JP7796551B2 - Fused ring chalcogenadiazole compound, its production method and organic transistor device - Google Patents

Description

The present invention relates to a fused-ring chalcogenadiazole compound, a method for producing the compound, and an organic transistor device containing the compound.

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

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 electron-withdrawing groups have 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 devices.

However, compared to p-type organic semiconductors, which use holes as charge carriers and have excellent charge mobility, there are very few reported examples of n-type organic semiconductors that exhibit electron mobility equivalent to that of p-type organic semiconductors. Furthermore, in order for organic transistor elements 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 lower, but there are only a limited number of examples of n-type organic semiconductors with such a deep LUMO level.

Japanese Patent Application Laid-Open No. 2017-59668 WO2015/041026

Science Advances, Vol. 6, eaaz0632, 2020.

The objective of the present invention is to provide a fused ring chalcogenadiazole compound that can be used in organic transistor elements that can be manufactured 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, as well as a method for manufacturing the same.

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

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

A fused-ring chalcogenadiazole compound represented by the following formula (1):

(In the formula, ^J1 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. ^R1 , ^R2 , ^R3 , ^R4 , ^R5 , and ^R6 each independently represent 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. ^X1 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).)

(In the formula, ^Y1 and ^Y2 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.)
[Summary 2]

A method for producing a fused-ring chalcogenadiazole compound represented by formula (1a) by reacting a chalcogenadiazole intermediate represented by formula (4) below with an acid.

(In the formula, ^J1 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. ^R1 , ^R2 , ^R3 , ^R4 , ^R5 , and ^R6 each independently represent 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.)

(In the formula, J ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the same meanings as defined above.)
[Summary 3]

A method for producing a fused-ring chalcogenadiazole compound represented by formula (1b), comprising reacting a fused-ring chalcogenadiazole compound represented by formula (1a) with an active methylene compound represented by Y ¹ -CH ₂ -Y ² (5) (wherein Y ¹ and Y ² 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).

(In the formula, ^J1 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. ^R1 , ^R2 , ^R3 , ^R4 , ^R5 , and ^R6 each independently represent 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. ^Y1 and ^Y2 have the same meaning as defined above.)
[Summary 4]

A method for producing a fused chalcogenadiazole compound represented by formula (1d) by reacting a fused chalcogenadiazole compound represented by formula (1c) below with a halogenating agent.

(In the formula, ^J1 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. ^R2 , ^R3 , ^R4 , ^R5 , and ^R6 each independently represent 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. ^X1 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).)

(In the formula, ^Y1 and ^Y2 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.)

(In the formula, ^J1 and ^X1 are defined as above. ^W1 represents a halogen atom. ^R8 , ^R9 , ^R10 , ^R11 , and ^R12 each independently represent 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.)
[Summary 5]

A method for producing a fused chalcogenadiazole compound represented by formula (1f), comprising reacting a fused chalcogenadiazole compound represented by formula (1e) with a metal reagent represented by R ¹³ -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; and M represents a metal group, a heteroatom group, or a hydrogen atom), in the presence of a palladium catalyst and, as the case may be, a base.

(In the formula, ^J1 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. ^W2 and ^W3 each independently represent 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 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, provided that at least one of ^W2 and ^W3 is a halogen atom. ^X1 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).)

(In the formula, ^Y1 and ^Y2 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.)

(In the formula, ^J1 and ^X1 are as defined above. ^R14 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, provided that two ^R14s cannot simultaneously be hydrogen atoms.)
[Summary 6]

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

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

An organic transistor device comprising the fused ring chalcogenadiazole compound described in [Summary 1].

The fused-ring chalcogenadiazole compounds of the present invention have both high solubility and heat resistance, allowing organic transistor elements using them as active layers to operate efficiently.

1A and 1B are diagrams showing the cross-sectional structure of an organic transistor element.

The following provides a detailed description of a fused-ring chalcogenadiazole compound (hereinafter sometimes simply referred to as a fused-ring chalcogenadiazole compound) according to one embodiment of the present invention.

A fused-ring chalcogenadiazole compound according to one embodiment of the present invention is a fused-ring chalcogenadiazole compound represented by formula (1) (hereinafter, sometimes referred to as 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).

[Regarding ^J1 ]
^J1 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.

Examples of the chalcogen atom represented by ^J1 include an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. An oxygen atom or a sulfur atom is preferred in terms of the good performance of the fused ring chalcogenadiazole compound (1) in an organic transistor device.

The nitrogen atom represented by ^J1 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 group, 2-hexyl group, 2-methylhexan-2-yl group, 5,5-dimethylhexan-2-yl group, 3-hexyl group, 2,4-dimethylhexan-3-yl group, cyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, 4,4-dimethylcyclohexyl group, heptyl group, 2-heptyl group, 3-heptyl group, 4-heptyl group, bicyclo[2.2.1]heptyl group Examples of the alkyl group include a butyl group, an octyl group, a 2-octyl group, a 3-octyl group, a 4-octyl group, a cyclooctyl group, a bicyclo[2.2.2]octyl group, a nonyl group, a 5-nonyl group, a decyl group, a 2-decyl group, a 5-decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an icosyl group.

The nitrogen atom represented by ^J1 may be substituted with a monocyclic, linked, or fused aromatic group having 3 to 18 carbon atoms. 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.

[Regarding R ¹ to R ⁶ and R ⁸ to R ¹⁴ ]
R ¹ to R ⁶ and R ⁸ to R ¹² each represent 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; 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 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; 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.

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

Examples of the electron-withdrawing group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² 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 view of the 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.

