Novel compounds, their manufacturing methods and uses

Abstract

To provide a novel compound that exhibits excellent thermal and chemical stability, high carrier mobility, and high solubility in solvents, and is particularly suitable as an organic semiconductor, as well as a method for producing the same. [Solution] A compound represented by the following general formula (1). TIFF2026061690000041.tif30142 (In general formula (1), R 1 and R 2 Each of these independently represents a hydrogen atom, a halogen atom, a perfluoroalkylsulfonyloxy group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, and may further have substituents, and may have the following divalent linking group A, where the divalent linking group A is -O-, -S-, -NR 4 R represents a divalent linking group of any of the following: -, -CO-, -SO-, and -SO2-, or a divalent linking group formed by the bonding of two or more of these divalent linking groups. 4 (This represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, or heteroaryl group.)

Description

[Technical Field]

[0001] This invention relates to novel compounds, methods for producing them, and uses thereof. [Background technology]

[0002] Organic semiconductors, possessing flexibility and pliability not found in inorganic semiconductors, and capable of film deposition at low temperatures near room temperature, are expected to have applications in flexible devices and printed electronic devices. One such application is being explored in the healthcare field as wearable electronic devices, including sensing devices. However, existing organic semiconductors struggle with advanced, high-speed signal processing, leading to approaches that attempt to overcome this by combining them with Si semiconductor devices. This approach limits the application of devices that leverage the advantages of organic semiconductors.

[0003] Currently, various things exist around us as edge devices of the Internet of Things (IoT), and everything is connected to the cloud. The role of edge computing is rapidly becoming more important than that of cloud computing. It's no longer just about collecting data; by using AI and other technologies that are expanding at an incredible pace, it's becoming increasingly important to transform this data into useful, high-value data at the edge and connect it to the cloud. Therefore, there is great anticipation for the realization of devices made from organic materials, including all-organic semiconductors, and for the arrival of devices capable of high-speed edge processing using only organic semiconductors.

[0004] To achieve this, both p-type and n-type organic semiconductor materials with higher mobility are required. Examples of organic compounds with semiconductor properties include polycyclic aromatic hydrocarbons and compounds having heterocyclic structures. One example of a p-type organic semiconductor is the picenodithiophene compound described in Patent Document 1. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2015-178491 [Overview of the project] [Problems that the invention aims to solve]

[0006] The compound described in Patent Document 1 has a piceno[4,3-b:9,10-b']dithiophene molecular structure, and it has been shown that this structure has properties as an organic semiconductor. However, Patent Document 1 only describes the hole mobility of this compound, and the mobility is low. Therefore, the present invention has excellent thermal and chemical stability, and 1 cm 2 The objective is to provide novel compounds that have a high carrier mobility of 1 / Vs or higher and high solubility in common organic solvents, and are particularly suitable as organic semiconductors, as well as a method for producing the same. [Means for solving the problem]

[0007] The inventors of this invention conducted extensive research to solve the above problems and, as a result, discovered that the following compounds can achieve the above objectives, thus completing the present invention. In other words, the present invention provides the following compounds, methods for producing the same, and uses thereof. [1] A compound represented by the following general formula (1). [ka] (In general formula (1), R 1 and R 2 Each of these independently represents a hydrogen atom, a halogen atom, a perfluoroalkylsulfonyloxy group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, and may further have substituents, and may have the following divalent linking group A, where the divalent linking group A is -O-, -S-, -NR 4-、 -CO-、 -SO- or -SO2-, or a divalent linking group formed by combining two or more of these divalent linking groups, and R 4 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.) [2] The compound according to [1] having a molecular weight of 3000 or less. [3] The compound according to [1] or [2], wherein the compound represented by the general formula (1) is a compound represented by the following general formula (1-1).

Chemical formula

[10] In the above general formula (1'-1), R 11 However, each independently represents an aryl group or a heteroaryl group, and may also have substituents, and may have the following divalent linking group A, where the divalent linking group A is -O-, -S-, -NR 4 R represents a divalent linking group of any of the following: -, -CO-, -SO-, and -SO2-, or a divalent linking group formed by the bonding of two or more of these divalent linking groups. 4 The compound described in [9] is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group.

[11] In the above general formula (1'-1), R 11However, independently of each other, an unsubstituted aryl group having 6 to 14 carbon atoms, an aryl group represented by the following general formula (2), or a heteroaryl group represented by the following general formula (3), or these groups may have the following divalent linking group group A, where the divalent linking group group A is -O-, -S-, -NR 4 R represents a divalent linking group of any of the following: -, -CO-, -SO-, and -SO2-, or a divalent linking group formed by the bonding of two or more of these divalent linking groups. 4 The compound described in

[10] is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. [ka] (In general formulas (2) and (3), R 3 Each of these is independently a halogen atom or an alkyl group having 1 to 20 carbon atoms, where n is a number from 1 to 5 and n' is a number from 1 to 3.

[12] The compound described in [7] or [8], wherein the compound represented by the general formula (1') is the compound represented by the general formula (1'-2) below. [ka] (In general formula (1'-2), R 12 (Each of these terms independently represents either a halogen atom or a perfluoroalkylsulfonyloxy group.)

[13] A method for producing the compound described in any one of items [3] to [5], comprising a cross-coupling reaction step using a compound represented by the following general formula (1-2). [ka] (In general formula (1-2), R 12 Each of these independently represents a halogen atom or a perfluoroalkylsulfonyloxy group, and R 2Each of these independently represents a hydrogen atom, a halogen atom, a perfluoroalkylsulfonyloxy group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, and may further have substituents, and may have the following divalent linking group A, where the divalent linking group A is -O-, -S-, -NR 4 R represents a divalent linking group of any of the following: -, -CO-, -SO-, and -SO2-, or a divalent linking group formed by the bonding of two or more of these divalent linking groups. 4 (This represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, or heteroaryl group.)

[14] An organic semiconductor material containing a compound described in any one of the items [1] to

[12] .

[15] A liquid containing any one of the compounds described in [1] to

[12] .

[16] An organic semiconductor film containing a compound described in any one of the items [1] to

[12] .

[17] An organic semiconductor device having the organic semiconductor film described in

[16] .

[18]

[16] An organic transistor having an organic semiconductor film. [Effects of the Invention]

[0008] The compounds of the present invention exhibit excellent thermal and chemical stability and high solubility in solvents. Furthermore, the compounds of the present invention have high carrier mobility. Therefore, the compounds of the present invention can be suitably used as organic semiconductors. Furthermore, according to the method for producing the compound of the present invention, compounds of the present invention having various substituents can be easily produced in a single step from one type of synthetic intermediate. [Brief explanation of the drawing]

[0009] [Figure 1] These are schematic cross-sectional diagrams of the organic transistors manufactured in Examples 2 and 4. [Figure 2] This is a schematic cross-sectional view of the organic transistor manufactured in Example 3. [Modes for carrying out the invention]

[0010] The present invention will be described in more detail below. In this specification, unless otherwise specified, the term "hydrogen atom" includes not only light hydrogen but also isotopes with different numbers of neutrons, namely deuterium and tritium. Furthermore, the term "substituted atom" includes its isotopes.

[0011] <Compound> The compound of the present invention is represented by the following general formula (1). [ka] In general formula (1), R 1 and R 2 Each of these independently represents a hydrogen atom, a halogen atom, a perfluoroalkylsulfonyloxy group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, and may further have substituents, and may have the following divalent linking group A, where the divalent linking group A is -O-, -S-, -NR 4 R represents a divalent linking group of any of the following: -, -CO-, -SO-, and -SO2-, or a divalent linking group formed by the bonding of two or more of these divalent linking groups. 4 The symbol represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group.

[0012] R 1 or R 2 If the atom is a hydrogen atom, it may be not only light hydrogen, but also deuterium, tritium, etc. R 1 or R 2 Examples of halogen atoms represented by include fluorine, chlorine, bromine, and iodine atoms. R 1 or R 2When represents a perfluoroalkylsulfonyloxy group, there are no particular restrictions on the perfluoroalkylsulfonyloxy group, but it is preferably a sulfonyloxy group substituted with a perfluoroalkyl group having 1 to 10 carbon atoms, and more preferably a trifluoromethylsulfonyloxy group (CF3SO2O-).

