiconductors that exhibit electron mobility equivalent to that of p-type organic semiconductors, which use holes as charge carriers and have excellent charge mobility. Furthermore, for organic transistor devices using n-type organic semiconductors to be stable in the atmosphere, it is desirable for the LUMO energy level of the n-type organic semiconductor to be -4.0 eV or less, but examples of n-type organic semiconductors with such a deep LUMO level are limited. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-59668 [Patent Document 2] WO2015 / 041026 issue [Non-patent literature]

[0006] [Non-Patent Document 1] Science Advances, Volume 6, eaaz0632, 2020. Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a fused ring chalcogenadiazole compound that can be used in an organic transistor element that can be produced by a coating process, has excellent solubility in organic solvents and heat resistance, and exhibits n-type semiconductor properties with a LUMO level of −4.0 eV or less, and a method for producing the same. [Means for solving the problem]

[0008] The present inventors have discovered that fused-ring chalcogenadiazole compounds containing a 6H-fluoreno[3,4-c][1,2,5]chalcogenadiazole skeleton have high solubility, high heat resistance, a deep LUMO level, and n-type semiconductor properties, and have completed the present invention.

[0009] That is, the present invention comprises the following gist. [Abstract 1]

[0010] A fused ring chalcogenadiazole compound represented by the following formula (1):

[0011] [ka]

[0012] (In the formula, J 1 represents a chalcogen atom; a nitrogen atom which may be substituted with an alkyl group having 1 to 20 carbon atoms or a monocyclic, linked or fused aromatic group having 3 to 18 carbon atoms. 1 , R 2 , R 3 , R 4 , R 5 and R 6each independently represents a hydrogen atom; a halogen atom; an electron-withdrawing group; an alkyl group having 1 to 20 carbon atoms; an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms; a monocyclic, linked or fused ring aromatic group having 3 to 18 carbon atoms which may be substituted with one or more electron-withdrawing groups or alkyl groups having 1 to 20 carbon atoms; or an aralkyl group having 7 to 14 carbon atoms. X 1 represents a chalcogen atom; a nitrogen atom substituted with an alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a cyano group; or a group represented by the following formula (2):

[0013] [ka]

[0014] (In the formula, Y 1 and Y 2 each independently represents a hydrogen atom, a fluorine atom, a trifluoromethyl group, a cyano group, a nitro group, or a phenyl group which may be substituted with one or more electron-withdrawing groups. [Abstract 2]

[0015] A method for producing a fused ring chalcogenadiazole compound represented by formula (1a), comprising reacting a chalcogenadiazole intermediate represented by the following formula (4) with an acid:

[0016] [ka]

[0017] (In the formula, J 1 represents a chalcogen atom; a nitrogen atom which may be substituted with an alkyl group having 1 to 20 carbon atoms or a monocyclic, linked or fused aromatic group having 3 to 18 carbon atoms. 1 , R 2 , R 3 , R 4 , R 5 and R 6each independently represents a hydrogen atom; a halogen atom; an electron-withdrawing group; an alkyl group having 1 to 20 carbon atoms; an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms; a monocyclic, linked, or fused aromatic group having 3 to 18 carbon atoms which may be substituted with one or more electron-withdrawing groups or alkyl groups having 1 to 20 carbon atoms; or an aralkyl group having 7 to 14 carbon atoms. Z represents a leaving group.

[0018] [ka]

[0019] (In the formula, J 1 , R 1 , R 2 , R 3 , R 4 , R 5 and R 6 represents the same meaning as above.) [Abstract 3]

[0020] A fused ring chalcogenadiazole compound represented by formula (1a) and Y 1 -CH2-Y 2 (5)(where, Y 1 and Y 2 and each independently represent a hydrogen atom, a fluorine atom, a trifluoromethyl group, a cyano group, a nitro group, or a phenyl group which may be substituted with one or more electron-withdrawing groups.

[0021] [ka]

[0022] (In the formula, J 1 represents a chalcogen atom; a nitrogen atom which may be substituted with an alkyl group having 1 to 20 carbon atoms or a monocyclic, linked or fused aromatic group having 3 to 18 carbon atoms. 1 , R 2 , R 3 , R 4 , R 5 and R 6each independently represents a hydrogen atom; a halogen atom; an electron-withdrawing group; an alkyl group having 1 to 20 carbon atoms; an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms; a monocyclic, linked or fused ring aromatic group having 3 to 18 carbon atoms which may be substituted with one or more electron-withdrawing groups or alkyl groups having 1 to 20 carbon atoms; or an aralkyl group having 7 to 14 carbon atoms. Y 1 and Y 2 represents the same meaning as above.) [Abstract 4]

[0023] A method for producing a fused ring chalcogenadiazole compound represented by formula (1d), comprising reacting a fused ring chalcogenadiazole compound represented by formula (1c) with a halogenating agent:

[0024] [ka]

[0025] (In the formula, J 1 represents a chalcogen atom; a nitrogen atom which may be substituted with an alkyl group having 1 to 20 carbon atoms or a monocyclic, linked or fused aromatic group having 3 to 18 carbon atoms. 2 , R 3 , R 4 , R 5 and R 6 each independently represents a hydrogen atom; a halogen atom; an electron-withdrawing group; an alkyl group having 1 to 20 carbon atoms; an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms; a monocyclic, linked or fused ring aromatic group having 3 to 18 carbon atoms which may be substituted with one or more electron-withdrawing groups or alkyl groups having 1 to 20 carbon atoms; or an aralkyl group having 7 to 14 carbon atoms. X 1 represents a chalcogen atom; a nitrogen atom substituted with an alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a cyano group; or a group represented by the following formula (2):

[0026] [ka]

[0027] (In the formula, Y 1 and Y2 each independently represents a hydrogen atom, a fluorine atom, a trifluoromethyl group, a cyano group, a nitro group, or a phenyl group which may be substituted with one or more electron-withdrawing groups.

[0028] [ka]

[0029] (In the formula, J 1 and X 1 has the same meaning as above. 1 represents a halogen atom. 8 , R 9 , R 10 , R 11 and R 12 each independently represents a hydrogen atom; a halogen atom; an electron-withdrawing group; an alkyl group having 1 to 20 carbon atoms; an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms; a monocyclic, linked, or fused ring aromatic group having 3 to 18 carbon atoms which may be substituted with one or more electron-withdrawing groups or alkyl groups having 1 to 20 carbon atoms; or an aralkyl group having 7 to 14 carbon atoms. [Abstract 5]

[0030] a fused ring chalcogenadiazole compound represented by formula (1e) and R 13 - a metal reagent represented by M(6) (wherein R 13 represents an alkyl group having 1 to 20 carbon atoms; an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms; a monocyclic, linked, or fused aromatic group having 3 to 18 carbon atoms which may be substituted with one or more electron-withdrawing groups or alkyl groups having 1 to 20 carbon atoms; or an aralkyl group having 7 to 14 carbon atoms. M represents a metal group, a heteroatom group, or a hydrogen atom. A method for producing a fused-ring chalcogenadiazole compound represented by formula (1f), comprising reacting

[0031] [ka]

[0032] (In the formula, J 1represents a chalcogen atom; a nitrogen atom which may be substituted with an alkyl group having 1 to 20 carbon atoms or a monocyclic, linked or fused aromatic group having 3 to 18 carbon atoms. 2 and W 3 each independently represents a halogen atom; a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms; a monocyclic, linked or fused ring aromatic group having 3 to 18 carbon atoms which may be substituted with one or more electron-withdrawing groups or alkyl groups having 1 to 20 carbon atoms; or an aralkyl group having 7 to 14 carbon atoms. 2 and W 3 At least one of X is a halogen atom. 1 represents a chalcogen atom; a nitrogen atom substituted with an alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a cyano group; or a group represented by the following formula (2):

[0033] [ka]

[0034] (In the formula, Y 1 and Y 2 each independently represents a hydrogen atom, a fluorine atom, a trifluoromethyl group, a cyano group, a nitro group, or a phenyl group which may be substituted with one or more electron-withdrawing groups.

[0035] [ka]

[0036] (In the formula, J 1 and X 1 has the same meaning as above. 14 represents a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms; a monocyclic, linked or fused aromatic group having 3 to 18 carbon atoms which may be substituted with one or more electron-withdrawing groups or alkyl groups having 1 to 20 carbon atoms; or an aralkyl group having 7 to 14 carbon atoms. 14 cannot be a hydrogen atom at the same time.) [Abstract 6]

[0037] A film-forming composition comprising the fused ring chalcogenadiazole compound according to [Summary 1]. [Abstract 7]

[0038] An organic thin film comprising the fused ring chalcogenadiazole compound according to [Summary 1]. [Abstract 8]

[0039] An organic transistor device comprising the fused ring chalcogenadiazole compound according to [Summary 1]. [Effects of the Invention]

[0040] The fused ring chalcogenadiazole compound according to the present invention has both high solubility and heat resistance, and can efficiently drive an organic transistor device using the compound as an active layer. [Brief explanation of the drawings]

[0041] [Figure 1] 1A and 1B are diagrams showing the cross-sectional structure of an organic transistor element. DETAILED DESCRIPTION OF THE INVENTION

[0042] Hereinafter, a fused-ring chalcogenadiazole compound according to one embodiment of the present invention (hereinafter, sometimes simply referred to as a fused-ring chalcogenadiazole compound) will be described in detail.

[0043] A fused-ring chalcogenadiazole compound according to one embodiment of the present invention is a fused-ring chalcogenadiazole compound represented by formula (1) (hereinafter, may be referred to as a fused-ring chalcogenadiazole compound (1)). Examples of the fused-ring chalcogenadiazole compound represented by formula (1) include the following fused-ring chalcogenadiazole compounds (1a), (1b), (1c), (1d), (1e), and (1f).

[0044] [ka]

[0045] [ka]

[0046] [ka]

[0047] [ka]

[0048] [ka]

[0049] [ka]

[0050] [ka]

[0051] [J 1 About J 1 represents a chalcogen atom; a nitrogen atom which may be substituted with an alkyl group having 1 to 20 carbon atoms or a monocyclic, linked or fused ring aromatic group having 3 to 18 carbon atoms.

[0052] J 1 Examples of the chalcogen atom represented by the formula (I) include an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. In terms of the good performance of the fused ring chalcogenadiazole compound (1) in an organic transistor device, an oxygen atom or a sulfur atom is preferred.

[0053] J 1The nitrogen atom represented by the formula (I) may be substituted with an alkyl group having 1 to 20 carbon atoms, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a 2-methylpropyl group, a 2,2-dimethylpropyl group, a 1-methylethyl group, a cyclopropyl group, a butyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 2-butyl group, a 3-methylbutan-2-yl group, a tert-butyl group, a cyclobutyl group, a pentyl group, a 2-methylpentyl group, a 3-ethylpentyl group, a 2,4-dimethylpentyl group, a 2-pentyl group, a 2-methylpentan-2-yl group, a 4,4-dimethylpentan-2-yl group, a 3-pentyl group, a 3-ethylpentan-3-yl group, a cyclopentyl group, a 2,5-dimethylcyclopentyl group, a 3-ethylcyclopentyl group, a hexyl group, a 2-methylhexyl group, a 3,3-dimethylhexyl group, a 4 -ethylhexyl, 2-hexyl, 2-methylhexan-2-yl, 5,5-dimethylhexan-2-yl, 3-hexyl, 2,4-dimethylhexan-3-yl, cyclohexyl, 4-ethylcyclohexyl, 4-propylcyclohexyl, 4,4-dimethylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, 4-heptyl, bicyclo[2.2.1]hexyl Examples of the alkyl group include butyl, octyl, 2-octyl, 3-octyl, 4-octyl, cyclooctyl, bicyclo[2.2.2]octyl, nonyl, 5-nonyl, decyl, 2-decyl, 5-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl groups.

[0054] J 1 The nitrogen atom represented by the formula (I) may be substituted with a monocyclic, linked, or fused aromatic group having 3 to 18 carbon atoms, and examples of the aromatic group include a thienyl group, a furyl group, a benzofuranyl group, a benzothienyl group, a dibenzofuranyl group, a dibenzothienyl group, a pyrimidyl group, a pyrazinyl group, a pyridyl group, a bipyridyl group, a terpyridinyl group, a quinolinyl group, an isoquinolinyl group, a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, a quinazolinyl group, an acridinyl group, a phenanthrolinyl group, and a phthalazinyl group.

[0055] [R 1 ~R 6 ,R 8 ~R 14 About R 1 ~R 6 , R 8 ~R 12 represents a hydrogen atom; a halogen atom; an electron-withdrawing group; an alkyl group having 1 to 20 carbon atoms; an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms; a monocyclic, linked or fused ring aromatic group having 3 to 18 carbon atoms which may be substituted with one or more electron-withdrawing groups or alkyl groups having 1 to 20 carbon atoms; or an aralkyl group having 7 to 14 carbon atoms; 13 represents an alkyl group having 1 to 20 carbon atoms; an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms; an aromatic group having 3 to 18 carbon atoms and a monocyclic, linked or fused ring structure, which may be substituted with one or more electron-withdrawing groups or alkyl groups having 1 to 20 carbon atoms; or an aralkyl group having 7 to 14 carbon atoms; 14 represents a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms; a monocyclic, linked or fused ring aromatic group having 3 to 18 carbon atoms which may be substituted with one or more electron-withdrawing groups or alkyl groups having 1 to 20 carbon atoms; or an aralkyl group having 7 to 14 carbon atoms.

[0056] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 and R 12 Examples of the halogen atom represented by the formula include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a bromine atom is preferred in terms of the excellent stability of the fused ring chalcogenadiazole compound (1).

[0057] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R9 , R 10 , R 11 and R 12 Examples of the electron-withdrawing group represented by the formula (I) include a cyano group, a nitro group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, an alkoxycarbonyl group, a formyl group, an imino group, a trifluoromethoxy group, a trifluoromethylthio group, a pentafluorosulfanyl group, a carboxyl group, a sulfo group, and a trifluoromethanesulfonyl group. In terms of good performance when the fused-ring chalcogenadiazole compound (1) is used as an organic transistor element, a trifluoromethyl group and a cyano group are preferred, and a cyano group is more preferred.

[0058] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14The alkyl group having 1 to 20 carbon atoms represented by the formula (I) may be any of a linear, branched or cyclic alkyl group, and examples thereof include a methyl group, a cyclohexylmethyl group, an ethyl group, a 2-cyclopentylethyl group, a propyl group, a 2-methylpropyl group, a 2,2-dimethylpropyl group, a 3-cyclopropylpropyl group, a 1-methylethyl group, a cyclopropyl group, a butyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 2-butyl group, a 3-methylbutan-2-yl group, a tert-butyl group, a cyclobutyl group, a pentyl group, a 2-methylpentyl group, a 3-ethylpentyl group, a 2,4-dimethylpentyl group, a 2-pentyl group, a 2-methylpentan-2-yl group, a 4,4-dimethylpentan-2-yl group, a 3-pentyl group, a 3-ethylpentan-3-yl group, a cyclopentyl group, a 2,5-dimethylcyclopentyl group, a 3-ethylcyclopentyl group, a hexyl group, a 2-methylpent ...2-methylpentyl group, a 2-methylpentyl group, a 4,4-dimethylpentan-2-yl group, a 3-pentyl group, a 3-ethylpentan-3-yl group, a cyclopentyl group, a 2,5-dimethylcyclopentyl group, a 3-ethylcyclopentyl group, a hexyl group, a 2-methylpentyl group, a 2-methylpentyl group, a 2-methylpentyl group, a 3- ethylhexyl 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, Examples of the alkyl group include bicyclo[2.2.1]heptyl, octyl, 2-octyl, 3-octyl, 4-octyl, cyclooctyl, bicyclo[2.2.2]octyl, nonyl, 5-nonyl, decyl, 2-decyl, 5-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl. In terms of high solubility of the fused ring-fused chalcogenadiazole compound (1), linear alkyl groups are preferred, alkyl groups having 1 to 12 carbon atoms are more preferred, and hexyl or dodecyl groups are particularly preferred.

