Compound and method for producing the same

Abstract

To provide a novel aromatic condensed ring compound having high solubility in an organic solvent without employing introduction of a long-chain alkyl group, conversion to liquid-crystalline molecules, or oligomerization, which are not effective for hole or electron transport.SOLUTION: A compound having a unit skeleton represented by the following formula (I) or the following formula (II).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to novel aromatic fused ring compounds having highly soluble spiro rings and a method for producing the same. [Background technology]

[0002] Aromatic fused rings are widely used as molecular backbones for functional molecules, such as hole transport materials, hole introduction materials, hole extraction materials, electron transport materials, electron introduction materials, electron extraction materials, and host materials used in organic semiconductor materials and organic-inorganic semiconductors, including OLEDs, OPVs, OFETs, perovskite solar cells, and perovskite quantum dots.

[0003] In order to produce a multilayer thin film using an organic semiconductor of an aromatic fused ring compound having hole or electron transport properties, it is essential to improve the solubility of the aromatic fused ring compound in organic solvents. However, aromatic fused ring compounds generally have very poor solubility in organic solvents. To address this issue, conventional methods for ensuring solubility have been adopted, such as introducing long-chain alkyl groups into aromatic fused ring compounds, converting them into liquid crystal-type molecules, and oligomerization. However, the effect of introducing these solubility-enhancing moieties is limited, and they have the major drawback of relatively reducing the proportion of aromatic fused rings in a molecule, which are necessary for hole and electron transfer. In addition, there is also the problem of increased intramolecular vibration, which reduces the function as a semiconductor.

[0004] For this reason, there is a limit to the application of conventional aromatic fused ring compounds to coating methods in which they are dissolved in organic solvents, and this has been an obstacle to their practical use. Therefore, the evaporation method is currently used for OLED smartphones and OLED TVs.

[0005] Studies have also been conducted to improve the solubility of aromatic fused ring compounds themselves so that they can be applied to coating methods. However, conventional techniques require multi-stage synthesis, which makes purification at each synthesis stage difficult, and even after purification, trace amounts of impurities remain, making them impractical and limiting them to academic research (Non-Patent Document 1).

[0006] Furthermore, methods for producing aromatic fused ring compounds, especially aromatic heterocyclic compounds, are limited, and ring construction has traditionally been carried out using precious metal catalysts, particularly palladium catalysts. However, while the development of production methods using non-precious metal catalysts is urgently needed from the perspective of realizing a sustainable society and green transformation, the production of diverse aromatic fused ring compounds with desirable physical properties using non-precious metal catalysts remains difficult. [Prior art documents] [Non-patent literature]

[0007] [Non-Patent Document 1] Solution-Processed Organic Light-emitting Devices, 2024 Published by Elsevier Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention aims to provide a novel aromatic fused ring compound that has high solubility in organic solvents without employing techniques such as the introduction of long-chain alkyl groups, liquid crystal molecularization, and oligomerization that are ineffective in hole or electron transport, and a production method for producing this aromatic fused ring compound using a non-noble metal catalyst that is suitable for a sustainable society. [Means for solving the problem]

[0009] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have constructed novel aromatic fused ring compounds having spiro skeletons that are highly soluble even without a long-chain alkyl group as a solubility group, and have established a method for producing the novel aromatic fused ring compounds by a synthesis method using a non-precious metal catalyst without using a precious metal. Furthermore, they have clarified that highly soluble p-type or n-type organic semiconductor compounds can be derived from these aromatic fused rings as the parent skeleton, thereby arriving at the present invention. That is, the gist of the present invention is as follows.

[0010] [1] A compound having a unit skeleton represented by the following formula (I) or (II):

[0011] [ka]

[0012] (In formula (I), Ar a represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocycle which may have a substituent, Ar b represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent. Ar 1 and Ar 2 each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent; Ar 1 and Ar 2 are bonded to each other directly or via a linker to form a fused ring containing an optionally substituted aromatic hydrocarbon ring and / or an optionally substituted aromatic heterocycle. In formula (II), Ar a and Ar c each independently represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocycle which may have a substituent. Ar 1 , Ar 2 , Ar 3 and Ar 4each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent; Ar 1 and Ar 2 , Ar 3 and Ar 4 are bonded to each other directly or via a linker to form a fused ring containing an optionally substituted aromatic hydrocarbon ring and / or an optionally substituted aromatic heterocycle.

[0013] [2] The compound having a unit skeleton represented by the formula (I) is 1 and Ar 2 and the solubility in chlorobenzene is at least twice that of a compound having a unit skeleton that does not form a fused ring containing an optionally substituted aromatic hydrocarbon ring and / or an optionally substituted aromatic heterocycle, The compound having a unit skeleton represented by the formula (II) is 1 and Ar 2 , Ar 3 and Ar 4 The compound according to [1] has a solubility in chlorobenzene that is at least twice as high as that of a compound having a unit skeleton that does not form a fused ring, including an optionally substituted aromatic hydrocarbon ring and / or an optionally substituted aromatic heterocycle.

[0014] [3] A method for producing the compound according to [1] or [2], comprising a reaction step of oxidizing a compound represented by the following formula (III) or the following formula (IV) in the presence of a divalent iron compound, a trivalent phosphorus compound, and magnesium:

[0015] [ka]

[0016] (In formula (III) and formula (IV), Z 1 , Z 2 , Z 3 each independently represents a silyl group or a methyl group which may have a substituent. Ar a , Ar b , Ar c , Ar 1 , Ar 2 , Ar 3 , Ar 4 are the same as defined in the formula (I) or (II).

[0017] [4] A method for producing the compound according to [3], characterized in that in the reaction step, lithium halide is co-present when forming the intermediate magnesium cyclized product.

[0018] [5] The method according to [3] or [4], wherein the oxidation reaction in the reaction step uses at least one oxidant selected from the group consisting of air, oxygen, a halogen compound, and an organic peroxide.