[0013] R 1 or R 2 When R is an alkyl group, the number of carbon atoms is preferably 1 to 30, more preferably 1 to 15 from the viewpoint of chemical stability and carrier mobility, and even more preferably 3 to 11. 1 and R 2 It is preferable that the alkyl group has a number of carbon atoms within the above range, from the viewpoint of increasing the linearity of the molecule and improving carrier mobility. R 1 or R 2 When the alkyl group is an alkyl group, it may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, but a linear alkyl group is preferred from the viewpoint of increasing the linearity of the molecule and thus increasing carrier mobility. R 1 or R 2 Examples of alkyl groups represented by include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, cyclopropyl group, cyclopentyl group, cyclocyclohexyl group, and cycloheptyl group. R 1 or R 2When is an alkyl group having substituents, there are no particular limitations on the substituents, but they include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl groups (alkyl groups having 1 to 40 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc., provided that 2,6-dimethyloctyl group, 2-decyltetradecyl group, 2-hexyldodecyl group, 2-ethyloctyl group, 2-decyltetradecyl group, 2-butyldecyl group, 1-octylnonyl group, 2-ethyloctyl group, 2-octyltetradecyl (including C6 groups, 2-ethylhexyl groups, cycloalkyl groups, bicycloalkyl groups, tricycloalkyl groups, etc.), alkenyl groups (including 1-pentenyl groups, cycloalkenyl groups, bicycloalkenyl groups, etc.), alkynyl groups (including 1-pentynyl groups, trimethylsilylethynyl groups, triethylsilylethynyl groups, tri-i-propylsilylethynyl groups, 2-p-propylphenylethynyl groups, etc.), aryl groups (including aryl groups with 6 to 20 carbon atoms such as phenyl groups, naphthyl groups, p-pentylphenyl groups, 3,4-dipentylphenyl groups, p-heptoxyphenyl groups, 3,4-diheptoxyphenyl groups, etc.), heterocyclic groups (may also be called heterocyclic groups).2-Hexylfuranyl groups (including, etc.), cyano groups, hydroxyl groups, nitro groups, acyl groups (including, hexanoyl and benzoyl groups), alkoxy groups (including, etc., butoxy groups), aryloxy groups, silyloxy groups, heterocyclic oxy groups, acyloxy groups, carbamoyloxy groups, amino groups (including, anilino groups), acylamino groups, aminocarbonylamino groups (including, ureido groups), alkoxy and aryloxycarbonylamino groups, alkyl and arylsulfonylamino groups, mercapto groups, alkyl and arylthio groups (including, methylthio and octylthio groups) Examples of substituents include heterocyclic thio groups, sulfamoyl groups, sulfo groups, alkyl and arylsulfinyl groups, alkyl and arylsulfonyl groups, alkyl and aryloxycarbonyl groups, carbamoyl groups, aryl and heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, phosphono groups, silyl groups (such as ditrimethylsiloxymethylbutoxy group), hydrazino groups, ureido groups, boronic acid groups (-B(OH)2), phosphat groups (-OPO(OH)2), sulfat groups (-OSO3H), and other known substituents.

[0014] R 1 or R 2 If the group is an alkenyl group, the number of carbon atoms is preferably 2 to 30, more preferably 2 to 10, and particularly preferably 2 to 4. R 1 or R 2 Examples of alkenyl groups represented by include vinyl group, propenyl group, butenyl group, 2-methyl-1-propenyl group, hexenyl group, octenyl group, and decenyl group. R 1 or R 2 When R is an alkenyl group having a substituent, there are no particular restrictions on the substituent, 1 or R 2 The same substituents as those given when the substituent is an alkyl group can be listed.

[0015] R 1 or R 2If the group is an alkynyl group, the number of carbon atoms is preferably 2 to 30, more preferably 2 to 10, and particularly preferably 2. R 1 or R 2 Examples of alkynyl groups represented by include ethynyl, propynyl, butynyl, hexynyl, octinyl, and desynyl groups. R 1 or R 2 When R is an alkynyl group having a substituent, there are no particular restrictions on the substituent, 1 or R 2 The same substituents as those given when the substituent is an alkyl group can be listed.

[0016] R 1 or R 2 If the group is an aryl group, the number of carbon atoms is preferably 6 to 30, more preferably 6 to 18, and particularly preferably 6 to 12. R 1 or R 2 Examples of aryl groups represented by this include phenyl groups, naphthyl groups, and biphenyl groups. R 1 or R 2 There are no particular restrictions on the substituent when R is an aryl group having a substituent. 1 or R 2 The same substituents as those given when the substituent is an alkyl group can be listed. R 1 or R 2 If the group is an aryl group, an unsubstituted aryl group having 6 to 14 carbon atoms or an aryl group represented by the following general formula (2) is preferred. [ka] In general formula (2), R 3 R is a halogen atom or an alkyl group having 1 to 20 carbon atoms. 3 As such, alkyl groups having 4 to 20 carbon atoms are preferred, and alkyl groups having 6 to 18 carbon atoms are more preferred, for example, the above-mentioned R 1 or R 2Groups similar to those exemplified as the alkyl group (n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, etc.) can be mentioned. In the general formula (2), n is a number from 1 to 5, preferably 1.

[0017] R 1 Or R 2 When it is a heteroaryl group, the number of carbon atoms is preferably 3 to 30, more preferably 4 to 20, and particularly preferably 4. R 1 Or R 2 The heteroaryl group represented by R or R includes a furanyl group, a pyrrolyl group (which may be substituted by a hydrogen atom), a pyrazolyl group, an imidazolyl group, a thienyl group, a thiazolyl group, a thienothienyl group, a benzothienyl group, a thienophenyl group, a pyridyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, etc. R 1 Or R 2 When it is a heteroaryl group having a substituent, the substituent is not particularly limited, and the same substituents as those exemplified when R or R is an alkyl group can be mentioned. 1 Or R 2 When it is a heteroaryl group, the heteroaryl group represented by the following general formula (3) is preferred. R 1 Or R 2 When it is a heteroaryl group, the heteroaryl group represented by the following general formula (3) is preferred.

Chemical formula

[0018] R 1 or R 2 It may have a group of divalent linking groups A, and the group of divalent linking groups A may be -O-, -S-, -NR 4 It represents a divalent linking group of any of the following: -, -CO-, -SO-, and -SO2-, or a divalent linking group formed by the bonding of two or more of these divalent linking groups. In particular, R 1 or R 2 R may be bonded to a benzene ring or thiophene ring via a divalent linking group A. Here, R 4 This represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, and may further have substituents.

[0019] The two sulfur atoms (S) in general formula (1) may be other atoms classified as chalcogens, such as oxygen (O) or selenium (Se), independently of each other.

[0020] The molecular weight of the compound represented by general formula (1) is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less, in order to improve its solubility in the solvent. Furthermore, the molecular weight of the compound represented by general formula (1) is preferably 390 or higher, more preferably 400 or higher, and even more preferably 500 or higher, in terms of improving carrier mobility, durability, and material stability. In the present invention, the compound represented by general formula (1) may be a compound having repeating units (a so-called oligomer). In this specification, the molecular weight of a compound can be determined by the following molecular weight measurement method. It can be obtained by mass spectrometry using ionization methods such as MALDI (Matrix Assisted Laser Desorption / Ionization), APCI (Atmospheric Pressure Chemical Ionization), and ESI (Electrospray Ionization), or by determining the weight-average molecular weight (Mw) expressed in polystyrene terms using GPC (Gel Permeation Chromatography) of a compound dissolved in tetrahydrofuran.

[0021] Substituent R in general formula (1) 1 and R 2 The appropriate compound can be selected depending on its intended use. For example, when forming a film of the compound of the present invention by a vapor phase process such as vapor deposition, R in general formula (1) 1 and R 2 It is preferable that it is a hydrogen atom.

[0022] Furthermore, when forming a film with the compound of the present invention by a liquid-phase process, R in general formula (1) 1 and R 2 Preferably, at least one of the compounds is an organic group such as an alkyl group, i.e., a compound represented by the following general formula (1-1). [ka] In general formula (1-1), R 11 Each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, and may further have substituents, and may have the following divalent linking group A, where the divalent linking group A is -O-, -S-, -NR 4 R represents a divalent linking group of any of the following: -, -CO-, -SO-, and -SO2-, or a divalent linking group formed by the bonding of two or more of these divalent linking groups. 4R represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, or heteroaryl group. 2 R in general formula (1) 2 These are synonymous and each independently represents a hydrogen atom, a halogen atom, a perfluoroalkylsulfonyloxy group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, and may further have substituents, and may have the following divalent linking group A, where the divalent linking group A is -O-, -S-, -NR 4 R represents a divalent linking group of any of the following: -, -CO-, -SO-, and -SO2-, or a divalent linking group formed by the bonding of two or more of these divalent linking groups. 4 The symbol represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. R 11 Examples of alkyl groups, alkenyl groups, alkynyl groups, aryl groups, or heteroaryl groups represented by and the substituents and divalent linking groups A that these groups may have include groups similar to those in the general formula (1) above. Among them, R 11 It is preferably an aryl group or heteroaryl group which may have substituents and / or divalent linking group group A, and more preferably an unsubstituted C6-C14 aryl group which may have divalent linking group group A, an aryl group represented by the following general formula (2), and a heteroaryl group represented by the following general formula (3). [ka] In general formulas (2) and (3), R 3 Each of these is independently a halogen atom or an alkyl group having 1 to 20 carbon atoms, where n is a number from 1 to 5 and n' is a number from 1 to 3.