[0059] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R10 , R 11 , R 12 , R 13 and R 14The unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms, represented by the formula (I), may be either an alkenyl group or an alkynyl group, and specific examples thereof include a vinyl group, a 1-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, a 5-hexenyl group, a 1-heptenyl group, a 2-heptenyl group, a 3-heptenyl group, a 4-heptenyl group, a 5-heptenyl group, 6-heptenyl group, 1-octenyl group, 2-octenyl group, 3-octenyl group, 4-octenyl group, 5-octenyl group, 6-octenyl group, 7-octenyl group, 1-nonenyl group, 2-nonenyl group, 3-nonenyl group, 4-nonenyl group, 5-nonenyl group, 6-nonenyl group, 7-nonenyl group, 8-nonenyl group, 1-decenyl group, 2-decenyl group, 3-decenyl group, 4-decenyl group, 5-decenyl group, 6-decenyl group, 7-decenyl group, 8-decenyl group, 9-decenyl group, ethynyl group, 1-propynyl group, 1 -butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-heptynyl, 2-heptynyl, 3-heptynyl, 4-heptynyl, 5-heptynyl, 6-heptynyl, 1-octynyl, 2-octynyl, 3-octynyl, 4-octynyl, 5-octynyl, 6-octynyl, 7-octynyl, 1-octynyl Examples include 1-octynyl, 2-nonynyl, 3-nonynyl, 4-nonynyl, 5-nonynyl, 6-nonynyl, 7-nonynyl, 8-nonynyl, 1-decynyl, 2-decynyl, 3-decynyl, 4-decynyl, 5-decynyl, 6-decynyl, 7-decynyl, 8-decynyl, 9-decynyl, triisopropylsilylethynyl, 2-methylpropen-1-yl, 2-ethylbuten-1-yl, 2-propylpenten-1-yl, and 2-butylhexen-1-yl. In view of the high solubility of the fused ring chalcogenadiazole compound (1), unsaturated aliphatic hydrocarbon groups having 2 to 10 carbon atoms are preferred, and a 1-octynyl group is particularly preferred.

[0060] R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 and R 14Examples of the monocyclic, linked or fused ring aromatic group having 3 to 18 carbon atoms, which may be substituted with one or more electron-withdrawing groups or alkyl groups having 1 to 20 carbon atoms, include a phenyl group, a 2-methylphenyl group, a 2-ethylphenyl group, a 2-propylphenyl group, a 2-butylphenyl group, a 2-pentylphenyl group, a 2-hexylphenyl group, a 2-heptylphenyl group, a 2-octylphenyl group, a 2-nonylphenyl group, a 2-decylphenyl group, a 2-undecylphenyl group, a 2-dodecylphenyl group, a 3-methylphenyl group, a 3-ethylphenyl group, a 3-propylphenyl group, a 3-butylphenyl group, a 3-pentylphenyl group, a 3-hexylphenyl group, a 3-heptylphenyl group, a nyl group, 3-octylphenyl group, 3-nonylphenyl group, 3-decylphenyl group, 3-undecylphenyl group, 3-dodecylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-butylphenyl group, 4-pentylphenyl group, 4-hexylphenyl group, 4-heptylphenyl group, 4-octylphenyl group, 4-nonylphenyl group, 4-decylphenyl group, 4-undecylphenyl group, 4-dodecylphenyl group, 4-cyanophenyl group, 4-nitrophenyl group, 4-trifluorophenyl group, 4-pentafluoroethylphenyl group, 4-heptafluoropropylphenyl group, 4-(2',2',3',3',4',4',4'-heptafluorobutyl)phenyl group, 4-cyano-3-methylphenyl group, 4-cyano-3-ethylphenyl group, 4-cyano-3-propylphenyl group, 3-butyl-4-cyanophenyl group, 4-cyano-3-pentylphenyl group, 4-cyano-3-hexylphenyl group, 4-cyano-3-heptylphenyl group, 4-cyano-3-octylphenyl group, 4-cyano-3-nonylphenyl group, 4-cyano- 3-decylphenyl group, 4-cyano-3-undecylphenyl group, 4-cyano-3-dodecylphenyl group, 3-cyanophenyl group, 3-cyano-4-methylphenyl group, 3-cyano-4-ethylphenyl group, 3-cyano-4-propylphenyl group, 4-butyl-3-cyanophenyl group, 3-cyano-4-pentylphenyl group, 3-cyano-4-hexylphenyl group, 3-cyano-4-heptylphenyl group, 3- Examples include a cyano-4-octylphenyl group, a 3-cyano-4-nonylphenyl group, a 3-cyano-4-decylphenyl group, a 3-cyano-4-undecylphenyl group, a 3-cyano-4-dodecylphenyl group, a 3,4-dicyanophenyl group, a 5-methylthiophenyl group, a 5-ethylthiophenyl group, a 5-propylthiophenyl group, a 5-butylthiophenyl group, a 5-pentylthiophenyl group, a 5-hexylthiophenyl group, a 5-heptylthiophenyl group, a 5-octylthiophenyl group, a 5-nonylthiophenyl group, a 5-decylthiophenyl group, a 5-undecylthiophenyl group, a 5-dodecylthiophenyl group, a [1,1'-biphenyl]-4-yl group, a 4'-cyano-[1,1'-biphenyl]-4-yl group, a [2,2'-bithiophenyl]-5-yl group, and a 5-cyano-[2,2'-biphenyl]-5-yl group. In terms of the good solubility and crystallinity of the fused ring chalcogenadiazole compound (1), a monocyclic, linked ring, or fused ring aromatic hydrocarbon group having 6 to 12 carbon atoms and substituted with one or more electron-withdrawing groups or alkyl groups having 1 to 12 carbon atoms is preferred, a phenyl group substituted with one or more electron-withdrawing groups or alkyl groups having 1 to 12 carbon atoms is more preferred, and a 4-cyanophenyl group or a 4-hexylphenyl group is particularly preferred.

[0061] R 1 , R 2 , R 3, R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 Examples of the aralkyl group having 7 to 14 carbon atoms represented by the formula (I) include a benzyl group, a 1-(2-thiophenyl)methyl group, a 1-(2-furyl)methyl group, a 2-phenylethyl group, a 2-(2-thiophenyl)ethyl group, a 2-(2-furyl)ethyl group, a 3-phenylpropyl group, a 3-(2-thiophenyl)ethyl group, a 3-(2-furyl)ethyl group, a 4-phenylbutyl group, a 4-(2-thiophenyl)ethyl group, and a 4-(2-furyl)ethyl group.

[0062] R 1 is preferably a hydrogen atom; a fluorine atom or a bromine atom; a cyano group; an alkyl group having 1 to 12 carbon atoms; an unsaturated aliphatic hydrocarbon group having 2 to 8 carbon atoms; a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 12 carbon atoms substituted with one or more electron-withdrawing groups or alkyl groups having 1 to 12 carbon atoms; or an aralkyl group having 7 to 10 carbon atoms, and particularly preferably a hydrogen atom, a bromine atom, a cyano group, a hexyl group, a 1-octynyl group, a 4-cyanophenyl group, a 4-hexylphenyl group, or the like.

[0063] R 4 is preferably a hydrogen atom; a fluorine atom or a bromine atom; a cyano group; an alkyl group having 1 to 12 carbon atoms; an unsaturated aliphatic hydrocarbon group having 2 to 8 carbon atoms; a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 12 carbon atoms substituted with one or more electron-withdrawing groups or alkyl groups having 1 to 12 carbon atoms; or an aralkyl group having 7 to 10 carbon atoms, and particularly preferably a hydrogen atom, a bromine atom, a cyano group, a hexyl group, a dodecyl group, a 1-octynyl group, or the like.

[0064] R 2 , R 3 , R 5 , R 6 , R 8 , R 9 , R10 , R 11 and R 12 As the alkyl group, a hydrogen atom; a fluorine atom or a bromine atom; a cyano group; an alkyl group having 1 to 12 carbon atoms; an unsaturated aliphatic hydrocarbon group having 2 to 8 carbon atoms; a monocyclic, linked ring, or fused ring aromatic hydrocarbon group having 6 to 12 carbon atoms substituted with one or more electron-withdrawing groups or alkyl groups having 1 to 12 carbon atoms; and an aralkyl group having 7 to 10 carbon atoms, and a hydrogen atom is particularly preferred.

[0065] R 13 Preferred examples of the alkyl group include alkyl groups having 1 to 20 carbon atoms; unsaturated aliphatic hydrocarbon groups having 2 to 20 carbon atoms; monocyclic, linked, or fused aromatic groups having 3 to 18 carbon atoms which may be substituted with one or more electron-withdrawing groups or alkyl groups having 1 to 20 carbon atoms; and aralkyl groups having 7 to 14 carbon atoms, with hexyl, dodecyl, 1-octynyl, 4-cyanophenyl, 4-hexylphenyl, and the like being particularly preferred.

[0066] R 14 is preferably a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms; a monocyclic, linked, or fused aromatic group having 3 to 18 carbon atoms which may be substituted with one or more electron-withdrawing groups or alkyl groups having 1 to 20 carbon atoms; or an aralkyl group having 7 to 14 carbon atoms, and particularly preferably a hydrogen atom, a hexyl group, a dodecyl group, a 1-octynyl group, a 4-cyanophenyl group, a 4-hexylphenyl group, or the like.

[0067] [X 1 , W 1 , W 2 , W 3 , Y 1 , Y 2 About X 1 represents a chalcogen atom; a nitrogen atom substituted with an alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a cyano group; or a group represented by the following formula (2):

[0068] [ka]

[0069] (In the formula, Y 1 and Y 2 each independently represents a hydrogen atom, a fluorine atom, a trifluoromethyl group, a cyano group, a nitro group, or a phenyl group which may be substituted with one or more electron-withdrawing groups.

[0070] X 1 Examples of the chalcogen atom represented by the formula (I) include an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom, and an oxygen atom is preferred in terms of the excellent stability of the fused ring chalcogenadiazole compound (1).

[0071] X 1The nitrogen atom represented by the formula (I) may be substituted with an alkyl group having 1 to 20 carbon atoms, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a 2-methylpropyl group, a 2,2-dimethylpropyl group, a 1-methylethyl group, a cyclopropyl group, a butyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 2-butyl group, a 3-methylbutan-2-yl group, a tert-butyl group, a cyclobutyl group, a pentyl group, a 2-methylpentyl group, a 3-ethylpentyl group, a 2,4-dimethylpentyl group, a 2-pentyl group, a 2-methylpentan-2-yl group, a 4,4-dimethylpentan-2-yl group, a 3-pentyl group, a 3-ethylpentan-3-yl group, a cyclopentyl group, a 2,5-dimethylcyclopentyl group, a 3-ethylcyclopentyl group, a hexyl group, a 2-methylhexyl group, a 3,3-dimethylhexyl group, a 4 -ethylhexyl, 2-hexyl, 2-methylhexan-2-yl, 5,5-dimethylhexan-2-yl, 3-hexyl, 2,4-dimethylhexan-3-yl, cyclohexyl, 4-ethylcyclohexyl, 4-propylcyclohexyl, 4,4-dimethylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, 4-heptyl, bicyclo[2.2.1]hexyl Examples of the alkyl group include butyl, octyl, 2-octyl, 3-octyl, 4-octyl, cyclooctyl, bicyclo[2.2.2]octyl, nonyl, 5-nonyl, decyl, 2-decyl, 5-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl groups.

[0072] X 1 The nitrogen atom represented by the formula (I) may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and examples of the aromatic hydrocarbon group include a phenyl group, a biphenylyl group, a terphenylyl group, a naphthylphenyl group, a naphthyl group, an acenaphthylenyl group, a phenanthryl group, an anthranyl group, a fluoranthenyl group, a pyrenyl group, a triphenylenyl group, a chrysenyl group, a fluorenyl group, a triptycenyl group, and a perylenyl group.

[0073] Y 1and Y 2 Examples of the phenyl group which may be substituted with one or more electron-withdrawing groups represented by the formula (I) include a 4-fluorophenyl group, a 3,5-difluorophenyl group, a 2,6-difluorophenyl group, a pentafluorophenyl group, a 4-trifluoromethylphenyl group, a 3,5-bis(trifluoromethyl)phenyl group, a 2,6-bis(trifluoromethyl)phenyl group, a 4-cyanophenyl group, a 3,5-dicyanophenyl group, a 2,6-dicyanophenyl group, a 4-nitrophenyl group, a 3,5-dinitrophenyl group, a 2,6-dinitrophenyl group, etc. The fused ring chalcogenadiazole compound (1) is preferred because of its excellent performance when used in an organic transistor device. 1 and Y 2 is preferably a fluorine atom, a trifluoromethyl group, a cyano group or a pentafluorophenyl group, more preferably a cyano group.

[0074] Among these, X 1 is an oxygen atom, a sulfur atom, a nitrogen atom substituted with a cyano group, or Y 1 and Y 2 is preferably a fluorine atom, a trifluoromethyl group, a cyano group, or a pentafluorophenyl group, and is particularly preferably a fused ring chalcogenadiazole compound (1) in terms of the excellent performance when used in an organic transistor device. 1 and Y 2 is preferably a cyano group.

[0075] W 1 represents a halogen atom, and W 2 and W 3 represents a halogen atom; a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms; a monocyclic, linked or fused ring aromatic group having 3 to 18 carbon atoms which may be substituted with one or more electron-withdrawing groups or alkyl groups having 1 to 20 carbon atoms; or an aralkyl group having 7 to 14 carbon atoms. 2 and W 3 At least one of the groups is a halogen atom.

[0076] W 1 , W 2and W 3 The halogen atoms represented by R 1 ~R 6 ,R 8 ~R 12 Examples of the halogen atoms include those similar to those exemplified in 1., and a bromine atom is preferred in that it provides high stability to the fused ring chalcogenadiazole compound (1).

[0077] W 2 and W 3 As the alkyl group having 1 to 20 carbon atoms represented by the formula 1 ~R 6 ,R 8 ~R 14 Examples of the alkyl group include the same alkyl groups as those exemplified in 1. In terms of high solubility of the fused ring-fused chalcogenadiazole compound (1), a linear alkyl group is preferred, an alkyl group having 1 to 12 carbon atoms is more preferred, and a hexyl group or a dodecyl group is particularly preferred.

[0078] W 2 and W 3 As the unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms represented by R 1 ~R 6 ,R 8 ~R 14 Examples of the unsaturated aliphatic hydrocarbon groups include those similar to those exemplified in 1. In terms of high solubility of the fused ring chalcogenadiazole compound (1), unsaturated aliphatic hydrocarbon groups having 2 to 10 carbon atoms are preferred, alkynyl groups having 2 to 10 carbon atoms are more preferred, and 1-octyl groups are particularly preferred.

[0079] W 2 and W 3 The aromatic group of a monocyclic, linked or fused ring having 3 to 18 carbon atoms, which may be substituted with one or more electron-withdrawing groups or alkyl groups having 1 to 20 carbon atoms, is represented by R 1 ~R 6 ,R 8 ~R 14Examples of the aromatic hydrocarbon group include those similar to those exemplified in 1., and from the viewpoint of good solubility and crystallinity of the fused ring chalcogenadiazole compound (1), a monocyclic, linked ring, or fused ring aromatic hydrocarbon group having 6 to 12 carbon atoms and substituted with one or more electron-withdrawing groups or alkyl groups having 1 to 12 carbon atoms is preferred, a phenyl group substituted with one or more electron-withdrawing groups or alkyl groups having 1 to 12 carbon atoms is more preferred, and a 4-cyanophenyl group or a 4-hexylphenyl group is particularly preferred.