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 The alkyl group having 1 to 20 carbon atoms represented by ¹⁴ 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- methylhexyl group, 3,3-dimethylhexyl group, 4-ethylhexyl group, 2-hexyl group, 2-methylhexan-2-yl group, 5,5-dimethylhexan-2-yl group, 3-hexyl group, 2,4-dimethylhexan-3-yl group, cyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, 4,4-dimethylcyclohexyl group, heptyl group, 2-heptyl group, 3-heptyl group, 4-heptyl group, 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.

The unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms represented by 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 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 and 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 group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexynyl group, 1-heptynyl group, 2-heptynyl group, 3-heptynyl group, 4-heptynyl group, 5-heptynyl group, 6-heptynyl group, 1-octynyl group, 2-octynyl group, 3-octynyl group, 4-octynyl group, 5-octynyl group, 6-octynyl group, 7-octynyl group, 1- Examples include a nonynyl group, a 2-nonynyl group, a 3-nonynyl group, a 4-nonynyl group, a 5-nonynyl group, a 6-nonynyl group, a 7-nonynyl group, an 8-nonynyl group, a 1-decynyl group, a 2-decynyl group, a 3-decynyl group, a 4-decynyl group, a 5-decynyl group, a 6-decynyl group, a 7-decynyl group, an 8-decynyl group, a 9-decynyl group, a triisopropylsilylethynyl group, a 2-methylpropen-1-yl group, a 2-ethyl-buten-1-yl group, a 2-propyl-penten-1-yl group, a 2-butyl-hexen-1-yl group, etc. In terms of 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.

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 Examples of the aromatic group of 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, represented by ¹⁴ , 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 3-octylphenyl group, a 3-nonylphenyl group, a 3-decylphenyl group, a nyl 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-cyano-4-octylphenyl group, 3-cyano-4-nonylphenyl group, 3- Examples include a 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.

Examples of the aralkyl group having 7 to 14 carbon atoms represented by 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 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, a 4-(2-furyl)ethyl group, and the like.

^R1 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 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; 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.

^R4 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 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; 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.

^R2 , ^R3 , ^R5 , ^R6 , ^R8 , ^R9 , ^R10 , ^R11 and ^R12 are 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, with a hydrogen atom being particularly preferred.

R ¹³ is preferably an alkyl group having 1 to 20 carbon atoms; an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms; a monocyclic, linked ring, 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, and particularly preferably a hexyl group, a dodecyl group, a 1-octynyl group, a 4-cyanophenyl group, a 4-hexylphenyl group, or the like.

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.

[Regarding ^X1 , ^W1 , ^W2 , ^W3 , ^Y1 , and ^Y2 ]
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).

(In the formula, ^Y1 and ^Y2 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.)

Examples of the chalcogen atom represented by X ¹ 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).

The nitrogen atom represented by ^X1 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 group, 2-hexyl group, 2-methylhexan-2-yl group, 5,5-dimethylhexan-2-yl group, 3-hexyl group, 2,4-dimethylhexan-3-yl group, cyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, 4,4-dimethylcyclohexyl group, heptyl group, 2-heptyl group, 3-heptyl group, 4-heptyl group, bicyclo[2.2.1]heptyl group Examples of the alkyl group include a butyl group, an octyl group, a 2-octyl group, a 3-octyl group, a 4-octyl group, a cyclooctyl group, a bicyclo[2.2.2]octyl group, a nonyl group, a 5-nonyl group, a decyl group, a 2-decyl group, a 5-decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an icosyl group.

The nitrogen atom represented by ^X1 may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms. 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.

Examples of phenyl groups which may be substituted with one or more electron-withdrawing groups, represented by ^Y1 and ^Y2 , 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. In terms of good performance when the fused ring-fused chalcogenadiazole compound (1) is used in an organic transistor element, ^Y1 and ^Y2 are preferably a fluorine atom, a trifluoromethyl group, a cyano group, or a pentafluorophenyl group, and more preferably a cyano group.

Among these, ^X1 is preferably an oxygen atom, a sulfur atom, or a nitrogen atom substituted with a cyano group, or ^Y1 and ^Y2 represented by formula (2) are preferably a fluorine atom, a trifluoromethyl group, a cyano group, or a pentafluorophenyl group. In particular, ^Y1 and ^Y2 represented by formula (2) are preferably a cyano group in terms of good performance when the fused-ring chalcogenadiazole compound (1) is used as an organic transistor element.

^W1 represents a halogen atom, and ^W2 and ^W3 represent 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, provided that at least one of ^W2 and ^W3 is a halogen atom.

Examples of halogen atoms represented by W ¹ , W ² and W ³ include the same halogen atoms as those exemplified for R ¹ to R ⁶ and R ⁸ to R ¹² , and a bromine atom is preferred in that it provides a fused ring chalcogenadiazole compound (1) with high stability.

Examples of the alkyl group having 1 to 20 carbon atoms represented by ^W2 and ^W3 include the same alkyl groups as those exemplified for ^R1 to ^R6 and ^R8 to ^R14. 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.

Examples of the unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms represented by ^W2 and ^W3 include the same unsaturated aliphatic hydrocarbon groups as exemplified for ^R1 to ^R6 and ^R8 to ^R14. In terms of high solubility of the fused ring chalcogenadiazole compound (1), an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms is preferred, an alkynyl group having 2 to 10 carbon atoms is more preferred, and a 1-octyl group is particularly preferred.

Examples of the monocyclic, linked, or fused ring aromatic group having 3 to 18 carbon atoms and optionally substituted with one or more electron-withdrawing groups or alkyl groups having 1 to 20 carbon atoms, represented by ^W2 and ^W3 , include the same groups as exemplified for ^R1 to ^R6 and ^R8 to ^R14. In terms of good solubility and crystallinity of the fused chalcogenadiazole compound (1), a monocyclic, linked, 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.