[0023] Furthermore, the two R's in general formula (1) 1 Compounds in which the group is a halogen atom or a trifluoromethanesulfonate group, that is, compounds represented by the following general formula (1-2), can be suitably used as synthetic intermediates in the production of the compounds of the present invention described below. [ka] In general formula (1-2), R 12 Each of these independently represents a halogen atom or a perfluoroalkylsulfonyloxy group, R 2 R in general formula (1) 2 These are synonymous and each independently represents a hydrogen atom, a halogen atom, a perfluoroalkylsulfonyloxy group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, and may further have substituents, and may have the following divalent linking group A, where the divalent linking group A is -O-, -S-, -NR 4 R represents a divalent linking group of any of the following: -, -CO-, -SO-, and -SO2-, or a divalent linking group formed by the bonding of two or more of these divalent linking groups. 4 The symbol represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group.

[0024] Among the compounds represented by general formula (1), the compound represented by the following general formula (1') is preferred. [ka] In general formula (1'), R 1 Each of these groups independently represents a hydrogen atom, a halogen atom, a perfluoroalkylsulfonyloxy group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, and may further have substituents, and may have the following divalent linking group A, where the divalent linking group A is -O-, -S-, -NR 4 R represents a divalent linking group of any of the following: -, -CO-, -SO-, and -SO2-, or a divalent linking group formed by the bonding of two or more of these divalent linking groups. 4 The symbol represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. R in general formula (1') 1 The preferred range for each group represented by is R in general formula (1). 1The preferred range is similar to that of each group represented by . Also, the two S (sulfur atoms) in general formula (1') may be other atoms classified as chalcogens, such as O (oxygen atom) or Se (selenium atom), independently of each other.

[0025] The molecular weight of the compound represented by general formula (1') is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less, in order to improve its solubility in the solvent. Furthermore, the molecular weight of the compound represented by general formula (1') is preferably 390 or higher, more preferably 400 or higher, and even more preferably 500 or higher, in terms of improving carrier mobility, durability, and material stability. In the present invention, the compound represented by general formula (1') may be a compound having repeating units (a so-called oligomer).

[0026] When forming a film by a liquid-phase process, the compound represented by general formula (1') is preferably the compound represented by the following general formula (1'-1). [ka] In general formula (1'-1), R 11 Each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, and may further have substituents, and may have the following divalent linking group A, where the divalent linking group A is -O-, -S-, -NR 4 R represents a divalent linking group of any of the following: -, -CO-, -SO-, and -SO2-, or a divalent linking group formed by the bonding of two or more of these divalent linking groups. 4 R represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, or heteroaryl group. 2 R in general formula (1') 2 It is synonymous with [the above]. R in general formula (1'-1) 11 R in general formula (1-1) 11 This is synonymous with R in general formula (1'-1) 11The preferred range for each group represented by is R in general formula (1-1). 11 This is similar to the preferred range for each group represented by .

[0027] If the compound represented by general formula (1') is the same as the compound represented by general formula (1'-2) below, it can be suitably used as a synthetic intermediate in the compound production of the present invention described below. [ka] In general formula (1'-2), R 12 Each of these independently represents either a halogen atom or a perfluoroalkylsulfonyloxy group.

[0028] <Method for producing compounds> An example of a method for producing the compound represented by general formula (1) of the present invention is shown below, but the invention is not limited to this method. The production method shown in the scheme below is an example of a method for producing the compound represented by general formula (1-2) among the compounds represented by general formula (1). R in the scheme below 1 , R 2 and R 12 Each of the units is equivalent to general formulas (1) and (1-2), respectively. R 1 and R 2 Each of these may be introduced using a starting compound having the desired group, or it may be introduced by a known reaction that introduces the desired group after any of the first to fifth steps shown below.

[0029] Method for producing compounds represented by general formula (1-2) As a compound represented by general formula (1), two R 1 A method for producing a compound in which is a halogen atom or a perfluoroalkylsulfonyloxy group, that is, a compound represented by general formula (1-2), includes, for example, the following method having steps 1 to 5. [ka]

[0030] The first step is a cross-coupling reaction between (2-formylthiophen-3-yl)boronic acid and 2,7-dibromophenanthrene to obtain an aldehyde derivative. The reaction conditions for the first step can be based on known conditions such as the Suzuki-Miyaura cross-coupling reaction. The second step is an acetalization reaction step between the aldehyde derivative obtained in the first step and ethylene glycol, yielding a 1,3-dioxolane derivative. The reaction conditions for the second step can be based on known acetalization reaction conditions. The third step involves halogenating the hydrogen atom bonded to the carbon atom at position 5 of the thiophene ring of the 1,3-dioxolane derivative obtained in the second step using a halogenating agent such as 1,2-dibromotetrachloroethane, followed by deacetalization with an acid catalyst, thereby obtaining a halogenated aldehyde derivative. 12 When introducing a perfluoroalkylsulfonyloxy group, perfluoroalkylsulfonic acid and its derivatives can be used instead of the halogenating agent. The reaction conditions for the third step can refer to the conditions for known halogenation and deacetalization reactions. The fourth step involves epoxidizing the aldehyde group of the halogenated aldehyde derivative obtained in the third step, thereby obtaining an epoxy derivative. The reaction conditions for the fourth step can be based on known epoxidation reaction conditions. Step 5 is a cyclization reaction step of the epoxy derivative obtained in Step 4, yielding a compound represented by general formula (1-2). The reaction conditions for Step 5 can be based on known conditions for epoxy group cyclization reactions.

[0031] As a compound represented by general formula (1), R 1 Compounds in which both atoms are hydrogen atoms can be produced, for example, by subjecting a compound represented by general formula (1-2) to a dehalogenation reaction. The dehalogenation reaction can be carried out according to known methods, for example, see Adv. Electron. Mater. 2022,8,2200452.

[0032] Method for producing compounds represented by general formula (1-1) Among the compounds represented by general formula (1), R 1 Compounds represented by general formula (1-1), in which R is an organic group such as an alkyl group, are, for example, compounds represented by general formula (1-2) and a desired organic group (R in general formula (1)). 1 It can be produced by subjecting it to a cross-coupling reaction with organometallic compounds, organoboron compounds, organosilicon compounds, alkenes, alkynes, or amines having the following properties: Cross-coupling reactions involve organic groups (R in general formula (1)). 1 Depending on the type of reaction, a known cross-coupling reaction may be appropriately selected. Examples include, but are not limited to, the Migita-Kosugi-Still coupling, Kumada-Tamao-Colieu coupling, Negishi coupling, Mizorogi-Heck reaction, Sonogashira coupling, Buchwald-Hartwick reaction, Suzuki-Miyaura coupling, and Hiyama coupling. The reaction conditions for cross-coupling can be determined by referring to known methods.

[0033] The compound of the present invention is desired R 1 and R 2 It may also be produced by using a raw material compound having and following a method corresponding to the first to fifth steps described above. However, the R in general formula (1) 1 When producing various compounds of different types, if a compound of general formula (1-2) is used as a synthetic intermediate and a production method having a cross-coupling reaction step is employed, R 1 Because it can produce different compounds, this method can produce a wide variety of compounds of the present invention much more efficiently than the method described above. Similarly, R in general formula (1) 2 If a manufacturing method is used that includes a cross-coupling reaction step, using a compound in which is a halogen atom or a perfluoroalkylsulfonyloxy group as a synthetic intermediate, then R 2 Different compounds can be efficiently produced.

[0034] <Applications of Compounds> In this specification, "organic semiconductor material" refers to an organic material that exhibits semiconductor properties. Similar to semiconductors made of inorganic materials, there are p-type (hole-transporting) organic semiconductor materials that conduct using holes as carriers, and n-type (electron-transporting) organic semiconductor materials that conduct using electrons as carriers. The compounds of the present invention have high carrier mobility (especially hole mobility) and excellent heat resistance, and can therefore be suitably used as organic semiconductor materials, particularly p-type organic semiconductor materials.

[0035] The organic semiconductor material of the present invention comprises a compound represented by general formula (1). The compound represented by general formula (1) alone may be used as an organic semiconductor material at room temperature or by melting it, or it may be used as an organic semiconductor material mixed with other components.