[0080] W 2 and W 3 As the aralkyl group having 7 to 14 carbon atoms represented by R 1 ~R 6 ,R 8 ~R 14 Examples of the aralkyl groups include the same as those exemplified in 1.

[0081] The fused ring chalcogenadiazole compound (1) includes compounds represented by the following formulae (1-1-1) to (1-1-133), (1-1-8-n6), (1-1-9-n12), (1-1-10-n6), (1-1-11-n6), (1-1-12-n6), (1-1-13-n6), (1-1-14-n6), (1-1-15-n6), (1-1-16-n6), (1-1-26-n6), (1-1-27-n6), (1-1-28-n6), (1-1-35-n6), (1-1-36-n6), (1-1-37-n6), (1-1-38-n6), and (1-1-39-n6): , (1-1-40-n6), (1-1-59-n6), (1-1-65-n6), (1-1-71-n6), (1-1-77-n6), ( 1-1-83-n6), (1-1-89-n6), (1-2-1) to (1-2-133), (1-2-8-n6), (1-2-9-n1 2), (1-2-10-n6), (1-2-11-n6), (1-2-12-n6), (1-2-13-n6), (1-2-14-n6) , (1-2-15-n6), (1-2-16-n6), (1-2-26-n6), (1-2-27-n6), (1-2-28-n6), ( 1-2-35-n6), (1-2-36-n6), (1-2-37-n6), (1-2-38-n6), (1-2-39-n6), (1 -2-40-n6), (1-2-59-n6), (1-2-65-n6), (1-2-71-n6), (1-2-77-n6), (1-2 -83-n6), (1-2-89-n6), (1-3-1) to (1-3-20), (1-3-8-n6), (1-3-9-n6), (1 -3-10-n6), (1-4-1) to (1-4-20), (1-4-8-n6), (1-4-9-n6), (1-4-10-n6), (1-5-1) to (1-5-10), (1-5-8-n6), (1-5-9-n6), (1-5-10-n6), (2-1-1) to (2-1-25), (2-1-8-n6), (2-1-9-n6), (2-1-10-n6), (2-2-1) to (2-2-25), (2-2-8-n6), (2-2-9-n6), (2-2-10-n6), (2-3-1) to (2-3-20), (2-3-8-n6), (2-3-9-n6), (2-3-10-n6), (2-4-1) to (2-4-20), (2-4-8-n6), (2-4-9-n6),Examples of the formula include (2-4-10-n6), (2-5-1) to (2-5-10), (2-5-8-n6), (2-5-9-n6), and (2-5-10-n6), but the present invention is not limited to these. In the formula, n is a natural number from 1 to 12, m is an integer from 0 to 10, and k is a natural number from 1 to 4.

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[0227] In the above formula, C n H 2n+1 and C m H 2m+1 represents a straight-chain alkyl group.

[0228] The compounds represented by formulas (1-2-1), (1-2-9-n6), (1-2-9-n12), (1-2-10-n6), (1-2-13-n6), (1-2-16-m6), (1-2-48), (1-2-59-n6), (1-2-61), (1-2-95), and (2-2-9-n6) are preferred because of their good performance when made into an organic transistor device.

[0229] Next, a method for producing the fused ring chalcogenadiazole compound (1) according to one embodiment of the present invention will be described. The production methods of the present invention are as shown below in Production Methods (A) to (D) (hereinafter, sometimes referred to as Production Method (A), Production Method (B), Production Method (C), and Production Method (D) respectively).

[0230] First, the production method (A) will be explained.

[0231] Production method (A) is a method for producing a fused-ring chalcogenadiazole compound (1a) included in the fused-ring chalcogenadiazole compound (1) according to one embodiment of the present invention, by reacting a chalcogenadiazole intermediate represented by formula (4) (hereinafter, also referred to as chalcogenadiazole intermediate (4)) with an acid. Manufacturing method (A)

[0232] [ka]

[0233] (In the formula, J 1 , R 1 , R 2 , R 3 , R 4 , R 5 and R 6 represents the same meaning as above. Z represents a leaving group.

[0234] Examples of the leaving group represented by Z include a hydrogen atom; a hydroxyl group; an alkoxy group; a chlorine atom; an acetoxy group; and a nitrogen atom which may be substituted with an alkyl group or a phenyl group. From the viewpoint of providing a good reaction yield of the fused ring chalcogenadiazole compound (1a), a hydroxyl group, a methoxy group, an ethoxy group, a chlorine atom, and an acetoxy group are preferred, and a methoxy group is more preferred.

[0235] Specific examples of the chalcogenadiazole intermediate (4) include those represented by the following formulae (3-1-1) to (3-1-23), (3-2-1) to (3-2-16), and (3-3-1) to (3-3-11), but the present invention is not limited thereto.

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[0248] The chalcogenadiazole intermediate (4) can be produced, for example, by referring to a method described in the literature (Angewante Chemie international edition, Vol. 46, pp. 7681-7684, 2007, etc.).

[0249] The production method (A) must be carried out in the presence of an acid, and the acid may be a Brønsted acid or a Lewis acid. Examples of the Brønsted acid include inorganic Brønsted acids such as hydroiodic acid, hydrogen chloride, hydrogen bromide, hydroxylamine-O-sulfonic acid, phosphonic acid, chlorosulfonic acid, and nitric acid, as well as acetic acid, glycolic acid, palmitic acid, sorbic acid, phthalic acid, chlorodifluoroacetic acid, palmitic acid, formic acid, difluoroacetic acid, aminomethanesulfonic acid, 2-hydroxybenzoic acid, maleic acid, croconic acid, tribromoacetic acid, thioacetic acid, anthranilic acid, bis(trifluoromethanesulfonyl)imide, benzenesulfonic acid, trifluoromethanesulfonic acid, thioctic acid, pyridinium p-toluenesulfonate, and 5-sulfosalic acid. Organic Bronsted acids such as carboxylic acid, fumaric acid, propionic acid, thioglycolic acid, sulfanilic acid, bromoacetic acid, tartaric acid, benzenesulfonic acid, gallic acid, ethylenediaminetetraacetic acid, hydroxypropionic acid, dichloroacetic acid, benzoic acid, succinic acid, malic acid, 2-hydroxypropionic acid, trichloroacetic acid, malonic acid, chloroacetic acid, methanesulfonic acid, 1,2-benzenedisulfonic acid imide, p-toluenesulfonic acid, camphorsulfonic acid, triglycolaminic acid, trifluoroacetic acid, citric acid, and ascorbic acid; Lewis acids such as aluminum isopropoxide, aluminum(III) chloride, and bis(2,Aluminum-based Lewis acids such as 6-di-tert-butyl-4-methylphenoxy)methylaluminum, aluminum bromide, triethylaluminum, trimethylaluminum, triethylaluminum, triisobutylaluminum, ethylaluminum dichloride, and diethylaluminum chloride; tin-based Lewis acids such as tin(IV) chloride; titanium-based Lewis acids such as titanium(IV) chloride and tetraisopropyl orthotitanate; boron-based Lewis acids such as boron trifluoride, boron trichloride, and dicyclohexyl(trifluoromethanesulfonyloxy)borane; cerium(III) trifluoromethanesulfonate; and lanthanum(III) trifluoromethanesulfonate. Examples of Lewis acids include triflate-based Lewis acids such as barium(II) trifluoromethanesulfonate, silver trifluoromethanesulfonate, zinc(II) trifluoromethanesulfonate, neodymium(III) trifluoromethanesulfonate, ytterbium(III) trifluoromethanesulfonate, scandium(III) trifluoromethanesulfonate, hafnium(IV) trifluoromethanesulfonate, copper(II) trifluoromethanesulfonate, thulium(III) trifluoromethanesulfonate, and yttrium(III) trifluoromethanesulfonate, and indium-based Lewis acids such as indium(III) chloride, and these may be mixed in any ratio. Bronsted acids are preferred in terms of good reaction yield, organic Bronsted acids are more preferred, and trifluoromethanesulfonic acid is particularly preferred.

[0250] There is no limitation on the amount of acid used in the production method (A), but in terms of good reaction yield, it is preferably 1.0 to 30 molar equivalents per equivalent of the chalcogenadiazole intermediate (4).

[0251] The production method (A) can be carried out in a solvent. The solvent that can be used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include aliphatic hydrocarbon solvents such as hexane, heptane, decane, and tridecane; ether solvents such as diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, and 1,2-dimethoxyethane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, and tetralin; carbonate ester solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and 4-fluoroethylene carbonate; ester solvents such as ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, and γ-lactone; amide solvents such as dimethyl sulfoxide (DMF), dimethylacetamide (DMAc), and N-methylpyrrolidone (NMP); and N,N,N',N'-tetramethylpropanol. Examples of suitable solvents include urea solvents such as tetramethylurea (TMU) and N,N'-dimethylpropyleneurea (DMPU); sulfoxide solvents such as dimethyl sulfoxide (DMSO); alcohol solvents such as methanol, ethanol, 2-propanol, butanol, octanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and 2,2,2-trifluoroethanol; halogen solvents such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, and orthodichlorobenzene (o-DCB); fluorine solvents such as bis(2,2,2-trifluoroethyl)N,N-diisopropylphosphoramidate (PF-37) and tris(2,2,2-trifluoroethyl)phosphate (TFEP); acidic solvents such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, and acetic acid; nitromethane; and water. These may be mixed in any ratio.

[0252] In view of good reaction yield, halogenated solvents are preferred, chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene and o-DCB are more preferred, and 1,2-dichloroethane is even more preferred.

[0253] Production method (A) can be carried out at a temperature appropriately selected from -80°C to 180°C, and is preferably carried out at a temperature appropriately selected from 20°C to 150°C in terms of good reaction yield.

[0254] The fused ring-fused chalcogenadiazole compound (1a) can be obtained by carrying out a conventional treatment after completion of the production method (A). If necessary, it may be purified using a general means used by those skilled in the art for purifying organic compounds, such as washing, precipitation, filtration, dialysis, recrystallization, column chromatography, preparative HPLC, or Soxhlet extraction.

[0255] Examples of the fused ring chalcogenadiazole compound (1a) obtained by production method (A) include those represented by the formulas (1-1-1) to (1-1-4), (1-1-44) to (1-1-49), (1-1-57), (1-1-99), (1-1-100), (1-1-103), (1-1-105), (1-1-106), (1-1-109), (1-1-123), (1-1-9-n6), (1-1-9-n12), (1-1-98-n6), (1-1-104-n6), (2-1-1) to (2-1-4), (2-1-11) to (2-1-20), and (2-1-9-n6).

[0256] Next, the production method (B) of the present invention will be explained. Manufacturing method (B)

[0257] The production method (B) is a method for producing a fused ring chalcogenadiazole compound (1a) and a compound Y 1 -CH2-Y 2 (5)(where, Y 1 and Y 2 has the same meaning as above.) with an active methylene compound represented by the formula (Ib), which is included in the fused chalcogenadiazole compound (1) according to one embodiment of the present invention.

[0258] [ka]

[0259] (In the formula, J 1 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Y 1 and Y 2 represents the same meaning as above.)

[0260] Active methylene compound Y used in production method (B) 1 -CH2-Y 2 (5) As for Y 1 and Y 2 are each independently a hydrogen atom, a fluorine atom, a trifluoromethyl group, a cyano group, a nitro group, a 4-fluorophenyl group, a 3,5-difluorophenyl group, a 2,6-difluorophenyl group, a pentafluorophenyl group, a 4-trifluoromethylphenyl group, a 3,5-bis(trifluoromethyl)phenyl group, a 2,6-bis(trifluoromethyl)phenyl group, a 4-cyanophenyl group, a 3,5-dicyanophenyl group, a 2,6-dicyanophenyl group, a 4-nitrophenyl group, a 3,5-dinitrophenyl group, or a 2,6-dinitrophenyl group.

[0261] The active methylene compound (5) used in the production method (B) can be a commercially available product.

[0262] In the production method (B), an additive can be added to promote the reaction. Examples of the additive include the Bronsted acids and Lewis acids exemplified in the production method (A). Lewis acids are preferred because they provide a good reaction yield of the fused ring chalcogenadiazole compound (1b), and aluminum oxide or titanium tetrachloride is more preferred.

[0263] In the production method (B), a base can be added as an additive. Examples of the base include metal hydroxide salts such as sodium hydroxide, potassium hydroxide, calcium hydroxide, etc., metal carbonate salts such as sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, etc., metal acetate salts such as potassium acetate, sodium acetate, etc., metal phosphate salts such as potassium phosphate, sodium phosphate, etc., metal fluoride salts such as sodium fluoride, potassium fluoride, cesium fluoride, etc., metal alkoxides such as sodium methoxide, potassium methoxide, sodium ethoxide, potassium isopropyl oxide, potassium tert-butoxide, etc., triethylamine, diethyl amine, etc., and the like. Examples of tertiary amines include isopropylethylamine, tributylamine, N-methylpyrrolidine, N-methylpiperidine, N,N'-dimethylpiperazine, N-methylmorpholine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]-7-undecene, N,N-dimethylaniline, N,N-diethylaniline, N,N-diethyltoluidine, pyridine, and picoline. Tertiary amines are preferred in terms of the good reaction yield of the fused-ring chalcogenadiazole compound (1b), and pyridine is more preferred.

[0264] There is no limitation on the amount of the active methylene compound used in the production method (B), but in terms of good reaction yield, it is preferably 1.0 to 10 molar equivalents per equivalent of the fused ring-fused chalcogenadiazole compound (1a).

[0265] Production method (B) can be carried out in a solvent. Examples of solvents that can be used include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and tridecane; ether solvents such as diisopropyl ether, dibutyl ether, CPME, THF, 2-methyltetrahydrofuran, 1,4-dioxane, and dimethoxyethane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, and tetralin; carbonate ester solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and 4-fluoroethylene carbonate; ethyl acetate, butyl acetate, methyl propionate, methyl propionate, methyl butyrate, and γ-laminatoacetate. Examples of suitable solvents include ester solvents such as methacrylate, amide solvents such as DMF, DMAc, and NMP, urea solvents such as TMU and DMPU, sulfoxide solvents such as DMSO, alcohol solvents such as methanol, ethanol, 2-propanol, butanol, octanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and 2,2,2-trifluoroethanol, halogenated solvents such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, and o-DCB, pyridine, triethylamine, and nitromethane, and these may be mixed in any ratio. In terms of high reaction yield, THF, 1,4-dioxane, DMF, benzene, toluene, chlorobenzene, o-DCB, pyridine, and mixed solvents thereof are preferred, with THF and pyridine being particularly preferred.

[0266] Production method (B) can be carried out at a temperature appropriately selected from 0°C to 180°C, and is preferably carried out at a temperature appropriately selected from 20°C to 130°C in terms of good reaction yield.

[0267] The fused ring-fused chalcogenadiazole compound (1b) can be obtained by carrying out a conventional treatment after the completion of Production Method (B), and may be purified, if necessary, by any conventional means used by those skilled in the art for purifying organic compounds, such as washing, precipitation, filtration, dialysis, recrystallization, column chromatography, preparative HPLC, or Soxhlet extraction.