[0019] [6] A semiconductor compound having a unit skeleton represented by the following formula (I) or (II) as a mother skeleton:

[0020] [ka]

[0021] (In formula (I), Ar a represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocycle which may have a substituent, Ar b represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent. Ar 1 and Ar 2 each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent; Ar 1 and Ar 2 are bonded to each other directly or via a linker to form a fused ring containing an optionally substituted aromatic hydrocarbon ring and / or an optionally substituted aromatic heterocycle. In formula (II), Ar a and Ar ceach independently represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocycle which may have a substituent. Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent; Ar 1 and Ar 2 , Ar 3 and Ar 4 are bonded to each other directly or via a linker to form a fused ring containing an optionally substituted aromatic hydrocarbon ring and / or an optionally substituted aromatic heterocycle.

[0022] [7] The semiconductor compound according to [6], which is a p-type semiconductor or an n-type semiconductor.

[0023] [8] An organic semiconductor device comprising an organic semiconductor device film containing the semiconductor compound according to [6] or [7].

[0024] [9] A film-forming ink for an organic semiconductor device, comprising the semiconductor compound according to [6] or [7] and an organic solvent. [Effects of the Invention]

[0025] According to the present invention, a highly soluble aromatic fused ring skeleton is provided without employing methods generally used to improve the organic solvent solubility of the aromatic fused ring mother skeleton, such as the introduction of a long-chain alkyl group, liquid crystal molecularization, oligomerization, etc. Therefore, the effect of hole or electron transfer is not reduced by the introduction of a functional group that is effective in improving solubility in organic solvents but is not involved in hole or electron transfer. The aromatic fused ring of the spiro skeleton according to the present invention is Ar 1 and Ar 2 , Ar in the formula (II) 1 and Ar 2 , Ar 3 and Ar 4are bonded to each other directly or via a linker to form a fused ring containing an aromatic hydrocarbon ring which may have a substituent and / or an aromatic heterocycle which may have a substituent, and therefore the molecular structure becomes rigid, and an effective main skeleton can be constructed from the viewpoints of improving the mobility of electrons and holes and suppressing side absorptions in the absorption spectrum. Furthermore, when the aromatic fused ring compound of the present invention is derivatized, it can be used as a p-type or n-type small molecule semiconductor compound for organic semiconductor devices. Due to its excellent solubility in organic solvents, it can be made into an ink using an organic solvent, and can be used to form a thin film by a coating method. DETAILED DESCRIPTION OF THE INVENTION

[0026] Hereinafter, an embodiment of the present invention will be described, but the embodiment of the present invention is not limited to the following embodiment. In the present invention, the terms "aromatic hydrocarbon ring" and "aromatic heterocycle" are not limited to monocyclic aromatic hydrocarbon rings and monocyclic aromatic heterocycles, but also include aromatic hydrocarbon rings and monocyclic aromatic heterocycles having two or more condensed rings. Furthermore, the compound having a unit skeleton in the present invention means a low molecular weight compound having the formula (I) or (II) described below as the minimum unit, or an oligomer or polymer formed by linking these molecules.

[0027] [Compounds of the present invention] One aspect of the present invention is a compound having a unit skeleton represented by the following formula (I) or the following formula (II).

[0028] [ka]

[0029] (In formula (I), Ar a represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocycle which may have a substituent, Ar b represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent. Ar 1 and Ar2 each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent; Ar 1 and Ar 2 are bonded to each other directly or via a linker to form a fused ring containing an optionally substituted aromatic hydrocarbon ring and / or an optionally substituted aromatic heterocycle. In formula (II), Ar a and Ar c each independently represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocycle which may have a substituent. Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent; Ar 1 and Ar 2 , Ar 3 and Ar 4 are bonded to each other directly or via a linker to form a fused ring containing an optionally substituted aromatic hydrocarbon ring and / or an optionally substituted aromatic heterocycle.

[0030] The mechanism by which the compound of the present invention has high solubility in organic solvents is believed to be as follows.

[0031] That is, an example of a partial structure of the compound of the present invention is shown below. The carbon atom C1 is an sp3 carbon atom, and the angle between the aromatic rings above and below it is approximately 90°. This prevents steric hindrance and fixes the structure, which is thought to impart high solubility. The high solubility of the compound of the present invention in organic solvents can be confirmed by its solubility in chlorobenzene. The solubility is measured at 25°C, and specifically, it is preferably measured by the method described in the Examples below.

[0032] [ka]

[0033] Ar in formula (I) a , Ar in formula (II) a , Ar c Examples of the aromatic hydrocarbon ring include aromatic hydrocarbon rings having 6 to 12 carbon atoms, such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, a phenanthrene ring, and an azulene ring. Examples of the aromatic heterocycle include aromatic heterocycles having 2 to 10 carbon atoms, such as a pyrrole ring, a furan ring, a pyridine ring, a thiophene ring, an imidazole ring, a pyrazole ring, a thiazole ring, a dibenzofuran ring, and a dibenzothiophene ring, and having one or more hetero atoms selected from sulfur atoms, oxygen atoms, and nitrogen atoms as hetero atoms. Among these, a monocyclic or bicondensed aromatic hydrocarbon ring having 12 or less carbon atoms, or a monocyclic or bicondensed aromatic heterocyclic ring is preferred, and an aromatic heterocyclic ring having 6 or less carbon atoms, such as a benzene ring, a thiophene ring, a pyrrole ring, a furan ring, or a pyridine ring, is more preferred. In addition, Ar in formula (II) a and Ar c may be the same or different.

[0034] Ar in formula (I) b , Ar 1 and Ar 2 , Ar in formula (II) 3 and Ar 4 Examples of the aromatic hydrocarbon ring group and aromatic heterocyclic group include Ar a ,Ar c Examples of the aromatic hydrocarbon ring and aromatic heterocyclic ring include aromatic hydrocarbon ring groups and aromatic heterocyclic groups in which one hydrogen atom has been removed from the aromatic hydrocarbon rings and aromatic heterocyclic rings exemplified above, and the same applies to preferred examples.