Examples of the aralkyl group having 7 to 14 carbon atoms represented by W ² and W ³ include the same aralkyl groups as those exemplified for R ¹ to R ⁶ and R ⁸ to R ¹⁴ .

Fused ring chalcogenadiazole compounds (1) include those represented by the following formulas (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), (1-1-39-n6), (1-1-40-n6), and (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-n12), (1-2-10-n6), (1-2-11-n6), (1-2-12-n 6), (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), (2-4-10-n6), (2-5-1) to (2-5-10), (2-5-8-n6), (2-5-9-n6), (2-5-10-n6), etc. can be exemplified, but the present invention is not limited thereto. In the formula, n is a natural number between 1 and 12, m is an integer between 0 and 10, and k is a natural number between 1 and 4.

In the above formula, C _n H _2n+1 and C _m H _2m+1 represent linear alkyl groups.

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 used in organic transistor devices.

Next, a method for producing 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)).

First, we will explain manufacturing method (A).

Production method (A) is a method for producing a fused chalcogenadiazole compound (1a) included in the fused 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)

(In the formula, J ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are as defined above, and Z represents a leaving group.)

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 optionally substituted with an alkyl group or a phenyl group. In terms of 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.

Specific examples of 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.

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

Production method (A) must be carried out in the presence of an acid, and such an acid can be a Brønsted acid or a Lewis acid. Brønsted acids 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, 5-sulfosalicylic acid, fumaric acid, and propiolic acid. Examples of the organic Bronsted acids include carboxylic 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; and examples of the Lewis acids include aluminum isopropoxide, aluminum chloride (III), and bis(2,6-di-tert-butyl-4-methylphenoxy). Aluminum-based Lewis acids such as 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, lanthanum(III) trifluoromethanesulfonate, trifluoromethanesulfonyloxy ... 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. These may be mixed in any ratio. From the viewpoint of good reaction yield, Brønsted acids are preferred, organic Brønsted acids are more preferred, and trifluoromethanesulfonic acid is particularly preferred.

There is no limit to the amount of acid used in production method (A), but in terms of good reaction yield, 1.0 to 30 molar equivalents per equivalent of chalcogenadiazole intermediate (4) is preferred.

Production method (A) can be carried out in a solvent. There are no particular restrictions on the solvent that can be used as long as it does not inhibit the reaction, and examples 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; halogenated solvents such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, and orthodichlorobenzene (o-DCB); fluorinated 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.

Halogenated solvents are preferred because they provide good reaction yields, with chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, and o-DCB being more preferred, and 1,2-dichloroethane being even more preferred.

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

The fused chalcogenadiazole compound (1a) can be obtained by carrying out conventional treatments after completion of Production Method (A). If necessary, it may be purified using any of the commonly used methods 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.

Examples of the fused 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).

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

Production method (B) is a method for producing a fused chalcogenadiazole compound (1b) included in the fused _{chalcogenadiazole} ^compound ( ¹ ) according to one embodiment of the present invention, by reacting a fused chalcogenadiazole compound (1a) with an active methylene compound represented by Y 1 -CH 2 -Y 2 (5) (wherein Y ¹ and Y ² have the same meanings as defined above).

(In the formula, J ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , Y ¹ and Y ² have the same meanings as defined above.)

Examples of the active methylene compound Y ¹ -CH ₂ -Y ² (5) used in production method (B) include compounds in which 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.

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

In Production Method (B), additives can be added to promote the reaction. Examples of such additives include the Brønsted acids and Lewis acids exemplified in 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 are even more preferred.

In manufacturing method (B), a base can be added as an additive. Examples of such bases include metal hydroxide salts 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 fluoride salts such as sodium fluoride and cesium fluoride; metal alkoxides such as sodium methoxide, potassium methoxide, sodium ethoxide, potassium isopropyl oxide, and potassium tert-butoxide; triethylamine; 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 chalcogenadiazole compound (1b), and pyridine is more preferred.

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

Production method (B) can be carried out in a solvent. Usable solvents 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-lanthate. Examples of 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 good 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.

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

The fused chalcogenadiazole compound (1b) can be obtained by carrying out the usual treatment after completion of production method (B). If necessary, it may be purified using any of the commonly used methods 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.

The fused ring chalcogenadiazole compound (1b) obtained by 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), and (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), (2-2-1) to (2-2- Examples include (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), and (2-4-10-n6).

Next, the production method (C) will be described.
Manufacturing method (C)

Production method (C) is a method for producing fused chalcogenadiazole compound (1d) included in fused chalcogenadiazole compound (1) according to one embodiment of the present invention, by reacting fused chalcogenadiazole compound (1c) included in fused chalcogenadiazole compound (1) according to one embodiment of the present invention with a halogenating agent.

(In the formula, ^J1 , ^X1 , ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R8 , ^R9 , ^R10 , ^R11 , ^R12 and ^W1 have the same meanings as defined above.)

The fused ring chalcogenadiazole compound (1c) used in production method (C) is a compound represented by the formula (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).

The fused chalcogenadiazole compound (1c) used in Production Method (C) can be prepared by the methods disclosed in Examples 3, 8, 15, and 21.

Halogenating agents used in production method (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; 1,3-diiodo-5,5- Dimethylhydantoin; N,N-dimethyl-N-(methylsulfanylmethylene)ammonium iodide; iodinating agents such as carbon tetraiodide, bromine; hydrobromic acid; 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-undecene hydrotribromide; Benzyltrimethylammonium tribromide; Bromotrichloromethane; Tetrabromoisocyanuric acid Examples of suitable chlorinating agents include brominating agents such as carbon bromide, and chlorinating agents such as 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. These may be mixed in any ratio. Brominating agents are preferred due to their good reaction yield, and bromine or hydrogen bromide are even more preferred.