[0268] The fused ring chalcogenadiazole compound (1b) obtained by the production method (B) includes compounds of the formulas (1-2-1) to (1-2-123), (1-2-8-n6), (1-2-9-n12), (1-2-10-n6), (1-2-11-n6), (1-2-12-n6), (1-2-13-n6), (1-2-14-n6), (1-2-15-n6), (1-2-16-n6), (1-2-17-n6), (1-2-18-n6), (1-2-19-n6), (1-2-20-n6), (1-2-21-n6), (1-2-22-n6), (1-2-23-n6), (1-2-24-n6), (1-2-25-n6), (1-2-26-n6), (1-2-27-n6), (1-2-28-n6), (1-2-29-n6), (1-2-30-n6), (1-2-31-n6), (1-2-32-n6), (1-2-33-n6), (1-2-34-n6), (1-2-35-n6), (1-2-36-n6), (1-2-37-n6), (1-2-38-n6), (1-2-39-n6), (1-2-40-n6), (1-2-41-n6), (1-2-42-n6), (1-2-43-n6), (1-2-44-n6), (1-2-45-n6), (1-2-46-n6), (1-2-47-n6), (1-2-48-n6), (1-2-49-n6), (1-2 -2-16-n6), (1-2-26-n6), (1-2-27-n6), (1-2-28-n6), (1-2-35-n6), (1-2-36-n6), (1-2-37 -n6), (1-2-38-n6), (1-2-39-n6), (1-2-40-n6), (1-2-59-n6), (1-2-65-n6), (1-2-71-n6), (1-2-77-n6), (1-2-83-n6), (1-2-89-n6), (1-3-1) to (1-3-20), (1-3-8-n6), (1-3-9-n6), (1-3-10-n6), (1-4-1) to (1-4-20), (1-4-8-n6), (1-4-9-n6), (1-4-10-n6), (2-2-1) to (2-2- 25), (2-2-8-n6), (2-2-9-n6), (2-2-10-n6), (2-3-1) to (2-3-20), (2-3-8-n6), (2-3-9-n6), (2-3-10-n6), (2-4-1) to (2-4-20), (2-4-8-n6), (2-4-9-n6), (2-4-10-n6), etc. can be exemplified.

[0269] Next, the production method (C) will be explained. Manufacturing method (C)

[0270] Production method (C) is a production method for a fused chalcogenadiazole compound (1d) included in a fused chalcogenadiazole compound (1) according to an embodiment of the present invention, in which a halogenating agent is allowed to act on a fused chalcogenadiazole compound (1c) included in a fused chalcogenadiazole compound (1) according to an embodiment of the present invention.

[0271] [ka]

[0272] (In the formula, J 1 , X 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 and W 1 represents the same meaning as above.)

[0273] The fused ring chalcogenadiazole compound (1c) used in the production method (C) may be any of the compounds represented by the above formulas (1-1-1), (1-1-3), (1-1-6), (1-1-18), (1-1-21), (1-1-24), (1-1-30), (1-1-33), (1-1-42), (1-1-45), (1-1-48), (1-1-51), (1-1-54), (1-1-57), ( Examples include (1-1-96), (1-1-9-n6), (1-1-12-n6), (1-1-15-m6), (1-1-27-n6), (1-1-36-n6), (1-1-39-n6), (2-1-1), (2-1-3), (2-1-6), (2-1-12), (2-1-14), (2-1-21), (2-1-22), and (2-1-9-n6).

[0274] The fused ring chalcogenadiazole compound (1c) used in the production method (C) can be produced by the methods disclosed in Examples 3, 8, 15 and 21.

[0275] The halogenating agents used in the process (C) include iodine, hydroiodic acid, N-iodosuccinimide, trimethylsilyl iodide, N-iodophthalimide, tetramethylammonium dichloroiodate, benzyltrimethylammonium dichloroiodate, N-iodosaccharin, bis(pyridine)iodonium tetrafluoroborate, bis(2,4,6-trimethylpyridine)iodonium hexafluorophosphate, 1-chloro-2-iodoethane, pyridine iodine monochloride, and 1,3-diiodo-5,5- Dimethylhydantoin;N,N-Dimethyl-N-(methylsulfanylmethylene)ammonium iodide;Iodinating agents such as carbon tetraiodide, bromine;Hydrogen bromide;N-Bromosuccinimide;1,2-Dibromo-1,1,2,2-tetrachloroethane;Trimethylsilyl bromide;N-Bromophthalimide;Tetrabutylammonium tribromide;N-Bromosaccharin;Bis(2,4,6-trimethylpyridine)bromonium hexafluorophosphate;Pyridinium bromide perbromide;4-Dimethylaminopyridinium Bromide perbromide;N-Bromoacetamide;Bromodimethylsulfonium bromide;1-Butyl-3-methylimidazolium tribromide;Boron tribromide;Phosphorus tribromide;Trimethylphenylammonium tribromide;1,3-Dibromo-5,5-dimethylhydantoin;2,4,4,6-Tetrabromo-2,5-cyclohexadienone;Dibromoisocyanuric acid;1,8-Diazabicyclo[5.4.0]-7-undecenehydrotribromide;Benzyltrimethylammonium tribromide;Bromotrichloromethane;Tetrabromide Examples of suitable chlorinating agents include brominating agents such as carbon bromide, oxalyl chloride, methoxyacetyl chloride, methanesulfonyl chloride, N-chlorosuccinimide, N-chlorophthalimide, trimethylsilyl chloride, 1,3-dichloro-5,5-dimethylhydantoin, thionyl chloride, benzyltrimethylammonium tetrachloroiodate, phosphorus trichloride, phosphorus pentachloride, cyanuric chloride, N-chlorosaccharin, trichloromethanesulfonyl chloride, and trichlorocyanuric acid, and these may be mixed in any ratio. Brominating agents are preferred in terms of good reaction yield, and bromine or hydrogen bromide is more preferred.

[0276] The amount of the halogenating agent used is not particularly limited, but is preferably 1.0 to 10 molar equivalents relative to the fused ring chalcogenadiazole compound (1c) in terms of good yield.

[0277] The production method (C) can be carried out in a solvent. The solvent that can be used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include aliphatic hydrocarbon solvents such as hexane, heptane, decane, and tridecane; ether solvents such as diisopropyl ether, dibutyl ether, CPME, THF, 2-methyltetrahydrofuran, 1,4-dioxane, and 1,2-dimethoxyethane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, and tetralin; carbonate ester solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and 4-fluoroethylene carbonate; ester solvents such as ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, and γ-lactone. Examples of solvents include methyl alcohol solvents, amide solvents such as DMF, DMAc, and NMP, urea solvents such as TMU and DMPU, sulfoxide solvents such as DMSO, alcohol solvents such as methanol, ethanol, 2-propanol, butanol, octanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and 2,2,2-trifluoroethanol, halogen solvents such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, and o-DCB, fluorine solvents such as PF-37 and TFEP, acidic solvents such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, and acetic acid, nitromethane, and water, and these may be mixed in any ratio. In terms of good yield, halogenated solvents, acidic solvents and mixed solvents thereof are preferred, chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, o-DCB, hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, acetic acid and mixed solvents thereof are more preferred, and a mixed solution of chloroform, hydrobromic acid and acetic acid is particularly preferred.

[0278] Production method (C) can be carried out at a temperature appropriately selected from -80°C to 180°C, and is preferably carried out at a temperature appropriately selected from 20°C to 150°C in terms of good yield.

[0279] The fused ring-fused chalcogenadiazole compound (1d) can be obtained by a conventional treatment after completion of the production method (C), and if necessary, it may be purified using a general method used by those skilled in the art for purifying organic compounds, such as washing, precipitation, filtration, dialysis, recrystallization, column chromatography, preparative HPLC, or Soxhlet extraction.

[0280] The fused chalcogenadiazole compound (1d) obtained by production method (C) includes (1-1-2), (1-1-4), (1-1-99), (1-1-100), (1-1-101), (1-1-102), (1-1-103), (1-1-110), (1-1-113), (1-1-114), (1-1-115), (1-1-117), (1-1-118), (1-1-121), (1-1 -122), (1-1-123), (1-1-98-n6), (1-1-111-n6), (1-1-112-m6), (1-1-116-n6), (1-1-119-n6), (1-1-120-n6), (2-1-2), (2-1-4), (2-1-15), (2-1-16), (2-1-17), (2-1-23), (2-1-24), (2-1-25), etc. can be exemplified.

[0281] Next, the production method (D) of the present invention will be explained. Manufacturing method (D)

[0282] The production method (D) is a method for producing a fused ring-type chalcogenadiazole compound (1e) included in the fused ring-type chalcogenadiazole compound (1) according to one embodiment of the present invention, and a compound represented by the formula (1e) of R 13 - a metal reagent represented by M(6) (wherein R 13has the same meaning as defined above. M represents a metal group, a heteroatom group, or a hydrogen atom.) in the presence of a palladium catalyst and, in some cases, a base.

[0283] [ka]

[0284] (In the formula, J 1 , X 1 , W 2 , W 3 and R 14 represents the same meaning as above.)

[0285] Examples of the fused ring chalcogenadiazole compound (1e) used in production method (D) include those represented by the formulae (1-1-2) to (1-1-4), (1-1-98) to (1-1-109), (2-1-2) to (2-1-4), (2-1-15) to (2-1-20), and (2-1-23) to (2-1-25).

[0286] The fused ring chalcogenadiazole compound (1e) used in the production method (D) can be produced by the methods disclosed in Examples 4, 9, 16, 22, 24 and 26.

[0287] In the metal reagent (6) used in the production method (D), M represents a metal group, a heteroatom group, or a hydrogen atom. Examples of the metal group include Li, Na, K, MgCl, MgBr, MgI, CuCl, CuBr, CuI, CuCN, AlMe2, AlEt2, Al( i Examples of the heteroatom group include MgBr, ZnCl, ZnBr, ZnI, and ZnCl(TMEDA). MgBr and ZnCl are preferred because of their ease of preparation. Examples of the heteroatom group include MeSi, EtSi, MeSn, BuSn, and B(OH) as well as the groups shown in (I) to (VIII) below, with B(OH) or the group shown in (II) being preferred because of their good reaction yield.

[0288] [ka]

[0289] Examples of the metal reagent (6) used in the production method (D) include alkylboronic acids, alkylboronic acid esters, arylboronic acids, arylboronic acid esters, organotin compounds, and terminal alkynes, with hexylboronic acid, 2-(4-hexylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and 1-octyne being particularly preferred.

[0290] The metal reagent (6) used in Production Method (D) can be produced according to the methods disclosed in, for example, Polymer Chemistry, Vol. 6, pp. 7410-7417, 2015; Tetrahedron Letter, Vol. 55, pp. 5195-5198, 2014; ACS Macro Letters, Vol. 4, pp. 689-692, 2015. Alternatively, a commercially available product may be used.

[0291] Examples of palladium catalysts used in Production Method (D) include palladium salts such as palladium chloride, palladium acetate, palladium trifluoroacetate, and palladium nitrate. Further examples include complex compounds such as π-allylpalladium chloride dimer, palladium acetylacetonate, tris(dibenzylideneacetone)dipalladium, bis(dibenzylideneacetone)palladium, dichlorobis(acetonitrile)palladium, and dichlorobis(benzonitrile)palladium; and palladium complexes having a tertiary phosphine as a ligand, such as dichlorobis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)palladium, dichloro(1,1'-bis(diphenylphosphino)ferrocene)palladium, bis(tri-tert-butylphosphine)palladium, bis(tricyclohexylphosphine)palladium, and dichlorobis(tricyclohexylphosphine)palladium. These catalysts can also be prepared in the reaction system by adding a tertiary phosphine to a palladium salt or complex compound.

[0292] Examples of the tertiary phosphine 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(diphenylphosphine), 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.

[0293] Among these, palladium complexes having a tertiary phosphine as a ligand are preferred in terms of good yield, and palladium complexes having triphenylphosphine, tri-(tert-butyl)phosphine or 1,1'-bis(diphenylphosphino)ferrocene as a ligand are more preferred.

[0294] The molar ratio of the tertiary phosphine to the palladium salt or complex compound is preferably in the range of 1:10 to 10:1, and from the viewpoint of a good yield, is more preferably in the range of 1:2 to 3:1. There is no limitation on the amount of the palladium catalyst used in Production Method (D), but from the viewpoint of a good yield, the molar equivalent of the palladium catalyst is preferably in the range of 0.01 to 20 mol percent relative to the ring-fused chalcogenadiazole compound (1e).

[0295] Production method (D) may be carried out in the presence of a base. Examples of the base include metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide; metal carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate; metal acetates such as potassium acetate and sodium acetate; metal phosphates such as potassium phosphate and sodium phosphate; metal fluorides such as sodium fluoride, potassium fluoride, and cesium fluoride; and metal alkoxides such as sodium methoxide, potassium methoxide, sodium ethoxide, potassium isopropyl oxide, and potassium tert-butoxide. Among these, metal carbonates and metal phosphates are preferred in terms of high reaction yield, and potassium carbonate and sodium carbonate are more preferred. The molar ratio of the base to the fused-ring chalcogenadiazole compound (1e) is preferably in the range of 1:2 to 10:1, and more preferably in the range of 1:1 to 4:1, in terms of high reaction yield.

[0296] Production method (D) can be carried out in a solvent. Examples of solvents that can be used include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and tridecane; ether solvents such as diisopropyl ether, dibutyl ether, CPME, THF, 2-methyltetrahydrofuran, 1,4-dioxane, and dimethoxyethane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, and tetralin; carbonate ester solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and 4-fluoroethylene carbonate; ethyl acetate, butyl acetate, methyl propionate, methyl butyrate, and γ- Examples of suitable solvents include ester solvents such as lactones, amide solvents such as DMF, DMAc, and NMP, urea solvents such as TMU and DMPU, sulfoxide solvents such as DMSO, alcohol solvents such as methanol, ethanol, 2-propanol, butanol, octanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and 2,2,2-trifluoroethanol, halogenated solvents such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, and o-DCB, triethylamine, nitromethane, and water, which may be mixed in any ratio. From the viewpoint of high reaction yield, ether solvents, aromatic hydrocarbon solvents, triethylamine, and water are preferred, and THF, 1,4-dioxane, toluene, triethylamine, and water are more preferred as single solvents or as mixed solvents in any ratio.

[0297] Production method (D) can be carried out at a temperature appropriately selected from 0°C to 180°C, and is preferably carried out at a temperature appropriately selected from 20°C to 130°C in terms of good yield.

[0298] The fused ring-fused chalcogenadiazole compound (1f) can be obtained by carrying out a conventional treatment after completion of Production Method (D), and may be purified, if necessary, by any conventional means used by those skilled in the art for purifying organic compounds, such as washing, precipitation, filtration, dialysis, recrystallization, column chromatography, preparative HPLC, or Soxhlet extraction.

[0299] The fused ring chalcogenadiazole compound (1f) obtained by the production method (D) includes compounds represented by the formulas (1-1-20) to (1-1-25), (1-1-29) to (1-1-34), (1-1-41) to (1-1-55), (1-1-60) to (1-1-64), (1-1-66) to (1-1-70), (1-1-71) and (1-1-72). 2) to (1-1-76), (1-1-78) to (1-1-82), (1-1-84) to (1-1-88), (1-1-90) to (1-1-97), (1-1-8-n6), (1-1-9-n6), (1-1-10-n6), (1-1-11-n6), (1-1-12-n6), (1-1-13-n6) , (1-1-14-m6), (1-1-15-m6), (1-1-16-m6), (1-1-26-n6), (1-1-27-n6), (1-1-28- n6), (1-1-35-n6), (1-1-36-n6), (1-1-37-n6), (1-1-38-n6), (1-1-39-n6), (1-1-4 Examples include (1-1-0-n6), (1-1-59-n6), (1-1-65-n6), (1-1-71-n6), (1-1-77-n6), (1-1-83-n6), (1-1-89-n6), (2-1-10), (2-1-21), (2-1-22), (2-1-8-n6), and (2-1-9-n6).

[0300] Next, a film-forming composition containing the fused ring chalcogenadiazole compound (1) according to one embodiment of the present invention (hereinafter referred to as the "film-forming composition according to the present invention") will be described.

[0301] In the film-forming composition according to the present invention, it is preferable that the fused ring chalcogenadiazole compound (1) contains a solvent.