[0035] Ar in formula (I) 1 and Ar 2 , Ar in formula (II) 1 and Ar 2 , Ar 3 and Ar 4are bonded to each other directly or via a linker to form a fused ring containing an optionally substituted aromatic hydrocarbon ring and / or an optionally substituted aromatic heterocycle. In this specification, Ar 1 and Ar 2 The fused ring formed by bonding these is called "Ar 1 -Ar 2 "Ar" 3 and Ar 4 The fused ring formed by bonding these is called "Ar 3 -Ar 4 It is called "ring". Ar 1 -Ar 2 Ring, Ar 3 -Ar 4 The aromatic hydrocarbon ring and aromatic heterocyclic ring which may have a substituent contained in the ring include Ar a ,Ar c The aromatic hydrocarbon rings and aromatic heterocycles exemplified above include the aromatic hydrocarbon rings and aromatic heterocycles exemplified above, and preferably, Ar 1 -Ar 2 Ring, Ar 3 -Ar 4 The fused rings are aromatic hydrocarbon rings having a total of 20 or less carbon atoms and 3 or less fused rings which may have a substituent, or aromatic heterocyclic rings having a total of 20 or less carbon atoms and 3 or less fused rings which may have a substituent, and specific examples thereof include the following aromatic fused rings: In the following structural formulas, the dashed lines represent the carbon-carbon bonds of the five-membered ring in formula (I) or formula (II).

[0036] [ka]

[0037] The above aromatic fused ring may have a substituent not shown in the above structural formula, which will be described later.

[0038] Ar a , Ar c Aromatic hydrocarbon rings, aromatic heterocycles, Ar bAromatic hydrocarbon ring groups, aromatic heterocyclic groups, Ar 1 -Ar 2 Ring, Ar 3 -Ar 4 The substituent that the ring may have is not particularly limited, and examples thereof include a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group, a heteroarylthio group, an amino group, an acyl group, an aminoacyl group, a ureido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a sulfamoylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a heteroarylsulfonyl group, an imido group, and a silyl group.

[0039] in particular, Alkyl groups with approximately 1 to 15 carbon atoms, such as methyl and ethyl groups; Alkenyl groups having approximately 2 to 10 carbon atoms, such as ethynyl and propylenyl groups; Alkynyl groups with 2 to 10 carbon atoms, such as acetylenyl groups; Aryl groups with approximately 6 to 20 carbon atoms, such as phenyl and naphthyl groups; Heteroaryl groups having approximately 3 to 20 carbon atoms, such as thienyl, furyl, and pyridyl groups; Alkoxy groups having approximately 1 to 15 carbon atoms, such as methoxy, ethoxy, and propoxy groups; Aryloxy groups with approximately 6 to 20 carbon atoms, such as phenoxy and naphthoxy groups; heteroaryloxy groups having about 3 to 20 carbon atoms, such as pyridyloxy groups and thienyloxy groups; Alkylthio groups having approximately 1 to 15 carbon atoms, such as methylthio and ethylthio groups; Arylthio groups having approximately 6 to 20 carbon atoms, such as phenylthio and naphthylthio groups; Heteroarylthio groups having about 3 to 20 carbon atoms, such as a pyridylthio group and a thienylthio group; an amino group having about 1 to 20 carbon atoms, such as a dimethylamino group or a diphenylamino group, which may have a substituent; Acyl groups with approximately 2 to 20 carbon atoms, such as acetyl and pivaloyl groups; Acylamino groups with approximately 2 to 20 carbon atoms, such as acetylamino and propionylamino groups; Ureido groups with approximately 2 to 20 carbon atoms, such as 3-methylureido groups; Sulfonamide groups having approximately 1 to 20 carbon atoms, such as methanesulfonamide groups and benzenesulfonamide groups; Carbamoyl groups having approximately 1 to 20 carbon atoms, such as dimethylcarbamoyl and ethylcarbamoyl groups; Sulfamoyl groups with approximately 1 to 20 carbon atoms, such as ethylsulfamoyl groups; Sulfamoylamino groups with approximately 1 to 20 carbon atoms, such as dimethylsulfamoylamino groups; Alkoxycarbonyl groups having approximately 2 to 6 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl groups; Aryloxycarbonyl groups having approximately 7 to 20 carbon atoms, such as phenoxycarbonyl and naphthoxycarbonyl groups; Heteroaryloxycarbonyl groups having approximately 6 to 20 carbon atoms, such as pyridyloxycarbonyl groups; Alkylsulfonyl groups having about 1 to 6 carbon atoms, such as methanesulfonyl, ethanesulfonyl, and trifluoromethanesulfonyl groups; Arylsulfonyl groups having approximately 6 to 20 carbon atoms, such as benzenesulfonyl and monofluorobenzenesulfonyl groups; Heteroaryloxysulfonyl groups having approximately 3 to 20 carbon atoms, such as thienylsulfonyl groups; Imide groups with carbon atoms of 4 to 20, such as phthalimide; a silyl group substituted with three substituents selected from the group consisting of alkyl groups and aryl groups; Examples include:

[0040] Among these, Ar 1 -Ar 2 Ring and Ar 3 -Ar 4The ring preferably has a halogen atom as a substituent in order to induce an organic semiconductor that transports electrons or holes, and more preferably has a bromine atom or an iodine atom from the viewpoint of reactivity.

[0041] Specific examples of the compound of the present invention having a unit skeleton represented by the above formula (I) or (II) are listed below, but the compound of the present invention is not limited to these exemplary compounds.

[0042] [ka]

[0043] [ka]

[0044] [ka]

[0045] [ka]

[0046] [ka]

[0047] The compounds of the present invention preferably have the following characteristics: That is, in formula (I), Ar 1 -Ar 2 The ring-forming compounds of the present invention are Ar 1 -Ar 2 The compound has the advantage of being more soluble in organic solvents than compounds that do not form a ring. 1 -Ar 2 Ring and Ar 3 -Ar 4 The ring-forming compounds of the present invention are Ar 1 -Ar 2Ring and Ar 3 -Ar 4 They are characterized by being more soluble in organic solvents than compounds that do not form a ring. Preferably, in formula (I), Ar 1 -Ar 2 The ring-forming compounds of the present invention are Ar 1 -Ar 2 The solubility in chlorobenzene is more than twice that of compounds that do not form a ring. 1 -Ar 2 Ring and Ar 3 -Ar 4 The ring-forming compounds of the present invention are Ar 1 -Ar 2 Ring and Ar 3 -Ar 4 It is preferable that the solubility in chlorobenzene is at least twice that of a compound that does not form a ring.