There are no particular restrictions on the amount of halogenating agent used, but in terms of good yield, a molar amount of 1.0 to 10 molar equivalents relative to the fused chalcogenadiazole compound (1c) is preferred.

Production method (C) can be carried out in a solvent. There are no particular limitations on the solvents that can be used as long as they do not inhibit the reaction, and examples 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 suitable 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 and used in any ratio. In terms of good yield, halogenated solvents, acidic solvents, and mixed solvents thereof are preferred, with chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, o-DCB, hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, acetic acid, and mixed solvents thereof being more preferred, and a mixed solution of chloroform, hydrobromic acid, and acetic acid being especially preferred.

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

The fused chalcogenadiazole compound (1d) can be obtained by carrying out the usual treatment after completion of production method (C). If necessary, it may be purified using any of the commonly used methods 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.

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), and (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 mentioned as examples.

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

Production method (D) is a method for producing a fused chalcogenadiazole compound (1f) included in the fused chalcogenadiazole compound (1) according to one embodiment of the present invention, by reacting a fused chalcogenadiazole compound (1e) included in the fused chalcogenadiazole compound (1) according to one embodiment of the present invention with a metal reagent represented by R ¹³ -M(6) (wherein R ¹³ has the same meaning as defined above, and M represents a metal group, a heteroatom group, or a hydrogen atom) in the presence of a palladium catalyst and, as the case may be, a base.

(In the formula, J ¹ , X ¹ , W ² , W ³ and R ¹⁴ have the same meanings as defined above.)

Examples of the fused 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).

The fused chalcogenadiazole compound (1e) used in Production Method (D) can be prepared by the methods disclosed in Examples 4, 9, 16, 22, 24, and 26.

In the metal reagent (6) used in 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( ^iPr ) ₂ , ZnCl, ZnBr, ZnI, and ZnCl(TMEDA). MgBr or ZnCl is preferred in terms of ease of preparation. Examples of the heteroatom group include _Me3Si , _Et3Si , _Me3Sn , _Bu3Sn , and B(OH) ₂ , as well as the groups shown in (I) to (VIII) below. In terms of good reaction yield, B(OH) ₂ or the group shown in (II) is preferred.

The metal reagent (6) used in production method (D) includes alkylboronic acids, alkylboronic acid esters, arylboronic acids, arylboronic acid esters, organotin compounds, terminal alkynes, etc., with hexylboronic acid, 2-(4-hexylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 1-octyne, etc. being particularly preferred.

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 Letters, Vol. 55, pp. 5195-5198, 2014; and ACS Macro Letters, Vol. 4, pp. 689-692, 2015. Alternatively, commercially available products may be used.

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.

Examples of tertiary phosphines 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), Examples include (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, and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl.

Among these, palladium complexes having a tertiary phosphine as a ligand are preferred because of their high yield, and palladium complexes having triphenylphosphine, tri-(tert-butyl)phosphine, or 1,1'-bis(diphenylphosphino)ferrocene as a ligand are even more preferred.

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 more preferably in the range of 1:2 to 3:1 in terms of good yield. There is no restriction on the amount of palladium catalyst used in production method (D), but in terms of good yield, the molar equivalent of the palladium catalyst is preferably in the range of 0.01 to 20 mole percent relative to the fused-ring chalcogenadiazole compound (1e).

Production method (D) may be carried out in the presence of a base. Examples of such bases include metal hydroxide salts 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 fluoride salts 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 or metal phosphates are preferred in terms of good reaction yield, and potassium carbonate or sodium carbonate is 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 good reaction yield.

Production method (D) can be carried out in a solvent. Usable solvents 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 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, and these may be mixed in any ratio. From the viewpoint of good reaction yield, ether solvents, aromatic hydrocarbon solvents, triethylamine, and water are preferred, and THF, 1,4-dioxane, toluene, triethylamine, and water are even more preferred as single solvents or as mixed solvents in any ratio.

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.

The fused chalcogenadiazole compound (1f) can be obtained by carrying out the usual treatment after completion of production method (D). If necessary, it may be purified using any of the commonly used methods 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.

The fused ring chalcogenadiazole compound (1f) obtained by production method (D) includes compounds of the formulae (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), (1-1-72) 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), and (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).

Next, a film-forming composition containing a 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.

The film-forming composition according to the present invention preferably contains a solvent in the fused ring chalcogenadiazole compound (1).

The solvent is not particularly limited as long as it can dissolve or disperse the fused-ring chalcogenadiazole compound (1) in the solvent, but examples thereof 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, and water, and these may be mixed in any ratio. Aromatic hydrocarbons and halogenated solvents are preferred due to their high boiling points and mild volatility, with toluene, xylene, mesitylene, cyclohexylbenzene, tetralin, anisole, 3,4-dimethylanisole, chlorobenzene, and o-DCB being even more preferred.

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

Dissolution or dispersion can be achieved by methods well known to those skilled in the art, such as stirring, shaking, or ball milling. Heating may also be used during this process.

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% by weight is preferred for good coatability.

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.

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

There are no particular restrictions on the film thickness of the organic thin film according to the present invention, but in terms of high carrier mobility, a thickness of 1 nm to 1000 nm is preferred, and a thickness of 10 nm to 500 nm is even more preferred.

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 off the solvent. There are no particular limitations on the film-forming method, and examples 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 because they allow for efficient film formation.

The drying temperature is preferably 20-150°C, and particularly preferably 20-80°C. If necessary, annealing may be performed at a temperature appropriately selected from the range of 40-400°C.

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

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

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, highly doped silicon, silicon oxide, tantalum dioxide, tantalum pentoxide, and indium tin oxide; and metal substrates such as gold, copper, chromium, titanium, and aluminum. Glass, silicon, and highly doped silicon are preferred due to their excellent transistor performance, with glass being more preferred.

