Compounds, organic semiconductor materials, organic electronic devices, and methods for producing ketone compounds from acetal compounds.

Abstract

The present invention provides an organic electronic device with high electron mobility and on / off ratio, an organic semiconductor material suitably usable as a material for the said device, and a compound suitably usable as the said material. [Solution] For example, a compound in which two thienonaphthalenetetracarboxydiimide units (Ac) are linked to an acetal-crosslinked bithiazole unit (Do-A) or a carbonyl-crosslinked bithiazole unit (Do-K), as shown below. TIFF2026095955000021.tif57136

Description

【Technical Field】 【0001】 The present invention relates to a compound suitably used for an organic semiconductor material, an organic semiconductor material containing the compound, an organic electronic device containing the organic semiconductor material, and a method for producing a ketone compound from an acetal compound. 【Background Art】 【0002】 Organic semiconductor materials are important materials in the field of organic electronics, and monomer compounds and polymer compounds are used as organic semiconductor materials. Organic semiconductor materials can be classified into electron-donating p-type organic semiconductor materials and electron-accepting n-type organic semiconductor materials, and various organic electronic devices can be manufactured by appropriately combining p-type organic semiconductor materials and n-type organic semiconductor materials. Examples of organic electronic devices include organic electroluminescence devices that emit light by the action of excitons formed by recombination of electrons and holes, organic thin-film transistor devices that control the amount of current or voltage, organic optoelectronic conversion devices, and organic thin-film solar cell modules that convert light into electric power. 【0003】 The applicant of the present application has proposed a compound suitably used for an organic semiconductor material in Patent Document 1. This compound has one or more donor units containing a unit represented by the following formula (Do-A) and acceptor units, and the donor units and acceptor units are linked to each other. In the following formula (Do-A), R a represents an alkylene group having 2 to 10 carbon atoms, and * represents a bond. 【0004】 【Chemical formula】 【Prior Art Documents】 【Patent Documents】 【0005】 【Patent Document 1】 WO2023 / 106405 [Overview of the Initiative] [Problems that the invention aims to solve] 【0006】 The characteristics of organic electronic devices are often evaluated by electron mobility, on / off ratio, and threshold voltage, and in recent years, there has been a particular demand for further improvements in electron mobility and on / off ratio. 【0007】 An object of the present invention is to provide an organic electronic device with high electron mobility and on / off ratio while maintaining a threshold voltage. Another object of the present invention is to provide an organic semiconductor material that can be suitably used as a material for such organic electronic devices. Another object of the present invention is to provide a compound that can be suitably used as such an organic semiconductor material. Another object of the present invention is to provide a method for producing ketone compounds from acetal compounds. [Means for solving the problem] 【0008】 This invention includes the following inventions. [1] Acetal crosslinked bithiazole unit represented by the following formula (Do-A), or A compound in which two thienonaphthalenetetracarboxydiimide units, represented by the following formula (Ac), are linked to a carbonyl-crosslinked bithiazole unit, represented by the following formula (Do-K). [ka] [In formula (Do-A), R a * represents an alkylene group with 2 to 10 carbon atoms, and * represents a bond. In the equation (Do-K), * represents a bond. In formula (Ac), R 1 Each of these is independently either a hydrogen atom, a hydrocarbon group, or -(CH2) p -OR 4 And R 4 is a hydrocarbon group. p is an integer from 1 to 5. Multiple R1 Among them, R that are identical to each other 1 may be present, and R that are different from each other 1 may be present. In formula (Ac), R 2 is a hydrocarbon group, and q is an integer from 0 to 2. When there are a plurality of R 2 they may be identical to each other, or R 2 that are different from each other 2 may be present. In formula (Ac), R 3 is a hydrocarbon group, and r is an integer from 0 to 1. In formula (Ac), * represents a bond.] [2] An organic semiconductor material containing the compound described in [1]. [3] An organic electronic device containing the organic semiconductor material described in [2]. [4] A method for producing a ketone compound from an acetal compound composed of an acetal-crosslinked bithiazole unit represented by the formula (Do-A) described in [1] and a thienonaphthalenetetracarboxydiimide unit represented by the formula (Ac) described in [1]. 【Effects of the Invention】 【0009】 According to the present invention, when used as a material for an organic electronic device, it is possible to provide a compound that can increase the electron mobility and on / off ratio while maintaining the threshold voltage of the organic electronic device. Further, according to the present invention, it is possible to provide an organic semiconductor material containing such a compound, and an organic electronic device containing the organic semiconductor material. Further, according to the present invention, it is possible to provide a method for producing a ketone compound from an acetal compound. 