[0048] [Method of producing the compound of the present invention] In one aspect of the present invention, the method for producing the compound of the present invention is a method for producing the compound of the present invention described above through a reaction step of oxidizing a compound represented by the following formula (III) or the following formula (IV) (hereinafter, these may be referred to as "starting compound") in the co-presence of a divalent iron compound, a trivalent phosphorus compound, and magnesium.

[0049] [ka]

[0050] (In formula (III) and formula (IV), Z 1 , Z 2 , Z 3 each independently represents a silyl group or a methyl group which may have a substituent. Ar a , Ar b , Ar c , Ar 1 , Ar 2 , Ar 3 , Ar 4are the same as defined in the formula (I) or (II).

[0051] Z in the above formulas (III) and (IV) 1 ~Z 3 Examples of the silyl group which may have a substituent include di- or trialkylsilyl groups such as trimethylsilyl group, triethylsilyl group, t-butyldiphenylsilyl group, n-butyldimethylsilyl group, dimethylethylsilyl group, dimethylphenylsilyl group, dimethylisopropylsilyl group, triisopropylsilyl group, and tert-butyldimethyl group. 1 ~Z 3 is particularly preferably a methyl group or a trimethylsilyl group, which has little steric hindrance.

[0052] The compounds represented by formula (III) and formula (IV) can be derived according to the method described in J. Am. Chem. Soc., 143, 6823-6828 (2021).

[0053] (divalent iron compounds) The divalent iron compound that is allowed to coexist with the raw material compound in the reaction step of this embodiment means that the iron in the compound is divalent. Examples of divalent iron compounds include iron halides such as FeCl2, FeBr2, and FeI2, and compounds such as Fe(OAc)2 and Fe(acac)2. The amount of the divalent iron compound to be present in the reaction step is not particularly limited. The divalent iron compound may be present stoichiometrically with the raw material compounds, but in order to maintain stirring efficiency, the amount of the divalent iron compound is preferably in the range of 1 mol % to 20 mol % relative to the raw material compounds.

[0054] (trivalent phosphorus compounds) The trivalent phosphorus compound that is allowed to coexist with the raw material compound in the reaction step of this embodiment means that the phosphorus in the compound is trivalent. Examples of trivalent phosphorus compounds include those selected from the trivalent phosphorus ligands listed in "Buchwald Portfolio 2019: Palladacycles and Ligands" and "Pd Catalyst and Ligand Application Guide for Cross-Coupling Reactions" published by Sigma-Aldrich. Among these, triphenylphosphine and tri(orthotolyl)phosphine are preferred because they can produce the target compound in high yield and are highly versatile, and tri-tert-butylphosphine is even more preferred because it can increase the reaction rate. Buchwald phosphorus ligands are preferred because the yield of the target compound in this reaction can be improved by selecting the optimum ligand depending on the substrate. As the trivalent phosphorus compound, those selected from the phosphorus ligands described in Nature Catal., 4, 631-638 (2021) are also preferably used.

[0055] The trivalent phosphorus compound is preferably used in a ratio of 1 to 3 mol per mol of the divalent iron compound, and particularly from the viewpoint of removability during purification, it is preferably used in a ratio of 1.5 to 2.5 mol.

[0056] (magnesium) The magnesium to be present together with the raw material compound in the reaction step of this embodiment is not particularly limited, and may be magnesium metal (magnesium powder) or a magnesium-containing compound, such as Rieke Magnesium and Turbo Magnesium manufactured by Aldrich. The amount of magnesium to be coexisted is preferably 3 mol to 10 mol per mol of the raw material compound, but more preferably 3 mol to 5 mol in order not to reduce the stirring efficiency in the system.

[0057] (lithium halide) In the reaction step of this embodiment, it is preferable to further coexist lithium halide, which can improve the rate of formation of the intermediate magnesium cyclized product formed with magnesium. Examples of lithium halides include lithium chloride, lithium bromide, and lithium iodide. These lithium halides are preferably present in an equal molar amount to magnesium. Specifically, the molar ratio of magnesium to lithium halide is preferably 1:0.5 to 1:1.5, and more preferably 1:0.8 to 1:1.2.

[0058] (solvent) The reaction step of this embodiment is usually carried out in a solvent. The solvent used in this case is, for example, Aromatic solvents such as toluene and chlorobenzene; ether solvents such as ether, 1,4-dioxane, tetrahydrofuran (THF), 4-methylhydropyran, 2-methyltetrahydrofuran, and cyclopentyl methyl ether; Aliphatic solvents such as hexane and heptane; halogenated solvents such as methylene chloride, chloroform, and 1,2-dichloroethane; You can choose from, etc. Among these, it is preferable to use tetrahydrofuran from the viewpoint of increasing the solubility in the reaction system as much as possible, and it is preferable to use 4-methylhydropyran (MTHP), 2-methyltetrahydrofuran (2-Me-THF), or cyclopentyl methyl ether (CPME) from the viewpoint of increasing the boiling point.

[0059] These solvents may be used alone or in combination of two or more. For example, when a solvent having low solubility of raw material compounds is used, the reaction results are improved by combining it with a halogenated solvent or an ether solvent. When a solvent having low dissolved oxygen concentration is used, the reaction results are improved by combining it with a non-polar solvent, more preferably a hydrocarbon solvent.

[0060] The amount of reaction solvent used is usually preferably in the range of 1 to 50 mL per 1 mmol of the starting compound. This upper limit is preferred from the viewpoint of production efficiency, while the lower limit is preferred from the viewpoint of stirring efficiency in the reaction system. In particular, the amount of reaction solvent used is preferably about 5 to 30 mL per 1 mmol of the starting compound.