[0302] The solvent is not particularly limited as long as it can dissolve or disperse the fused ring chalcogenadiazole compound (1) in the solvent. Examples of the solvent include ether solvents such as diisopropyl ether, dibutyl ether (CPME), THF, 2-methyltetrahydrofuran, 1,4-dioxane, and dimethoxyethane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, and tetralin; carbonate ester solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and 4-fluoroethylene carbonate; ethyl acetate, butyl acetate, methyl propionate, and ethyl propionate. Examples of suitable solvents include ester solvents such as methyl butyrate and γ-lactone, amide solvents such as DMF, DMAc, and NMP, urea solvents such as TMU and DMPU, sulfoxide solvents such as DMSO, alcohol solvents such as methanol, ethanol, 2-propanol, butanol, octanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and 2,2,2-trifluoroethanol, halogenated solvents such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, and o-DCB, nitromethane, water, etc. These may be mixed in any ratio. Aromatic hydrocarbons and halogenated solvents are preferred because of their high boiling points and mild volatility, and toluene, xylene, mesitylene, cyclohexylbenzene, tetralin, anisole, 3,4-dimethylanisole, chlorobenzene, and o-DCB are more preferred.

[0303] There is no particular limitation on the amount of solvent used, and the solvent is added so that the concentration of fused ring chalcogenadiazole compound (1) is preferably 0.001 to 95% by weight, more preferably 0.01 to 30% by weight.

[0304] The dissolution or dispersion may be carried out by any method well known to those skilled in the art, such as stirring, shaking, ball milling, etc. Heating may be performed during this process.

[0305] The film-forming composition of the present invention may contain a binder to improve film-forming properties. Examples of such binders include polymers such as polystyrene, poly-α-methylstyrene, polyvinylnaphthalene, poly(ethylene-co-norbornene), polymethyl methacrylate, polytriarylamine, and poly(9,9-dioctylfluorene-co-dimethyltriphenylamine). There are no particular restrictions on the concentration of the binder, but a concentration of 0.1 to 10.0 wt % is preferred in terms of good coatability.

[0306] The film-forming composition according to the present invention can be produced, for example, by dissolving or dispersing the fused ring chalcogenadiazole compound (1) in a solvent.

[0307] Next, an organic thin film containing the fused ring chalcogenadiazole compound (1) according to one embodiment of the present invention (hereinafter referred to as "organic thin film according to the present invention") will be described.

[0308] There is no particular limitation on the thickness of the organic thin film according to the present invention, but in terms of high carrier mobility, it is preferably 1 nm to 1000 nm, more preferably 10 nm to 500 nm.

[0309] The organic thin film according to the present invention can be produced by forming a film using the film-forming composition according to the present invention and then drying the solvent. The film-forming method is not particularly limited, and examples thereof include simple coating methods such as spin coating, drop casting, dip coating, and cast coating, and printing methods such as dispenser, inkjet, slit coating, blade coating, flexographic printing, screen printing, gravure printing, and offset printing. Among these, spin coating, drop casting, and inkjet are preferred in terms of efficient film formation.

[0310] The drying temperature is preferably 20 to 150° C., particularly preferably 20 to 80° C. If necessary, annealing may be carried out at a temperature appropriately selected from the range of 40 to 400° C.

[0311] An organic transistor element including a fused ring chalcogenadiazole compound (1) according to one embodiment of the present invention (hereinafter referred to as "organic transistor element according to the present invention") will be described.

[0312] Figure 1 shows the structure of an organic transistor element according to the present invention, where (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 transistor element, and 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.

[0313] Examples of substrates include plastic substrates such as 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, and cellulose triacetate; inorganic substrates such as glass, quartz, aluminum oxide, silicon, hydrodoped silicon, silicon oxide, tantalum dioxide, tantalum pentoxide, and indium tin oxide; and metal substrates such as gold, copper, chromium, titanium, and aluminum. In terms of good transistor performance, glass, silicon, and hydrodoped silicon are preferred, and glass is more preferred.

[0314] Examples of the gate electrode include inorganic electrodes such as aluminum, gold, silver, copper, highly doped silicon, tin oxide, indium oxide, indium tin oxide, chromium, titanium, tantalum, chromium, graphene, and carbon nanotubes, and organic electrodes such as doped conductive polymers (PEDOT-PSS). Inorganic electrodes are preferred because of their good conductivity, and gold and silver are more preferred.

[0315] Examples of insulating layers include inorganic insulating layers 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; and organic insulating layers such as 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, polycyclopentane, polycyclohexane-ethylene copolymer, polyfluorinated cyclopentane, Cytop™, polyfluorinated cyclohexane, polyfluorinated cyclohexane-ethylene copolymer, Parylene N™, Parylene C™, Parylene D™, Parylene HT™, and Parylene C-UVF™. In view of their excellent insulating properties, organic insulating layers are preferred, with parylene C being more preferred. Furthermore, the surfaces of these insulating layers may be modified with, for example, silanes such as octadecyltrichlorosilane, decyltrichlorosilane, decyltrimethoxysilane, octyltrichlorosilane, octadecyltrimethoxysilane, β-phenethyltrichlorosilane, β-phenethyltrimethoxysilane, phenyltrichlorosilane, and phenyltrimethoxysilane; phosphonic acids such as octadecylphosphonic acid, decylphosphonic acid, and octylphosphonic acid; and amines such as hexamethyldisilazane. In view of improving the carrier mobility and current on-off ratio of the organic transistor element according to the present invention and reducing the threshold voltage, octadecyltrichlorosilane, octyltrichlorosilane, β-phenethyltrichlorosilane, octadecylphosphonic acid, octylphosphonic acid, and hexamethyldisilazane are preferred.

[0316] As the source electrode and the drain electrode, electrodes similar to those exemplified for the gate electrode can be exemplified. In terms of good conductivity, inorganic electrodes are preferable, and gold is more preferable. Further, in order to improve the carrier injection efficiency, surface treatment can be performed on these electrodes using a surface treatment material. Examples of such a surface treatment material include benzenethiol, pentafluorobenzenethiol, and the like.

[0317] The organic transistor element according to the present invention is obtained by forming an organic thin film according to 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.

Example

[0318] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

[0319] The compound obtained in the example was 1 structurally analyzed by 1H-NMR measurement. Commercially available products were used as reagents. <NMR measurement conditions> Measuring device: Bruker ASCEND TM ADVANCE III HD (400 MHz) Measuring solvent: deuterated chloroform (CDCl3) Internal standard substance: tetramethylsilane (TMS) <TGA measurement conditions> Measuring device: SII Corporation EXSTAR6000 TGA / DTA6200 Sample container: aluminum pan Measurement atmosphere: nitrogen T d3 、T d5 and T d10 represent the 3%, 5%, and 10% weight loss temperatures, respectively. <DSC measurement conditions> Measuring device: SII Corporation EXSTAR6000 DSC6220 Sample container: aluminum pan Measurement conditions: Nitrogen atmosphere, 10 °C / min, 0 to 300 °C, results adopt the second Heating Scan. <CV measurement conditions> Measuring device: VSP-300 from BioLogic Working electrode: Glassy carbon (φ = 3 mm) Counter electrode: Platinum wire (φ = 0.5 mm) Reference electrode: Platinum wire (φ = 0.5 mm) Internal standard substance: Ferrocene / ferricenium (Fc / Fc + ) Electrolyte: 0.10 M tetrabutylammonium tetrafluoroborate (Bu4NBF4) / dichloromethane solution Concentration of the measured compound: 1 g / L using the above electrolyte as the solvent.

[0320] Scanning speed: 100 mV / s A reversible cyclic voltammogram was obtained under the above conditions. The oxidation-reduction potential E sample (V vs.Fc / Fc + ) is obtained from the half-potentials of the oxidation peak and reduction peak of the voltammogram corrected with the horizontal axis being Fc / Fc + , and the LUMO level E LUMO is calculated by Equation (1) assuming that the oxidation-reduction potential of Fc / Fc + is -5.07 eV with respect to the vacuum level.

[0321] E LUMO =-5.07 - E sample (1) [Reference Example 1]

[0322]

Chemical formula

[0323] To a mixture of methyl 3,4-diaminobenzoate (6.00 g, 36.1 mmol), triethylamine (20.0 mL, 144 mmol), and dichloromethane (200 mL), thionyl chloride (5.20 mL, 71.7 mmol) was added and the mixture was refluxed for 4.5 hours. The resulting mixture was cooled to 0 °C, saturated aqueous sodium bicarbonate was added, and the mixture was extracted with chloroform. The combined organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 3 / 2 → 0 / 1) to yield methyl benzo[c][1,2,5]thiadiazole-5-carboxylate (4.98 g, 71%) as a white solid. 1 H-NMR (CDCl3,400MHz)δ(ppm):8.75(dd,J=1.6,0.83Hz,1H),8.21(dd,J=9.2,1.6Hz,1H),8.05(dd,J=9.2,0.83Hz,1H),4.02(s,3H). [Reference example 2]

[0324] [ka]

[0325] To a mixture of 2,2,6,6-tetramethylpiperidine (960 μL, 5.64 mmol) and THF (5.6 mL), 1.56 M n-butyllithium n-hexane solution (3.60 mL, 5.62 mmol) was added at -40 °C and stirred at the same temperature for 30 minutes. Then, 1.0 M 2,2,6,6-tetramethylpiperidinylmagnesium chloride lithium chloride complex THF / toluene solution (5.70 mL, 5.70 mmol) was added and stirred at 0 °C for 30 minutes and then at room temperature for 1 hour. The solvent was evaporated under reduced pressure, and THF (8.0 mL) was added to prepare a TMP2Mg·2LiCl solution.

[0326] To a mixture of methyl benzo[c][1,2,5]thiadiazole-5-carboxylate (1.00 g, 5.15 mmol) synthesized in Reference Example 1 and THF (32 mL), TMP2Mg·2LiCl solution was added at −40°C and stirred for 1.5 hours. Then, under an argon stream, 1.0 M zinc chloride THF solution (6.20 mL, 6.20 mmol), bis(dibenzylideneacetone)palladium(0) (60 mg, 104 μmol), tri(2-furyl)phosphine (48 mg, 208 μmol), and iodobenzene (860 μL, 7.71 mmol) were added and stirred at 70°C for 18 hours. The resulting mixture was cooled to 0°C, saturated aqueous ammonium chloride solution was added, and the mixture was extracted with chloroform. The combined organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by silica gel column chromatography (chloroform) to obtain methyl 4-phenylbenzo[c][1,2,5]thiadiazole-5-carboxylate (1.22 g, 88%) as an orange yellow solid. 1 H-NMR(CDCl3,400MHz)δ(ppm):8.03(m,2H),7.55-7.44(m,5H),3.67(s,3H). [Reference example 3]

[0327] [ka]

[0328] To a mixture of 2,2,6,6-tetramethylpiperidine (960 μL, 5.64 mmol) and THF (5.6 mL), 1.56 M n-butyllithium n-hexane solution (3.60 mL, 5.62 mmol) was added at -40 °C and stirred at the same temperature for 30 minutes. Then, 1.0 M 2,2,6,6-tetramethylpiperidinylmagnesium chloride lithium chloride complex THF / toluene solution (5.70 mL, 5.70 mmol) was added and stirred at 0 °C for 30 minutes and then at room temperature for 1 hour. The solvent was evaporated under reduced pressure, and THF (8.0 mL) was added to prepare a TMP2Mg·2LiCl solution.

[0329] To a mixture of methyl benzo[c][1,2,5]thiadiazole-5-carboxylate (1.00 g, 5.15 mmol) synthesized in Reference Example 1 and THF (32 mL), TMP2Mg·2LiCl solution was added at −40°C and stirred for 1.5 hours. Then, under an argon stream, 1.0 M zinc chloride THF solution (6.20 mL, 6.20 mmol), bis(dibenzylideneacetone)palladium(0) (60 mg, 104 μmol), tri(2-furyl)phosphine (48 mg, 208 μmol), and 4-tert-butyliodobenzene (1.37 mL, 7.73 mmol) were added and stirred at 70°C for 18 hours. The resulting mixture was cooled to 0°C, saturated aqueous ammonium chloride solution was added, and the mixture was extracted with chloroform. The combined organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 1 / 2 → 0 / 1) to give methyl 4-(4-(tert-butyl)phenyl)benzo[c][1,2,5]thiadiazole-5-carboxylate (1.06 g, 63%) as a pale yellow solid. 1 H-NMR (CDCl3,400MHz)δ(ppm):8.03(m,2H),7.53(d,J=8.4Hz,2H),7.44(d,J=8.4Hz,2H),3.67(s,3H),1.39(s,9H). [Reference example 4]

[0330] [ka]

[0331] To a mixture of 2,2,6,6-tetramethylpiperidine (960 μL, 5.64 mmol) and THF (5.6 mL), 1.56 M n-butyllithium n-hexane solution (3.60 mL, 5.62 mmol) was added at -40 °C and stirred at the same temperature for 30 minutes. Then, 1.0 M 2,2,6,6-tetramethylpiperidinylmagnesium chloride lithium chloride complex THF / toluene solution (5.70 mL, 5.70 mmol) was added and stirred at 0 °C for 30 minutes and then at room temperature for 1 hour. The solvent was evaporated under reduced pressure, and THF (8.0 mL) was added to prepare a TMP2Mg·2LiCl solution.

[0332] To a mixture of methyl benzo[c][1,2,5]thiadiazole-5-carboxylate (1.00 g, 5.15 mmol) synthesized in Reference Example 1 and THF (32 mL), TMP2Mg·2LiCl solution was added at −40°C and stirred for 1.5 hours. Then, under an argon stream, 1.0 M zinc chloride THF solution (6.20 mL, 6.20 mmol), bis(dibenzylideneacetone)palladium(0) (60 mg, 104 μmol), tri(2-furyl)phosphine (48 mg, 208 μmol), and 4-hexylbromobenzene (1.75 mL, 8.56 mmol) were added and stirred at 70°C for 2 days. The resulting mixture was cooled to 0°C, saturated aqueous ammonium chloride solution was added, and the mixture was extracted with chloroform. The combined organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane / chloroform=1 / 1→0 / 1) to obtain methyl 4-(4-hexylphenyl)benzo[c][1,2,5]thiadiazole-5-carboxylate (1.29 g, 71%) as an orange liquid. 1 H-NMR(CDCl3,400MHz)δ(ppm):8.00(m,2H),7.41(d,J=8.2Hz,2H),7.32(d,J=8.2Hz, 2H),3.68(s,3H),2.70(t,J=7.8Hz,2H),1.70(m,2H),1.45-1.28(m,6H),0.90(m,3H). [Reference example 5]

[0333] [ka]

[0334] To a mixture of 2,2,6,6-tetramethylpiperidine (972 μL, 5.71 mmol) and THF (5.7 mL), 1.56 M n-butyllithium n-hexane solution (3.67 mL, 5.73 mmol) was added at -40 °C and stirred at the same temperature for 30 minutes. Then, 1.0 M 2,2,6,6-tetramethylpiperidinylmagnesium chloride lithium chloride complex THF / toluene solution (5.70 mL, 5.70 mmol) was added and stirred at 0 °C for 30 minutes and then at room temperature for 1 hour. The solvent was removed from the resulting mixture under reduced pressure, and THF (8.0 mL) was added to prepare a TMP2Mg·2LiCl solution.