【Modes for Carrying Out the Invention】 【0010】 The compound in the embodiment of the present invention has two thienonaphthalenetetracarboxydiimide units represented by the following formula (Ac) linked to an acetal-crosslinked bithiazole unit represented by the following formula (Do-A) or a carbonyl-crosslinked bithiazole unit represented by the following formula (Do-K). In the following formula (Do-A), R aR represents an alkylene group with 2 to 10 carbon atoms, and * represents a bond with the thienonaphthalenetetracarboxydiimide unit represented by formula (Ac). In the following formula (Do-K), * represents a bond with the thienonaphthalenetetracarboxydiimide unit represented by formula (Ac). In the following formula (Ac), R 1 Each of these is independently either a hydrogen atom, a hydrocarbon group, or -(CH2) p -OR 4 And R 4 is a hydrocarbon group. p is an integer from 1 to 5. Multiple R 1 Among them, they are all the same R 1 It is also possible for them to be different R 1 It may be present. In the following formula (Ac), R 2 R is a hydrocarbon group, and q is an integer between 0 and 2. 2 If there are multiple instances, they are all the same R. 2 It is also possible for them to be different R 2 It may be present. In the following formula (Ac), R 3 is a hydrocarbon group, and r is an integer between 0 and 1. In the following formula (Ac), * represents a bond with an acetal-crosslinked bithiazole unit represented by the following formula (Do-A), or a carbonyl-crosslinked bithiazole unit represented by the following formula (Do-K). The acetal-crosslinked bithiazole unit represented by formula (Do-A) and the carbonyl-crosslinked bithiazole unit represented by formula (Do-K) are common in that they contain a cyclopentavithiazole skeleton. 【0011】 [ka] 【0012】 Compounds in which two thienonaphthalenetetracarboxydiimide units represented by formula (Ac) are linked to an acetal crosslinked bithiazole unit represented by formula (Do-A) are represented by the following formula (Ac-Do-A), and compounds represented by the following formula (Ac-Do-A-1) are preferred. 【0013】 [ka] 【0014】 [ka] 【0015】 Compounds in which two thienonaphthalenetetracarboxydiimide units represented by formula (Ac) are linked to a carbonyl-crosslinked bithiazole unit represented by formula (Do-K) are represented by the following formula (Ac-Do-K), and compounds represented by the following formula (Ac-Do-K-1) are preferred. 【0016】 [ka] 【0017】 [ka] 【0018】 The acetal-crosslinked bithiazole unit represented by the above formula (Do-A) exhibits excellent electron-donating properties due to the presence of thiazole. Furthermore, the presence of a spiro skeleton containing an acetal structure results in good solubility of the compound in solvents. The carbon chain R constituting this spiro skeleton... a As the number of carbon atoms increases, crystallization is thought to be further inhibited, and therefore the solubility of the compound in the solvent is expected to improve. 【0019】 In the formula (Do-A), R a The alkylene group represented by is preferably 2 to 8 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. 【0020】 R a The alkylene group represented by may be a linear alkylene group or a branched alkylene group, but a linear alkylene group is preferred. 【0021】 R aExamples of such groups include ethylene, n-propylene, 1-methylethane-1,2-yl, 1,2-dimethylethane-1,2-yl, and 1-methylpropane-1,3-yl, with ethylene or n-propylene being preferred among them. 【0022】 In the unit represented by equation (Do-A), R a If is an ethylene group with 2 carbon atoms, the unit represented by formula (Do-A) is represented by the following formula (Do-a). 【0023】 [ka] 【0024】 The carbonyl-crosslinked bithiazole unit represented by the above formula (Do-K) possesses electron-accepting properties due to the presence of a carbonyl group, and it is believed that deepening of the LUMO improves device stability. Furthermore, improved orientation can be expected due to intermolecular interactions by the carbonyl group. Therefore, the performance of organic electronic devices can be improved by including the carbonyl-crosslinked bithiazole unit represented by the formula (Do-K). 【0025】 The thienonaphthalenetetracarboxydiimide unit represented by the above formula (Ac) is a unit in which one thiophene ring is fused to the benzene ring that constitutes naphthalenediimide. In formula (Ac), R 1 Each of these is independently either a hydrogen atom, a hydrocarbon group, or -(CH2) p -OR 4 That is. R 1 When R is a hydrocarbon group (hereinafter sometimes referred to as hydrocarbon group R), it is preferable that the hydrocarbon group is an aliphatic hydrocarbon group, an aralkyl group, etc. 1 If R is an aliphatic hydrocarbon group, 1The group may be a linear aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group, but a linear aliphatic hydrocarbon group is preferred. Because the linear aliphatic hydrocarbon group is expected to improve orientation, it is believed that the electron mobility of the organic electronic device will improve. 【0026】 The number of carbon atoms in the hydrocarbon group R is not particularly limited, but for example, 1 to 30 is preferred. A smaller number of carbon atoms in the hydrocarbon group R is preferable, as the orientation improves as the number of carbon atoms decreases, electrons move more easily between molecules, and the electron mobility of organic electronic devices improves. The number of carbon atoms in the hydrocarbon group R is more preferably 26 or less, even more preferably 22 or less, particularly preferably 20 or less, and most preferably 18 or less. The number of carbon atoms in the hydrocarbon group R may be 2 or more, or 3 or more. That is, the number of carbon atoms in the hydrocarbon group R is more preferably 1 to 26, even more preferably 1 to 22, particularly preferably 1 to 20, and most preferably 1 to 18. Also, the number of carbon atoms in the hydrocarbon group R is more preferably 2 to 26, even more preferably 2 to 22, particularly preferably 2 to 20, and most preferably 2 to 18. Also, the number of carbon atoms in the hydrocarbon group R is more preferably 3 to 26, even more preferably 3 to 22, particularly preferably 3 to 20, and most preferably 3 to 18. When the hydrocarbon group R is an aralkyl group, it is more preferable that the lower limit of the number of carbon atoms in the hydrocarbon group R is 7 or more. That is, the number of carbon atoms in the aralkyl group is more preferably 7 to 30, even more preferably 7 to 26, even more preferably 7 to 22, particularly preferably 7 to 20, and most preferably 7 to 18. 