Examples of gate electrodes 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, as well as organic electrodes such as doped conductive polymers (PEDOT-PSS). Inorganic electrodes are preferred due to their good conductivity, and gold and silver are more preferred.

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, as well as organic insulating layers such as polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polymethyl acrylate, polyethylene, polypropylene, polystyrene, cyclic polyolefins, 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 (trademark), polyfluorinated cyclohexane, polyfluorinated cyclohexane-ethylene copolymer, Parylene N (trademark), Parylene C (trademark), Parylene D (trademark), Parylene HT (trademark), and Parylene C-UVF (trademark). Organic insulating layers are preferred due to their excellent insulating properties, with parylene C being even more preferred. Furthermore, the surface 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. Octadecyltrichlorosilane, octyltrichlorosilane, β-phenethyltrichlorosilane, octadecylphosphonic acid, octylphosphonic acid, and hexamethyldisilazane are preferred in terms 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.

Examples of the source electrode and drain electrode include the same electrodes as those exemplified for the gate electrode. Inorganic electrodes are preferred due to their good conductivity, and gold is even more preferred. Furthermore, to improve carrier injection efficiency, these electrodes can be surface-treated using a surface treatment material. Examples of such surface treatment materials include benzenethiol and pentafluorobenzenethiol.

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

The present invention will be explained in more detail below using examples, but the present invention is not limited to the following examples.

The compounds obtained in the examples were subjected to structural analysis by ¹ H-NMR measurement. Commercially available reagents were used.
<NMR measurement conditions>
Measurement equipment: Bruker ASCEND ^™ ADVANCE III HD (400 MHz)
Measurement solvent: deuterated chloroform (CDCl ₃ )
Internal standard: tetramethylsilane (TMS)
<TGA measurement conditions>
Measurement equipment: SII Corporation EXSTAR6000 TGA/DTA6200
Sample container: aluminum pan Measurement atmosphere: nitrogen T _d3 , T _d5 and T _d10 represent the temperatures at which the weight is reduced by 3%, 5% and 10%, 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 obtained using the second HeatingScan.
<CV measurement conditions>
Measuring device: BioLogic VSP-300
Working electrode: glassy carbon (φ=3 mm)
Counter electrode: platinum wire (φ=0.5 mm)
Reference pole: platinum wire (φ=0.5mm)
Internal standard: ferrocene/ferrocenium (Fc/Fc ⁺ )
Electrolyte: 0.10 M tetrabutylammonium tetrafluoroborate (Bu ₄ NBF ₄ )/dichloromethane solution. Concentration of the measured compound: The above electrolyte solution was used as a solvent, and the concentration was 1 g/L.

Scanning speed: 100 mV/s
A reversible cyclic voltammogram was obtained under the above conditions. The redox potential E _sample (V vs. Fc/Fc ⁺ ) of the measured compound was determined from the half-potentials between the oxidation peak and reduction peak of the voltammogram, with the horizontal axis corrected to Fc/Fc ⁺ . The LUMO level E _LUMO was calculated using equation (1), assuming that the redox potential of Fc/Fc ⁺ was −5.07 eV relative to the vacuum level.

E _LUMO = -5.07 - E _sample (1)
[Reference example 1]

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, and then saturated aqueous sodium bicarbonate solution was added, followed by extraction with chloroform. The combined organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and filtered, and the solvent was distilled off 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 (CDCl ₃ , 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]

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, after which 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 from the resulting mixture under reduced pressure, and THF (8.0 mL) was added to prepare a TMP ₂ Mg·2LiCl solution.

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), TMP ₂ Mg·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., and saturated aqueous ammonium chloride solution was added, followed by extraction with chloroform. The combined organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and filtered. The solvent was then 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 (CDCl ₃ , 400 MHz) δ (ppm): 8.03 (m, 2H), 7.55-7.44 (m, 5H), 3.67 (s, 3H).
[Reference example 3]

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, after which 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 from the resulting mixture under reduced pressure, and THF (8.0 mL) was added to prepare a TMP ₂ Mg·2LiCl solution.

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), TMP ₂ Mg·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., and saturated aqueous ammonium chloride solution was added, followed by extraction with chloroform. The combined organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and filtered. The solvent was then evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane/chloroform=1/2→0/1) to obtain 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 (CDCl ₃ , 400 MHz) δ (ppm): 8.03 (m, 2H), 7.53 (d, J = 8.4 Hz, 2H), 7.44 (d, J = 8.4 Hz, 2H), 3.67 (s, 3H), 1.39 (s, 9H).
[Reference example 4]

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, after which 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 from the resulting mixture under reduced pressure, and THF (8.0 mL) was added to prepare a TMP ₂ Mg·2LiCl solution.

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), TMP ₂ Mg·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., and saturated aqueous ammonium chloride solution was added, followed by extraction with chloroform. The combined organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and filtered. The solvent was then 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 (CDCl ₃ , 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]

To a mixture of 2,2,6,6-tetramethylpiperidine (972 μL, 5.71 mmol) and THF (5.7 mL) was added 1.56 M n-butyllithium n-hexane solution (3.67 mL, 5.73 mmol) at −40° C. and stirred at the same temperature for 30 minutes, after which 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 from the resulting mixture under reduced pressure, and THF (8.0 mL) was added to prepare a TMP ₂ Mg·2LiCl solution.

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), TMP ₂ Mg·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., and saturated aqueous ammonium chloride solution was added, followed by extraction with chloroform. The combined organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and filtered. The solvent was then 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.
¹ H-NMR (CDCl ₃ , 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]

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 the mixture was 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 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 yield a yellow solid (4.80 g).