[0061] (oxidizing agent) In the reaction step of this embodiment, it is preferable to carry out the oxidation reaction using an oxidizing agent. The oxidizing agent is air, oxygen, Halogen compounds; for example, alkyl dihalides such as iodine, bromine, tetrabutylammonium tribromide, bromine-1,4-dioxane complex, 1,2-dibromo-1,1,2,2-tetrachloroethane, 1,2-dichloroethane pyridinium bromide perbromide, 1,8-diazabicyclo[5.4.0]-7-undecene hydrogen tribromide, NBS (N-bromosuccinimide), 5,5-dibromo Meldrum's acid, trimethylsilyl bromide, 1-chloro-2-iodoethane, NIS (N-iodosuccinimide), tetramethylammonium dichloroiodate, pyridine iodine monochloride, TMSI (N-trimethylsilylimidazole), 1,2-dichloropropane, 1,2-dibromopropane, 1,2-dichloroethane, and 1,2-dibromoethane. Organic peroxides; for example, diacyl peroxides, alkyl peroxyesters, peroxydicarbonates, peroxycarbonates, peroxyketals, dialkyl peroxides, alkyl hydroperoxides, mCPBA (metachloroperbenzoic acid), t-butyl hydroperoxide, bis(trimethylsilyl) peroxide, di-t-butyl peroxide, 2-hydroperoxy-4,5-diphenyl-1,3,5-triazine, and methyl ethyl ketone peroxide. Diketone compounds having a divalent -C(=O)-C(=O)-; specifically, 2,3-butanedione, pyruvic acid, oxamide, oxamic acid, 2,3-pentanedione, 2-oxobutyric acid, methyl pyruvate, 1,2-cyclohexanedione, 3-methyl-1,2-cyclopentanedione, parabanic acid, 3,4-hexanedione, methyl 2-oxobutyrate, ethyl pyruvate, 2-oxovaleric acid, ethyl oxamate, N,N-dimethyloxamic acid, dimethyl oxalate, 3,4- Dimethyl-1,2-cyclopentanedione, 2,3-heptanedione, 5-methyl-2,3-hexanedione, 4-methyl-2-oxovaleric acid, 3-methyl-2-oxovaleric acid, 3,3-dimethyl-2-oxobutyric acid, methyl 2-oxovalerate, oxalacetic acid, 1-ethyl-2,3-dioxopiperazine, butyl oxamate, 2-oxoglutaric acid, diethyl oxalate, 1,2-indandione, isatin, 1-phenyl-1,2-propanedione, benzoylformic acid, trifluoroacetic acid Methyl 2,4-dioxovalerate, 1,2-naphthoquinone, 1-methylisatin, methyl benzoylformate, phenylpyruvic acid, 2,3-bornanedione, triquinoyl hydrate, ethyl trifluoropyruvate, diethyl mesoxalate, dimethyl 2-oxoglutarate, dimethyloxaloylglycine, N,N'-dimethoxy-N,N'-dimethyloxamide, ethyl benzoylformate, 4-hydroxyphenylpyruvic acid, diethyl oxalate, furyl, 1,1'-Oxalyldiimidazole, diethyl methyloxalacetate, dibutyl oxalate, 9,10-phenanthrenequinone, 1,10-phenanthroline-5,6-dione, benzyl, 3,5-di-tert-butyl-1,2-benzoquinone, diethyl chlorooxalacetate, 1,3-diphenylpropanetrione, diphenyl oxalate, o-chloranil, 1,4-bisbenzyl, bis(2,4-dinitrophenyl) oxalate, bis(2,4,6-trichlorophenyl) oxalate Examples include: However, among these oxidizing agents, since the redox potential of iron is low, it is not necessary to use a strong oxidizing agent, and in order to suppress side reactions, an oxidizing agent with weak nucleophilicity is preferred, and from the viewpoint of having an appropriate oxidation potential, an alkyl dihalide or a dialkyl oxalate is particularly preferred.

[0062] The amount of oxidizing agent is appropriately determined, but is usually 1.0 equivalent or more, preferably 2.0 equivalents or more, relative to the starting compound, and is usually 10.0 equivalents or less, preferably 5.0 equivalents or less.

[0063] (Reaction conditions) The reaction temperature in the reaction step of this embodiment is usually −5° C. or higher, preferably 0° C. or higher, more preferably 10° C. or higher, and is particularly preferably in the range of about 25° C. to the boiling point of the solvent. The reaction temperature can be set arbitrarily within the range up to the reflux temperature of the solvent used, depending on the rate at which the reaction proceeds. When the oxidation is slow (that is, when the yield is poor), it is preferable to irradiate the reaction solution with ultrasound or microwaves, or to autoclave the reaction solution.

[0064] The reaction time is usually 30 minutes to 24 hours, but may be set arbitrarily since it depends on the type of solvent used and other reaction conditions.

[0065] The progress of the reaction can be confirmed by high performance liquid chromatography (HPLC).

[0066] After the reaction is completed, the target compound of the present invention having the unit skeleton represented by formula (I) or (II) can be obtained using known isolation and purification methods. After the reaction, it is preferable to further extract the product with a dilute aqueous hydrochloric acid solution in order to remove the divalent iron compound used.

[0067] [Semiconductor compounds] (p-type organic semiconductor compound) By using the unit skeleton represented by the formula (I) or (II) as a mother skeleton and introducing a hole transporting moiety such as a benzodithiophene structure, a thiophene structure, a carbazole structure, a dibenzofuran structure, a triarylamine structure, or a naphthalene structure into the mother skeleton, a compound that functions as a p-type organic semiconductor can be obtained. That is, a p-type organic semiconductor compound can be provided by the following method.

[0068] Building long conjugated systems: Molecules with long conjugated systems, such as polycyclic aromatic compounds and extended conjugation, enable efficient hole transport. The longer the conjugated system, the more free the π electrons can move, thereby increasing hole mobility. Introduction of electron-rich functional groups: For example, electron-rich functional groups such as amino and alkoxy groups increase the electron density of the molecule, facilitating hole injection and transport. Construction of planar molecular structure: When molecules have a planar structure, the π-π interactions between molecules become stronger, which promotes efficient hole transport. As a result, better intermolecular stacking is promoted, thereby increasing hole mobility. Furthermore, the high solubility of these frameworks is ensured by the rigid spiro ring, which allows for smaller molecular angles and the introduction of π-π stacking effects.