【0027】 Examples of hydrocarbon groups R include C1 alkyl groups such as methyl; C2 alkyl groups such as ethyl; C3 alkyl groups such as n-propyl and isopropyl; C4 alkyl groups such as n-butyl; C5 alkyl groups such as n-pentyl; C6 alkyl groups such as n-hexyl; C7 alkyl groups such as n-heptyl; n-octyl, 1-n-butylbutyl, 1-n-propylpentyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, and 1-methylhexyl groups. C8 alkyl groups such as butyl group, 2-methylheptyl group, 6-methylheptyl group, 2,4,4-trimethylpentyl group, and 2,5-dimethylhexyl group; C9 alkyl groups such as n-nonyl group, 1-n-propylhexyl group, 2-n-propylhexyl group, 1-ethylheptyl group, 2-ethylheptyl group, 1-methyloctyl group, 2-methyloctyl group, 6-methyloctyl group, 2,3,3,4-tetramethylpentyl group, and 3,5,5-trimethylhexyl group; n-decyl group, 1-n-pentylpentyl group, and 1-n-butylhexyl C10 alkyl groups such as n-undecyl group, 1-n-butylheptyl group, 1-n-propylheptyl group, 1-ethyloctyl group, 2-ethyloctyl group, 1-methylnonyl group, 2-methylnonyl group, and 3,7-dimethyloctyl group; C11 alkyl groups such as n-undecyl group, 1-n-butylheptyl group, 2-n-butylheptyl group, 1-n-propyloctyl group, 2-n-propyloctyl group, 1-ethylnonyl group, and 2-ethylnonyl group; n-dodecyl group, 1-n-pentylheptyl group, 2-n-pentylheptyl group, and 1-n-butyloctyl C12 alkyl groups such as n-, 2-n-butyloctyl, 1-n-propylnonyl, and 2-n-propylnonyl; C13 alkyl groups such as n-tridecyl, 1-n-pentyloctyl, 2-n-pentyloctyl, 1-n-butylnonyl, 2-n-butylnonyl, 1-methyldodecyl, and 2-methyldodecyl; C14 alkyl groups such as n-tetradecyl, 1-n-heptylheptyl, 1-n-hexyloctyl, 2-n-hexyloctyl, 1-n-pentylnonyl, and 2-n-pentylnonyl;C15 alkyl groups such as n-pentadecyl group, 1-n-heptyloctyl group, 1-n-hexylnonyl group, and 2-n-hexylnonyl group; C16 alkyl groups such as n-hexadecyl group, 2-n-hexyldecyl group, 1-n-octyloctyl group, 1-n-heptylnonyl group, and 2-n-heptylnonyl group; C17 alkyl groups such as n-heptadecyl group and 1-n-octylnonyl group; C18 alkyl groups such as n-octadecyl group and 1-n-nonylnonyl group; C19 alkyl groups such as n-nonadecyl group; C20 alkyl groups such as n-eicosyl group and 2-n-octyldodecyl group; n- Examples include C21 alkyl groups such as hexacosyl groups; C22 alkyl groups such as n-docosyl groups; C23 alkyl groups such as n-tricosyl groups; C24 alkyl groups such as n-tetracosyl groups and 2-n-decyltetradecyl groups; C25 alkyl groups such as n-pentacosyl; C26 alkyl groups such as n-hexacosyl; C27 alkyl groups such as n-heptacosyl; C28 alkyl groups such as n-octacosyl; C29 alkyl groups such as n-nonacosyl; C30 alkyl groups such as n-triacontyl; and aralkyl groups such as phenylmethyl and phenylethyl groups. 【0028】 R 1 ga-(CH2) p -OR 4 And R 4 If R is a hydrocarbon group, 4 Examples of hydrocarbon groups represented by include those similar to the hydrocarbon group R described above. 4 The number of carbon atoms in the hydrocarbon group represented is preferably 1 to 30, more preferably 3 or more, even more preferably 6 or more, more preferably 28 or less, and even more preferably 26 or less. That is, R 4 The number of carbon atoms in the hydrocarbon group represented is more preferably 3 to 28, and even more preferably 6 to 26. p is preferably an integer from 1 to 4, and more preferably an integer from 1 to 3. 【0029】 In formula (Ac), R 1 A hydrocarbon group is preferred. 【0030】 In formula (Ac), R 2 R is a hydrocarbon group. 2 Examples of hydrocarbon groups represented by include those similar to the hydrocarbon group R described above. 2 The number of carbon atoms in the hydrocarbon group represented is preferably 1 to 30, more preferably 3 or more, even more preferably 6 or more, more preferably 28 or less, and even more preferably 26 or less. That is, R 4 The number of carbon atoms in the hydrocarbon group represented is more preferably 3 to 28, and even more preferably 6 to 26. 【0031】 In formula (Ac), q is preferably an integer between 0 and 1. 【0032】 In formula (Ac), R 3 R is a hydrocarbon group. 3 Examples of hydrocarbon groups represented by include those similar to the hydrocarbon group R described above. 3 The number of carbon atoms in the hydrocarbon group represented is preferably 1 to 30, more preferably 3 or more, even more preferably 6 or more, more preferably 28 or less, and even more preferably 26 or less. That is, R 3 The number of carbon atoms in the hydrocarbon group represented is more preferably 3 to 28, and even more preferably 6 to 26. 【0033】 The above compounds exhibit good solubility in solvents, particularly halogenated organic solvents and / or non-halogenated organic solvents. Examples of halogenated organic solvents include chloroform, tetrachloroethane, and chlorobenzene. Examples of non-halogenated organic solvents include toluene, 1-methylnaphthalene, 2-methylnaphthalene, and orthoxylene. 【0034】 Embodiments of the present invention also include organic semiconductor materials containing the above-mentioned compounds. The carbonyl-crosslinked bithiazole represented by formula (Do-K) contains a carbonyl group and therefore exhibits excellent electron-accepting properties and intermolecular interactions. Consequently, it is expected that device stability will be improved by deepening the LUMO and electron mobility will be enhanced by improved orientation. On the other hand, the acetal-crosslinked bithiazole represented by formula (Do-A) has a spiro skeleton containing an acetal structure, resulting in good solubility in compounds, improved film quality of the coated film, and improved electron mobility of organic electronic devices. 