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 mixture was cooled to 0°C, and water (40 mL) and 6.0 M aqueous hydrochloric acid (2.0 mL) were added. The reaction mixture 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 yield a crude product as a brown liquid.

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 (CDCl ₃ , 400 MHz) δ (ppm): 8.64 (t, J = 1.2 Hz, 1H), 8.02 (dd, J = 9.4, 1.2 Hz, 1H), 7.91 (dd, J = 9.4, 1.2 Hz, 1H), 4.01 (s, 3H).
[Reference example 7]

To a mixture of 2,2,6,6-tetramethylpiperidine (1.05 mL, 6.17 mmol) and THF (6.2 mL) was added 1.56 M n-butyllithium n-hexane solution (4.00 mL, 6.24 mmol) 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 from the resulting mixture under reduced pressure, and THF (10 mL) was added to prepare a TMP ₂ Mg.2LiCl solution.

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), TMP ₂ Mg·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 (6.80 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., and saturated aqueous ammonium chloride solution was added, followed by extraction with chloroform. The combined organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and filtered. 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]oxadiazole-5-carboxylate (904 mg, 52%) as an orange liquid.
¹ H-NMR (CDCl ₃ , 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]

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, after which 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 and then at room temperature for 1 hour. The solvent was evaporated from the resulting mixture under reduced pressure, and THF (8.0 mL) was added to prepare a TMP ₂ Mg.2LiCl solution.

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), TMP ₂ Mg·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., and saturated aqueous ammonium chloride solution was added, followed by extraction with chloroform. The combined organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and filtered. The solvent was then evaporated under reduced pressure. The obtained 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 (CDCl ₃ , 400 MHz) δ (ppm): 8.05 (m, 2H), 7.64 (d, J = 8.5 Hz, 2H), 7.35 (d, J = 8.5 Hz, 2H), 3.72 (s, 3H).
[Example 1]

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 a saturated aqueous solution of sodium bicarbonate 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=1/3) to give compound (1-1-1) (180 mg, 55%) as an orange solid.
¹ H-NMR (CDCl ₃ , 400MHz) δ (ppm): 8.18 (d, J = 7.3 Hz, 1H), 7.97 (d, J = 8.8 Hz, 1H), 7.87 (d, J = 8.8 Hz, 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]

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 give compound (1-2-1) (208 mg, 87%) as a dark green solid.
¹ H-NMR (CDCl ₃ , 400MHz) δ (ppm): 8.61 (d, J = 9.3Hz, 1H), 8.42 (d, J = 7.6Hz, 1H), 8.34 (d, J = 7.6Hz, 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).
_Td3 : 212°C, _Td5 : 240°C, _Td10 : 259°C.
Phase transition temperature: None.
LUMO level: -4.16 eV.
[Example 3]

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, and 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 give compound (1-1-2) (108 mg, 81%) as an orange-yellow solid.
¹ H-NMR (CDCl ₃ , 400MHz) δ (ppm): 8.17 (d, J = 7.3Hz, 1H), 8.11 (s, 1H), 7.70 (d, J = 7.3Hz, 1 H), 7.59 (ddd, J=7.6, 7.4, 1.0Hz, 1H), 7.41 (ddd, J=7.6, 7.4, 1.0Hz, 1H).
[Example 4]

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 solution (1.0 mL), tetrakis(triphenylphosphine)palladium(0) (9.2 mg, 7.96 μmol) was added under an argon stream, 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, 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 (chloroform) to give compound (1-1-95) (52 mg, 96%) as a pink solid.
¹ H-NMR (CDCl ₃ , 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]

Malononitrile (10 mg, 151 μmol) was added to a mixture of 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 compound ( 1-2-95 ) (38 mg, 78%) as a light green solid.
¹ H-NMR (CDCl ₃ , 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°C, T _d5 : 334°C, T _d10 : 359°C.
Phase transition temperature: None.
LUMO level: -4.21 eV.
[Example 6]

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 a saturated aqueous solution of sodium bicarbonate 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 (CDCl ₃ , 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]

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 (CDCl ₃ , 400MHz) δ (ppm): 8.59 (d, J = 9.3 Hz, 1H), 8.52 (d, J = 1.6 Hz, 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).
_Td3 : 248°C, _Td5 : 262°C, _Td10 : 284°C.
Phase transition temperature: None.
LUMO level: -4.11 eV.
[Example 8]

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 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, and 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 give compound (1-1-100) (235 mg, 93%) as an orange solid.
¹ H-NMR (CDCl ₃ , 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]

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 solution (3.3 mL), tetrakis(triphenylphosphine)palladium(0) (29 mg, 24.7 μmol) was added under an argon stream, and the mixture was 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, 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 → 1/3) to give compound (1-1-61) (140 mg, 72%) as a red solid.
¹ H-NMR (CDCl ₃ , 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]

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 (CDCl ₃ , 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).
_Td3 : 270°C, _Td5 : 322°C, _Td10 : 356°C.
Phase transition temperature: 252°C.
LUMO level: -4.17 eV.
[Example 11]

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, and then a saturated aqueous solution of sodium bicarbonate 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 = 1/1 → 0/1) to obtain compound (1-1-9-n6) (861 mg, 75%) as an orange solid.
¹ H-NMR (CDCl ₃ , 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]

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.
¹ H-NMR (CDCl ₃ , 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]

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, and then a saturated aqueous solution of sodium bicarbonate 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=4/1) to obtain compound (1-1-9-n12) (992 mg, 73%) as an orange solid.
¹ H-NMR (CDCl ₃ , 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]

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 obtain compound (1-2-9-n12) (111 mg, 50%) as a dark brown solid.
¹ H-NMR (CDCl ₃ , 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]