[0036] (liquid) The present invention also relates to a liquid containing a compound represented by general formula (1). In particular, when forming a film of a compound represented by general formula (1) in a liquid-phase process, it is preferable to use a liquid containing the compound represented by general formula (1), and the liquid can be in a form suitable for the application, such as a coating liquid or an ink. The liquid containing the compound represented by general formula (1) is preferably a mixture of the compound represented by general formula (1) and a solvent. Examples of solvents include hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, mesitylene, ethylbenzene, amylbenzene, decalin, 1-methylnaphthalene, 1-ethylnaphthalene, 1,6-dimethylnaphthalene, and tetralin; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, propiophenone, and butyrophenone; and dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, and chloromethane. Halogenated hydrocarbon solvents such as chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, chlorotoluene, 4-fluorotoluene, 1-fluoronaphthalene, and 1-chloronaphthalene; heterocyclic solvents such as pyridine, picoline, quinoline, thiophene, 3-butylthiophene, and thieno[2,3-b]thiophene; 2-chlorothiophene, 3-chlorothiophene, 2,5-dichlorothiophene, 3,4-dichlorothiophene, 2-bromothiophene, 3-bromothiophene, 2,3-dibromothiophene, and 2,4-dibromothiophene. Halogenated heterocyclic solvents such as ofhen, 2,5-dibromothiophene, 3,4-dibromothiophene, and 3,4-dichloro-1,2,5-thiadiazole; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, 2-ethylhexyl acetate, γ-butyrolactone, and phenyl acetate; alcohol solvents such as methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, and ethylene glycol; and dibutyl ether, tetrahydrofuran, and dioxane. Ether-based solvents such as dimethoxyethane, anisole, 1,3-dimethoxybenzene, ethoxybenzene, propoxybenzene, isopropoxybenzene, butoxybenzene, 2-methylanisole, 3-methylanisole, 4-methylanisole, 4-ethylanisole, dimethylanisole (any of 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-, 3,6-), 4-fluoroanisole, 3-phenoxytoluene, 1-methoxynaphthalene, 1,4-benzodioxane, etc., for example, N,N-dimethylformamide, N,Examples include amide-imide solvents such as N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone, and 1,3-dimethyl-2-imidazolidinone; sulfoxide solvents such as dimethyl sulfoxide; phosphate ester solvents such as trimethyl phosphate; nitrile solvents such as acetonitrile and benzonitrile; and nitro solvents such as nitromethane and nitrobenzene. Other solvents suitable for the molecular structure of the compound represented by general formula (1) can be used, and a single solvent may be used, or multiple solvents may be used in combination. Among these, hydrocarbon solvents, halogenated hydrocarbon solvents, heterocyclic solvents, halogenated heterocyclic solvents, or ether solvents are preferred, and from the viewpoint of solubility and film-forming properties of the compound represented by general formula (1), organic solvents having aromatic rings such as anisole, 1,3-dimethoxybenzene, 4-fluoroanisole, 3-phenoxytoluene, 3-chlorothiophene, chlorobenzene, 4-fluorotoluene, butylphenyl ether, o-dichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, and 1-methoxynaphthalene are particularly preferred.

[0037] The concentration of the compound represented by general formula (1) in a solution containing the compound represented by general formula (1) and a solvent is not particularly limited and can be appropriately determined by its solubility in the solvent, but is, for example, 0.005 to 5% by mass, more preferably 0.01 to 3% by mass, and particularly preferably 0.02 to 1% by mass.

[0038] The liquid containing the compound represented by general formula (1) may optionally contain a polymer binder as an optional component, to the extent that it does not impair the effects of the present invention. Polymer binders include insulating polymers such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose, polyethylene, polypropylene, and copolymers thereof, ethylene-propylene rubber, acrylonitrile-butadiene rubber, hydrogenated nitrile rubber, fluororubber, perfluoroelastomer, tetrafluoroethylene propylene copolymer, ethylene-propylene-diene copolymer, styrene-butadiene rubber, polychloroprene, polyneoprene, butyl rubber, methylphenyl silicone resin, and methylphenyl Examples of semiconductor polymers include vinyl-silicone resins, methyl-vinyl-silicone resins, fluorosilicone resins, acrylic rubber, ethylene-acrylic rubber, chlorosulfonated polyethylene, chloropolyethylene, epichlorohydrin copolymers, polyisoprene-natural rubber copolymers, polyisoprene rubber, styrene-isoprene block copolymers, polyester urethane copolymers, polyether urethane copolymers, polyether ester thermoplastic elastomers, and polybutadiene rubber, as well as other rubbers or thermoplastic elastomers, photoconductive polymers such as polyvinylcarbazole and polysilane, conductive polymers such as polythiophene, polypyrrole, polyaniline, and poly(p-phenylenevinylene), and semiconductor polymers as described in, for example, Chemistry of Materials, 2014, 26, 647. The polymer binder may be used alone or in combination of multiple types. While a polymer binder with a high glass transition temperature is preferable for the mechanical strength of the film, a polymer binder with a low glass transition temperature is preferable for the purpose of imparting flexibility to the film. Considering charge mobility, polymer binders with structures that do not contain polar groups or semiconductor polymers are preferable.

[0039] The liquid containing the compound represented by general formula (1) of the present invention may also contain various additives used in organic semiconductor materials, such as surfactants, antioxidants, crystallization control agents, and crystal orientation control agents.

[0040] Examples of surfactants are not limited to these, but include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters, as well as Megafac F171, F176 (manufactured by Dainippon Ink and Chemicals) and Florard FC430 (manufactured by Sumitomo 3M). Examples include fluorinated surfactants such as Surfinol E1004 (manufactured by Asahi Glass Co., Ltd.), PF656 and PF6320 (manufactured by OMNOVA), and organosiloxane polymers such as polysiloxane polymers KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-410 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-412 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-96-100cs (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-322 (manufactured by BYK), and BYK-323 (manufactured by BYK). The surfactant content is preferably about 0.001 to about 1% by mass in the liquid.

[0041] Examples of antioxidants include phenolic antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Specific examples of phenolic antioxidants include 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate, tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 4,4'-butylidenebis-(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate], and 3,9-bis{2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane. Commercially available phenolic antioxidants include Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, Irganox 245, Irganox 259, Irganox 295, and Irganox 3114 (all manufactured by BASF), Adeka Stab AO-20, Adeka Stab AO-30, Adeka Stab AO-40, Adeka Stab AO-50, Adeka Stab AO-60, Adeka Stab AO-70, Adeka Stab AO-80, Adeka Stab AO-90, and Adeka Stab AO-330 (all manufactured by ADEKA), Sumirizer BHT, Sumirizer BP-101, Sumirizer GA-80, Sumirizer MDP-S, Sumirizer BBM-S, Sumirizer Examples include GM, Sumirizer GS(F), and Sumirizer GP (all manufactured by Sumitomo Chemical Co., Ltd.), HOSTANOX O10, HOSTANOX O16, HOSTANOX O14, and HOSTANOX O3 (all manufactured by Clariant), Antage BHT, Antage W-300, Antage W-400, and Antage W500 (all manufactured by Kawaguchi Chemical Industry Co., Ltd.), SEENOX 224M and SEENOX 326M (all manufactured by Cipro Chemical Co., Ltd.), Yoshinox BHT, Yoshinox BB, Tominox TT, Tominox 917 (all manufactured by Yoshitomi Pharmaceutical Co., Ltd.), and TTHP (manufactured by Toray Industries, Inc.). Specific examples of phosphorus-based antioxidants include trisnonylphenyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl) pentaerythritol phosphite, bis(2,6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octyl phosphite, and tetrakis(2,4-di-t-butylphenyl)-4,4-biphenylene-diphosphonite. Commercially available phosphorus-based antioxidants include Adekastab 1178 (manufactured by Asahi Denka Co., Ltd.), Sumirizer TNP (manufactured by Sumitomo Chemical Co., Ltd.), JP-135 (manufactured by Johoku Chemical Co., Ltd.), Adekastab 2112 (manufactured by Asahi Denka Co., Ltd.), JPP-2000 (manufactured by Johoku Chemical Co., Ltd.), Weston 618 (manufactured by GE), Adekastab PEP-24G (manufactured by Asahi Denka Co., Ltd.), Adekastab PEP-36 (manufactured by Asahi Denka Co., Ltd.), Adekastab HP-10 (manufactured by Asahi Denka Co., Ltd.), Sandstab P-EPQ (manufactured by Sand Co., Ltd.), and Phosphite 168 (manufactured by Ciba Specialty Chemicals Co., Ltd.). Specific examples of sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, and pentaerythritol tetrakis(3-laurylthiopropionate). Commercially available sulfur-based antioxidants include Sumirizer TPL (manufactured by Sumitomo Chemical Co., Ltd.), Yoshinox DLTP (manufactured by Yoshitomi Pharmaceutical Co., Ltd.), Antiox L (manufactured by Nippon Oil & Fats Co., Ltd.), Sumirizer TPM (manufactured by Sumitomo Chemical Co., Ltd.), Yoshinox DMTP (manufactured by Yoshitomi Pharmaceutical Co., Ltd.), Antiox M (manufactured by Nippon Oil & Fats Co., Ltd.), Sumirizer TPS (manufactured by Sumitomo Chemical Co., Ltd.), Yoshinox DSTP (manufactured by Yoshitomi Pharmaceutical Co., Ltd.), Antiox S (manufactured by Nippon Oil & Fats Co., Ltd.), Adekastab AO-412S (manufactured by Asahi Denka Co., Ltd.), SEENOX 412S (manufactured by Cipro Chemical Co., Ltd.), and Sumirizer TDP (manufactured by Sumitomo Chemical Co., Ltd.). The antioxidant content is preferably about 0.01 to about 5% by mass in the liquid.