【0035】 The above organic semiconductor material can preferably be used as an n-type organic semiconductor material. 【0036】 Embodiments of the present invention also include organic electronic devices containing the above-mentioned organic semiconductor material. That is, the above-mentioned organic semiconductor material can be suitably used as a material for organic electronic devices, and can be used as a material for organic electronic devices such as organic electroluminescent elements, organic thin-film transistor elements, organic field-effect transistor elements, organic photoelectric conversion elements, and organic thin-film solar cell modules. 【0037】 Next, a method for producing the compound in the embodiment of the present invention will be described. The above compound can be produced, for example, by coupling a compound in which a tin atom having an organic substituent is bonded to the bond of an acetal crosslinked bithiazole unit represented by formula (Do-A) (hereinafter sometimes referred to as raw material A) with a compound in which a halogen atom is bonded to the bond of a thienonaphthalenetetracarboxydiimide unit represented by formula (Ac) (hereinafter sometimes referred to as raw material B) (hereinafter sometimes referred to as the coupling step). 【0038】 For raw material A, a compound represented by the following formula (do-A), corresponding to the acetal crosslinked bithiazole unit represented by the above formula (Do-A), can be used. In the following formula (do-A), R a This is synonymous with the above. 【0039】 [ka] 【0040】 In the compound represented by formula (do-A), R a If is an ethylene group with 2 carbon atoms, the compound represented by formula (do-A) is represented by the following formula (do-a). 【0041】 [ka] 【0042】 In equations (do-A) and (do-a), R 11 and R 12 R represents an organic group, and each is independently a hydrocarbon group. 11 Among them, they are all identical R 11 It is also acceptable to have different R values. 11 It's okay to have multiple R's. 12 Among them, they are all identical R 12 It is also acceptable to have different R values. 12 It's okay to have R 11 , R 12 Examples of hydrocarbon groups represented by include those similar to the hydrocarbon group R described above. 11 , R 12 The number of carbon atoms in the hydrocarbon group represented is preferably 1 to 10, more preferably 2 or more, even more preferably 3 or more, more preferably 5 or less, and even more preferably 4 or less. That is, R 11 , R 12 The number of carbon atoms in the hydrocarbon group represented is more preferably 2 to 5, and even more preferably 3 to 4. 11 and R 12 They may be different from each other, but it is preferable that they be the same. 【0043】 The compound represented by formula (do-A) can be produced, for example, by the method described in Japanese Patent Publication No. 2009-215278. 【0044】 For raw material B, a compound represented by the following formula (ac), corresponding to the thienonaphthalenetetracarboxydiimide unit represented by the above formula (Ac), can be used, and it is preferable to use a compound represented by the following formula (ac-1). In the following formulas (ac) and (ac-1), X represents a halogen atom. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine, with bromine being particularly preferred. In the following formulas (ac) and (ac-1), R 1 , R 2 , R 3 , q, and r are R in equation (Ac). 1 , R 2 , R 3 It is synonymous with q and r. 【0045】 [ka] 【0046】 [ka] 【0047】 It is preferable to carry out a coupling reaction between the organotin compound represented by the above formula (do-A) and the halide represented by the above formula (ac) in the presence of a metal catalyst. 【0048】 Examples of metal catalysts used in coupling reactions include transition metal catalysts such as palladium-based catalysts, nickel-based catalysts, iron-based catalysts, copper-based catalysts, rhodium-based catalysts, and ruthenium-based catalysts. Among these, palladium-based catalysts are preferred. The valency of the palladium contained in the palladium-based catalyst is not particularly limited and may be 0 or 2. 【0049】 Examples of palladium-based catalysts include palladium(II) chloride, palladium(II) bromide, palladium(II) iodide, palladium(II) oxide, palladium(II) sulfide, palladium(II) telluride, palladium(II) hydroxide, palladium(II) selenide, palladium cyanide, palladium acetate, palladium trifluoroacetate, palladium acetylacetonate, diacetate bis(triphenylphosphine)palladium(II), tetrakis(triphenylphosphine)palladium(II), dichlorobis(triphenylphosphine)palladium(II), dichlorobis(acetonitrile)palladium(II), dichlorobis(benzonitrile)palladium(II), dichloro[1,2-bis(diphenylphosphine)ethane]palladium(II), dichloro[1,3-bis(diphenylphosphine)propane]palladium(II), and dichloro[1,4-bis(diphenylphosphine) [1,1-bis(diphenylphosphino)butane]palladium(II), dichloro[1,1-bis(diphenylphosphinoferrocene)]palladium(II), dichloro[1,1-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane adduct, bis(dibenzylideneacetone)palladium(O), tris(dibenzylideneacetone)dipalladium(O), tris(dibenzylideneacetone)dipalladium(O) chloroform adduct, dichloro[1 Examples include ,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene](3-chloropyridyl)palladium(II), bis(tri-tert-butylphosphine)palladium(O), dichloro[2,5-norbornadiene]palladium(II), dichlorobis(ethylenediamine)palladium(II), dichloro(1,5-cyclooctadiene)palladium(II), and dichlorobis(methyldiphenylphosphine)palladium(II). Among these, it is preferable to use tris(dibenzylideneacetone)dipalladium(O) or tris(dibenzylideneacetone)dipalladium(O) chloroform adduct. 