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, and 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 give compound (1-1-98-n6) (582 mg, 94%) as an orange solid.
¹ H-NMR (CDCl ₃ , 400MHz) δ (ppm): 8.08 (s, 1H), 8.03 (d, J = 7.5Hz, 1H), 7.52 (d, J = 1.3Hz, 1H), 7.38 (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]

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 solution (10 mL) was added tetrakis(triphenylphosphine)palladium(0) (72 mg, 62.7 μmol) under an argon stream, 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 give compound (1-1-59-n6) (401 mg, 76%) as a red solid.
¹ H-NMR (CDCl ₃ , 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 = 1.4H) z, 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]

Malononitrile (72 mg, 1.08 mmol) was added to a mixture of 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 ( 1-2-59-n6 ) (400 mg, 95%) as a green solid.
¹ H-NMR (CDCl ₃ , 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).
_Td3 : 345°C, _Td5 : 353°C, _Td10 : 368°C.
Phase transition temperature: 211°C.
LUMO level: -4.16 eV.
[Example 18]

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, and then a saturated aqueous solution of sodium bicarbonate 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 = 1/1) to obtain compound (2-1-9-n6) (572 mg, 72%) as an orange solid.
¹ H-NMR (CDCl ₃ , 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]

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 obtain compound (2-2-9-n6) (121 mg, 70%) as a green solid.
¹ H-NMR (CDCl ₃ , 400MHz) δ (ppm): 8.42 (d, J = 9.6 Hz, 1H), 8.22 (d, J = 0.74 Hz, 1H), 7.94 (d, J = 7.6 Hz, 1H), 7.82 (d, J = 9.6 Hz) , 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]

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, 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 = 4/1 → 0/1) to give compound (1-1-3) (1.23 g, 79%) as an orange solid.
¹ H-NMR (CDCl ₃ , 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]

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, and 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 (CDCl ₃ , 400 MHz) δ (ppm): 8.09 (s, 1 H), 8.02 (d, J = 7.8 Hz, 1 H), 7.79 (d, J = 1.9 Hz, 1 H), 7.72 (dd, J = 7.8, 1.9 Hz, 1 H).
[Example 22]

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 solution (1.0 mL) was added tetrakis(triphenylphosphine)palladium(0) (12 mg, 10.2 μmol) and tri(tert-butyl)phosphonium tetrafluoroborate (6.2 mg, 21.4 μmol) under an argon stream, 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 = 10/1 → 3/1) to give compound (1-1-10-n6) (132 mg, 60%) as an orange solid.
¹ H-NMR (CDCl ₃ , 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, 1.2Hz, 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]

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 then 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 (CDCl ₃ , 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]

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 solution (2.0 mL), tetrakis(triphenylphosphine)palladium(0) (30 mg, 26.0 μmol) was added under an argon stream, and the mixture was stirred at 105°C for 3 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 = 1/1) to give compound (1-1-13-n6) (245 mg, 87%) as a red solid.
¹ H-NMR (CDCl ₃ , 400MHz) δ (ppm): 8.21 (d, J = 7.7Hz, 1H), 7.99 (s, 1H), 7.94 (d, J = 1.5 Hz, 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]

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 then distilled off 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 (CDCl ₃ , 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]

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), bis(triphenylphosphine)palladium(II) dichloride (16 mg, 22.2 μmol) and copper(I) iodide (5.2 mg, 27.3 μmol) were added under an argon stream, and the mixture was stirred at 90°C for 1.5 hours. The resulting mixture was cooled to 0°C, and a saturated aqueous ammonium chloride 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 = 3/1 → 0/1) to give compound (1-1-16-m6) (189 mg, 82%) as a red solid.
¹ H-NMR (CDCl ₃ , 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]

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 then distilled off 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.
¹ H-NMR (CDCl ₃ , 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°C, T _d5 : 374°C, T _d10 : 413°C.
Phase transition temperature: 170°C.
LUMO level: -4.22 eV.
[Example 28]
(Evaluation of Solubility)
Chloroform, THF, toluene, and chlorobenzene were added to each of the fused-ring chalcogenadiazole compounds (1 mg) obtained in Examples 2, 7, 10, 12, 14, 17, 19, 23, 25, and 27 to obtain a film-forming composition. 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 time when the compound was completely dissolved was determined visually. The solubility of the evaluated fused-ring chalcogenadiazole compounds is shown in Table 1.

[Example 29]

Under a nitrogen atmosphere, 1.00 mg of 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%).

Next, a silver electrode was formed on a glass substrate by vapor deposition, and a gate insulating film of Parylene C was formed by CVD. The above-mentioned film-forming composition was then drop-cast in a glove box at 60°C in a nitrogen atmosphere 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, creating a bottom-gate-top-contact organic transistor device (the gate electrode was silver, the gate insulating layer was Parylene C, and the source and drain electrodes were gold).

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

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 to 50°C, and allowed to cool to room temperature (25°C) to prepare a composition for forming organic thin films (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.

A bottom-gate/top-contact organic transistor device was fabricated using the same procedure as in Example 29, except that the organic thin film was deposited at room temperature.

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]

Under a nitrogen atmosphere, 0.87 mg of the compound ( 1-2-59-n6 ) synthesized in Example 17, 0.44 mg of polystyrene (Sigma-Aldrich), and 436 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 film-forming composition (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.

A bottom-gate/top-contact organic transistor device was fabricated using the same procedure as in Example 30, except that the organic thin film was formed by spin coating.

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]

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.

The fused-ring chalcogenadiazole compounds provided by the present invention possess high solubility in organic solvents, high heat resistance, a deep LUMO level, and n-type semiconductor properties, and are therefore expected to be used as materials for semiconductor devices, such as organic transistor elements and organic thin-film solar cells.