[0042] A liquid containing the compound represented by general formula (1) can be produced by mixing the compound represented by general formula (1), a solvent, a polymer binder, and additives other than polymers under non-heating conditions, or preferably under heating conditions. The heating temperature can be set appropriately depending on the type of solvent, for example, 30 to 200°C.

[0043] (film) The organic semiconductor film of the present invention can be manufactured by a liquid-phase process or a gas-phase process using the compound of the present invention.

[0044] A liquid-phase process involves applying or printing the liquid of the present invention onto a substrate and then drying it. For coating methods, for example, drop casting, spin coating, dip coating, blade coating, edge casting, and continuous edge casting methods can be used. For printing methods, for example, screen printing, inkjet printing, mask printing, offset printing, flexography, microcontact printing, lithography, intaglio printing, and relief printing can be used. After applying or printing the liquid of the present invention onto a substrate, the substrate may be heated or cooled during the drying process to form a film. By changing the temperature of the substrate, it is possible to control the film quality and the packing of molecules within the film. There are no particular restrictions on the temperature of the substrate, but it is preferably between 0°C and 200°C, more preferably between 15°C and 100°C, and particularly preferably between 20°C and 95°C. Furthermore, drying may be carried out under atmospheric pressure or under reduced pressure.

[0045] For the gas phase process, for example, vacuum deposition, physical vapor transport, sputtering, ion plating, etc., can be used.

[0046] The thickness of the organic semiconductor film of the present invention is not particularly limited, but for example, it is preferably about 1 to 1000 nm, more preferably 1 to 100 nm, and even more preferably 1 to 30 nm.

[0047] (Organic semiconductor devices, organic transistors) The present invention also relates to an organic semiconductor device having the compound of the present invention. Preferably, the organic semiconductor device of the present invention is a non-luminescent organic semiconductor device having an organic semiconductor film containing the compound of the present invention. In this specification, "non-luminescent organic semiconductor device" means a device not intended to emit light. In particular, "non-luminescent organic semiconductor device" means a device not intended to emit visible light. It is preferable that the non-luminescent organic semiconductor device is a non-luminescent organic semiconductor device that uses electronic elements having a film layer structure. Non-luminescent organic semiconductor devices include organic transistors, organic photoelectric conversion elements (solid-state image sensors for photosensor applications, solar cells for energy conversion applications, etc.), gas sensors, organic rectifier elements, organic inverters, information recording elements, etc. Organic photoelectric conversion elements can be used for either photosensor applications (solid-state image sensors) or energy conversion applications (solar cells). Preferably, it is an organic photoelectric conversion element or an organic transistor, and more preferably an organic transistor.

[0048] The organic transistor of the present invention has an organic semiconductor film containing the compound of the present invention as a semiconductor active layer. The organic transistor of the present invention may further include other layers in addition to the semiconductor active layer. The organic transistor of the present invention is preferably used as an organic field-effect transistor (FET), and more preferably as an insulated-gate type FET in which the gate-channel is insulated. Figures 1 and 2 are schematic diagrams illustrating an example of an organic transistor having an organic semiconductor film of the compound of the present invention, but the present invention is not limited to these, and known constituent materials other than the semiconductor active layer can be used. Preferred embodiments of each layer of the organic transistor of the present invention will be described below, but the present invention is not limited to these embodiments.

[0049] The organic transistor of the present invention is characterized by having an organic semiconductor film containing the compound of the present invention as a semiconductor active layer. The semiconductor active layer may be a layer made of a compound represented by general formula (1), or it may be a layer further containing the polymer binder in addition to the compound represented by general formula (1). It may also contain residual solvent from the time of film formation. The content of the polymer binder in the semiconductor active layer is not particularly limited, but is preferably in the range of 0 to 95% by mass, more preferably in the range of 10 to 90% by mass, even more preferably in the range of 20 to 80% by mass, and particularly preferably in the range of 30 to 70% by mass. There are no particular restrictions on the thickness of the semiconductor active layer, but if thinning is required, the thickness is preferably 10 to 400 nm, more preferably 10 to 200 nm, and particularly preferably 10 to 100 nm.

[0050] The organic transistor of the present invention preferably includes a substrate. There are no particular restrictions on the substrate material, and known materials can be used. Examples include polyester films such as polyethylene naphthalate (PEN) and polyethylene terephthalate (PET), cycloolefin polymer films, polycarbonate films, triacetylcellulose (TAC) films, polyimide films, and these polymer films laminated onto ultrathin glass, as well as ceramics, silicon, quartz, and glass, with silicon being preferred.

[0051] The organic transistor of the present invention preferably includes electrodes. The constituent materials of the electrodes can be any known conductive material without particular limitations, such as metallic materials or alloys thereof, such as Cr, Al, Ta, Mo, Nb, Cu, Ag, Au, Pt, Pd, In, Ni, and Nd, or carbon materials, or conductive polymers. There are no particular restrictions on the thickness of the electrode, but it is preferable to have a thickness of 10 to 50 nm. There are no particular restrictions on the gate width (or channel width) W and gate length (or channel length) L, but it is preferable that their ratio W / L be 10 or more, and more preferable that it be 20 or more.

[0052] The organic transistor of the present invention preferably includes an acceptor to promote carrier injection. Preferred materials include known materials such as 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ). There are no particular restrictions on the thickness of the acceptor, but it is preferable to keep it to 5 nm or less.

[0053] The materials constituting the insulating layer are not particularly limited as long as the necessary insulating effect is obtained, but examples include silicon dioxide, silicon nitride, fluoropolymer insulating materials such as PTFE (polytetrafluoroethylene), and CYTOP, polyester insulating materials, polycarbonate insulating materials, acrylic polymer insulating materials, epoxy resin insulating materials, polyimide insulating materials, polyvinylphenol resin insulating materials, and polyparaxylylene resin insulating materials. The upper surface of the insulating layer may be surface-treated. For example, an insulating layer in which the silicon dioxide surface has been surface-treated by coating with hexamethyldisilazane (HMDS), octadecyltrichlorosilane (OTS), or β-phenityltrimethoxysilane can be preferably used, and an insulating layer in which the surface has been surface-treated by coating with β-phenityltrimethoxysilane can be more preferably used. There are no particular restrictions on the thickness of the insulating layer, but if thinning is required, the thickness is preferably 10 to 500 nm, more preferably 20 to 200 nm, and particularly preferably 50 to 200 nm.

[0054] Furthermore, the organic transistor of the present invention may be an insulated-gate type FET in which the channel, which is the current path between the drain and source, is insulated from the gate, and may also be a top-gate, top-contact type element or a top-gate, bottom-contact type element in which the insulator and gate electrode are located on top of the semiconductor active layer.

[0055] If a thinner transistor is required, the organic transistor of the present invention preferably has an overall thickness of 0.1 to 0.5 μm, for example.

[0056] Furthermore, in order to shield the organic transistor element from the atmosphere and moisture and improve its shelf life, the entire organic transistor element may be sealed in a metal encapsulant, glass, an inorganic material such as silicon nitride, a polymer material such as parylene, or a low molecular weight material.

[0057] The organic transistor of the present invention can be used, for example, in flexible devices such as electronic paper and flexible displays. Furthermore, the present invention may be used in organic semiconductor devices such as organic photoelectric devices having the organic semiconductor film of the present invention as a photoelectric conversion layer of a photoelectric conversion device, or organic thermoelectric devices having the organic semiconductor film of the present invention as a thermoelectric conversion layer of a thermoelectric conversion device. [Examples]

[0058] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. The method for measuring the physical properties of the synthetic compound is as follows.

[0059] 1 The 1H-NMR spectrum was measured using a JEOL Ltd. JNM-ECZ400S spectrometer. Chemical shifts were expressed in parts per million (ppm). 1 The values ​​shown are based on the residual protons in the deuterated solvent in 1H-NMR, with the reference values ​​being 5.93 ppm for CDCl2 and 7.26 ppm for CDCl3.