【0050】 Examples of copper-based catalysts include copper, copper(I) fluoride, copper(I) chloride, copper(I) bromide, copper(I) iodide, copper(II) fluoride, copper(II) chloride, copper(II) bromide, copper(II) iodide, and other copper halide compounds; as well as copper(I) oxide, copper(I) sulfide, copper(II) oxide, copper(II) sulfide, copper(I) acetate, copper(II) acetate, and copper(II) sulfate. 【0051】 The metal catalyst may be used individually or in a mixture of two or more types. 【0052】 In the coupling process, the molar ratio of the organotin compound represented by formula (do-A) to the metal catalyst [organotin compound represented by formula (do-A):metal catalyst] is, for example, about 1:0.0001 to 1:0.5, preferably 1:0.001 to 1:0.4, more preferably 1:0.005 to 1:0.3, and even more preferably 1:0.01 to 1:0.2. 【0053】 In the coupling step, ligands may be coordinated to the metal catalyst. Examples of ligands include trimethylphosphine, triethylphosphine, tri(n-butyl)phosphine, tri(isopropyl)phosphine, tri(tert-butyl)phosphine, bis(tert-butyl)methylphosphine, tricyclohexylphosphine, diphenyl(methyl)phosphine, triphenylphosphine, tris(o-tolyl)phosphine, tris(m-tolyl)phosphine, tris(p-tolyl)phosphine, tris(2-furyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(3- Methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tri-tert-butylphosphonium tetrafluoroborate, 2-dicyclohexylphosphinobiphenyl, 2-dicyclohexylphosphino-2'-methylbiphenyl, 2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl, 2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl, 2-dicyclohexylphosphino-2'-(N,N'-dimethylamino)biphenyl, 2- Diphenylphosphino-2'-(N,N'-dimethylamino)biphenyl, 2-(di-tert-butyl)phosphino-2'-(N,N'-dimethylamino)biphenyl, 2-(di-tert-butyl)phosphinobiphenyl, 2-(di-tert-butyl)phosphino-2'-methylbiphenyl, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(dicyclohexylphosphino)ethane, 1,3-bis(dicyclohexyl Xylphosphino)propane, 1,4-bis(dicyclohexylphosphino)butane, 1,2-bisdiphenylphosphinoethylene, 1,1'-bis(diphenylphosphino)ferrocene, 1,2-ethylenediamine, N,N,N',N'-tetramethylethylenediamine, 2,2'-bipyridyl, 1,3-diphenyldihydroimidazolylidene, 1,3-dimethyldihydroimidazolylidene, diethyldihydroimidazolylidene, 1,3-bis(2,Examples include 6-diisopropylphenyl)dihydroimidazolylidene, 1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, and batphenanthroline. Among these, trimethylphosphine, triethylphosphine, tri(n-butyl)phosphine, tri(isopropyl)phosphine, tri(tert-butyl)phosphine, bis(tert-butyl)methylphosphine, tricyclohexylphosphine, diphenyl(methyl)phosphine, triphenisphosphine, tris(o-tolyl)phosphine, tris(m-tolyl)phosphine, tris(p-tolyl)phosphine, tris(2-furyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(3-methoxyphenyl)phosphine, and tris(4-methoxyphenyl)phosphine are preferred, with tris(2-methoxyphenyl)phosphine being more preferred. 【0054】 Ligands may be used individually or in combination of two or more types. 【0055】 When a ligand is coordinated to a metal catalyst, the molar ratio of the metal catalyst to the ligand (metal catalyst:ligand) is, for example, about 1:0.5 to 1:10, preferably 1:1 to 1:8, more preferably 1:1 to 1:7, and even more preferably 1:1 to 1:5. 【0056】 In the coupling step, it is preferable to use a solvent, and the solvent is not particularly limited as long as it does not affect the reaction. For example, ether-based solvents, aromatic solvents, ester-based solvents, hydrocarbon-based solvents, halogen-based solvents, ketone-based solvents, amide-based solvents, nitrile-based solvents, sulfoxide-based solvents, sulfone-based solvents, etc., can be used. 【0057】 Examples of ether-based solvents include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, tert-butyl methyl ether, and dioxane. Examples of aromatic solvents include benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, and tetralin. Examples of ester-based solvents include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, and butyl acetate. Examples of hydrocarbon-based solvents include pentane, hexane, heptane, octane, and decalin. Examples of halogen-based solvents include dichloromethane, chloroform, dichloroethane, and dichloropropane. Examples of ketone-based solvents include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and 1,3-dimethyl-3,4,5,6-tetrahydro-(1H)-pyrimidine. Examples of nitrile solvents include acetonitrile. Examples of sulfoxide solvents include dimethyl sulfoxide. Examples of sulfone solvents include sulfolane. Among these, aromatic solvents are preferred, and chlorobenzene is more preferred. 【0058】 The solvent may be used alone or as a mixture of two or more solvents. 【0059】 The amount of solvent used in the coupling step is, for example, 1 mL to 150 mL, preferably 5 mL or more, more preferably 8 mL or more, preferably 100 mL or less, and more preferably 80 mL or less, per 1 g total of the organotin compound represented by formula (do-A) and the halide represented by formula (ac). That is, it is about 1 to 150 mL, preferably 5 to 100 mL, and more preferably 8 to 80 mL. 【0060】 The reaction temperature in the coupling step is not particularly limited, but from the viewpoint of increasing the reaction yield, it is preferably 0°C or higher and 200°C or lower, more preferably 30°C or higher, even more preferably 40°C or higher, even more preferably 180°C or lower, and even more preferably 150°C or lower. That is, the reaction temperature is preferably 0 to 200°C, more preferably 30 to 180°C, and even more preferably 40 to 150°C. 【0061】 After the coupling reaction, solid-liquid separation is performed according to a conventional method, and the recovered solid is washed to produce a compound in which two thienonaphthalenetetracarboxydiimide units represented by the above formula (Ac) are bonded to an acetal crosslinked bithiazole unit represented by the above formula (Do-A). The compound can be isolated, for example, by removing the catalyst by Celite filtration, concentrating the compound, and then dispersing and washing the resulting solid. 