[0335] To a mixture of methyl benzo[c][1,2,5]thiadiazole-5-carboxylate (1.00 g, 5.15 mmol) synthesized in Reference Example 1 and THF (32 mL), TMP2Mg·2LiCl solution was added at −40°C and stirred for 1.5 hours. Then, under an argon stream, 1.0 M zinc chloride THF solution (6.20 mL, 6.20 mmol), bis(dibenzylideneacetone)palladium(0) (47 mg, 81.7 μmol), tri(2-furyl)phosphine (31 mg, 134 μmol), and 4-dodecylbromobenzene (2.10 mL, 6.97 mmol) were added and stirred at 70°C for 18 hours. The resulting mixture was cooled to 0°C, saturated aqueous ammonium chloride solution was added, and the mixture was extracted with chloroform. The combined organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane / chloroform=4 / 1) to obtain methyl 4-(4-dodecylphenyl)benzo[c][1,2,5]thiadiazole-5-carboxylate (1.51 g, 67%) as an orange liquid. 1H-NMR(CDCl3,400MHz)δ(ppm):8.00(m,2H),7.40(d,J=8.2Hz,2H),7.32(d,J=8.2Hz,2H) ,3.68(s,3H),2.69(dd,J=8.0,7.6Hz,2H),1.69(m,2H),1.42-1.21(m,18H),0.88(m,3H). [Reference example 6]

[0336] [ka]

[0337] Potassium hydroxide (4.04 g, 72.0 mmol) was dissolved in a mixed solvent of ethanol (40 mL) and water (40 mL), and then 4-amino-3-nitrobenzoic acid (5.46 g, 30.0 mmol) was added and stirred at 70 °C for 2 hours. A 13 wt% aqueous solution of sodium hypochlorite (160 mL) was added to the reaction solution cooled to 0 °C and stirred at room temperature for 21 hours. After cooling the reaction solution to 0 °C, water (70 mL), 6.0 M aqueous hydrochloric acid (30 mL), and sodium chloride (3.80 g) were added. The organic layer obtained by extracting the reaction solution with chloroform was washed with saturated brine, dried over anhydrous sodium sulfate, and filtered. The solvent was evaporated under reduced pressure to give a yellow solid (4.80 g).

[0338] The resulting solid was dissolved in ethanol (75 mL), triethyl phosphite (7.80 mL, 45.1 mmol) was added, and the mixture was refluxed for 6 hours. The reaction solution was cooled to 0°C, and water (40 mL) and 6.0 M aqueous hydrochloric acid solution (2.0 mL) were added. The reaction solution was then extracted with chloroform, and the resulting organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and filtered. The solvent was then distilled off under reduced pressure to obtain a crude product as a brown liquid.

[0339] To a mixture of the obtained crude product and methanol (60 mL), concentrated sulfuric acid (1.6 mL) was added and stirred at 80 °C for 3 hours. Next, the reaction solution was diluted with chloroform, and the organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 2 / 1 → 3 / 2) to give methyl benzo[c][1,2,5]oxadiazole-5-carboxylate (4.30 g, 80%) as a colorless solid. 1 H-NMR (CDCl3,400MHz)δ(ppm):8.64(t,J=1.2Hz,1H),8.02(dd,J=9.4,1.2Hz,1H),7.91(dd,J=9.4,1.2Hz,1H),4.01(s,3H). [Reference example 7]

[0340] [ka]

[0341] To a mixture of 2,2,6,6-tetramethylpiperidine (1.05 mL, 6.17 mmol) and THF (6.2 mL), 1.56 M n-butyllithium n-hexane solution (4.00 mL, 6.24 mmol) was added at -40 °C and stirred at the same temperature for 30 minutes. Then, 1.0 M 2,2,6,6-tetramethylpiperidinylmagnesium chloride lithium chloride complex THF / toluene solution (6.20 mL, 6.20 mmol) was added and stirred at 0 °C for 30 minutes and then at room temperature for 1 hour. The solvent was evaporated under reduced pressure, and THF (10 mL) was added to prepare a TMP2Mg·2LiCl solution.

[0342] To a mixture of methyl benzo[c][1,2,5]oxadiazole-5-carboxylate (920 mg, 5.16 mmol) synthesized in Reference Example 6 and THF (32 mL), TMP2Mg·2LiCl solution was added at −40°C and stirred for 1.5 hours. Then, under an argon atmosphere, 1.0 M zinc chloride THF solution (6.80 mL, 6.80 mmol), bis(dibenzylideneacetone)palladium(0) (60 mg, 104 μmol), tri(2-furyl)phosphine (48 mg, 208 μmol), and 4-hexylbromobenzene (1.27 mL, 6.21 mmol) were added and stirred at 70°C for 17 hours. The resulting mixture was cooled to 0°C, saturated aqueous ammonium chloride solution was added, and the mixture was extracted with chloroform. The combined organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform=1 / 1→0 / 1) to obtain methyl 4-(4-hexylphenyl)benzo[c][1,2,5]oxadiazole-5-carboxylate (904 mg, 52%) as an orange liquid. 1 H-NMR(CDCl3,400MHz)δ(ppm):7.84(d,J=9.3Hz,1H),7.74(d,J=9.3Hz,1H),7.46(d,J=8.2Hz,2H),7. 31(d,J=8.2Hz,2H),3.70(s,3H),2.69(t,J=7.8Hz,2H),1.68(m,2H),1.42-1.28(m,6H),0.91(m,3H). [Reference example 8]

[0343] [ka]

[0344] To a mixture of 2,2,6,6-tetramethylpiperidine (1.30 mL, 7.64 mmol) and THF (7.6 mL), 1.56 M n-butyllithium n-hexane solution (4.90 mL, 7.64 mmol) was added at -40 °C and stirred at the same temperature for 30 minutes. Then, 1.0 M 2,2,6,6-tetramethylpiperidinylmagnesium chloride lithium chloride complex THF / toluene solution (7.60 mL, 7.60 mmol) was added and stirred at 0 °C for 30 minutes, then at room temperature for 1 hour. The solvent was evaporated under reduced pressure, and THF (8.0 mL) was added to prepare a TMP2Mg·2LiCl solution.

[0345] To a mixture of methyl benzo[c][1,2,5]thiadiazole-5-carboxylate (1.35 g, 6.95 mmol) synthesized in Reference Example 1 and THF (54 mL), TMP2Mg·2LiCl solution was added at −40°C and stirred for 1.5 hours. Then, under an argon stream, 1.0 M zinc chloride THF solution (8.40 mL, 8.40 mmol), bis(dibenzylideneacetone)palladium(0) (38 mg, 66.1 μmol), tri(2-furyl)phosphine (32 mg, 138 μmol), and 1-bromo-4-iodobenzene (1.97 g, 6.96 mmol) were added and stirred at 70°C for 14 hours. The resulting mixture was cooled to 0°C, saturated aqueous ammonium chloride solution was added, and the mixture was extracted with chloroform. The combined organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform=2 / 1→0 / 1) to obtain methyl 4-(4-bromophenyl)benzo[c][1,2,5]thiadiazole-5-carboxylate (1.97 g, 81%) as a pale yellow solid. 1 H-NMR(CDCl3,400MHz)δ(ppm):8.05(m,2H),7.64(d,J=8.5Hz,2H),7.35(d,J=8.5Hz,2H),3.72(s,3H). [Example 1]

[0346] [ka]

[0347] Trifluoromethanesulfonic acid (610 μL, 6.89 mmol) was added to a mixture of methyl 4-phenylbenzo[c][1,2,5]thiadiazole-5-carboxylate (374 mg, 1.38 mmol) synthesized in Reference Example 2 and 1,2-dichloroethane (23 mL), and the mixture was refluxed for 17 hours. The resulting mixture was cooled to 0°C, and then saturated aqueous sodium bicarbonate solution was added and extracted with chloroform. The collected organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 1 / 3) to give compound (1-1-1) (180 mg, 55%) as an orange solid. 1 H-NMR(CDCl3,400MHz)δ(ppm):8.18(d,J=7.3Hz,1H),7.97(d,J=8.8Hz,1H),7.87(d, J=8.8Hz,1H),7.69(m,1H),7.58(dt,J=7.5,1.0Hz,1H),7.37(dt,J=7.5,1.0Hz,1H). [Example 2]

[0348] [ka]

[0349] Malononitrile (118 mg, 1.79 mmol) was added to a mixture of compound (1-1-1) (200 mg, 839 μmol) synthesized in Example 1, aluminum oxide (840 mg), and THF (8.4 mL), and the mixture was refluxed for 10 minutes. The resulting mixture was filtered, and the solvent was then distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (chloroform) to obtain compound (1-2-1) (208 mg, 87%) as a dark green solid. 1H-NMR(CDCl3,400MHz)δ(ppm):8.61(d,J=9.3Hz,1H),8.42(d,J=7.6Hz,1H),8.34(d,J=7.6 Hz,1H),7.98(d,J=9.3Hz,1H),7.60(dt,J=7.6,0.80Hz,1H),7.40(dt,J=7.6,0.80Hz,1H). T d3 :212℃, T d5 :240℃, T d10 :259℃. Phase transition temperature: None. LUMO level: -4.16 eV. [Example 3]

[0350] [ka]

[0351] Bromine (25 μL, 485 μmol) was added to a mixture of compound (1-1-1) (100 mg, 420 μmol) synthesized in Example 1, 30% hydrogen bromide-acetic acid solution (1.0 mL), and chloroform (2.0 mL), and the mixture was refluxed for 4 hours. The resulting mixture was cooled to 0°C, and then saturated aqueous sodium bicarbonate and 10 wt% aqueous sodium thiosulfate were added, followed by extraction with chloroform. The collected organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then filtered. The solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 2 / 1 → 1 / 9) to yield compound (1-1-2) (108 mg, 81%) as an orange-yellow solid. 1 H-NMR(CDCl3,400MHz)δ(ppm):8.17(d,J=7.3Hz,1H),8.11(s,1H),7.70(d,J=7 .3Hz,1H),7.59(ddd,J=7.6,7.4,1.0Hz,1H),7.41(ddd,J=7.6,7.4,1.0Hz,1H). [Example 4]

[0352] [ka]

[0353] To a mixture of compound (1-1-2) (50 mg, 158 μmol) synthesized in Example 3, 4-cyanophenylboronic acid (35 mg, 235 μmol), 1,4-dioxane (2.0 mL), and 2.0 M aqueous potassium carbonate (1.0 mL), tetrakis(triphenylphosphine)palladium(0) (9.2 mg, 7.96 μmol) was added under an argon atmosphere, and the mixture was stirred at 105°C for 1 hour. After cooling the resulting mixture to 0°C, the reaction solution was diluted with chloroform. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then filtered. The solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (chloroform) to yield compound (1-1-95) (52 mg, 96%) as a pink solid. 1 H-NMR(CDCl3,400MHz)δ(ppm):8.24(d,J=7.3Hz,1H),8.11(d,J=8.3Hz,2H),8.04(s,1H), 7.84(d,J=8.3Hz,2H),7.72(d,J=7.3Hz,1H),7.63(t,J=7.3Hz,1H),7.42(t,J=7.3Hz,1H). [Example 5]

[0354] [ka]

[0355] Malononitrile (10 mg, 151 μmol) was added to a mixture of the compound (1-1-95) (43 mg, 126 μmol) synthesized in Example 4, aluminum oxide (260 mg), and THF (2.6 mL), and the mixture was refluxed for 15 minutes. The resulting mixture was filtered, and the solvent was then distilled off under reduced pressure. The resulting residue was purified by recrystallization (1,2-dichloroethane) to give the compound (1-2- 95 ) (38 mg, 78%) was obtained. 1H-NMR(CDCl3,400MHz)δ(ppm):8.81(s,1H),8.46(d,J=7.5Hz,1H),8.40(d,J=7.5Hz,1H), 8.12(d,J=8.5Hz,2H),7.86(d,J=8.5Hz,2H),7.64(t,J=7.8Hz,1H),7.45(t,J=7.8Hz,1H). T d3 :325℃, T d5 :334℃, T d10 :359℃. Phase transition temperature: None. LUMO level: -4.21 eV. [Example 6]

[0356] [ka]

[0357] Trifluoromethanesulfonic acid (1.27 mL, 14.4 mmol) was added to a mixture of methyl 4-(4-(tert-butyl)phenyl)benzo[c][1,2,5]thiadiazole-5-carboxylate (937 mg, 2.87 mmol) synthesized in Reference Example 3 and 1,2-dichloroethane (30 mL), and the mixture was refluxed for 20 hours. The resulting mixture was cooled to 0°C, and then saturated aqueous sodium bicarbonate solution was added, followed by extraction with chloroform. The collected organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 2 / 1 → 0 / 1) to obtain compound (1-1-48) (810 mg, 95%) as an orange solid. 1 H-NMR(CDCl3,400MHz)δ(ppm):8.07(dd,J=7.7,0.48Hz,1H),7.94(d,J=8.8Hz,1H),7.86 (d,J=8.8Hz,1H),7.76(dd,J=1.8,0.48Hz,1H),7.59(dd,J=7.7,1.8Hz,1H),1.38(S,9H). [Example 7]

[0358] [ka]

[0359] Malononitrile (52 mg, 792 μmol) was added to a mixture of compound (1-1-48) (201 mg, 684 μmol) synthesized in Example 6, aluminum oxide (700 mg), and THF (7.0 mL), and the mixture was refluxed for 15 minutes. The resulting mixture was filtered, and the solvent was then distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (chloroform / methanol = 2 / 1) to obtain compound (1-2-48) (173 mg, 74%) as a brown solid. 1 H-NMR(CDCl3,400MHz)δ(ppm):8.59(d,J=9.3Hz,1H),8.52(d,J=1.6Hz,1H),8.21 (d,J=7.9Hz,1H),7.94(d,J=9.3Hz,1H),7.60(dd,J=7.9,1.6Hz,1H),1.40(s,9H). T d3 :248℃, T d5 :262℃, T d10 :284℃. Phase transition temperature: None. LUMO level: -4.11 eV. [Example 8]

[0360] [ka]

[0361] Bromine (42 μL, 815 μmol) was added to a mixture of compound (1-1-48) (200 mg, 679 μmol) synthesized in Example 6, 30% hydrogen bromide-acetic acid solution (1.5 mL), and chloroform (3.0 mL), and the mixture was refluxed for 1.5 hours. The resulting mixture was cooled to 0°C, and saturated aqueous sodium bicarbonate and 10 wt% aqueous sodium thiosulfate were added, followed by extraction with chloroform. The combined organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then filtered. The solvent was removed under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 2 / 1 → 1 / 9) to yield compound (1-1-100) (235 mg, 93%) as an orange solid. 1 H-NMR (CDCl3,400MHz)δ(ppm):8.09(s,1H),8.04(d,J=7.8Hz,1H),7.75(d,J=1.7Hz,1H),7.59(dd,J=7.8,1.7Hz,1H),1.37(s,9H). [Example 9]

[0362] [ka]

[0363] To a mixture of compound (1-1-100) (185 mg, 496 μmol) synthesized in Example 8, 4-cyanophenylboronic acid (111 mg, 754 μmol), 1,4-dioxane (6.6 mL), and 2.0 M aqueous potassium carbonate (3.3 mL) was added tetrakis(triphenylphosphine)palladium(0) (29 mg, 24.7 μmol) under an argon atmosphere and stirred at 110 °C for 1 hour. After cooling the resulting mixture to 0 °C, the reaction solution was diluted with chloroform, and the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 2 / 1 → 1 / 3) to yield compound (1-1-61) (140 mg, 72%) as a red solid. 1H-NMR(CDCl3,400MHz)δ(ppm):8.11(d,J=8.6Hz,1H),8.02(s,1H),7.83(d,J=8.7Hz ,2H),7.78(m,2H),7.69(d,J=8.6Hz,1H),7.62(dd,J=7.8,1.9Hz,1H),1.39(s,9H). [Example 10]

[0364] [ka]