[0060] <Synthesis of Compounds> [Example 1] Synthesis of piceno[3,4-b:10,9-b']dithiophene Synthesis of 2,7-bis(2-(oxiran-2-yl)thiophene-3-yl)phenanthrene [ka] 3,3'-(phenanthrene-2,7-diyl)bis(thiophene-2-carbaldehyde) (1.39 g, 3.5 mmol), trimethylsulfonium iodide (1.64 g, 8.1 mmol), and potassium hydroxide (1.08 g, 19.3 mmol) were placed in a flask, purged with argon gas, and then acetonitrile (70 ml) was added. The mixture was heated and stirred at 70°C for 3 hours. The reaction solution was cooled to room temperature, distilled water was added, and then extraction was performed using chloroform. The organic layer was separated and dried over sodium sulfate. After filtering off the sodium sulfate and removing the solvent by distillation, the pale yellow compound described in the title (1.51 g, quant.) was obtained. 1 H NMR (400 MHz, CDCl3) δ 3.16-3.18 (m, 2H), 3.29 (t, J = 4.6 Hz, 2H), 4.21-4.25 (m, 2H), 7.28 (d, J = 5.2 Hz, 2H), 7.35 (d, J = 5.2 Hz, 2H), 7.83 (s, 2H), 7.84 (dd, J = 8.4 Hz, J = 2.0 Hz, 2H), 8.03 (d, J = 1.6 Hz, 2H), 8.77 (d, J = 8.4 Hz, 2H). Synthesis of piceno[3,4-b:10,9-b']dithiophene [ka] 2,7-Bis(2-(oxiran-2-yl)thiophen-3-yl)phenanthrene (778 mg, 1.82 mmol) was placed in a flask, purged with argon gas, and then dichloroethane (91 ml) and indium(III) chloride (80.7 mg, 0.364 mmol) were added. The mixture was heated and stirred under reflux for 13 hours. The reaction solution was cooled to 60°C, and the precipitated solid was collected by filtration. The obtained solid was washed with dichloroethane, then dissolved in 1,2-dichlorobenzene and passed through silica gel to remove the solvent by distillation. Further washing with dichloroethane yielded the pale yellow compound of the title (35 mg, 5%). 1H NMR (400 MHz, CDCl2CDCl2, 100 °C, R = Br) δ 7.68 (d, J = 5.2 Hz, 2H), 8,12 (d, J = 5.2 Hz, 2H), 8.17 (d, J = 8.0 Hz, 2H), 8.59 (d, J = 8.4 Hz, 2H), 8,79 (d, J = 8.8 Hz, 2H), 8.97 (d, J = 8.8 Hz, 2H), 9.00 (s, 2H).

[0061] [Example 2] Synthesis of 2,11-bis(4-decylthiophen-2-yl)piceno[3,4-b:10,9-b']dithiophene (Step 1) Synthesis of 3,3'-(phenanthrene-2,7-diyl)bis(thiophene-2-carbaldehyde) [ka] 2,7-Dibromophenanthrene (12.3g, 36.6 mmol), (2-Formylthiophen-3-yl)boronic acid (13.1g, 84.2 mmol), potassium carbonate (30.6g, 221.4 mmol), and [1,1'-Bis(diphenylphosphino)ferrocene]palladium(II) dichloride dichloromethane adduct (1.5g, 1.8 mmol) were placed in a flask, purged with argon gas, and then THF (396 ml) and argon-purged distilled water (110 ml) were added. The mixture was heated and stirred under reflux for 3 hours. The reaction solution was cooled to room temperature, distilled water (640 ml) was added, the precipitate was filtered off, and washed with distilled water and methanol to obtain the light brown title compound (14.7 g, quant.). 1 H NMR (400 MHz, CDCl3) δ 7.40 (d, J = 4.8 Hz, 2H), 7.81-7.84 (m, 4H), 7.87 (s, 2H), 8.04 (d, J = 1.6 Hz, 2H), 8.82 (d, J = 8.4 Hz, 2H), 10.01(s, 2H).

[0062] (Step 2) Synthesis of 2,7-bis(2-(1,3-dioxolan-2-yl)thiophene-3-yl)phenanthrene [ka] 3,3'-(phenanthrene-2,7-diyl)bis(thiophene-2-carbaldehyde) (14.7 g, 36.9 mmol) and p-toluenesulfonic acid monohydrate (0.71 g, 3.7 mmol) were placed in a flask equipped with a Dean-Stark apparatus, purged with argon gas, and then toluene (740 ml) and ethylene glycol (30.6 ml, 593 mmol) were added. The mixture was heated and stirred under reflux for 2 hours and 30 minutes. The reaction solution was cooled to room temperature, washed with saturated sodium bicarbonate aqueous solution, and the organic layer was extracted. The aqueous layer was then washed with chloroform. The collected organic layer was further washed with saturated sodium chloride aqueous solution, and the organic layer was separated and dried over sodium sulfate. After filtering off the drying agent, the solution was passed through silica gel, and the solvent was removed by distillation to obtain the yellow title compound (16.4 g, 91%). 1 H NMR (400 MHz, CDCl3) δ 4.01-4.09 (m, 4H), 4.22-4.30 (m, 4H), 6.09 (s, 2H), 7.25 (d, J = 5.2 Hz, 2H), 7.43 (d, J = 5.2 Hz, 2H), 7.82 (s, 2H), 7.83 (dd, J = 8.4 Hz, J = 1.8 Hz, 2H), 8.05 (d, J =2.0 Hz, 2H), 8.73 (d, J = 8.4 Hz, 2H)

[0063] (Step 3) Synthesis of halogenated mixture of 3,3'-(phenanthrene-2,7-diyl)bis(thiophene-2-carbaldehyde) [ka] 2,7-Bis(2-(1,3-dioxolan-2-yl)thiophen-3-yl)phenanthrene (16.0 g, 33.0 mmol) was mixed with THF (439 ml) and cooled to 0°C. Then, n-butyllithium (1.56 M, 48.5 ml, 75.9 mmol) was added dropwise and the mixture was stirred for 1 hour. Subsequently, a THF solution of 1,2-dibromotetrachloroethane (2 M, 165 mmol, 82.5 ml) was added dropwise and the mixture was stirred at 0°C for another 1 hour. Then, hydrochloric acid (2 M, 165 ml) was added and the mixture was stirred at room temperature for 16 hours. The precipitate was filtered and washed with heated hexane to obtain the pale yellow compound described in the title (12.9 g, 70%, Br:Cl=2:1). 1 H NMR (400 MHz, CDCl3, R = Br) δ 7.38 (s, 2H), 7.78 (dd, J = 8.4 Hz, J = 2.0 Hz, 2H), 7.87 (s, 2H), 8.01 (d, J = 1.6 Hz, 2H), 8.81 (d, J = 8.4 Hz, 2H), 9.86 (s, 2H).

[0064] (Step 4) Synthesis of halogenated mixture of 2,7-bis(2-(oxiran-2-yl)thiophen-3-yl)phenanthrene [ka] A halogenated mixture of 3,3'-(phenanthrene-2,7-diyl)bis(thiophene-2-carbaldehyde) (12.8 g, 23 mmol), trimethylsulfonium iodide (10.8 g, 52.9 mmol), and potassium hydroxide (7.1 g, 126.5 mmol) was placed in a flask, purged with argon gas, and then acetonitrile (460 ml) was added and the mixture was heated and stirred at 70°C for 13 hours. The reaction solution was cooled to room temperature, distilled water was added, and the precipitated solid was filtered to obtain the pale yellow compound described in the title (12.9 g, 96%, Br:Cl=2:1). 1H NMR (400 MHz, CDCl3, R = Br) δ 3.08-3.10 (m, 2H), 3.25 (t, J = 4.6 Hz, 2H), 4.15-4.17 (m, 2H), 7.23 (s, 2H), 7.78 (dd, J = 8.6 Hz J = 2.2 Hz, 2H), 7.81 (s, 2H), 7.97 (d, J = 2.4 Hz, 2H), 8.74 (d, J = 8.4 Hz, 2H).