【0062】 A ketone compound can be produced by heating and stirring an acetal compound, in which two thienonaphthalenetetracarboxydiimide units represented by the above formula (Ac) are bonded to an acetal cross-linked bithiazole unit represented by the above formula (Do-A), in the presence of water under acidic conditions, thereby changing the acetal structure to a ketone structure. A ketone compound is a compound in which two thienonaphthalenetetracarboxydiimide units represented by the above formula (Ac) are bonded to a carbonyl cross-linked bithiazole unit represented by the above formula (Do-K). 【0063】 When heating and stirring acetal compounds, acidic conditions can be maintained using inorganic and / or organic acids. For example, hydrochloric acid can be used as an inorganic acid. For example, acetic acid can be used as an organic acid. Inorganic and organic acids may be used individually or in combination. 【0064】 The heating temperature when heating and stirring the acetal compound is not particularly limited, but from the viewpoint of increasing the reaction yield, it is preferably 20°C or higher and 150°C or lower, more preferably 30°C or higher, even more preferably 40°C or higher, even more preferably 140°C or lower, and even more preferably 130°C or lower. That is, the reaction temperature is preferably 20 to 150°C, more preferably 30 to 140°C, and even more preferably 40 to 130°C. [Examples] 【0065】 The present invention will be described in more detail below with reference to examples, but the present invention is not limited by the following examples, and it is of course possible to implement it with modifications within the scope that is consistent with the spirit described above and below, and all such modifications are included within the technical scope of the present invention. In the following, unless otherwise specified, "%" means "mass%". 【0066】 A predetermined compound was synthesized, and an organic electronic device was manufactured using this compound as an organic semiconductor material. The performance of the organic electronic device was then evaluated. 【0067】 In the following example, 1 H-NMR spectroscopy was performed using the following instrument. ( 1 (H-NMR spectroscopy measurement) For the measurement of compound 1 and comparative compound 1, a Varian "400-MR" instrument was used, and for the measurement of compounds 2-4, a Bruker "AVANCE NEO 500" instrument was used. 1 1H-NMR spectroscopy was performed. 【0068】 (Raw material for compounds) Compound H was prepared based on Example 2 described in Japanese Patent Publication No. 2009-215278. Compound H is 2,5-Bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bisthiazole-7,2'-[1,3]dioxolane], and may hereafter be referred to as Ac-CBTZ-SB. The formation of the target compound H was confirmed by... 1 This was confirmed by 1H-NMR spectroscopy. N,N'-dioctyl-2-bromonaphtho[2,3-b]thiophene-4,5,8,9-diimide (hereinafter sometimes referred to as no-NDIThBr) and N,N'-didodecyl-2-bromonaphtho[2,3-b]thiophene-4,5,8,9-diimide (hereinafter sometimes referred to as DDE-NDITh-Br) were synthesized according to J.Mater.Chem.C,2016,4,8879-8883. 【0069】 (Compound 1) In a 20 mL flask, Ac-CBTZ-SB (16.9 mg, 0.020 mmol), no-NDIThBr (25.2 mg, 0.040 mmol), tris(dibenzylideneacetone)dipalladium(0)chloroform adduct (2 mg, 0.006 mmol), tris(2-methoxyphenyl)phosphine (2.8 mg, 0.025 mmol), and chlorobenzene (0.6 mL) were added and reacted at 130 °C for 17 hours. After the reaction was complete, the mixture was concentrated, chloroform (4 mL) and methanol (1 mL) were added, and the precipitated solid was filtered off. As a result, 8 mg of a dark blue solid (yield 29.1%) was obtained. NMR spectroscopy revealed that the obtained dark blue solid was Ac-CBTZ-2 (no-NDITh) (hereinafter sometimes referred to as compound 1). 1 H NMR (400MHz, CDCl3):9.475(s, 2H),8.774(s, 4H),4.633(s, 4H),4.258-4.2 08(m, 8H), 1.796-1.738(m, 8H), 1.408-1.314(m, 40H), 0.889-0.778(m, 12H) 【0070】 [ka] 【0071】 (Compound 2) Compound 1, Ac-CBTZ-2(no-NDITh) (~0.1 mg), was placed in an NMR tube and dissolved in deuterated chloroform (0.75 g). Acetic acid (0.1 mL) and hydrochloric acid (0.1 mL) were added, and the mixture was reacted at 55°C for 24 hours. After the reaction was complete, the sample was removed from the tube and concentrated. The NMR spectrum of the concentrated sample was measured, and the resulting dark blue solid was identified as CBTZ-2(no-NDITh) (hereinafter sometimes referred to as Compound 2). 1 H NMR (500MHz, CDCl3): 9.515 (s, 2H), 8.813 (s, 4H), 4.258-4.210 (m, 8H), 1.741-1.605 (m, 8H), 1.408-1.214 (m, 40H), 0.868-0.853 (m, 12H) 【0072】 [ka] 【0073】 (Compound 3) In a 20 mL flask, Ac-CBTZ-SB (60.7 mg, 0.0735 mmol), DDE-NDITh-Br (108.6 mg, mmol), tris(dibenzylideneacetone)dipalladium(0)chloroform adduct (6 mg, mmol), tris(2-methoxyphenyl)phosphine (9.2 mg, mmol), and chlorobenzene (2.4 mL) were added and reacted at 130 °C for 17 hours. After the reaction was complete, the filtrate was filtered by Celite and concentrated. Chloroform (7 mL) and methanol (10 mL) were added, and the precipitated solid was collected by filtration. As a result, 85.9 mg (75% yield) of a dark blue solid was obtained. NMR spectroscopy revealed that the obtained dark blue solid was Ac-CBTZ-2 (DDE-NDITh) (hereinafter sometimes referred to as compound 3). 【0074】 [ka] 【0075】 (Compound 4) Ac-CBTZ-2(DDE-NDITh) (30 mg) was placed in a 20 mL flask and dissolved in chlorobenzene (15 mL). Acetic acid (3 mL) and hydrochloric acid (0.75 mL) were added and the mixture was reacted at 100 °C for 15 hours. After the reaction was complete, the mixture was washed with water and sodium bicarbonate aqueous solution, and the resulting organic layer was dried over magnesium sulfate, filtered, and concentrated. The obtained solid was dispersed in methanol (3 mL), and the precipitated solid was filtered off to obtain 9.6 mg (yield 33%) of a dark blue solid. NMR spectroscopy revealed that the obtained dark blue solid was CBTZ-2(DDE-NDITh) (hereinafter sometimes referred to as compound 4). 