[0069] (n-type organic semiconductor compound) Using the unit skeleton represented by formula (I) or (II) as the parent skeleton, it is also possible to introduce polycyclic aromatic rings containing conjugated systems, such as fullerene, naphthalenediimide, perylenediimide, and diphenylamine, which serve as electron transport moieties. Furthermore, by introducing the ITIC moiety of a nonfullerene acceptor (NFA), it is possible to produce an NFA with high solubility. Specifically, the introduction of electron-deficient functional groups (e.g., cyano and fluoro groups) can improve electron transport properties. As structural moieties contributing to electron transport, functional groups with high electron-attracting capabilities are preferred, and rigid structures that promote highly planar intermolecular π-π interactions are preferred. These functional groups can be introduced into the unit skeleton represented by formula (I) or (II), thereby imparting high solubility.

[0070] An organic semiconductor made of a compound having a unit skeleton of formula (I) or (II) has excellent solubility in organic solvents, and therefore can be formed into a thin film by a coating method. In addition, the rigid conjugated skeleton constituting the compound allows a certain intermolecular orientation, and therefore the formed thin film exhibits excellent semiconductor properties.

[0071] [Film-forming ink for organic semiconductor devices] When forming an active layer by a coating method, a film-forming ink for an organic semiconductor device is prepared by dissolving a p-type organic semiconductor compound or an n-type organic semiconductor compound, which is an organic semiconductor, in an organic solvent, as well as other necessary substances as additives, and the film-forming ink for an organic semiconductor device (hereinafter referred to as "organic semiconductor ink") is applied onto a substrate by a spin coating method or the like, and dried to form a thin film.

[0072] In this case, the conditions for spin coating may be appropriately determined in accordance with a standard method, taking into consideration the viscosity of the organic semiconductor ink, etc. The drying conditions are not particularly limited as long as they allow the organic solvent in the organic semiconductor ink to be removed. For example, the organic semiconductor ink can be dried by heat annealing at atmospheric pressure at 70 to 130°C for 5 to 20 minutes. These organic semiconductor inks are also another aspect of the present invention.

[0073] The content of the semiconductor compound in the organic semiconductor ink is not particularly limited as long as an active layer can be formed by coating. The content of the p-type organic semiconductor in the organic semiconductor ink is usually 0.5% by mass or more, and may be 0.7% by mass or more, and is usually 1.5% by mass or less, and may be 1.3% by mass or less. Furthermore, the content of the n-type organic semiconductor compound in the organic semiconductor ink is typically 0.7% by mass or more, and may be 1.0% by mass or more, and is typically 2.0% by mass or less, and may be 1.8% by mass or less.

[0074] The organic solvent used in the organic semiconductor ink is not particularly limited, and any organic solvent generally used in a coating liquid for forming an active layer of an organic semiconductor device can be used. Specific examples include halogen-based solvents such as chloroform and dichloroethane, aromatic hydrocarbon-based solvents such as toluene, xylene, chlorobenzene, and dichlorobenzene, and ether-based solvents such as THF, CPME, MTHP, 2-Me-THF, and dibutyl ether. In general, organic semiconductor compounds have high solubility in these organic solvents, and the use of these organic solvents is expected to improve photoelectric conversion efficiency.

[0075] Of the above organic solvents, xylene, chlorobenzene, or chloroform is preferred, although this depends on the type of organic semiconductor compound. Furthermore, when adjusting the solubility, the organic solvent may be a mixed organic solvent of two or more kinds. The content ratio is not particularly limited, and may be in the range of 1:9 to 9:1. The difference in boiling point between these organic solvents is preferably 50°C or less, more preferably 40°C or less, and even more preferably 30°C or less.

[0076] The organic semiconductor ink preferably contains, in addition to the p-type organic semiconductor compound and the n-type organic semiconductor compound, an additive that promotes alignment. Examples of such additives include compounds that promote stacking of the aromatic moiety of the p-type organic semiconductor compound and the aromatic moiety of the n-type organic semiconductor compound and that have the effect of shortening the intermolecular distance between the p-type organic semiconductor compound and the n-type organic semiconductor compound, such as polycyclic aromatic compounds and 1,8-diiodooctane. Examples of polycyclic aromatic compounds include naphthalene, anthracene, pyrene, etc. Among these, the additive is preferably a bicyclic fused ring such as 1-chloronaphthalene.

[0077] The content of additives in the organic semiconductor ink is usually 1.5% by mass or more, preferably 2.0% by mass or more, and usually 4.0% by mass or less, preferably 3.5% by mass or less.

[0078] Furthermore, the organic semiconductor ink may contain other components to the extent that the effects of the present invention are not impaired. The content of other components is usually 2.0% by mass or less relative to the organic solvent.

[0079] [Organic semiconductor devices] Using the organic semiconductor ink of the present invention, an organic semiconductor device having an organic semiconductor device film containing the semiconductor compound of the present invention can be produced by a coating method. [Example]

[0080] The following examples will explain the present invention in more detail, but the present invention is not limited to these examples as long as they do not depart from the gist of the present invention. The numbers below the compounds in the reaction formulas are the compound numbers.

[0081] The produced compounds were identified by a proton NMR apparatus ("ECZ-500" manufactured by JEOL Ltd.) using CDCl3 as a heavy solvent.

[0082] [Production of Compounds] (Production of raw material compounds) [ka]

[0083] Butyllithium (4.1 mL, 1.60 M) was added dropwise to a solution of 1,2-bis(2-bromophenyl)ethyne (1.0 g, 3.0 mmol) in diethyl ether (30 mL) at 0°C and stirred for 2 hours. 9H-Fluoren-9-one (1.0 g, 6.0 mmol) was added to the reaction solution and stirred for an additional 4 hours. The reaction mixture was allowed to warm to room temperature and then quenched by adding water. The organic layer was extracted with dichloromethane, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The resulting crude product was purified by column chromatography to obtain the desired alcohol precursor (99%) as a white solid.