[0065] (Step 5) Synthesis of halogenated mixture of piceno[3,4-b:10,9-b']dithiophene [ka] A halogenated mixture of 2,7-bis(2-(oxiran-2-yl)thiophen-3-yl)phenanthrene (12.5 g, 21.4 mmol) was placed in a flask, purged with argon gas, and then dichloroethane (1070 ml), methanol (0.87 ml, 21.4 mmol), and iron(III) chloride (THF, 0.2 M, 21.3 ml) were added. The mixture was heated and stirred under reflux for 4 hours. The reaction solution was cooled to room temperature, methanol was added, and the precipitated solid was collected by filtration. The obtained solid was washed with heated acetone, ethyl acetate, chloroform, toluene, and 1,2-dichlorobenzene, respectively, to obtain the brown compound indicated in the title (3.0 g, 26%, Br:Cl=2:1). 1 H NMR (400 MHz, CDCl2CDCl2, 100 °C, R = Br) δ 8.02 (d, J = 9.6 Hz, 2H), 8.10 (s, 2H), 8.45 (d, J = 9.2 Hz, 2H), 8.76 (d, J = 9.2 Hz, 2H), 8.94-8.97 (m, 4H)

[0066] (Step 6) Synthesis of 2,11-bis(4-decylthiophen-2-yl)piceno[3,4-b:10,9-b']dithiophene [ka] A halogenated mixture of piceno[3,4-b:10,9-b']dithiophene (467 mg, 0.85 mmol) and (4-decylthiophen-2-yl)trimethylstannane (989 mg, 2.55 mmol) were placed in a flask, purged with argon gas, and then NMP (43 ml), LiCl (0.5 M in THF, 5.1 ml, 2.55 mmol), and Pd(PPh3)4 (97.2 mg, 0.085 mmol) were added. The mixture was heated and stirred at 140°C for 5 hours. The reaction solution was cooled to room temperature, and potassium fluoride aqueous solution was added and stirred. The precipitated solid was filtered and washed with distilled water and methanol. The resulting crude product was purified by recrystallization using anisole and silica gel column chromatography (eluent: chloroform, heptane). The obtained solid was dissolved in heated orthodichlorobenzene, passed through silica gel, alumina, and Florisil, and the filtrate was concentrated to obtain the pale yellow compound indicated in the title (67 mg, 9%). Hereinafter, the compound obtained in Example 2 will be referred to as C10Th-PiDT-α. 1 H NMR (400 MHz, CDCl2CDCl2, 100 °C) δ 0.90 (t, J = 5.6 Hz, 6H), 1.24-1.39 (m, 28H), 1.65-1.74 (m, 4H), 2.65 (t, J = 8.4 Hz, 4H), 6.95 (s, 2H), 7.24 (s, 2H), 8.06 (d, J = 6.8 Hz, 2H), 8.12 (s, 2H), 8.56 (d, J = 9.2 Hz, 2H), 8.75 (d, J = 9.6 Hz, 2H), 8.95 (d, J = 9.6 Hz, 2H), 8.97 (s, 2H)

[0067] [Example 3] Synthesis of 2,11-diphenylpiceno[3,4-b:10,9-b']dithiophene [ka] After replacing the flask with argon gas, phenylmagnesium bromide (0.725 M in THF, 3.79 ml, 2.75 mmol), zinc chloride (1 M in THF, 3.03 ml, 3.03 mmol), and lithium chloride (0.5 M in THF, 6.05 ml, 3.03 mmol) were added at 0°C and the mixture was stirred for 15 minutes at 0°C. Then, xylene (27.5 ml), the halogenated mixture of piceno[3,4-b:10,9-b']dithiophene obtained in step 5 of Example 2 (302 mg, 0.55 mmol), and [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride dichloromethane adduct (26.9 mg, 0.033 mmol) were added and the mixture was heated and stirred under reflux for 6.5 hours. After the reaction solution was cooled to room temperature, methanol was added and the precipitated solid was collected by filtration. The obtained solid was dissolved in heated orthodichlorobenzene, passed through silica gel, alumina, and Florisil, and the filtrate was concentrated to obtain the crude product. Further purification was performed by recrystallization using orthodichlorobenzene to obtain the pale yellow compound indicated in the title (78 mg, 14%). Hereinafter, the compound obtained in Example 3 will be referred to as Ph-PiDT-α. 1 H NMR (400 MHz, CDCl2CDCl2, 100 °C) δ 7.36-7.40 (m, 2H), 7.38 (t, J = 7.4 Hz, 4H), 7.84 (d, J = 7.6 Hz, 4H), 8.13 (d, J = 9.2 Hz, 2H), 8.31 (s, 2H), 8.62 (d, J = 8.8 Hz, 2H), 8.78 (d, J = 8.8 Hz, 2H), 8.98 (d, J = 8.4 Hz, 2H), 9.00 (s, 2H).

[0068] [Example 4] Synthesis of 2,11-bis(4-octylphenyl)piceno[3,4-b:10,9-b']dithiophene [ka] 1-Bromo-4-octylbenzene (161.4 mg, 0.60 mmol) was placed in a flask, purged with argon gas, and then THF (1.2 ml) was added and stirred. After cooling to -78°C, n-butyllithium (1.56 M in hexane, 0.38 ml, 0.59 mmol) was added dropwise and stirred at -78°C for 30 minutes. Then, zinc chloride (1 M in THF, 0.63 ml, 0.63 mmol) was added dropwise and stirred at 0°C for 15 minutes, after which the solvent was removed by distillation. Dioxane (1.2 ml), xylene (7.5 ml), and [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride dichloromethane adduct (9.78 mg, 0.012 mmol) were added to prepare the organozinc reagent. The halogenated mixture of piceno[3,4-b:10,9-b']dithiophene obtained in step 5 of Example 2 (27.4 mg, 0.05 mmol) was placed in three Schlenk tubes, each replaced with argon gas, and the organozinc reagent was divided into three equal parts and added to each Schlenk tube. The mixture was heated and stirred under reflux for 6 hours. After the reaction solution was cooled to room temperature, methanol was added to each of the three Schlenk tubes, and the precipitated solids were combined and filtered off. The obtained solids were dissolved in heated orthodichlorobenzene, passed through silica gel, alumina, and Florisil, and the filtrate was concentrated to obtain the crude product. Further purification was performed by recrystallization using orthodichlorobenzene, and washing with methanol to obtain the pale yellow title compound (26 mg, 23%). Hereinafter, the compound obtained in Example 4 will be referred to as C8Ph-PiDT-α. 1H NMR (400 MHz, CDCl2CDCl2, 100 °C) δ 0.86-0.92 (m, 6H), 1.24-1.39 (m, 20H), 1.65-1.74 (m, 4H), 2.68 (t, J = 7.6 Hz, 4H), 7.29(d, J = 7.6 Hz, 4H), 7.74 (d, J = 7.6 Hz, 4H), 8.11 (d, J = 8.8 Hz, 2H), 8.26 (s, 2H), 8.61 (d, J = 9.2 Hz, 2H), 8.76 (d, J = 9.2 Hz, 2H), 8.97 (d, J = 9.0 Hz, 2H), 8.99 (s, 2H).

[0069] <Manufacturing and Evaluation of Disposable Organic Semiconductor Thin-Film Transistors> [Example 2: C10Th―PiDT-α] Figure 1 shows a schematic diagram of an organic transistor fabricated using the compound obtained in Example 2. A P-doped Si substrate with a thermal oxide film of SiO2 (thickness: 200 nm) on its surface was used as a substrate for measuring the characteristics of organic transistors. To control wettability, the surface of the thermal oxide film was coated with an insulating resin (50 nm). The powder of the compound obtained in Example 2 was weighed into a screw vial, and 1-chloronaphthalene was added as a solvent to a concentration of 0.05 wt%. The mixture was then heated on a hot plate at 100°C until completely dissolved. The resulting organic semiconductor solution was applied to the above-mentioned organic transistor characteristic measurement substrate on the hot plate by edge casting, and the solvent was evaporated by heating to 70°C to form an organic semiconductor thin film. After the thin film formation, it was annealed in a vacuum oven at 60°C for 12 hours. Next, numerous organic transistors were fabricated using the deposited crystal film as the active layer, and their mobility was calculated from their transfer characteristics. First, a metal shadow mask designed to have a channel length of 20 μm or 50 μm was placed on the thin film, and 5 nm of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), which is the acceptor molecule, and 40 nm of gold (Au) were deposited as carrier implantation electrodes using vacuum deposition. To prevent current from flowing outside the channel, the active layer was formed by etching with a pulsed laser with a wavelength of 266 nm. Using a Keithley 4200-SCS semiconductor parameter analyzer, the transfer characteristics were measured under air conditions and with a drain voltage of -80 V, by sweeping the gate voltage in the range of +10 V to -80 V. From the obtained transfer characteristics, the hole mobility in the saturation region was calculated according to the following formula.

number

[0070] [Example 3: Ph-PiDT-α] Figure 2 shows a schematic diagram of an organic transistor fabricated using the compound obtained in Example 3. A P-doped Si substrate with a thermal oxide film of SiO2 (thickness: 500 nm) on its surface was used as a substrate for measuring the characteristics of organic transistors. To eliminate the OH groups on the surface of the thermal oxide film, which serve as trapping sites for conduction carriers, the substrate was UV-ozone cleaned and then surface-modified with trimethoxy(1H,1H,2H,2H-heptadecafluorodecyl)silane (F-DTS). Organic semiconductor thin films were fabricated using a physical vapor transport method. This method was performed in a two-zone tubular furnace under an argon flow (30 mL / min), with the high-temperature side set to 390°C and the low-temperature side to 310°C. The obtained organic semiconductor thin film was attached to a substrate, and a metal shadow mask designed to have a channel length of 100 μm was placed on the organic semiconductor thin film. 5 nm of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) and 100 nm of gold (Au) were deposited as carrier implantation electrodes using vacuum deposition. The transfer characteristics of the fabricated organic transistors were measured using a Keithley 4200-SCS semiconductor parameter analyzer under atmospheric pressure and a drain voltage of -150 V, with the gate voltage swept from +30 V to -150 V. The hole mobility in the saturation region was calculated according to the above formula.