【0076】 [ka] 【0077】 (Comparative compound 1) In a 20 mL flask, Ac-CBTZ-SB (60 mg, 0.0735 mmol), 4-bromo-2,7-dioctyl-benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetrone (no-NDI-MB, 83.5 mg, 0.147 mmol), tris(dibenzylideneacetone)dipalladium(0)chloroform adduct (6 mg, 5.9 μmol), tris(2-methoxyphenyl)phosphine (8.9 mg, 25.0 μmol), and chlorobenzene (4 mL) were added and reacted at 130 °C for 16 hours. After the reaction was complete, the mixture was filtered by Celite and concentrated. Further, methanol (7 mL) was added, and the precipitated solid was filtered off, yielding a dark blue solid of 71.7 mg (80% yield). NMR spectroscopy revealed that the resulting dark blue solid was Ac-CBTZ-2(no-NDI) (hereinafter sometimes referred to as comparative compound 1). 1H NMR(400MHz,CDCl3):9.341(s,2H),8.832(d,2H),8.787(d,2H),4.596(s,4H),4.218(quin,8H),1.535-1.153(m,48H),0.826(t,12H) 【0078】 [ka] 【0079】 Next, an organic electronic device is manufactured using the obtained compounds 1-4 and comparative compound 1 as organic semiconductor materials, and the electron mobility μ of the organic electronic device is determined. e (cm 2 / Vs), threshold voltage Vth (V), on / off ratio (I on / I off ) was measured. 【0080】 (Example 1-1) An ozone-treated silicon substrate was treated with octadecyltrichlorosilane (ODTS). A 1-methylnaphthalene solution with a concentration of 1% by mass (10 mg / mL) of compound 1 was prepared, filtered, and then spin-coated onto the treated substrate surface to fabricate organic field-effect transistor (OFET) elements. The fabricated OFTE elements were annealed at 100°C for 30 minutes, allowed to cool, annealed at 150°C for 30 minutes, allowed to cool, and then the Id-Vg characteristics were measured. The Id-Vg characteristics were measured under a nitrogen atmosphere. A Keithley Instruments "4200-SCS" was used for Id-Vg characteristic measurement, with a channel length of 25 μm and a channel width of 294 mm for the organic semiconductor element. From the Id-Vg characteristics measurement, electron mobility, threshold voltage, and on / off ratio were determined. 【0081】 (Examples 1-2) In Example 1-1, the electron mobility, threshold voltage, and on / off ratio were determined under the same conditions as in Example 1-1, except that hexamethyldisilazane (HMDS) was used instead of octadecyltrichlorosilane (ODTS) for the ozone-treated silicon substrate, and the Id-Vg characteristics were measured after annealing at 100°C for 30 minutes and cooling of the fabricated OFT element. 【0082】 (Examples 1-3) In Example 1-1, the electron mobility, threshold voltage, and on / off ratio were determined under the same conditions as in Example 1-1, except that the ozone-treated silicon substrate was treated with hexamethyldisilazane (HMDS) instead of octadecyltrichlorosilane (ODTS), and the fabricated OFTE element underwent annealing at 100°C for 30 minutes, followed by cooling, annealing at 150°C for 30 minutes, cooling, annealing at 180°C for 30 minutes, and then the Id-Vg characteristics were measured. 【0083】 (Examples 1-4) An ozone-treated silicon substrate was treated with octadecyltrichlorosilane (ODTS). A tetrachloroethane solution of compound 1 at a concentration of 1% by mass (16 mg / mL) was prepared, filtered, and then drop-cast onto the treated substrate surface to fabricate an organic field-effect transistor (OFET) element. The Id-Vg characteristics of the fabricated OFT elements were measured (without annealing). The Id-Vg characteristics were measured under a nitrogen atmosphere. A Keithley Instruments "4200-SCS" was used for Id-Vg characteristic measurement, with a channel length of 25 μm and a channel width of 294 mm for the organic semiconductor element. From the Id-Vg characteristics measurement, electron mobility, threshold voltage, and on / off ratio were determined. 【0084】 (Examples 1-5) In Examples 1-4, the electron mobility, threshold voltage, and on / off ratio were determined under the same conditions as in Examples 1-3, except that hexamethyldisilazane (HMDS) was used instead of octadecyltrichlorosilane (ODTS) for the ozone-treated silicon substrate, and the fabricated OFT elements were annealed at 100°C for 30 minutes, allowed to cool, then annealed at 150°C for 30 minutes, allowed to cool, and then the Id-Vg characteristics were measured. 【0085】 (Example 2-1) An ozone-treated silicon substrate was treated with octadecyltrichlorosilane (ODTS). A 1-methylnaphthalene solution with a concentration of compound 2 at 1% by mass (10 mg / mL) was prepared, filtered, and then spin-coated onto the treated substrate surface to fabricate an organic field-effect transistor (OFET) element. The Id-Vg characteristics of the fabricated OFTE element were measured (without annealing). The Id-Vg characteristics were measured under a nitrogen atmosphere. A Keithley Instruments "4200-SCS" was used for Id-Vg characteristic measurement, with a channel length of 25 μm and a channel width of 294 mm for the organic semiconductor element. From the Id-Vg characteristics measurement, electron mobility, threshold voltage, and on / off ratio were determined. 【0086】 (Example 2-2) In Example 2-1, the electron mobility, threshold voltage, and on / off ratio were determined under the same conditions as in Example 2-1, except that hexamethyldisilazane (HMDS) was used instead of octadecyltrichlorosilane (ODTS) for the ozone-treated silicon substrate, and the Id-Vg characteristics were measured after annealing at 100°C for 30 minutes, cooling, annealing at 150°C for 30 minutes, cooling, annealing at 180°C for 30 minutes, and cooling of the fabricated OFT element. 