(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: Substrate 3: Gate electrode 4: Gate insulating layer 5: Source electrode 6: Drain electrode

Claims (13)

A fused ring chalcogenadiazole compound represented by the following general formula (1):
(In the formula, ^J1 represents an oxygen atom, a sulfur atom, or a selenium atom ^{. R1} and R4 ^each independently represent a hydrogen atom; 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 selected from the group consisting of cyano, nitro, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, 2,2,3,3,4,4,4-heptafluorobutyl, alkoxycarbonyl, formyl, imino, trifluoromethoxy, trifluoromethylthio, pentafluorosulfanyl, carboxyl, sulfo, and trifluoromethanesulfonyl, or an alkyl group having 1 to 20 carbon atoms; ^R2 , ^R3 , ^R5 , and ^R6 each represent a hydrogen atom; and ^X1 represents a group represented by the following formula (2):
(In the formula, ^Y1 and ^Y2 represent a cyano group.) The fused ring chalcogenadiazole compound according to claim 1, wherein J ¹ is an oxygen atom or a sulfur atom. The fused chalcogenadiazole compound according to claim 1 or ² , wherein ^R1 and R4 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. 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:
(In the formula, ^J1 represents an oxygen atom, a sulfur atom, or a selenium atom ^{. R1} and R4 ^each independently represent a hydrogen atom; 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 selected from the group consisting of cyano, nitro, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, 2,2,3,3,4,4,4-heptafluorobutyl, alkoxycarbonyl, formyl, imino, trifluoromethoxy, trifluoromethylthio, pentafluorosulfanyl, carboxyl, sulfo, and trifluoromethanesulfonyl, or an alkyl group having 1 to 20 carbon atoms; ^R2 , ^R3 , ^R5 , and ^R6 each represent a hydrogen atom; and Z represents a leaving group.)
(In the formula, J ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the same meanings as defined above.) 5. The process of claim 4 , wherein the acid is an organic Bronsted acid. A method for producing a fused ring chalcogenadiazole compound represented by formula (1b), comprising reacting a fused ring chalcogenadiazole compound represented by formula (1a) with an active methylene compound represented by Y ¹ -CH ₂ -Y ² (5) (wherein Y ¹ and Y ² represent cyano groups).
(In the formula, ^J1 represents an oxygen atom, a sulfur atom, or a selenium atom ^{. R1} and R4 ^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 cyano, nitro, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, 2,2,3,3,4,4,4-heptafluorobutyl, alkoxycarbonyl, formyl, imino, trifluoromethoxy, trifluoromethylthio, pentafluorosulfanyl, carboxyl, sulfo, or trifluoromethanesulfonyl groups, or an alkyl group having 1 to 20 carbon atoms; and ^R2 , ^R3 , ^R5 , and ^R6 each represent a hydrogen atom.)
(In the formula, J ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , Y ¹ and Y ² have the same meanings as defined above.) 7. The method according to claim 6 , wherein Y ¹ and Y ² are both cyano groups. 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:
(In the formula, ^J1 represents an oxygen atom, a sulfur atom, or a selenium atom ^. R4 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 selected from the group consisting of cyano, nitro, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, 2,2,3,3,4,4,4-heptafluorobutyl, alkoxycarbonyl, formyl, imino, trifluoromethoxy, trifluoromethylthio, pentafluorosulfanyl, carboxyl, sulfo, and trifluoromethanesulfonyl, or an alkyl group having 1 to 20 carbon atoms; ^R2 , ^R3 , ^R5 , and ^R6 represent a hydrogen atom; and ^X1 represents a group represented by the following formula (2).)
(In the formula, ^Y1 and ^Y2 represent a cyano group.)
(In the formula, ^J1 and ^X1 are as defined above. ^W1 represents a halogen atom. R10 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 cyano group, nitro group, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, alkoxycarbonyl group, formyl group, imino group, trifluoromethoxy group, trifluoromethylthio group, pentafluorosulfanyl group, carboxyl group, sulfo group, trifluoromethanesulfonyl group, or alkyl group having 1 to 20 carbon atoms; and ^R8 , ^R9 , ^R11 , and ^R12 represent a hydrogen atom.
.) 9. The method for producing a fused ring chalcogenadiazole compound according to claim 8 , wherein the halogenating agent is bromine. A fused ring chalcogenadiazole compound represented by formula (1e) and a metal reagent represented by 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 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 a monocyclic, linked or fused ring aromatic group having 3 to 18 carbon atoms which may be substituted with one or more alkyl groups having 1 to 20 carbon atoms; or an aralkyl group having 7 to 14 carbon atoms. M represents a metal group, Me ₃ Si, Et ₃ Si, Me ₃ Sn, Bu ₃ A method for producing a fused ring chalcogenadiazole compound represented by formula (1f), comprising reacting Sn, B(OH) ₂ , and a group represented by any one of (I) to (VIII) below in the presence of a palladium catalyst and, in some cases, a base.
(In the formula, ^J1 represents an oxygen atom, a sulfur atom, or a selenium atom . ^W2 and ^W3 each independently represent 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 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, with the proviso that at least one of ^W2 and ^W3 is a halogen atom. ^X1 represents a group represented by the following formula (2).)
During the ceremony,
^Y1 and ^Y2 each represent a cyano group.
(In the formula, ^J1 and ^X1 are as defined above. ^R14 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 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, provided that two ^R14s cannot be hydrogen atoms at the same time.) A film-forming composition comprising the fused ring chalcogenadiazole compound according to claim 1 . An organic thin film comprising the fused ring chalcogenadiazole compound according to claim 1 . An organic transistor device comprising the fused ring chalcogenadiazole compound according to claim 1 .