[0071] [Example 4: C8Ph―PiDT-α] Using the powder of the compound obtained in Example 4, an organic semiconductor thin film was prepared by dissolving it at a concentration of 0.03 wt% on a hot plate at 120°C, heating it to 120°C to evaporate the solvent, and then annealing the thin film in a vacuum oven at 80°C for 12 hours. An organic transistor was then fabricated in the same manner as in Example 2, and its characteristics were evaluated.

[0072] Table 1 shows the organic transistor characteristics of each compound measured above. For comparison, the characteristics of compound (1-1) (hereinafter referred to as "PiDT-β") and compound (1-18) (hereinafter referred to as "C8-PiDT-β") described in Patent Document 1, which have isomers of the skeletal structure, are also listed in Table 1 below as comparative examples, based on the description in the same document. Furthermore, the hole mobility value was determined to fall into one of the following evaluation criteria, and the results are also listed in Table 1. Evaluation Criteria A: 3.1 × 10 0 cm 2 / Vs or more B: 1.1 × 10 0 cm 2 / Vs or more 3.1×10 0 cm 2 / Vs less than C:5.1×10 -1 cm 2 / Vs or more 1.1×10 0 cm 2 / Vs less than D: 5.1 × 10 -1 cm 2 / Vs less than [Table 1] The compounds in Examples 2 and 4 could be fabricated by coating crystallization (edge ​​casting), and the compound in Example 3 could be fabricated by physical vapor transport; all exhibited high hole mobility. In particular, the high mobility of C8Ph-PiDT-α in Example 4 was found to make it even more preferable as an organic semiconductor material. [Explanation of Symbols]

[0073] 10 P-doped Si substrate (gate electrode) 20 Thermal oxide film SiO2 30 Insulating resin coating layer or F-DTS surface modification layer 40. Organic semiconductor film (semiconductor active layer) 50 F4-TCNQ (Acceptor) 60 gold (carrier injection electrode)

Claims

1. A compound represented by the following general formula (1). 【Chemistry 1】 (In general formula (1), R 1 and R 2 Each independently represents a hydrogen atom, a halogen atom, a perfluoroalkylsulfonyloxy group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, and may further have substituents, and may have the following divalent linking group A, where the divalent linking group A is -O-, -S-, -NR 4 -, -CO-, -SO-, and -SO 2 - represents any of the divalent linking groups, or a divalent linking group formed by the bonding of two or more of these divalent linking groups, R 4 (This represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, or heteroaryl group.)

2. The compound according to claim 1, wherein the molecular weight is 3000 or less.

3. The compound according to claim 1, wherein the compound represented by the general formula (1) is the compound represented by the following general formula (1-1). 【Chemistry 2】 (In general formula (1-1), R 11 independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group, may further have a substituent, and may have a divalent linking group group A described below. The divalent linking group group A is -O-, -S-, -NR 4 -, -CO-, -SO- and -SO 2 - represents any divalent linking group, or a divalent linking group formed by bonding two or more of these divalent linking groups. R 4 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group. R 2 is synonymous with R 2 in general formula (1).)

4. In the above general formula (1-1), R 11 However, each independently represents an aryl group or a heteroaryl group, and may also have substituents, and may have the following divalent linking group A, where divalent linking group A is -O-, -S-, -NR 4 -, -CO-, -SO-, and -SO 2 - represents any of the divalent linking groups, or a divalent linking group formed by the bonding of two or more of these divalent linking groups, R 4 The compound according to claim 3, wherein is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group.

5. In the above general formula (1-1), R 11 However, independently of each other, an unsubstituted aryl group having 6 to 14 carbon atoms, an aryl group represented by the following general formula (2), or a heteroaryl group represented by the following general formula (3), or these groups may have the following divalent linking group group A, where the divalent linking group group A is -O-, -S-, -NR 4 -, -CO-, -SO-, and -SO 2 - represents any of the divalent linking groups, or a divalent linking group formed by the bonding of two or more of these divalent linking groups, R 4 The compound according to claim 4, wherein is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. 【Transformation 3】 (In general formulas (2) and (3), R 3 Each of these is independently a halogen atom or an alkyl group having 1 to 20 carbon atoms, where n is a number from 1 to 5 and n' is a number from 1 to 3.

6. The compound according to claim 1, wherein the compound represented by the general formula (1) is the compound represented by the following general formula (1-2). 【Chemistry 4】 (In general formula (1-2), R 12 Each of these independently represents a halogen atom or a perfluoroalkylsulfonyloxy group, R 2 R in general formula (1) 2 (This is synonymous with...)

7. A compound represented by the following general formula (1'). 【Transformation 5】 (In general formula (1'), R 1 Each independently represents a hydrogen atom, a halogen atom, a perfluoroalkylsulfonyloxy group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, and may further have substituents, and may have the following divalent linking group A, where the divalent linking group A is -O-, -S-, -NR 4 -, -CO-, -SO-, and -SO 2 - represents any of the divalent linking groups, or a divalent linking group formed by the bonding of two or more of these divalent linking groups, R 4 (This represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, or heteroaryl group.)

8. The compound according to claim 7, wherein the molecular weight is 3000 or less.

9. The compound according to claim 7, wherein the compound represented by the general formula (1') is the compound represented by the following general formula (1'-1). 【Transformation 6】 (In general formula (1'-1), R 11 Each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, and may further have substituents, and may have the following divalent linking group A, where the divalent linking group A is -O-, -S-, -NR 4 -, -CO-, -SO-, and -SO 2 - represents any of the divalent linking groups, or a divalent linking group formed by the bonding of two or more of these divalent linking groups, R 4 (This represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, or heteroaryl group.)

10. In the above general formula (1'-1), R 11 However, each independently represents an aryl group or a heteroaryl group, and may also have substituents, and may have the following divalent linking group A, where divalent linking group A is -O-, -S-, -NR 4 -, -CO-, -SO-, and -SO 2 - represents any of the divalent linking groups, or a divalent linking group formed by the bonding of two or more of these divalent linking groups, R 4 The compound according to claim 9, wherein is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group.

11. In the above general formula (1'-1), R 11 However, independently of each other, an unsubstituted aryl group having 6 to 14 carbon atoms, an aryl group represented by the following general formula (2), or a heteroaryl group represented by the following general formula (3), or these groups may have the following divalent linking group group A, where the divalent linking group group A is -O-, -S-, -NR 4 -, -CO-, -SO-, and -SO 2 - represents any of the divalent linking groups, or a divalent linking group formed by the bonding of two or more of these divalent linking groups, R 4 The compound according to claim 10, wherein is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. 【Transformation 7】 (In general formulas (2) and (3), R 3 Each of these is independently a halogen atom or an alkyl group having 1 to 20 carbon atoms, where n is a number from 1 to 5 and n' is a number from 1 to 3.

12. The compound according to claim 7, wherein the compound represented by the general formula (1') is the compound represented by the following general formula (1'-2). 【Transformation 8】 (In general formula (1'-2), R 12 (Each of these terms independently represents a halogen atom or a perfluoroalkylsulfonyloxy group.)

13. A method for producing the compound according to claim 3, comprising a cross-coupling reaction step using a compound represented by the following general formula (1-2). 【Chemistry 9】 (In general formula (1-2), R 12 Each of these independently represents a halogen atom or a perfluoroalkylsulfonyloxy group, R 2 Each independently represents a hydrogen atom, a halogen atom, a perfluoroalkylsulfonyloxy group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, and may further have substituents, and may have the following divalent linking group A, where the divalent linking group A is -O-, -S-, -NR 4 -, -CO-, -SO-, and -SO 2 - represents any of the divalent linking groups, or a divalent linking group formed by the bonding of two or more of these divalent linking groups, R 4 (This represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, or heteroaryl group.)

14. An organic semiconductor material comprising the compound described in any one of claims 1 to 12.

15. A liquid containing the compound according to any one of claims 1 to 12.

16. An organic semiconductor film comprising the compound according to any one of claims 1 to 12.

17. An organic semiconductor device having an organic semiconductor film according to claim 16.

18. An organic transistor having an organic semiconductor film according to claim 16.

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