【0087】 (Comparative Example 1-1) Ozone-treated silicon substrates were treated with octadecyltrichlorosilane (ODTS). Organic field-effect transistor (OFET) elements were fabricated by spin-coating a 1-methylnaphthalene solution containing comparative compound 1 at a concentration of 1% by mass (10 mg / mL) onto the treated substrate surface. The fabricated OFTE elements were annealed at 100°C for 30 minutes, allowed to cool, annealed at 150°C for 30 minutes, and allowed to cool before measuring the Id-Vg characteristics. The Id-Vg characteristics were measured under a nitrogen atmosphere. A Keithley Instruments "4200-SCS" was used for measuring the Id-Vg characteristics, with a channel length of 25 μm and a channel width of 294 mm for the organic semiconductor element. Electron mobility, threshold voltage, and on / off ratio were determined from the Id-Vg characteristics. 【0088】 (Comparative Example 1-2) In Comparative Example 1-1, the electron mobility, threshold voltage, and on / off ratio were determined under the same conditions as in Comparative Example 1-1, except that hexamethyldisilazane (HMDS) was used instead of octadecyltrichlorosilane (ODTS) for the ozone-treated silicon substrate, and the Id-Vg characteristics were measured after annealing at 100°C for 30 minutes and cooling of the fabricated OFT element. 【0089】 (Comparative Examples 1-3) In Comparative Example 1-1, the electron mobility, threshold voltage, and on / off ratio were determined under the same conditions as in Comparative Example 1-1, except that the ozone-treated silicon substrate was treated with hexamethyldisilazane (HMDS) instead of octadecyltrichlorosilane (ODTS), and the fabricated OFT element underwent annealing at 100°C for 30 minutes, followed by cooling, annealing at 150°C for 30 minutes, cooling, annealing at 180°C for 30 minutes, and then the Id-Vg characteristics were measured. 【0090】 The conditions, along with the calculated electron mobility, threshold voltage, and on / off ratio, are shown in Tables 1-1 and 1-2 below. 【0091】 [Table 1-1] 【0092】 Table 1-2 【0093】 From Tables 1-1 and 1-2, the following can be considered: Compound 1 used in Examples 1-1 to 1-5 is a compound in which two thienonaphthalenetetracarboxydiimide units represented by formula (Ac) are linked to an acetal-crosslinked bithiazole unit represented by formula (Do-A). Compound 2 used in Examples 2-1 and 2-2 is a compound in which two thienonaphthalenetetracarboxydiimide units represented by formula (Ac) are linked to a carbonyl-crosslinked bithiazole unit represented by formula (Do-K). Comparative compound 1 used in Comparative Examples 1-1 to 1-3 contains a naphthalenetetracarboxydiimide skeleton and is a compound that does not satisfy the requirements defined in the present invention. It can be seen that by using compound 1 as a material for organic electronic devices, electron mobility and on / off ratio can be improved while maintaining a threshold voltage of 30V or less, compared to when comparative compound 1 is used as a material for organic electronic devices. Specifically, Example 1-1 and Comparative Example 1-1 are examples of organic field-effect transistor elements fabricated under the same conditions except for a change in the compound. A comparison of these shows that using compound 1 improves electron mobility and on / off ratio while maintaining a threshold voltage of 30V or less. Similarly, Example 1-2 and Comparative Example 1-2 are examples of organic field-effect transistor elements fabricated under the same conditions except for a change in the compound. A comparison of these shows that using compound 1 improves electron mobility and on / off ratio while maintaining a threshold voltage of 30V or less. Similarly, Example 1-3 and Comparative Example 1-3 are examples of organic field-effect transistor elements fabricated under the same conditions except for a change in the compound. A comparison of these shows that in Comparative Example 1-3, insulation occurred and it did not function as an organic field-effect transistor element, but by using compound 1, it was possible to exhibit the characteristics of an organic field-effect transistor element. Furthermore, it can be seen that organic electronic devices can be manufactured by both spin coating and drop casting using compound 1. It has been found that by using compound 2 as a material for organic electronic devices, electron mobility and on / off ratio can be improved, and the threshold voltage can be further reduced.

Claims

[Claim 1] Acetal crosslinked bithiazole unit represented by the following formula (Do-A), or The carbonyl crosslinked bithiazole unit represented by the following formula (Do-K) A compound in which two thienonaphthalenetetracarboxydiimide units, represented by the following formula (Ac), are linked together. 【Chemistry 1】 [In formula (Do-A), R ａ represents an alkylene group with 2 to 10 carbon atoms, and * represents a bond. In equation (Do-K), * represents a bond. In formula (Ac), R １ is, independently of one another, a hydrogen atom, a hydrocarbon group, or -(CH ２ ) ｐ -OR ４ where R ４ is a hydrocarbon group. p is an integer from 1 to 5. Among a plurality of R １ , there may be R １ that are identical to each other, or there may be R １ that are different from each other. In formula (Ac), R ２ R is a hydrocarbon group, and q is an integer between 0 and 2. ２ If there are multiple instances, they are all the same R. ２ There may be different R values. ２ It's okay to have that. In formula (Ac), R ３ is a hydrocarbon group, and r is an integer between 0 and 1. In equation (Ac), * represents a bond. [Claim 2] An organic semiconductor material comprising the compound described in claim 1. [Claim 3] An organic electronic device comprising the organic semiconductor material described in claim 2. [Claim 4] A acetal crosslinked bithiazole unit represented by formula (Do-A) as described in claim 1, A method for producing a ketone compound from an acetal compound composed of a thienonaphthalenetetracarboxydiimide unit represented by formula (Ac) as described in claim 1.

Images