[0365] Malononitrile (21 mg, 315 μmol) was added to a mixture of compound (1-1-61) (100 mg, 253 μmol) synthesized in Example 9, aluminum oxide (500 mg), and THF (5.0 mL), and the mixture was refluxed for 15 minutes. The resulting mixture was filtered, and the solvent was then distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (chloroform) to obtain compound (1-2-61) (71 mg, 63%) as a green solid. 1 H-NMR(CDCl3,400MHz)δ(ppm):8.76(s,1H),8.54(d,J=1.5Hz,1H),8.24(d,J=7.9Hz,1H) ,8.11(d,J=8.5Hz,2H),7.84(d,J=8.5Hz,2H),7.63(dd,J=7.9,1.5Hz,1H),1.39(s,9H). T d3 :270℃, T d5 :322℃, T d10 :356℃. Phase transition temperature: 252℃. LUMO level: -4.17 eV. [Example 11]

[0366] [ka]

[0367] Trifluoromethanesulfonic acid (1.60 mL, 18.1 mmol) was added to a mixture of methyl 4-(4-hexylphenyl)benzo[c][1,2,5]thiadiazole-5-carboxylate (1.26 g, 3.55 mmol) synthesized in Reference Example 4 and 1,2-dichloroethane (36 mL), and the mixture was refluxed for 1 day. The resulting mixture was cooled to 0°C, saturated aqueous sodium bicarbonate solution was added, and the mixture was extracted with chloroform. The collected organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then filtered. The solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 1 / 1 → 0 / 1) to obtain compound (1-1-9-n6) (861 mg, 75%) as an orange solid. 1 H-NMR(CDCl3,400MHz)δ(ppm):8.05(d,J=7.5Hz,1H),7.93(d,J=8.8Hz,1H),7.84(d,J=8.8Hz,1H),7.51(d,J =1.4Hz,1H),7.36(dd,J=7.5,1.4Hz,1H),2.67(t,J=7.7Hz,2H),1.66(m,2H),1.40-1.28(m,6H),0.89(m,3H). [Example 12]

[0368] [ka]

[0369] Malononitrile (52 mg, 792 μmol) was added to a mixture of compound (1-1-9-n6) (203 mg, 630 μmol) synthesized in Example 11, aluminum oxide (630 mg), and THF (6.3 mL), and the mixture was refluxed for 15 minutes. The resulting mixture was filtered, and the solvent was then distilled off under reduced pressure. The resulting residue was purified by recrystallization (chloroform / methanol = 1 / 1) to obtain compound (1-2-9-n6) (197 mg, 84%) as a brown solid. 1H-NMR(CDCl3,400MHz)δ(ppm):8.55(d,J=9.3Hz,1H),8.20(s,1H),8.18(d,J=7.6Hz,1H),7.91(d,J=9 .3Hz,1H),7.37(d,J=7.6Hz,1H),2.69(t,J=7.8Hz,2H),1.67(m,2H),1.42-1.28(m,6H),0.90(m,3H). LUMO level: -4.11 eV. [Example 13]

[0370] [ka]

[0371] Trifluoromethanesulfonic acid (1.48 mL, 16.7 mmol) was added to a mixture of methyl 4-(4-dodecylphenyl)benzo[c][1,2,5]thiadiazole-5-carboxylate (1.46 g, 3.33 mmol) synthesized in Reference Example 5 and 1,2-dichloroethane (40 mL), and the mixture was refluxed for 20 hours. The resulting mixture was cooled to 0°C, saturated aqueous sodium bicarbonate solution was added, and the mixture was extracted with chloroform. The collected organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 4 / 1) to obtain compound (1-1-9-n12) (992 mg, 73%) as an orange solid. 1 H-NMR(CDCl3,400MHz)δ(ppm):8.06(d,J=7.5Hz,1H),7.93(d,J=8.8Hz,1H),7.85(d,J=8.8Hz,1H),7.52(d,J=1. 4Hz,1H),7.37(dd,J=7.5,1.4Hz,1H),2.67(dd,J=7.9,7.6Hz,2H),1.65(m,2H),1.39-1.20(m,18H),0.87(m,3H). [Example 14]

[0372] [ka]

[0373] Malononitrile (71 mg, 1.08 mmol) was added to a mixture of compound (1-1-9-n12) (198 mg, 488 μmol) synthesized in Example 13, aluminum oxide (1.09 g), and THF (10 mL), and the mixture was refluxed for 30 minutes. The resulting mixture was filtered, and the solvent was then distilled off under reduced pressure. The resulting residue was purified by recrystallization (hexane / ethyl acetate = 10 / 1) to give compound (1-2-9-n12) (111 mg, 50%) as a dark brown solid. 1 H-NMR(CDCl3,400MHz)δ(ppm):8.57(d,J=9.3Hz,1H),8.22(d,J=1.0Hz,1H),8.20(d,J=7.6Hz,1H),7.93(d,J= 9.3Hz,1H),7.38(dd,J=7.6,1.0Hz,1H),2.69(t,J=7.7Hz,2H),1.67(m,2H),1.41-1.20(m,18H),0.87(m,3H). LUMO level: -4.12 eV. [Example 15]

[0374] [ka]

[0375] Bromine (160 μL, 3.11 mmol) was added to a mixture of compound (1-1-9-n6) (500 mg, 1.55 mmol) synthesized in Example 11, 30% hydrogen bromide-acetic acid solution (3.0 mL), and chloroform (6.0 mL), and the mixture was refluxed for 1 hour. The resulting mixture was cooled to 0°C, and then saturated aqueous sodium bicarbonate and 10 wt% aqueous sodium thiosulfate were added, followed by extraction with chloroform. The collected organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then filtered. The solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 2 / 1 → 1 / 4) to yield compound (1-1-98-n6) (582 mg, 94%) as an orange solid. 1H-NMR(CDCl3,400MHz)δ(ppm):8.08(s,1H),8.03(d,J=7.5Hz,1H),7.52(d,J=1.3Hz,1H),7.3 8(dd,J=7.5,1.3Hz,1H),2.66(t,J=7.7Hz,2H),1.65(m,2H),1.40-1.27(m,6H),0.89(m,3H). [Example 16]

[0376] [ka]

[0377] To a mixture of compound (1-1-98-n6) (500 mg, 1.25 mmol) synthesized in Example 15, 4-cyanophenylboronic acid (278 mg, 1.89 mmol), 1,4-dioxane (20 mL), and 2.0 M aqueous potassium carbonate (10 mL), tetrakis(triphenylphosphine)palladium(0) (72 mg, 62.7 μmol) was added under an argon atmosphere, and the mixture was stirred at 110 °C for 2 hours. After cooling the resulting mixture to 0 °C, the reaction solution was diluted with chloroform, and the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then filtered. The solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 1 / 2 → 0 / 1) to yield compound (1-1-59-n6) (401 mg, 76%) as a red solid. 1 H-NMR(CDCl3,400MHz)δ(ppm):8.08(d,J=8.7Hz,2H),7.98(d,J=7.5Hz,1H),7.91(s,1H),7.82(d,J=8.7Hz,2H),7.46(d,J =1.4Hz,1H),7.34(dd,J=7.5,1.4Hz,1H),2.64(dd,J=9.9,7.6Hz,2H),1.69-1.59(m,2H),1.41-1.28(m,6H),0.90(m,3H). [Example 17]

[0378] [ka]

[0379] Malononitrile (72 mg, 1.08 mmol) was added to a mixture of the compound (1-1-59-n6) (380 mg, 897 μmol) synthesized in Example 16, aluminum oxide (1.00 g), and THF (10 mL), and the mixture was refluxed for 15 minutes. The resulting mixture was filtered, and the solvent was then distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (chloroform / methanol = 3 / 1) to obtain compound (1-1-59-n6) as a green solid. 1-2-59-n6 ) (400 mg, 95%) was obtained. 1 H-NMR(CDCl3,400MHz)δ(ppm):8.77(s,1H),8.25(m,2H),8.11(d,J=8.6Hz,2H),7.85(d,J=8.6Hz,2H),7 .42(d,J=8.8Hz,1H),2.71(dd,J=7.8,7.6Hz,2H),1.68(m,2H),1.44-1.29(m,6H),0.90(t,J=7.1Hz,3H). T d3 :345℃, T d5 :353℃, T d10 :368℃. Phase transition temperature: 211℃. LUMO level: -4.16 eV. [Example 18]

[0380] [ka]

[0381] Trifluoromethanesulfonic acid (1.15 mL, 13.0 mmol) was added to a mixture of methyl 4-(4-hexylphenyl)benzo[c][1,2,5]oxadiazole-5-carboxylate (880 mg, 2.60 mmol) synthesized in Reference Example 7 and 1,2-dichloroethane (26 mL), and the mixture was refluxed for 1 hour. The resulting mixture was cooled to 0°C, saturated aqueous sodium bicarbonate solution was added, and the mixture was extracted with chloroform. The collected organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then filtered. The solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 1 / 1) to obtain compound (2-1-9-n6) (572 mg, 72%) as an orange solid. 1 H-NMR(CDCl3,400MHz)δ(ppm):7.80(d,J=7.4Hz,1H),7.80(d,J=9.1Hz,1H),7.67(d,J=9.1Hz,1H),7. 51(d,J=1.1Hz,1H),7.38(m,1H),2.67(t,J=7.7Hz,2H),1.65(m,2H),1.40-1.27(m,6H),0.89(m,3H). [Example 19]

[0382] [ka]

[0383] Malononitrile (40 mg, 599 μmol) was added to a mixture of compound (2-1-9-n6) (150 mg, 489 μmol) synthesized in Example 18, aluminum oxide (500 mg), and THF (5.0 mL), and the mixture was refluxed for 15 minutes. The resulting mixture was filtered, and the solvent was then distilled off under reduced pressure. The resulting residue was purified by recrystallization (chloroform / methanol = 7 / 10) to give compound (2-2-9-n6) (121 mg, 70%) as a green solid. 1H-NMR(CDCl3,400MHz)δ(ppm):8.42(d,J=9.6Hz,1H),8.22(d,J=0.74Hz,1H),7.94(d,J=7.6Hz,1H),7.82(d,J =9.6Hz,1H),7.41(dd,J=7.6,0.74Hz,1H),2.71(t,J=7.7Hz,2H),1.67(m,2H),1.43-1.27(m,6H),0.90(m,3H). LUMO level: -4.26 eV. [Example 20]

[0384] [ka]

[0385] Trifluoromethanesulfonic acid (13.1 mL, 148 mmol) was added to a mixture of methyl 4-(4-bromophenyl)benzo[c][1,2,5]thiadiazole-5-carboxylate (1.71 g, 4.90 mmol) synthesized in Reference Example 8 and 1,2-dichloroethane (50 mL), and the mixture was refluxed for 2 days. The resulting mixture was cooled to 0 °C, saturated aqueous sodium bicarbonate solution was added, and the mixture was extracted with chloroform. The combined organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then filtered. The solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 4 / 1 → 0 / 1) to give compound (1-1-3) (1.23 g, 79%) as an orange solid. 1 H-NMR (CDCl3,400MHz)δ(ppm):8.05(d,J=7.8Hz,1H),8.00(d,J=8.9Hz,1H),7.86(d,J=8.9Hz,1H),7.79(d,J=1.8Hz,1H),7.72(dd,J=7.8,1.8Hz,1H). [Example 21]

[0386] [ka]

[0387] Bromine (1.95 mL, 37.9 mmol) was added to a mixture of compound (1-1-3) (1.20 g, 3.78 mmol) synthesized in Example 20, 30% hydrogen bromide-acetic acid solution (7.0 mL), and chloroform (21 mL), and the mixture was refluxed for 5 hours. The resulting mixture was cooled to 0°C, and then saturated aqueous sodium bicarbonate and 10 wt% aqueous sodium thiosulfate were added, followed by extraction with chloroform. The collected organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then filtered. The solvent was distilled off under reduced pressure. The resulting residue was purified by recrystallization (chloroform) to give compound (1-1-4) (928 mg, 62%) as a red solid. 1 H-NMR (CDCl3,400MHz)δ(ppm):8.09(s,1H),8.02(d,J=7.8Hz,1H),7.79(d,J=1.9Hz,1H),7.72(dd,J=7.8,1.9Hz,1H). [Example 22]

[0388] [ka]

[0389] To a mixture of compound (1-1-4) (200 mg, 505 μmol) synthesized in Example 21, hexylboronic acid (198 mg, 1.52 mmol), 1,4-dioxane (2.0 mL), and 2.0 M aqueous potassium carbonate (1.0 mL), tetrakis(triphenylphosphine)palladium(0) (12 mg, 10.2 μmol) and tri(tert-butyl)phosphonium tetrafluoroborate (6.2 mg, 21.4 μmol) were added under an argon atmosphere, and the mixture was stirred at 110 °C for 2 hours. After cooling the resulting mixture to 0 °C, the reaction solution was diluted with chloroform. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then filtered. The solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 10 / 1 → 3 / 1) to give compound (1-1-10-n6) (132 mg, 60%) as an orange solid. 1H-NMR(CDCl3,400MHz)δ(ppm):7.99(d,J=7.5Hz,1H),7.62Hz(s,1H),7.49(d,J=1.2Hz,1H),7.34(dd,J=7.5,1.2 Hz,1H),3.15(t,J=7.7Hz,2H),2.65(t,J=7.7Hz,2H),1.81(m,2H),1.65(m,2H),1.48-1.25(m,12H),0.89(m,6H). [Example 23]

[0390] [ka]

[0391] Malononitrile (23 mg, 354 μmol) was added to a mixture of compound (1-1-10-n6) (120 mg, 295 μmol) synthesized in Example 22, aluminum oxide (300 mg), and THF (3.0 mL), and the mixture was refluxed for 3 hours. The resulting mixture was filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 3 / 1 → 2 / 1) to obtain compound (1-2-10-n6) (117 mg, 87%) as a black solid. 1 H-NMR(CDCl3,400MHz)δ(ppm):8.33(s,1H),8.17(s,1H),8.11(d,J=7.6Hz,1H),7.34(d,J=7.6Hz,1H),3 .15(t,J=7.7Hz,2H),2.67(t,J=7.7Hz,2H),1.82(m,2H),1.66(m,2H),1.47-1.25(m,12H),0.89(m,6H). LUMO level: -4.07 eV. [Example 24]

[0392] [ka]

[0393] To a mixture of compound (1-1-4) (200 mg, 505 μmol) synthesized in Example 21, 2-(4-hexylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (450 mg, 1.56 mmol), 1,4-dioxane (4.0 mL), and 2.0 M aqueous potassium carbonate (2.0 mL), tetrakis(triphenylphosphine)palladium(0) (30 mg, 26.0 μmol) was added under an argon atmosphere and stirred at 105 °C for 3 hours. After cooling the resulting mixture to 0 °C, the reaction solution was diluted with chloroform. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then filtered. The solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 1 / 1) to yield compound (1-1-13-n6) (245 mg, 87%) as a red solid. 1 H-NMR(CDCl3,400MHz)δ(ppm):8.21(d,J=7.7Hz,1H),7.99(s,1H),7.94(d,J=1.5Hz,1H),7.89(d,J=8.2Hz,2H),7.80(dd,J=7.7,1.5Hz,1H),7. 58(d,J=8.2Hz,2H),7.37(d,J=8.2Hz,2H),7.30(d,J=8.2Hz,2H),2.73- 2.64(m,4H),1.73-1.63(m,4H),1.43-1.28(m,12H),0.93-0.86(m,6H). [Example 25]

[0394] [ka]

[0395] Malononitrile (130 mg, 1.98 mmol) was added to a mixture of compound (1-1-13-n6) (220 mg, 394 μmol) synthesized in Example 24, aluminum oxide (400 mg), THF (4.0 mL), and pyridine (2.0 mL), and the mixture was refluxed for 30 minutes. The resulting mixture was filtered, and the solvent was removed under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 4 / 1 → 2 / 3) to obtain compound (1-2-13-n6) (232 mg, 97%) as a dark blue solid. 1 H-NMR(CDCl3,400MHz)δ(ppm):8.69(s,1H),8.63(d,J=1.3Hz,1H),8.20(d,J=7.8Hz,1H),7.85(d,J=8.2Hz,2H),7.71(dd,J=7.8,1.3Hz,1H) ,7.52(d,J=8.2Hz,2H),7.35(d,J=8.2Hz,2H),7.27(d,J=8.2Hz,2H),2.73-2.63(m,4H),1.74-1.61(m,4H),1.45-1.29(m,12H),0.91(m,6H). LUMO level: -4.15 eV. [Example 26]