[0084] [ka]

[0085] To a methanol suspension (20 mL) of the above alcohol precursor (0.8 g, 1.8 mmol), diammonium cerium(IV) nitrate (CAN, 0.79 g, 1.44 mmol, 80 mmol%) was added, and the mixture was heated at 100°C for 4 hours, then cooled to room temperature. The resulting solid was collected by filtration and washed with methanol to obtain Compound 1, which was used as a starting compound in Example 1, as a white solid in 70% yield.

[0086] Example 1 [ka]

[0087] Sodium chloride (25.4 mg, 0.6 mmol) was added to a Schlenk tube and heated with a heat gun under vacuum. After cooling to room temperature, FeCl2(II) (1.3 mg, 0.01 mmol), triphenylphosphine (5.2 mg, 0.02 mmol), magnesium powder (14.6 mg, 0.6 mmol), and compound 1 (114 mg, 0.2 mmol) were quickly added under an argon stream. To this was added anhydrous tetrahydrofuran (0.4 mL) and heated with stirring for 7 hours. Subsequently, 1,2-dichloropropane (39 μL, 0.4 mmol) was added and heated with stirring for 5 hours. After cooling to room temperature, the reaction mixture was diluted with 15 mL of methylene chloride and extracted with water. The methylene chloride layer was washed with 10 mL of 1 M hydrochloric acid and then with 15 mL of saturated brine. The organic layer was evaporated under reduced pressure and purified by silica gel column chromatography (developing solvent: methylene chloride-hexane) to obtain Compound 2 in a 72% yield.

[0088] 1H NMR(500MHz,CDCl3)δ7.95(d,J=7.8Hz,4H),7.45(td,J=1.2Hz,7.5Hz,4H),7.22(td,J=1.2Hz,7 .4Hz,4H),7.03(d,J=7.5Hz,4H),6.83-6.91(m,4H),6.67(d,J=6.9Hz,2H),6.34(d,J=7.5Hz,2H)

[0089] Example 2 [ka]

[0090] The reaction was carried out in the same manner as in Example 1, except that compound 3 was used instead of compound 1 and heavy water was used instead of water in the post-treatment, whereby compound 4 was obtained in a yield of 83%. 1 H NMR(500MHz,CDCl3)δ7.69(t,J=3.8Hz,1H),7.35-7.39(m,5H),7.09-7.19(m,6H),7.97(t,J=7.5Hz,1H),6.91(d,J=7.5Hz,2H),6.83(t,J=7.2Hz,2H)

[0091] Example 3 [ka]

[0092] The reaction was carried out in the same manner as in Example 1, except that compound 5 was used instead of compound 1 and heavy water was used instead of water in the post-treatment, whereby compound 6 was obtained in a yield of 92%. 1 H NMR(500MHz,CDCl3)δ7.59(d,J=8.0Hz,2H),7.44(d,J=7.5Hz,1H),7.74-7.33(m,3H),7.19-7.24(m,4H),7.05 (d,J=6.0Hz,2H)6.97(t,J=7.5Hz,1H),6.88(t,J=7.5Hz,2H),6.72(d,J=7.8Hz,2H),1.93(s,3H),1.84(s,3H)

[0093] Example 4 [ka]

[0094] The reaction was carried out in the same manner as in Example 1, except that compound 7 was used instead of compound 1 and heavy water was used instead of water in the post-treatment, whereby compound 8 was obtained in a yield of 94%. 1 H NMR(500MHz,CDCl3)δ7.41(d,J=7.5Hz,1H),7.36(d,J=6.9Hz,2H),7.09-7.21(m,8H ),7.02(d,J=3.2Hz,2H),6.77(td,J=1.4Hz,7.7Hz,2H)6.69(dd,J=1.5Hz,7.8Hz,2H)

[0095] Example 5 [ka]

[0096] The reaction was carried out in the same manner as in Example 1, except that compound 9 was used instead of compound 1 and heavy water was used instead of water in the post-treatment, whereby compound 10 was obtained in a yield of 83%. 1 H NMR(500MHz,CDCl3)δ7.87(d,J=7.5Hz,2H),7.46(d,J=7.7Hz,1H),7.36(td,J=1.2Hz,7.5Hz,2H),7.22(td,J=6 .5Hz,7.5Hz,1H),7.11(td,J=6.3Hz,7.5Hz,2H)6.92-7.03(m,6H),6.88(d,J=7.8Hz,2H),6.48(d,J=7.5Hz,1H)

[0097] Example 6 [ka]

[0098] The reaction was carried out in the same manner as in Example 1, except that compound 11 was used instead of compound 1 and heavy water was used instead of water in the post-treatment, whereby compound 12 was obtained in a yield of 82%. 1 H NMR(500MHz,CDCl3)δ7.58(d,J=7.5Hz,2H),7.47(d,J=7.5Hz,1H),7.32(t,J=7.5Hz,1H),7.26(td,J =1.2Hz,7.5Hz,2H),7.00-7.08(m,2H),6.67(d,J=7.5Hz,1H),6.54(s,2H),2.07(s,3H),1.79(s,6H)

[0099] Example 7 [ka]

[0100] The reaction was carried out in the same manner as in Example 1, except that compound 13 was used instead of compound 1 and heavy water was used instead of water in the post-treatment, to give compound 14 in a yield of 83%. 1 H NMR(500MHz,CDCl3)δ7.86(d,J=7.5Hz,1H),7.82(d,J=7.8Hz,1H),7.53(d, J=7.5Hz,1H),7.37-7.40(m,1H),7.30-7.34(m,2H),7.27(d,J=7.5Hz,2H),7 .16-7.22(m,5H),7.07(dd,J=1.2Hz,8.0Hz,2H),7.01(td,J=1.2Hz,7.5Hz, 2H),6.78-6.90(m,6H),6.44(d,J=7.8Hz,1H),6.34(dd,J=1.2Hz,8.0Hz,2H)

[0101] Example 8 [ka]