[0396] [ka]

[0397] To a mixture of compound (1-1-4) (200 mg, 505 μmol) synthesized in Example 21, 1-octyne (230 μL, 1.57 mmol), 1,4-dioxane (2.5 mL), and triethylamine (5.0 mL) was added bis(triphenylphosphine)palladium(II) dichloride (16 mg, 22.2 μmol) and copper(I) iodide (5.2 mg, 27.3 μmol) under an argon atmosphere, followed by stirring at 90°C for 1.5 hours. The resulting mixture was cooled to 0°C, saturated aqueous ammonium chloride solution was added, and the mixture was extracted with chloroform. The combined organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 3 / 1 → 0 / 1) to give compound (1-1-16-m6) (189 mg, 82%) as a red solid. 1 H-NMR(CDCl3,400MHz)δ(ppm):8.05(dd,J=7.6,0.52Hz,1H),7.89(s,1H),7.66(m,1H),7.57(dd, J=7.6,1.5Hz,1H),2.60(d,J=7.2Hz,2H),2.44(d,J=7.2Hz,2H),1.75-1.30(m,16H),0.92(m,6H). [Example 27]

[0398] [ka]

[0399] Malononitrile (65 mg, 984 μmol) was added to a mixture of compound (1-1-16-m6) (90 mg, 198 μmol) synthesized in Example 26, aluminum oxide (200 mg), THF (2.0 mL), and pyridine (1.0 mL), and the mixture was refluxed for 30 minutes. The resulting mixture was filtered, and the solvent was removed under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 3 / 1 → 1 / 9) to obtain compound (1-2-16-m6) (83 mg, 83%) as a blue solid. 1H-NMR(CDCl3,400MHz)δ(ppm):8.50(s,1H),8.28(s,1H),8.07(d,J=7.8Hz,1H),7.51(d,J= 7.8Hz,1H),2.60(d,J=7.2Hz,2H),2.44(d,J=7.2Hz,2H),1.75-1.30(m,16H),0.92(m,6H). T d3 :342℃, T d5 :374℃, T d10 :413℃. Phase transition temperature: 170℃. LUMO level: -4.22 eV. [Example 28] (Evaluation of solubility) Chloroform, THF, toluene, and chlorobenzene were added to the fused-ring chalcogenadiazole compounds (1 mg) obtained in Examples 2, 7, 10, 12, 14, 17, 19, 23, 25, and 27 to obtain film-forming compositions. The volume of each organic solvent required to completely dissolve the fused-ring chalcogenadiazole compound at room temperature (25°C) was measured, and the solubility (wt%) was calculated. The point at which the compound was completely dissolved was determined visually. The solubility of the evaluated fused-ring chalcogenadiazole compounds is shown in Table 1.

[0400] [Table 1]

[0401] [Example 29]

[0402] Under a nitrogen atmosphere, 1.00 mg of the compound (1-2-1) synthesized in Example 2 and 500 mg of anisole were added to a 7 mL sample tube and heated at 60° C. to prepare a film-forming composition (concentration of the organic semiconductor: 0.2 wt %).

[0403] Next, a silver electrode was formed on a glass substrate by vapor deposition, and a film of Parylene C was formed as a gate insulating film by CVD. The above-mentioned film-forming composition was then drop-cast in a glove box under a nitrogen atmosphere at 60°C to produce an organic thin film. A shadow mask with a channel length of 100 μm and a channel width of 500 μm was placed on the organic thin film, and source and drain electrodes were attached by vapor-depositing gold under vacuum. A film of Parylene C was then formed by CVD to produce a bottom-gate-top-contact organic transistor element (the gate electrode was silver, the gate insulating layer was Parylene C, and the source and drain electrodes were gold).

[0404] The organic transistor device was connected to a semiconductor parameter analyzer (Keithley, Model 4200A-SCS) under atmospheric conditions, and the gate voltage (Vg) was scanned from -10 to +50 V in 1 V increments at a drain voltage (Vd = +50 V) to evaluate the transfer characteristics. The organic transistor device exhibited n-type characteristics, and its electron carrier mobility was 8.8 × 10 -4 cm 2 / Vs. [Example 30]

[0405] Under a nitrogen atmosphere, 0.87 mg of the compound (1-2-9-n6) synthesized in Example 12 and 435 mg of toluene were added to a 7 mL sample tube, heated at 50°C, and allowed to cool to room temperature (25°C) to prepare a composition for forming an organic thin film (concentration of organic semiconductor: 0.2 wt%). The solution state was maintained even after 10 hours at 25°C, confirming that the compound is suitable for film formation by drop casting, spin coating, and inkjet.

[0406] A bottom gate-top contact type organic transistor device was fabricated in the same manner as in Example 29, except that the organic thin film was formed at room temperature.

[0407] The transfer characteristics of the organic transistor device were evaluated under the same conditions as in Example 29. The organic transistor device exhibited n-type characteristics, and its electron carrier mobility was 2.2 × 10 -4 cm 2 / Vs. [Example 31]

[0408] Under a nitrogen atmosphere, the compound ( 1-2-59-n6 A film-forming composition was prepared by adding 0.87 mg of toluene, 0.44 mg of polystyrene (Sigma-Aldrich), and 436 mg of toluene, heating the mixture at 50°C, and allowing it to cool to room temperature (25°C) (concentration of organic semiconductor: 0.2 wt%). The solution remained in solution even after 10 hours at 25°C, confirming that the compound is suitable for film formation by drop casting, spin coating, and inkjet printing.

[0409] A bottom gate-top contact type organic transistor device was fabricated in the same manner as in Example 30, except that the organic thin film was formed by spin coating.

[0410] The transfer characteristics of the organic transistor device were evaluated under the same conditions as in Example 29. The organic transistor device exhibited n-type characteristics, and its electron carrier mobility was 1.4×10 -4 cm 2 / Vs. [Comparative Example 1]

[0411] Under a nitrogen atmosphere, 0.87 mg of PhC2-BQQDI (Fujifilm Wako Pure Chemical Industries) and 434 mg of toluene were added to a 7 mL sample tube and heated at 60°C, but it was confirmed that solids remained dissolved. Due to its low solubility, it was confirmed that the compound is unsuitable for film formation by drop casting, spin coating, or inkjet.

[0412] [ka] [Industrial Applicability]

[0413] The fused chalcogenadiazole compounds provided by the present invention are highly soluble in organic solvents, highly heat-resistant, have a deep LUMO level, and exhibit n-type semiconducting properties. Therefore, they are expected to be used as materials for semiconductor devices, such as organic transistor elements and organic thin-film solar cells. [Explanation of symbols]

[0414] (A): Bottom-gate / top-contact organic transistor (B): Bottom-gate / bottom-contact organic transistor (C): Top-gate-top-contact organic transistor (D): Top-gate-bottom-contact organic transistor 1: Organic semiconductor layer 2: Circuit board 3: Gate electrode 4: Gate insulating layer 5: Source electrode 6: Drain electrode

Claims

1. A fused ring chalcogenadiazole compound represented by the following general formula (1): 【Chemistry 1】 (In the formula, J １ represents an oxygen atom, a sulfur atom, or a selenium atom. R 1 and R 4 each independently represent a hydrogen atom; or an alkyl group having 1 to 20 carbon atoms; or a monocyclic, linked, or fused aromatic group having 3 to 18 carbon atoms which may be substituted with one or more groups such as a cyano group, a nitro group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, an alkoxycarbonyl group, a formyl group, an imino group, a trifluoromethoxy group, a trifluoromethylthio group, a pentafluorosulfanyl group, a carboxyl group, a sulfo group, a trifluoromethanesulfonyl group, or an alkyl group having 1 to 20 carbon atoms; R ２ , R ３ , R ５ and R ６ represents a hydrogen atom. １ represents a group represented by the following formula (2): 【Chemistry 2】 (In the formula, Y １ and Y ２ represents a cyano group.

2. J １ The fused ring chalcogenadiazole compound according to claim 1 , wherein is an oxygen atom or a sulfur atom.

3. R １ and R ４ are each independently a hydrogen atom; an alkyl group having 1 to 12 carbon atoms; or a monocyclic, linked, or fused aromatic group having 6 to 12 carbon atoms substituted with one or more of a cyano group, a nitro group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, an alkoxycarbonyl group, a formyl group, an imino group, a trifluoromethoxy group, a trifluoromethylthio group, a pentafluorosulfanyl group, a carboxyl group, a sulfo group, a trifluoromethanesulfonyl group, or an alkyl group having 1 to 12 carbon atoms.

4. A method for producing a fused ring chalcogenadiazole compound represented by formula (1a) by reacting a chalcogenadiazole intermediate represented by the following formula (4) with an acid: 【Transformation 3】 (In the formula, J １ represents an oxygen atom, a sulfur atom, or a selenium atom. R 1 and R 4 each independently represent a hydrogen atom; or an alkyl group having 1 to 20 carbon atoms; or a monocyclic, linked, or fused aromatic group having 3 to 18 carbon atoms which may be substituted with one or more groups such as a cyano group, a nitro group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, an alkoxycarbonyl group, a formyl group, an imino group, a trifluoromethoxy group, a trifluoromethylthio group, a pentafluorosulfanyl group, a carboxyl group, a sulfo group, a trifluoromethanesulfonyl group, or an alkyl group having 1 to 20 carbon atoms; R ２ , R ３ , R ５ and R ６ represents a hydrogen atom. Z represents a leaving group. 【Chemistry 4】 (In the formula, J １ , R １ , R ２ , R ３ , R ４ , R ５ and R ６ represents the same meaning as above.)

5. 5. The process of claim 4, wherein the acid is an organic Bronsted acid.

6. A fused ring chalcogenadiazole compound represented by formula (1a) and Y １ -CH ２ -Y ２ (5) (wherein, Y １ and Y ２ represents a cyano group. 【Transformation 5】 (In the formula, J １ represents an oxygen atom, a sulfur atom, or a selenium atom. R 1 and R 4 each independently represent a hydrogen atom; or an alkyl group having 1 to 20 carbon atoms; or a monocyclic, linked, or fused aromatic group having 3 to 18 carbon atoms which may be substituted with one or more groups such as a cyano group, a nitro group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, an alkoxycarbonyl group, a formyl group, an imino group, a trifluoromethoxy group, a trifluoromethylthio group, a pentafluorosulfanyl group, a carboxyl group, a sulfo group, a trifluoromethanesulfonyl group, or an alkyl group having 1 to 20 carbon atoms; R ２ , R ３ , R ５ and R ６ represents a hydrogen atom.) 【Transformation 6】 (In the formula, J １ , R １ , R ２ , R ３ , R ４ , R ５ , R ６ , Y １ and Y ２ represents the same meaning as above.)

7. Y １ and Y ２ The method according to claim 6, wherein both are cyano groups.

8. A method for producing a fused ring chalcogenadiazole compound represented by formula (1d), comprising reacting a fused ring chalcogenadiazole compound represented by formula (1c) with a halogenating agent: 【Transformation 7】 (In the formula, J １ represents an oxygen atom, a sulfur atom, or a selenium atom. R 4 represents a hydrogen atom; or an alkyl group having 1 to 20 carbon atoms; or a monocyclic, linked, or fused aromatic group having 3 to 18 carbon atoms which may be substituted with one or more groups such as a cyano group, a nitro group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, an alkoxycarbonyl group, a formyl group, an imino group, a trifluoromethoxy group, a trifluoromethylthio group, a pentafluorosulfanyl group, a carboxyl group, a sulfo group, a trifluoromethanesulfonyl group, or an alkyl group having 1 to 20 carbon atoms; R ２ , R ３ , R ５ and R ６ represents a hydrogen atom. １ represents a group represented by the following formula (2): 【Transformation 8】 (In the formula, Y １ and Y ２ represents a cyano group. 【Chemistry 9】 (In the formula, J １ and X １ has the same meaning as above. １ R 10 represents a hydrogen atom; or an alkyl group having 1 to 20 carbon atoms; or a monocyclic, linked or fused ring aromatic group having 3 to 18 carbon atoms which may be substituted with one or more groups such as a cyano group, a nitro group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, an alkoxycarbonyl group, a formyl group, an imino group, a trifluoromethoxy group, a trifluoromethylthio group, a pentafluorosulfanyl group, a carboxyl group, a sulfo group, a trifluoromethanesulfonyl group, or an alkyl group having 1 to 20 carbon atoms; R ８ , R ９ , R １１ and R １２ represents a hydrogen atom. 。）

9. 9. The method for producing a fused ring chalcogenadiazole compound according to claim 8, wherein the halogenating agent is bromine.

10. a fused ring chalcogenadiazole compound represented by formula (1e) and R １３ -M(6) (wherein R １３ represents an alkyl group having 1 to 20 carbon atoms; or an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms; or a monocyclic, linked or fused ring aromatic group having 3 to 18 carbon atoms which may be substituted with one or more groups such as cyano, nitro, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, 2,2,3,3,4,4,4-heptafluorobutyl, alkoxycarbonyl, formyl, imino, trifluoromethoxy, trifluoromethylthio, pentafluorosulfanyl, carboxyl, sulfo, trifluoromethanesulfonyl, or an alkyl group having 1 to 20 carbon atoms; or an aralkyl group having 7 to 14 carbon atoms. M represents a metal group, Me3Si, Et3Si, Me3Sn, Bu3Sn, B(OH)2, or a group shown in (I) to (VIII) below. ) in the presence of a palladium catalyst and, optionally, a base. 【Chemistry 10】 【Chemistry 11】 (In the formula, J １ represents an oxygen atom, a sulfur atom, or a selenium atom. ２ and W ３ each independently represents a halogen atom; or a hydrogen atom; or an alkyl group having 1 to 20 carbon atoms; or an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms; or a monocyclic, linked or fused ring aromatic group having 3 to 18 carbon atoms which may be substituted with one or more groups such as a cyano group, a nitro group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, an alkoxycarbonyl group, a formyl group, an imino group, a trifluoromethoxy group, a trifluoromethylthio group, a pentafluorosulfanyl group, a carboxyl group, a sulfo group, a trifluoromethanesulfonyl group, or an alkyl group having 1 to 20 carbon atoms; or an aralkyl group having 7 to 14 carbon atoms. ２ and W ３ At least one of X is a halogen atom. １ represents a group represented by the following formula (2): 【Chemistry 12】 During the ceremony, Y １ and Y ２ represents a cyano group. 【Chemistry 13】 (In the formula, J １ and X １ has the same meaning as above. １４ represents a hydrogen atom; or an alkyl group having 1 to 20 carbon atoms; or an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms; or a monocyclic, linked or fused ring aromatic group having 3 to 18 carbon atoms which may be substituted with one or more groups such as cyano, nitro, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, 2,2,3,3,4,4,4-heptafluorobutyl, alkoxycarbonyl, formyl, imino, trifluoromethoxy, trifluoromethylthio, pentafluorosulfanyl, carboxyl, sulfo, trifluoromethanesulfonyl, or alkyl groups having 1 to 20 carbon atoms; or an aralkyl group having 7 to 14 carbon atoms. １４ cannot be a hydrogen atom at the same time.)

11. A film-forming composition comprising the fused ring chalcogenadiazole compound according to claim 1 .

12. An organic thin film comprising the fused ring chalcogenadiazole compound according to claim 1 .

13. An organic transistor device comprising the fused ring chalcogenadiazole compound according to claim 1 .

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