[0102] When the reaction was carried out in the same manner as in Example 1 except that Compound 15 was used instead of Compound 1, Compound 16 was obtained in a yield of 66%. 1 H NMR(500MHz,CDCl3)δ7.26-7.30(m,6H),7.24(dd,J=1.2Hz,8.0Hz,2H),7.16(d,J=7.2Hz,2H),7.09(td,J=1.2Hz,7.5Hz ,2H),7.04(td,J=1.5Hz,7.5Hz,2H),6.99(d,J=7.5Hz,2H),6.87(td,J=1.7Hz,8.0Hz,4H),6.69(dd,J=1.7Hz,8.0Hz,4H)

[0103] Example 9 [ka]

[0104] When the reaction was carried out in the same manner as in Example 1 except that Compound 17 was used instead of Compound 1, Compound 18 was obtained in a yield of 80%. 1 H NMR(500MHz,CDCl3)δ8.11(d,J=7.6Hz,2H),7.53(d,J=7.8Hz,4H),7.23(t,J=7.5Hz,4H),7.07(t,J=8.0Hz,6H),6.97-7.02(m,6H),6.93(d,J=7.2Hz,2H)

[0105] Example 10 [ka]

[0106] Compound 19 was used instead of compound 1, and the reaction was carried out in the same manner as in Example 1, whereby compound 20 was obtained in a yield of 66%. 1 H NMR(500MHz,CDCl3)δ7.20(d,J=6.5Hz,4H),7.89(t,J=6.0Hz,4H),6.65(t,J=5.5Hz, 4H),6.60(t,J=8.2Hz,4H),6.46(td,J=5.5Hz,17.8Hz,8H),2.74(s,6H),2.63(s,6H)

[0107] (Comparative Examples 1 and 2) The following compounds were synthesized as comparative compounds 1 and 2 by the method described in Journal of the American Chemical Society (2009), 131(38), 13596-13597.

[0108] [ka]

[0109] [Evaluation of solubility] The solubility of Compound 2 produced in Example 1 and Comparative Compounds 1 and 2 in organic solvents was evaluated. A predetermined amount of each compound shown in Table 1 was added to 1 mL of chlorobenzene, and the mixture was stirred at 1200 rpm on a hot plate at 60°C for 5 minutes, then allowed to stand at 25°C for 24 hours, after which the presence or absence of precipitation of the compound was examined.

[0110] [Table 1]

[0111] As shown in Table 1, it can be seen that compound 2 of Example 1 has superior solubility in chlorobenzene to comparative compounds 1 and 2, with the solubility being at least twice as high.

Claims

1. A compound having a unit skeleton represented by the following formula (I) or (II): 【Chemical 1】 (In formula (I), Ar ａ represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocycle which may have a substituent, Ar ｂ represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent. Ar １ and Ar ２ each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent; Ar １ and Ar ２ are bonded to each other directly or via a linker to form a fused ring containing an optionally substituted aromatic hydrocarbon ring and / or an optionally substituted aromatic heterocycle. In formula (II), Ar ａ and Ar ｃ each independently represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocycle which may have a substituent. Ar １ , Ar ２ , Ar ３ and Ar ４ each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent; Ar １ and Ar ２ , Ar ３ and Ar ４ are bonded to each other directly or via a linker to form a fused ring containing an optionally substituted aromatic hydrocarbon ring and / or an optionally substituted aromatic heterocycle.

2. The compound having a unit skeleton represented by the formula (I) is １ and Ar ２ the solubility in chlorobenzene is at least twice that of a compound having a unit skeleton that does not form a fused ring containing an optionally substituted aromatic hydrocarbon ring and / or an optionally substituted aromatic heterocycle, The compound having a unit skeleton represented by the formula (II) is １ and Ar ２ , Ar ３ and Ar ４ The compound according to claim 1, which has a solubility in chlorobenzene that is at least twice as high as that of a compound having a unit skeleton that does not form a fused ring, which unit skeleton contains an optionally substituted aromatic hydrocarbon ring and / or an optionally substituted aromatic heterocycle.

3. 3. A method for producing the compound according to claim 1 or 2, comprising a reaction step of oxidizing a compound represented by the following formula (III) or the following formula (IV) in the presence of a divalent iron compound, a trivalent phosphorus compound, and magnesium: 【Chemistry 2】 (In formula (III) and formula (IV), Z １ , Z ２ , Z ３ each independently represents a silyl group or a methyl group which may have a substituent. Ar ａ , Ar ｂ , Ar ｃ , Ar １ , Ar ２ , Ar ３ , Ar ４ are the same as defined in formula (I) or formula (II).

4. The method for producing the compound according to claim 3, wherein the intermediate magnesium cyclized product is formed in the reaction step in the presence of lithium halide.

5. 4. The method according to claim 3, wherein the oxidation reaction in the reaction step uses at least one oxidant selected from the group consisting of air, oxygen, halogen compounds, and organic peroxides.

6. A semiconductor compound having a unit skeleton represented by the following formula (I) or (II) as a mother skeleton. 【Chemistry 3】 (In formula (I), Ar ａ represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocycle which may have a substituent, Ar ｂ represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent. Ar １ and Ar ２ each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent; Ar １ and Ar ２ are bonded to each other directly or via a linker to form a fused ring containing an optionally substituted aromatic hydrocarbon ring and / or an optionally substituted aromatic heterocycle. In formula (II), Ar ａ and Ar ｃ each independently represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocycle which may have a substituent. Ar １ , Ar ２ , Ar ３ and Ar ４ each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent; Ar １ and Ar ２ , Ar ３ and Ar ４ are bonded to each other directly or via a linker to form a fused ring containing an optionally substituted aromatic hydrocarbon ring and / or an optionally substituted aromatic heterocycle.

7. 7. The semiconductor compound of claim 6, which is a p-type semiconductor or an n-type semiconductor.

8. An organic semiconductor device comprising an organic semiconductor device film containing the semiconductor compound according to claim 6 or 7.

9. A film-forming ink for an organic semiconductor device, comprising the semiconductor compound according to claim 6 or 7 and an organic solvent.

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